European Commission Final report

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1 European Commission Final report Analysis of the likelihood, risks and consequences of major accidents involving category acute toxic 3 dermal substances and assessment of the impact of covering this category under Seveso (contract /ENV/2012/628236/C3) AMEC Environment & Infrastructure UK Limited

2 Copyright and Non-Disclosure Notice The contents and layout of this report are subject to copyright owned by AMEC ( AMEC Environment & Infrastructure UK Limited 2013). save to the extent that copyright has been legally assigned by us to another party or is used by AMEC under licence. To the extent that we own the copyright in this report, it may not be copied or used without our prior written agreement for any purpose other than the purpose indicated in this report. The methodology (if any) contained in this report is provided to you in confidence and must not be disclosed or copied to third parties without the prior written agreement of AMEC. Disclosure of that information may constitute an actionable breach of confidence or may otherwise prejudice our commercial interests. Any third party who obtains access to this report by any means will, in any event, be subject to the Third Party Disclaimer set out below. Third-Party Disclaimer Any disclosure of this report to a third party is subject to this disclaimer. The report was prepared by AMEC at the instruction of, and for use by, our client named on the front of the report. It does not in any way constitute advice to any third party who is able to access it by any means. AMEC excludes to the fullest extent lawfully permitted all liability whatsoever for any loss or damage howsoever arising from reliance on the contents of this report. We do not however exclude our liability (if any) for personal injury or death resulting from our negligence, for fraud or any other matter in relation to which we cannot legally exclude liability. Document Revisions No. Details Date 1 Intermediate report 8 March Revised intermediate report 24 April Draft final report 13 May Final report 10

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4 iv Executive Summary This report This report presents the results of a study to gather and assess data related to the likelihood, risks and consequences of major accidents involving certain chemical substances that are classified under EU legislation as acutely toxic via the dermal exposure route ( acute toxic 3 dermal substances). Following alignment of the Seveso directive on the control of major-accident hazards involving dangerous substances with the globally harmonised system for classification and labelling, these substances were ultimately not included within the scope of the Seveso III Directive (2012/18/EU), while other substance types were (e.g. acute toxic 3 inhalation substances). Scope of work The objectives of the project were to: collect and analyse data on major accidents and near misses over the past 10 years, with a view to assessing the relevance and impact of each exposure route and toxicity level, focusing on dangerous substances classified as acute toxic 3; complement this analysis with an analysis of major accident scenarios, to assess the importance of various exposure routes, in particular for the acute toxic 3 category (in terms of frequency and impact of major accidents); draw conclusions on the need to cover, not cover or partially cover acute toxic 3 dermal substances under Seveso; and undertake an assessment of the economic, administrative and social impacts of possible amendments to Seveso to include these substances. Acute dermal and inhalation toxicity Classification of substances for both inhalation and dermal toxicity is based on standard laboratory tests. Substances relevant for these two exposure routes have been a key focus of the study, particularly given that substances classified as acute toxic 3 for inhalation toxicity are included within the scope of Seveso while those classified as acute toxic 3 for dermal toxicity are not. Both routes, in principle, have the potential to be relevant in the case of a major accident. There is already an existing body of occupational safety and health legislation in place in the EU, which places requirements on employers to prevent and manage accidents involving dangerous substances within the workplace including the substances that are the subject of the current study.

5 v Consultation It was not practicable within this study to consult with everyone potentially affected by a change in scope of the directive to include acute toxic 3 dermal substances. With the aim of gathering expert opinion and data on the implications of a change to the directive, an on-line survey was launched in late 2012, in which over 1000 organisations and individuals were approached. Additional direct enquiries were made with identified suppliers of chemicals classified as acute toxic 3 dermal, in order to better understand the potential implications of a change to the directive. The level of response was satisfactory and in line with the expectations at the outset of this study, for what is a relatively niche issue. Number of chemical substances potentially affected Around 200 substances were identified as having classification as acute toxic 3 dermal that is 'harmonised' at an EU level and incorporated in the CLP Regulation. However, many of these are also classified for other health or environmental effects, meaning that establishments holding large inventories of these chemicals will already fall within the scope of Seveso. There are also many other substances that do not have EU-harmonised classification as acute toxic 3 dermal but which may be self-classified as such by some (but often not all) of the chemical suppliers, based on available data on toxicity. This means that companies holding large inventories of these substances could also fall within the scope of the directive. Data on past accidents Several national and international databases on historical accidents were reviewed, covering over 55,000 accidents. Around 800 were of relevance for the current study and, of these, significantly more accidents in the period 2000 to 2012 involved the inhalation exposure route (57.5%) as compared to those involving the dermal exposure route (3.6%). Furthermore, past accidents involving the toxic dermal exposure route led to lower human consequences than those involving the toxic inhalation exposure route. Overall, these data suggest that the risk generated by products that are acute toxic category 3 for inhalation exposure is higher than the risk generated by products that are acute toxic category 3 for dermal exposure. No accidents involving acute toxic 3 dermal substances were identified where there were consequences outside the establishment while 65 accidents with consequences outside the establishment were identified involving substances that are acute toxic 3 for inhalation exposure. However, some accidents involving substances that are acute toxic 3 dermal may have led to severe consequences (i.e. potentially major accidents as defined in the Seveso directive). Development of accident scenarios In order to compare the significance of the inhalation and dermal exposure routes, a number of accident scenarios have been developed. There are numerous uncertainties in assessing the potential consequences of accidents

6 vi involving these substances, and the uncertainties are greater for substances classified for acute dermal toxicity than for those classified for inhalation toxicity. Accident scenarios were developed using a selection of substances intended to represent the range of toxicity values for substances falling within the category acute toxic 3 for inhalation exposure and for dermal exposure. For 4 out of the 5 scenarios, the distances at which lethal effects are likely to be felt are greater for toxic inhalation exposure than for dermal toxic dermal exposure (by a factor of between 1.1 and 1000). No significant difference was found for the 5th scenario. Whilst, in theory, the expected effects of accidents involving acute toxic 3 dermal substances could be greater than those assessed in this study (for example with substances combining dermal toxicity and severe skin corrosions effects, and/or having a very rapid absorption rates), such a substance has not been found among the identified substances relevant for this study. Although a major accident potential does exist for substances classified as acute toxic 3 dermal, these accidents are unlikely compared to accidents related to toxic exposure through the inhalation route. They are also unlikely to produce the same level of harmful/lethal consequences in the event that they do occur. Overall, evidence from past accidents and analysis of possible accident scenarios suggest that it may be justifiable to apply a different approach to controlling major hazards related to substances classified as acute toxic 3 dermal compared to that which applies for acute toxic 3 inhalation substances. Potential costs and benefits of a change in scope The two key elements determining the economic implications of a possible change to the directive are: (a) the number of establishments potentially affected, including establishments newly covered by the directive, those with increased requirements due to a change from the lower to upper tier under Seveso and those existing Seveso establishments that would face additional compliance requirements because they hold inventories of these substances in addition to other existing Seveso-relevant substances; and (b) the additional cost per establishment related to changes to the directive, compared to the baseline situation. It is not possible to derive a fully accurate estimate of the number of establishments that would be affected, as has been confirmed by the major EU trade associations and some of the largest suppliers of the relevant chemicals during the consultation undertaken for this study. Nonetheless, it is clear that the most significant costs would be associated with establishments newly coming into the scope of the directive, particularly those that would become upper tier establishments as a result of holding large inventories of acute toxic 3 dermal substances. It is estimated that as many as 500 establishments could newly come into the scope of the directive, with some being upper tier and others lower tier. Only a modest number (15-30) of establishments would be expected to change tier as a result of a change in scope, based on extrapolation from data in France and the UK. There would also be a substantial number of existing establishments (estimated at around 200) which could be affected by a change in scope due to the need to address additional substances, but which would not change tier.

7 vii Whilst there are various uncertainties involved, the overall additional costs (over and above the baseline situation) to establishments of a change in scope could be in the range of 10 million to 60 million per year (as an equivalent annualised cost), depending on the data used for per-establishment costs and assumptions regarding numbers of establishments affected. Costs will vary significantly by establishment and amongst Member States and these estimates do not include technical modifications to plant/equipment, which are considered too variable and too uncertain to quantify in a high-level analysis such as this. The figure below illustrates the range of cost estimate for operators of establishments. Total EU costs using different sources for per-establishment costs ( m, equivalent annual costs) Total equivalent annual cost ( m/yr) impact assessment Consultation for current study UK authorities' estimates Chemical industry estimates 0 In addition, administrative costs for competent authorities associated with a change in scope are estimated to be in the region of 4 million per year (as an annualised value for the EU as a whole). The costs per establishment of being covered by the Seveso directive are relatively high, in the order of several tens of thousands of Euros per year (excluding technical modifications to plant). This is particularly true for establishments that would become upper tier Seveso establishments as a result of a change. There could be significant affordability implications for such establishments, particularly for micro or small-sized enterprises, where the costs could be equivalent to such a large proportion of the average gross operating surplus of companies (using the chemical industry as an example) that it could have an impact on business viability. While in practice few SMEs would probably be affected (since most Seveso sites are thought to be owned/operated by large

8 viii companies), those that would be affected by a change in scope could bear proportionately much higher costs than large companies. One way of comparing these costs to the potential benefits is to consider whether incurring these costs can be justified in terms of the potential harm to humans and the environment that would be avoided. The concept of the value of a statistical life (VOSL) puts a monetary value on the willingness to accept slightly higher or lower levels of risk of 1-2 million, and has been used here in preference to other measures (such as value of life years lost) because of the acute nature of the effects of the substances concerned. The above cost estimates for operators are equivalent to between 5 and 60 times the VOSL estimates provided in the Commission's impact assessment guidelines, implying that this number of fatal accidents would need to be avoided each year in order for the benefits of including these substances to outweigh the risks of not imposing this additional level of regulation (taking into account fatalities alone). Conclusions on the merits of a change in scope The costs of including acute toxic 3 dermal substances in the scope of Seveso could be significant, so it is important that there would be benefits in terms of reduced risks of death and injury to people on-site and off-site at establishments that would be affected. A review of past accidents indicates that significantly more accidents in recent years involved the inhalation exposure route than the dermal exposure route and accidents involving the toxic dermal exposure route tend to lead to lower human consequences than those involving the toxic inhalation exposure route. Likewise, consideration of a number of accident scenarios involving substances relevant for acute toxicity via the inhalation and dermal routes suggests that serious accidents involving the latter are less likely to occur and are also unlikely to produce the same harmful/lethal consequences in the event that they do occur. Nonetheless, future major accidents involving acute toxic 3 dermal substances cannot be definitively ruled out.

9 ix Contents 1. Introduction Study Background Project Tasks Purpose and Structure of the Report Purpose of this report Structure of this report General Considerations about Inhalation and Dermal Toxicity Inhalation toxicity Dermal toxicity Classification of substances for the inhalation and dermal routes Risk management under other occupational legislation Methodology Overview Stakeholder Consultation Overview Consultation questionnaire Additional consultation with manufacturer/importers of chemicals Review of Accident Data Development of Accident Scenarios Assessment of Economic Impacts Identification of Substances Potentially Affected Review of Hazard Classification Data Background Method Results Substances Potentially Affected Harmonised Classification Substances Potentially Affected Self-classification Substances Identified in Previous Studies Results of Stakeholder Consultation Overview 33

10 x 4.2 Main Project Consultation Summary of response levels Main findings by question area Key conclusions Additional Consultation with Industry Analysis of Data on Past Accidents Background Accident Databases Overview Uses of accident databases Accident databases selected The compiled database Analysis of the Compiled Database Overview Methodology Comparison of the number of accidents involving dermal exposure and those involving inhalation exposure Comparison of human consequences of accidents involving dermal exposure and those involving inhalation exposure Comparison of environment and property damages of accidents involving dermal exposures and those involving inhalation exposures Key Conclusions Accident Scenarios Detailed Methodological Approach General discussion Scenario selection Selection of the substances studied Consequence calculations Scenario Selection Description of scenarios A first step in the quantification of the effects: basic hypothesis Selection of Substances used for Consequence Calculations Overview Substances that are classified acute toxic 3 for dermal and inhalation route 75

11 xi Substances that are classified Acute Toxic 3 for dermal exposure and that are not covered under Seveso III for other health hazard Substances identified in the stakeholder consultation exercise Summary of selected substances Lethal Concentrations of Products Comparison between inhalation and dermal route general consideration Extrapolation and uncertainties Comparison of inhalation and dermal route with Mc Dougal s approach Substances Selected for Analysis in Accident Scenarios Scenario Modeling Overview Scenario Scenario Scenario Scenario Scenario Synthesis Conclusions on Accident Scenarios Potential Socio-economic Impacts Overview Types of establishments affected How establishments would be affected Possible number of establishments affected Data sources Non-Seveso establishments coming into scope Number of establishments moving from lower to upper tier Number of Seveso establishments not changing tier Summary of number affected and cross-checking Per-establishment costs of amendment to Seveso Background Impact assessment for the Seveso II directive Consultation for the present study Cost estimates from UK authorities Chemical industry estimates Summary of cost estimates 118

12 xii 7.6 Overall costs Costs to operators Costs to authorities Social impacts Significance of costs Impacts on SMEs Study Conclusions Work undertaken Substances potentially affected Stakeholder consultation Review of accident databases Development of accident scenarios Potential costs and benefits of a change in scope Conclusions on the merits of a change in scope 132 Table 2.1 Key stages in implementation of the study questionnaire 15 Table 3.1 Identification and prioritisation of chemical substances as potentially affected by a change in scope 21 Table 3.2 Substances classified as H311 but not other relevant health effects, and also REACH registered 22 Table 3.3 Potentially relevant substances identified through stakeholder consultation 27 Table 4.1 Questionnaire responses on potential number of establishments affected 38 Table 4.2 Survey responses on estimated costs of inclusion in Seveso ( per establishment) 39 Table 4.3 Summary of responses received (up to 6 March 2013) on potential numbers of establishments relevant to REACHregistered substances 43 Table 5.1 Uses of accident databases (Pineau, 1997) 45 Table 5.2 Number of accidents occurred in some countries (among the 794 accidents) 50 Table 5.3 Comparison of the proportion of activities linked to a major accident recorded in the compiled database for the Table 5.4 French dataset and the dataset concerning other countries 51 Comparison of the proportion of main substances involved in major accident recorded in the compiled database for the French dataset and the other countries dataset 52 Table 5.5 Detailed analysis of the 29 accidents potentially involving dermal exposure route 56 Table 5.6 Classification for acute toxicity (dermal and inhalation exposure routes) for accidents with toxic effects 57 Table 5.7 Details on classification of the 21 main substances (+1) (dermal toxicity and skin corrosion hazards) 57 Table 5.8 Details on classification of the 21 main substances (+1) (inhalation toxicity) 58 Table 5.9 Detailed classification of the 10 main substances 58 Table 5.10 Consequences of accidents involving toxic dermal and inhalation exposure routes 60 Table 6.1 Loss of containment events identified in accident database analysis 72 Table 6.2 Scenarios selected 73 Table 6.3 Toxicity data for substance identified in the review of CLP and REACH data 81 Table 6.4 Toxicity data for substances acute toxic 3 dermal and acute toxic 4 inhalation 82 Table 6.5 Toxicity data for selected substances with clearly defined data 85 Table 6.6 Identification of whether toxicity data are available in REACH registrations for substances identified through stakeholder consultation 86 Table 6.7 Classification and LD 50/LC 50 values for selected substances 88 Table 6.8 Extrapolation factors for selected substances 95 Table 6.9 Lethal dose values for substances used in modelling accident scenarios 96 Table 6.10 Equivalent concentrations to dermal thresholds LD Table 6.11 Scenario 1 Effects distances 99 Table 6.12 Saturation concentration 99 Table 6.13 Scenario 2 Effects distances 100

13 xiii Table 6.14 Scenario 3 Distances to rain-out 101 Table 6.15 Scenario 5 Distances to rain-out 103 Table 6.16 Substances investigated related to coverage shown in Figure Table 6.17 Synthesis of the results of the scenario assessment 104 Table 7.1 Additional requirements for establishments affected by possible change in the scope of the directive 110 Table 7.2 Summary of estimated numbers of establishments affected by possible change in scope of the directive 113 Table 7.3 Survey responses on estimated costs of additional requirements under Seveso ( per establishment) 115 Table 7.4 Estimated costs of compliance per establishment based on survey results 116 Table 7.5 Estimated costs of compliance per establishment based on UK data 116 Table 7.6 Estimated costs of compliance per establishment based on Cefic data 118 Table 7.7 Summary of cost estimates per establishment ( k, equivalent annual costs) 118 Table 7.8 Total EU cost estimates ( m, equivalent annual costs, central estimate of number of establishments) 119 Table 7.9 Total administrative costs to EU competent authorities ( k, equivalent annual costs) 121 Table 7.10 Annual cost estimates per establishment as a proportion of gross operating surplus for different sizes of enterprise in the chemicals sector 126 Total EU costs using different sources for per-establishment costs ( m, equivalent annual costs) vii Figure 1.1 Summary of Seveso II and Seveso III scope based on substance classification 1 Figure 1.2 Deposition of particles in the respiratory tract 6 Figure 1.3 Correspondence between the former and the new classification system for acute toxic inhalation exposure 8 Figure 1.4 Correspondence between the former and the new classification system for acute toxic dermal exposure 11 Figure 4.1 Identity of respondents 35 Figure 4.2 Views on whether the substances have the potential to cause major accident hazards 36 Figure 4.3 Views on whether these substances should be included in the scope of Seveso 40 Figure 5.1 The compiled accident database 48 Figure 5.2 Distribution of the 794 accidents selected as a function of their original database 49 Figure 5.3 Distribution of the 794 accidents as a function of the continent 50 Figure 5.4 Proportions of various exposure routes for accidents involving toxic substances 55 Figure 6.1 Illustration of substance selection to cover the relevant range of hazards 65 Figure 6.2 Methodology for selecting substances acute toxic 3 for dermal and inhalation exposure routes 67 Figure 6.3 Methodology for selecting substances acute toxic 3 for dermal exposure routes 70 Figure 6.4 Lethal dose values for selected substances shown against classification criteria 89 Figure 6.5 Illustration of substance selection to cover the relevant range of hazards 103 Figure 7.1 Total EU costs using different sources for per-establishment costs ( m, equivalent annual costs) 120 Figure 7.2 Total annual cost estimates per establishment as a proportion of gross operating surplus for SMEs in the chemical sector (based on different sources of costs, including costs to operators only) 125 Appendix A Appendix B Appendix C Appendix D Appendix E Appendix F Compiled accident database Results of analysis of accident database France versus other countries Details of main substances involved in dermal-relevant accidents from accident databases Detailed results of questionnaire responses Lists of substances potentially relevant based on harmonised classification data Potentially affected substances based on data from French ministry

14 1 1. Introduction 1.1 Study Background The European Commission (DG Environment) has let a contract with AMEC, supported by EU-VRi, INERIS and REC, with a view to gathering and assessing data related to the likelihood, risks and consequences of major accidents involving category acute toxic 3 dermal substances. This substance classification category is part of the new globally harmonised system (GHS) for classification and labelling of chemicals, as applied in the EU by the Regulation on Classification, Packaging and Labelling of chemicals (Regulation 1272/2008, the CLP Regulation). The introduction of CLP has led to many pieces of legislation being updated in line with its provisions. As part of this process, the Seveso legislation on the control of major-accident hazards involving dangerous substances has recently changed, with Seveso II (Directive 96/82/EC) being repealed and replaced in June 2015 by Seveso III (Directive 2012/18/EU). The Commission s original proposal for Seveso III was to include substances classified under GHS/CLP as acute toxic category 1, 2 and 3 for both the inhalation and the dermal routes. However, the final political agreement did not include acute toxic 3 dermal substances and these are therefore not included in the scope of Seveso III. As can be seen from the figure below, this category overlaps the toxic and harmful substance categories under the previous classification and labelling legislation (Directive 67/548/EEC and Directive 1999/45/EC). The figure illustrates the scope of the Seveso Directive with regard to toxic substances. A potential change to the Directive would bring substances within the areas A3 and A4 within the scope. Figure 1.1 Summary of Seveso II and Seveso III scope based on substance classification

15 2 The Commission wishes to undertake further analysis on the likelihood, risks and consequences of major accidents involving dangerous substances classified as acute toxic 3 dermal. Depending on the outcome of the analysis, the Commission may propose an amendment to the new (Seveso III) directive to include these substances, or some of these substances. The objectives of this project were to: Collect and analyse data on a representative number of major accidents and near misses that have taken place over the past 10 years, with a view to assessing the relevance and impact of each exposure route and toxicity level, focusing on dangerous substances classified as acute toxic 3; Complement this analysis with an analysis of major accident scenarios; Seek to appreciate the importance of various exposure routes, in particular for the acute toxic 3 category (in terms of frequency and impact of major accidents); Draw conclusions on the need to cover, not cover or partially cover category acute toxic 3 dermal substances under Seveso. This is to include consideration of the level of impact and hence possible level of protection needed for acute toxic 3 dermal substances, using the level of protection for acute toxic 3 inhalation substances as a benchmark; Undertake an assessment of the economic, administrative and social impacts of possible amendments to Seveso to take into account the conclusions from the above, taking into account the Commission s Impact Assessment guidelines. The Commission s suggestion for the project was that the study should work top-down, starting with a representative number of major accidents and accident scenarios involving dangerous substances classified as acute toxic 1, 2 and in particular 3. It should analyse and compare the relevance (consequences for man and environment) of the dermal exposure route for acute toxic 3 substances (other categories for this route of exposure could potentially be considered to complete this analysis) and compare this with the relevance of the inhalation exposure route within these toxicity levels. Then, depending on whether this analysis suggests that acute toxic 3 dermal substances should also be covered, assess the possible impacts of potential changes to Seveso, taking into account the additional number of establishments affected in particular. 1.2 Project Tasks The project consisted of a number of discrete but inter-related tasks, based on the Commission s specifications for the work and the consultants proposal. These are: Task 1 Data gathering, encompassing: Task 1.1 Gathering relevant data on past major accidents / near misses: - Gather detailed data on a representative number of major accidents/near misses over the past ten years, in the EU 27, distinguishing between the various exposure routes involved. The data is to include information on the establishment, its location, its activities, the substances involved, the

16 3 immediate and long term consequences of the accident in terms of impact on the environment, on health and safety and on property, as well as the economic impact (costs resulting from damage and from remediation); - Focus on major accidents involving substances classified as acute toxic 3 under the new chemicals classification. This implies, for each accident involved, a translation of the former classification into the new classification to verify if covered under the category acute toxic 3; - Gather useful data from accidents involving substances classified in a higher toxicity class (acute toxic 1 or 2) with a view to comparing in a more general way the relative impact and seriousness of accidents involving substances classified under the dermal exposure route with accidents involving substances classified under the inhalation exposure route. Task 1.2 Complement these data on the basis of accident scenarios. The aim here is to complement the existing information with possible accident scenarios, established for a relevant list of (harmonised) acute toxic 3 substances, for all exposure routes. Task 2 Analysis of data: Analysing and comparing the impacts of accidents on man and on the environment, distinguishing between the various exposure routes of the substances involved. Drawing conclusions as regards the relative importance of various exposure routes, in terms of the various impacts, in particular for accidents involving substances classified as acute toxic 3. Draw conclusions from accidents involving substances classified in a higher toxicity class (acute toxic 1 or 2), comparing in a more general way the seriousness of accidents involving substances classified under the dermal exposure route with accidents involving substances classified under the inhalation exposure route. Within the category acute toxic 3 dermal, possibly identify those substances which can be considered most relevant in terms of frequency and impact of accidents. Task 3 Assessment of the economic impact of (partly) covering acute toxic 3 dermal substances: Gather data on the number and location of establishments where acute toxic 3 dermal substances are present. Identify how many of those establishments would be covered under Seveso III in any case. This is the case where there are other substances present above the applicable thresholds or because the acute toxic 3 dermal substances can also be classified within a different category, causing it to be covered under Seveso in any case. Identify the net additional share of establishments that would be covered should the category acute toxic 3 dermal substances be included in the scope of the Directive. Gather information on the economic costs (compliance costs for operators and Member States) and benefits (in terms of absence of potential post-accident recovery costs) of covering the whole/part of the category acute toxic 3 dermal substances, building upon the information contained in the IA accompanying the Commission proposal.

17 4 1.3 Purpose and Structure of the Report Purpose of this report This is the final report on the project, which is intended to present the information gathered and a thorough analysis of these data, including an assessment of the potential economic impacts. Comments from the Commission on the draft report have been taken into account. The report is intended to provide the Commission with an understanding of the information available (including gaps/uncertainties) on the implications of including this class of substances within Seveso Structure of this report Section 2 of this report outlines the methodology used to undertake the project in more detail. Details of some of the chemical substances potentially affected by a change in the Directive are set out in Section 3 and the results of information collected through consultation with stakeholders are set out in Section 4. Section 5 presents the results of the analysis of data on past accidents involving relevant substances and Section 6 provides details of the work completed on development of accident scenarios, including the information collected. Section 7 presents the findings of an analysis of the potential socio-economic implications of a change to Seveso to include these substances. Finally, Section 8 presents the overall conclusions of the study. 1.4 General Considerations about Inhalation and Dermal Toxicity Inhalation toxicity General considerations on inhalation toxicity The respiratory tract is the first port of entry into the body of a pollutant released into the air. The effects due to inhalation toxicity are complex due to different local and/or systemic modes of action. The local effect occurs on biological target which are directly in contact with the chemical (for example, the respiratory tract and the lungs). The respiratory tract shows different local anatomical features that interact with the physicochemical nature of a substance and determine particle or gas deposition and clearance 1. The different target organ sites for local effects on the respiratory system are the upper respiratory tract, the tracheobronchial tract, the gas-exchange region, the extracellular fluids compartments and the pulmonary surfactant. Many substances may settle in the mucus layers and impact the epithelial cells of the nasal passage and the pharynx in the upper respiratory tract. This may lead to irritation and corrosion of the respiratory mucosa. For example, 1 ACUTEX (2006) - Methodology to develop AETLs. European Commission.

18 5 hydrochloric acid 2 induces a local effect on the upper respiratory tract (corrosion) that can lead to death. Other substances are more likely to penetrate further into the respiratory tract. From here, they may be cleared by various mechanisms such as mucociliary clearance (in this case, the toxic substance could be not absorbed), retained and accumulate locally in pulmonary macrophage (with potentially local effects).the intensity of the effects is related to the concentration, deposition pattern and depth of penetration of the pollutant into the respiratory tract, and the duration of contact with the different cell types of the respiratory epithelium. These local effects are not related to a distribution of the chemical in the organism. In other cases, after penetration further into the respiratory tract, substances may also be dissolved and absorbed into the systemic circulation. In this case, the reactive substance can be translocated towards another site such as the heart, liver, kidney or brain, and induce systemic effects. For example, arsine (arsenic trihydride 3 ) induces effects on the central nervous system after blood distribution and metabolism. In the case of systemic modes of action, the site of effect is different to the application site. The differentiation between local toxicity and systemic toxicity depends on the physicochemical properties of the 1 pollutant, and its ability to penetrate into the blood circulation. For particles, deposition mechanisms include inertial impaction, sedimentation, diffusion and interception. Generalisations regarding the deposition site of particles of a given size are problematic due to their dynamic change within the respiratory tract. In the average adult human, most particles larger than 10µm in aerodynamic diameter are deposited in the nose or oral pharynx and are unlikely to penetrate to tissues distal to the pharynx. Very fine particles (0.01µm and smaller) are also trapped relatively efficiently in the upper airways by diffusion 1. For gases, water-solubility is the critical factor in determining how deeply a given gas penetrates into the respiratory tract. The figure below illustrates the deposition of particles in respiratory tract CAS , harmonised classification: skin corrosion 1B (H314), STOT SE 3 (H335) CAS , harmonised classification: Flam. Gas 1 (H220), Acute tox. 2 (H330), STOT RE 2 (H373), Aquatic acute and chronic 1 (H400-H410) Morman S.A. and Plumlee G.S. (2013): The role of airborne mineral dusts in human disease. Aeolian Research, in press.

19 6 Figure 1.2 Deposition of particles in the respiratory tract Source: Morman S.A. and Plumlee G.S. (2013). Different methods can be used to assess inhalation toxicity. In particular, two OECD guidelines are used in several regulatory frameworks: OECD guideline no403 5 : This test guideline allows the determination of a concentration-response relationship ranging from non-lethal to lethal outcomes in order to derive a median lethal concentration (LC 50 ), non-lethal threshold concentration (e.g. LC 01 ), and slope, and to identify possible sex susceptibility. The LC 50 or the LC 01 is the concentration which results in death of 50% or 1% respectively of the exposed population. 6 OECD guideline no436 : This method provides information on hazardous properties and allows the substance to be ranked and classified according to the United Nations (UN) Globally Harmonized System of Classification and Labelling of Chemicals (GHS) for the classification of chemicals that cause acute toxicity. The inhalation Acute Toxicity Class (ATC) Test Guideline will allow the use of serial steps of fixed target concentrations to provide a ranking of test article toxicity. Lethality is used as the key endpoint. 5 6 OECD (2009) - OECD Guidelines for the Testing of Chemicals, Test No. 403: Acute Inhalation Toxicity Organisation for Economic Co-operation and Development. OECD (2009) - OECD Guidelines for the Testing of Chemicals, Test No. 436: Acute Inhalation Toxicity Acute Toxic Class Method. Organisation for Economic Co-operation and Development.

20 7 For these two guidelines, the duration of the exposure is 4 hours in a single exposure and the duration of observation is 14 days. The preferred species is the rat. An assessment factor may be used when extrapolating experimental data from rodents to humans. Example of an accident mainly involving toxic inhalation route exposure In 1984, the Bhopal accident in which nearly 40 metric tonnes of methyl isocyanate were released into the atmosphere led to over 3,500 deaths for people residing in areas adjacent to the plant. Methyl isocyanate 7 is a local irritant for the respiratory tract and induces pulmonary oedema that leads to suffocation and death. This substance is also an irritant through the dermal route but the effects felt in Bhopal were less severe than those due to inhalation of the product. Classification of substances as acutely toxic by inhalation route according to Regulation 1272/2008/EC (CLP) The acute toxicity by inhalation of a substance or mixture corresponds to adverse effects occurring following a single exposure of a given duration (generally 4 hours). Based on this test, a LC 50 can be determined. These studies are usually undertaken on rats. Regulation 1272/2008/EC (CLP) defines four hazard categories (categories 1 to 4) and the substances and mixtures are classified according to the numeric value of LC 50. For the inhalation route of exposure, the thresholds used to define the 4 hazard categories depend on the three kinds of physical state possible depending of the substance or the mixture: Dust: solid particles of a substance or mixture suspended in a gas (usually air); Mist: liquid droplets of a substance or mixture suspended in a gas (usually air); Vapour: the gaseous form of a substance or mixture released from its liquid or solid state. In the CLP Regulation, the four hazard categories corresponding respectively to the following hazard statement are: fatal if inhaled (category 1 and 2), toxic if inhaled (category 3) and harmful if inhaled (category 4). In the previous regulation for the classification of substances, Directive 67/548/EEC, there were three hazard categories corresponding to the following hazard statements: very toxic by inhalation (T+; R26), toxic by inhalation (T; R23) and harmful by inhalation (Xn; R20). The correspondences between the old and the new system of classification are presented in the following diagram. 7 CAS , harmonised classification Flam.liquid 2 (H225), acute tox 3 (H301, H311), Skin irrit. 2 (H315), Skin sens. 1 (H317), Eye Dam. 1 (H318), acute tox 2 (H330), Resp. Sens. 1 (H335), Repr. 2 (H361d)

21 8 Figure 1.3 Correspondence between the former and the new classification system for acute toxic inhalation exposure Inhalation route (gas): CLP Regulation Threshold values (ppm) Cat.1 Cat.2 Cat.3 Cat ,000 Directive n 67/548/EEC Threshold values (mg/l) T+ / R26 T / R23 Xn / R Inhalation route (vapour): CLP Regulation Cat.1 Cat.2 Cat.3 Cat.4 Directive n 67/548/EEC Threshold values (mg/l) T+ / R26 T / R23 Xn / R Inhalation route (dust/mist): CLP Regulation Cat.1 Cat.2 Cat.3 Cat.4 Directive n 67/548/EEC T+ / R26 T / R23 Xn / R20 Threshold values (mg/l) As shown in the figure, the classification according to the criteria in Directive 67/54/EEC does not correspond directly to the classification in a hazard category under the CLP regulation. Depending of the physical state, the category 3 (toxic if inhaled) substance could correspond to an older classification as Xn/R20 (harmful by inhalation) or T/R23 (toxic by inhalation). In such cases, when the classifications of substances are implemented into the CLP regulation, the classification of the substance or mixture was considered as a minimum classification. For example:

22 9 for substances/mixtures (gas) which are classified as T/R23 under Directive 67/548/EEC, a minimum classification in category 3 was established; and for substances/mixtures (dust/mist) which are classified as T/R23 under Directive 67/548/EEC, a minimum classification in category 3 was established. Concerning substances in the vapour state, no substance was classified in Category 3 when implementing the CLP regulation. Indeed, for substances/mixtures which are classified as Xn/R20 under Directive 67/548/EEC, a minimum classification in category 4 was established, and, for substances/mixtures which are classified as T/R23 under Directive 67/548/EEC, a classification in category 2 was established Dermal toxicity General considerations on dermal toxicity In general, the skin as a target organ in case of accidental airborne exposure is of limited significance as more sensitive tissues, like the eyes or the respiratory tract, will respond and/or be affected at much lower concentrations. The most relevant effects on the skin as a consequence of accidental airborne exposure are limited to direct injuries (local effects) i.e. skin irritation and corrosion. These two effects do not fall under the hazard categories listed in Annex 1 Part 1 of the Seveso III directive. The skin forms an effective two-way barrier that controls the loss of chemicals from the body as well as the absorption of many foreign chemicals into the body. However, many chemicals do enter via the skin and some, when specifically applied to the skin, have been found to be sufficiently well absorbed to produce systemic toxicity. For example, hydrazine 8 is absorbed after dermal contact and can lead to neurological effects. Furthermore, local effects like irritation could increase dermal absorption and then lead to more serious systemic effects. Different factors affect percutaneous absorption: the integrity of the skin barrier, the physicochemical properties of the substances, the vehicle containing the substance, the site of application, and some physiological and intra-individual factors such as age, temperature, and metabolism 9. The stratum corneum, the skin s outermost layer, plays an important role in barrier properties by providing protection against the ingress of environmental materials. However, the intercellular lipid lamella of the stratum corneum plays a major role in the mechanism of diffusion-controlling barrier. A number of major secondary factors governing the extent of percutaneous absorption for response and toxicity include permeant clearance from 10 the skin and desquamation CAS , harmonised classification: flam. Liq 3 (H226), Acute tox 3 (H301, 311, 331), Skin corrosion 1B (H314), Skin sens 1 (H317), Carc 1B (H350), Aquatic acute and chronic 1 (H410) Thong H.-Y., Freeman S. and Maibach H.I. (2008): Systemic Toxicity caused by absorption of drugs and chemicals through skin. vol, In: Dermal Absorption and Toxicity assessment, second edition., I. Healthcare Eds. Roberts M.S. and Walters K.A. (2008): Human Skin morphology and dermal absorption. vol, In: Dermal absorption and toxicity assessment, I. healthcare Eds.

23 10 OECD guideline no can be used to assess the dermal toxicity: This test guideline provides information on health hazards likely to arise from a short-term exposure by the dermal route. Data from an acute dermal toxicity study may serve as a basis for classification and labelling. The test substance is applied to the skin, during 24 hours, in graduated doses to several groups of experimental animals, one dose being used per group. Subsequently, observations of effects and deaths are made. The observation period may be at least 14 days. Example of accident involving the dermal exposure route The Aria database describes the case of a 29-year-old man sprayed by 2,4-dichlorophenol 12 while repairing a leak on a pipe (2,4-dichlorophenol is toxic by the dermal route (category 3, harmonised classification) and readily absorbed through the skin and the absorption is increased by the corrosive effects of this substance). The skin of the worker was heavily exposed (head, arm, face and knee). He lost consciousness and had a cardiovascular collapse. The employee was declared dead at the hospital one hour later. Note that the above is just one example of an accident involving a substance relevant to the context of the current report. Accidents of a range of different scales could potentially occur. Classification of substances as acutely toxic by the dermal route according to Regulation 1272/2008/EC (CLP) The acute toxicity by dermal route of a substance or mixture corresponds to adverse effects which occur following a single exposure of a given duration (generally 24 hours). Regulation 1272/2008/EC (CLP) defines four hazard categories (categories 1 to 4) and the substances and mixtures are classified according to the numeric value of LD 50. These values are determined in experimental studies which are usually undertaken on rabbits. In the CLP Regulation, the four hazard categories corresponding respectively to the following hazard statements are: fatal in contact with skin (category 1 and 2), toxic in contact with skin (category 3) and harmful in contact with skin (category 4). The physical form of the substance/mixture is not taken into account. In the previous regulation for the classification of substances, Directive 67/548/EEC, there were three hazard categories corresponding to the following hazard statements: very toxic in contact with skin (T+; R27), toxic in contact with skin (T; R24) and harmful in contact with skin (Xn; R21). The correspondence between the old and the new system of classification are presented in the following diagram OECD (1987): OECD Guidelines for the Testing of Chemicals, Test No. 402: Acute Dermal Toxicity, Organisation for Economic Co-operation and Development. CAS ; harmonised classification: acute tox 4 (), acute tox 3 (H311), skin corro. 1B (H314), aquatic chronic 2 (H411).

24 11 Figure 1.4 Correspondence between the former and the new classification system for acute toxic dermal exposure Dermal route: CLP Regulation Cat.1 Cat.2 Cat.3 Cat.4 Directive n 67/548/EEC T+ / R27 T / R24 Xn / R21 Threshold values (mg/kg) With regard to substances classified T +, there is a direct correspondence between the CLP Regulation and Directive 67/548. These substances are then classified in category 1 under CLP regulation. For the others classes, however, there is no direct correspondence between the CLP Regulation and Directive 67/548/EEC. When the classifications of substances were implemented into the CLP Regulation, the classification of the substance or mixture was given as a minimum classification: for substances/mixtures which are classified as Xn/R21 under Directive 67/548/EEC, a minimum classification in category 4 was established, and for substances/mixtures which are classified as T/R24 under Directive 67/548/EEC, a minimum classification in category 3 was established (meaning there were no category 2 substances at that time but substances can still move into or be added to that category) Classification of substances for the inhalation and dermal routes Under Regulation 1272/2008/EC (CLP), substances are classified for acute toxicity according to the numerical value of LD 50 for the dermal route and LC 50 for the inhalation route. The LD 50 corresponds to the lethal dose (applied to the skin) which, following 24 hour exposure, induces 50% mortality among the sample population after 14 days of observation. This dose is expressed in mg/kg (mg of substance per kg of body weight). In acute dermal toxicity studies, a given quantity of substance (in mg) is applied onto a skin surface of 10 cm 2 during 24 hours. Afterwards, this quantity is linked to the animal body weight in order to obtain a dose in mg/kg. The LC 50 corresponds to the lethal concentration (in the air) which, following a four hour exposure, induces 50% mortality among the sample population after 14 days of observation. This concentration is expressed in mg/l (or mg/m 3 ). The LD 50 and LC 50 values are retained from studies for which the quality and completeness of data are assessed as described in section One of the validity criteria for the assessment of studies is the test method used. The study retained must have been undertaken according to OECD guidelines (or equivalent) in order to provide reliable numerical toxicity values or ranges of values that can be used for classification (for example, > 10 mg/l but < 20 mg/l for classification in category 4 (inhalation route, vapour)).

25 12 A substance can lead to both inhalation and dermal toxicity. As example, hydrofluoric acid is classified (harmonised classification) in category 1 for the dermal route, category 2 for the inhalation route (minimal classification) and also as corrosive for the skin Risk management under other occupational legislation Management of the risks posed by dermal and inhalation toxic substances is determined both by the Seveso directive and by wider occupational safety and health (OSH) legislation. While the former is the main focus of this study, it is worth briefly summarising the risk management provisions laid out in OSH legislation, especially as many of the potential impacts of accidents involving acute toxic 3 dermal substances are likely to be on-site, as described in Sections 5 and 6. The general principles of OSH in the EU are set out in the European Framework Directive on Safety and Health at Work (Directive 89/391 EEC), which contains general principles concerning the prevention of occupational risks, the protection of safety and health, the elimination of risk and accident factors, the informing, consultation, balanced participation in accordance with national laws and/ or practices and training of workers and their representatives, as well as general guidelines for the implementation of the said principles (Art. 1). The OSH Framework Directive has a number of daughter directives,, of which the most relevant to the risks posed by chemicals is the Chemical Agents Directive (Directive 98/24/EC). This lays down minimum requirements for the protection of workers from risks to their safety and health arising, or likely to arise, from the effects of chemical agents that are present at the workplace or as a result of any work activity involving chemical agents (Art. 1). The Chemical Agents Directive places a number of additional requirements on employers relating to: determination and assessment of risk of hazardous chemical agents (which will include acute toxic 3 dermal substances); general principles for prevention of risks associated with hazardous chemical agents; specific protection and prevention measures; arrangements to deal with accidents, incidents and emergencies; and information and training for workers (Art. 8). Of these, the most relevant requirements for this study are those relating to accidents, incidents and emergencies (Art. 7), specifically: A requirement to establish procedures (action plans) which can be put into effect in case of an accident, incident or emergency involving hazardous chemical agents, including relevant safety drills which are to be performed at regular intervals, and the provision of appropriate first aid facilities.

26 13 A requirement to implement appropriate measures immediately in case of an accident, including a prohibition on all workers from the affected areas, other than those workers who are essential to the carrying out of repairs and other necessary work. A requirement to provide workers who are permitted to work in the affected area with appropriate protective clothing, personal protective equipment, specialised safety equipment and plant which they must use as long as the situation persists, along with a prohibition on all unprotected workers from the area. A requirement to provide the warning and other communication systems required to signal an increased risk to safety and health, to enable an appropriate response and to launch remedial actions, assistance, escape and rescue operations immediately if the need arises. A requirement to provide information on emergency arrangements involving hazardous chemical agents to the relevant internal and external accident and emergency services, so that they may prepare their own response procedures and precautionary measures. It is therefore clear that there are already provisions in place to control risks from chemical accidents associated with these substances, regardless of whether these substances are brought into the scope of Seveso in relation to major accident potential.

27 14 2. Methodology 2.1 Overview In order to identify relevant data to inform the analysis, the project methodology involves a number of key elements: Identification of relevant substances. This was initially done through a review of relevant classification under EU legislation, focusing on substances with harmonised (or possible) classification as acute toxic 3 dermal. Information was also sought from some of the other project stages on the substances potentially affected. Extensive consultation with relevant stakeholders from amongst industry, the authorities and other organisations. Information was sought on: identification of relevant substances that would be affected by a change to the directive; views on the significance of risks from these substances; available information on past accidents / near misses involving these substances and on possible future accidents; data on the potential number of establishments affected; and information on the potential costs and benefits of amending the directive. An extensive review of data on past accidents. Development of accident scenarios, to assess the seriousness of accidents involving substances classified under the dermal route with accidents involving substances classified under the inhalation exposure route. Assessing the economic implications of possible changes to the Directive to include these substances. 2.2 Stakeholder Consultation Overview There were two elements to the process of seeking information from relevant stakeholders, including: Dissemination of an extensive questionnaire to various stakeholders. Direct contact with a number of manufacturers / importers of the chemical substances potentially falling within the scope of a possible change to the Directive Consultation questionnaire The main information collection process was undertaken through use of a questionnaire. An announcement of the consultation was sent to key stakeholders who were contacted initially before the questionnaire was made available to stimulate their participation in the survey. The stakeholders who were contacted were:

28 15 The participants in the F-SEVESO project which took place in 2007; The registered participants in the activities of the European Technology Platform on Industrial Safety; The main industry associations potentially concerned by the topic of the consultation; Member States and relevant EU-level authorities. In total, over 1000 individuals and organizations were approached to take part in the survey. The important dates for the consultation are presented in the table below. Table 2.1 Key stages in implementation of the study questionnaire Dates / period Activities September October 2012 October 17, 2012 and reminder on October 26, 2012 End October to early November 2012 Preparation of the questionnaire Information to the stakeholders about the preparation of a survey and request to register by 31 October, to receive the questionnaire Review and validation by the European Commission of the questionnaire 8 November 2012 Consultation of key stakeholders to check the final draft of the questionnaires 20 November 2012 Final version of the questionnaire ready to be distributed November 20, January 2013 Questionnaire available on-line and link to participate sent to stakeholders: November 20, 2012: distribution to registered participants November 23, 2012: distribution to associations with personalised message First deadline: 9 December 2012 (with reminders sent before the deadline) Second deadline: 19 December 2012 (with reminders sent before the deadline) Final deadline proposed for those who were asking for additional time: 20 January Additional consultation with manufacturer/importers of chemicals Since the start of the project, ECHA has released information on (some of) the companies that registered chemicals under REACH by the 2010 deadline. In order to allow for additional estimates from industry as to the potential scale of impacts of a change to the Directive (in terms of numbers of establishments affected), companies that had registered a number of chemicals relevant for this study were asked targeted questions regarding the potential number of establishments that would come into the scope of Seveso. These companies were: Companies that had registered specific named substances by 2010 which had harmonised CLP classification as acute toxic 3 dermal and not other classification for toxic effects that would lead to them already being included within the scope of Seveso; Companies that had registered substances that were identified during the stakeholder consultation process. Specifically, this included a number of substances that were self-classified as acute toxic 3

29 16 dermal (as notified on ECHA s classification and labelling industry) but which did not have harmonised classification for toxic hazards. 2.3 Review of Accident Data An extensive review of historical data on accidents has been undertaken. The purpose of this review was to collect, compile and analyse data available on major accidents involving toxic substances. The analysis focused on the identification of exposure routes involved in the accidents. The following accident databases were analysed: e-mars, ARIA and the accident database (IChemE). Taking all of the relevant accidents in these databases, those that were relevant to toxic effects were first identified. The number of accidents involving the inhalation and dermal exposure routes were compared. Of the substances for which the dermal exposure route is relevant, a review of the relevant hazard classification of the substances involved according to EU legislation was undertaken. Finally, conclusions were drawn on the significance of the consequences of accidents involving the toxic dermal exposure route led compared to those involving the toxic inhalation exposures route. Further details on the methodology are set out in Section 5 of this report. 2.4 Development of Accident Scenarios The accident database analysis and the stakeholder consultation provided first results on the likelihood, risks and consequences of major accidents involving acute toxic 3 dermal substances. This still provides only a partial picture as they are exclusively based on past experience. These elements were therefore complemented with a more analytical and illustrative approach based on the evaluation of accident scenarios. The aim of this task is to provide a clearer insight into the difference in dangerous potential between dermal and inhalation exposure to acute toxic category 3 products through a comparative approach. It does not aim to assess the potential for all acute dermal toxic category 3 products to generate a major accident this objective would need extensive resources and a broad consensus on a precise definition of a major accident. The methodology involves a number of realistic but theoretical accident situations, with the same parameters used for the dermal and inhalation calculations, meaning that the results should be valid for comparison purposes. The main steps in the analysis include the following: scenario selection; selection of the substances studied; theoretical consequence calculations.

30 Assessment of Economic Impacts The potential economic impacts were assessed by considering two key elements: the number of establishments that would be affected by a change in the scope of Seveso, and the costs per establishment. Based on data from the literature and from consultation for the current study, costs for establishments in different situations were estimated: those that would newly come into the scope of Seveso (either upper or lower tier), those that would change tier from lower to upper tier and finally those existing Seveso establishments that would not change tier but which would nonetheless be affected by a change in scope. Estimates were also made of the administrative costs to authorities associated with a change in scope (and hence increased regulatory responsibilities). Social impacts were also considered.

31 18 3. Identification of Substances Potentially Affected 3.1 Review of Hazard Classification Data Background In order to identify which chemical substances (and associated mixtures) could be affected by a possible change in the scope of the Seveso Directive to cover acute dermal toxic 3 substances, a review of relevant public data on substances has been undertaken. In the event that the Directive was to be amended, the following substances could potentially be brought within the scope: Substances that have harmonised EU classification as acute toxic 3 dermal (these are assigned the hazard class H311), but which are not already included within the scope of the Directive due to other health, environmental, or physicochemical properties; Substances and associated which are self-classified by suppliers as acute toxic 3 dermal but not subject to harmonised classification as such (and again which are not already included within the scope of the Directive due to other health, environmental, or physicochemical properties) 13. This could include substances that already have a harmonised EU classification for a lower toxicity level such as acute toxic 4 dermal, particularly where this is indicated in the relevant legislation as being a minimum classification. This could also include substances that are self-classified as acute toxic 3 dermal with no current harmonised classification. The overall purpose of this section of the report is to gain a better understanding of the substances that would be affected by a possible change in the directive, in terms of numbers of substances. This may also provide useful indications of the potential number of establishments that would be affected. However, this is only one of the routes used in the current project to estimate the potential scale of impacts in the event of a change to the directive Method In order to identify the specific chemical substances that could be affected, the focus of the analysis has been on substances that are already subject to harmonised classification as acute toxic 3 dermal, and those that have 13 Under the CLP Regulation, suppliers of chemicals are required to classify their substances in accordance with the Regulation. In addition to the harmonised classification set out in the Regulation itself, suppliers must decide on the appropriate classification for all substances, based on available information ( self-classification ). Suppliers are required to notify the European Chemicals Agency of the classification and labelling within one month of placing the substance on the market for the first time. The process of self-classification and notification to ECHA means that, often, substances with no harmonised classification are in practice self-classified by the suppliers. Similarly, substances with a minimum harmonised classification may be self-classified in a higher hazard class (e.g. acute toxic 3 dermal instead of 4* dermal), meaning that these substances could come within the scope of the Directive. However, it is of note that not all suppliers of any one substance will always self-classify a substance in the same way.

32 19 harmonised classification as acute toxic 4 dermal as a minimum classification, for which it is thus reasonably likely that some chemical suppliers could self-classify the substances in a higher category. Data on harmonised classification were based on information in the CLP Regulation 14. It was first necessary to identify those substances that were classified as acute toxic 3 dermal and not classified for other hazards that would (or could) lead to the substances already being included in the scope of the Directive Results A total of over 4,000 substances with harmonised classification were identified. Of these, around 420 individual substances were classified as acute toxic 3 and of these 187 were classified as acute toxic 3 dermal 15. Investigating these substances in more detail, 41 substances were classified as acute toxic 3 dermal (H311) and not classified for other acute health hazards (dermal 1/2, oral 1/2, inhalation 1/2/3 or STOT SE 1). All of these substances were subject to minimum classification meaning that in some cases the substances could be selfclassified in a higher hazard class. Of these 41 substances, 15 were classified as H311 and not classified for other acute health hazards (as above) and also not classified for relevant environmental hazards (aquatic acute 1 or aquatic chronic 1 or 2). Note, however, that the thresholds for environmental hazards are higher than for acute health hazards, meaning that a change in the scope of the Directive to include acute toxic 3 dermal substances could bring more installations within the scope of the Directive 16. A review was also undertaken as to whether the substances had been pre-registered under the REACH Regulation and also whether the substances had been registered in the first batch of substances that were registered in The latter point is indicative of a large European market and hence (indirectly) of a relatively higher chance that Regulation (EC) No 1272/2008 on the classification, labelling and packaging of substances and mixtures. Data were accessed through an online version available at: (accessed October 2012). This list contains details of the hazard classes for all substances in Table 3.1 of Annex VI to the CLP Regulation. However, it does not include the third adaptation to technical progress of the regulation (Commission Regulation (EU) No 618/2012 of 10 July 2012) which was searched manually and did not appear to contain any relevant substance classifications. The list of harmonised classifications is therefore understood to be the same as the harmonised classification listed on ECHA s classification and labelling inventory. There were 187 dermal, 202 inhalation and 321 oral = 710 total, but only around 420 when double-counting is removed due to some substances being in 2 or 3 of the hazard classes. It should be noted that, in the whole classification and labelling inventory as included on ECHA s website, if one searches for substances with harmonised classification that include the hazard class H311(acute toxic 3 dermal), a larger number of substances than 187 is identified around 350 for a search done in March However, as well as substances with harmonised classification as H311, these substances also include some that have harmonised classification for other endpoints but which are self-classified by some (not all) companies as H311 (i.e. no harmonised classification as H311). Under the Seveso III Directive, the thresholds for acute toxic substances are 50t for lower tier and 200t for upper tier establishments. The upper and lower tier thresholds for environmental hazards are 100t and 200t respectively for aquatic acute 1 or chronic 1 substances and 200t and 500t respectively for aquatic chronic 2 substances. Pre-registration under REACH took place in the period 1 June to 1 December 2008 and allowed companies expecting to register a substance to get together and submit a registration dossier jointly, as well as providing notification to ECHA that the substance was expected to be registered (and when).

33 20 large inventories could be stored at a single site 18. This provides an indicative but far from definitive illustration of the substances which might be most expected to come within the scope of the Directive. A similar analysis was also undertaken for substances that have harmonised classification as acute toxic 4 dermal, as these may potentially be self-classified by some suppliers as acute toxic 3 dermal. (For almost all of these 19 substances, the harmonised classification was indicated to be a minimum classification, meaning that companies can self-classify the substance in a higher category, and indeed there are several instances where this is done.) The table below summarises the numbers of substances falling within each of the above categories, for both types of substance classification. This illustrates that, of the substances likely to be stored in greatest volumes in Europe (those that have already been registered under REACH): There are only three registered substances that have harmonised classification as acute toxic 3 dermal and which are not classified for any other relevant health, environmental or physical hazards. These would be expected to come within the scope of the Directive. There are a total of 10 registered substances that have harmonised classification as acute toxic 3 dermal of which 7 are not classified for other relevant health hazards but are classified for relevant environmental hazards. For these installations, some establishments could come within the scope of the Directive if the relevant thresholds are below those for environmental hazards or above those for acute health hazards Under REACH, there are three deadlines by which companies must register information with ECHA on the properties, uses, exposure, hazards and risks associated with chemicals. In the chemical safety report, the risk management measures and operational conditions required to demonstrate adequate control must be set out. Substances that are placed on the EU market at 1000t per year, as well as substances classified as CMR (carcinogenic, mutagenic, reprotoxic category 1A or 1B) at over 1t and substances very toxic to the aquatic environment had to be registered by November 2010, The deadline for other substances placed on the market at 100t per year is 31 May 2013 and the deadline for substances at 1t per year is 31 May As a result, those substances where there is a good likelihood of being stored above the (lower) threshold for toxic substances (50t) are most likely to have been registered by the 2010 deadline, although some of the substances expected to be registered by the 31 May 2013 deadline may also be relevant, although it was not possible to investigate these substances as the work was undertaken in late 2012 and early It is of note that the chemical safety report under REACH covers reasonably foreseeable conditions of use and does not cover accidents. The minimum classification (indicated by * in Table 3.1 of the CLP Regulation) applies where the classification according to the criteria in Directive 67/548/EEC (the pre-existing legislation) does not correspond directly to the classification in a hazard class and category under the CLP Regulation.

34 21 Table 3.1 Identification and prioritisation of chemical substances as potentially affected by a change in scope Acute toxic 3 dermal Acute toxic 4 dermal 1. Hazard class H Total number with this (harmonised) classification No not classified for other relevant acute health hazards (Note 1) No also not classified for relevant environmental hazards (Note 2) No of row 3 that have been REACH registered by No of row 3 that were REACH pre-registered No of row 4 that have been REACH registered by Notes: 1) This relates to the number which do not also have classification as acute toxic dermal 1/2, oral 1/2, inhalation 1/2/3 or STOT SE 1. These are already covered by the scope of the Directive. 2) This relates to the number of those included in the previous line which do not also have classification as aquatic acute 1 or aquatic acute 1 or 2. Note that relevant physicochemical properties included in the Seveso III Directive were also reviewed. None of above numbers are affected for acute toxic 3 dermal substances but two substances classified as acute toxic 4 dermal have relevant classification for physical hazards that could mean they would already be included within the scope of the Directive. The 41 category 3 and 249 category 4 substances identified above which are not classified for relevant acute health hazards are included in Appendix E. 3.2 Substances Potentially Affected Harmonised Classification The above provides a basis for identification of a number of substances that are considered most likely to fall within the scope of the Directive in the event of a change to include acute toxic 3 dermal substances. It is important to note that these do not necessarily represent the majority of the substances that would be affected by number or by volume. Substances which have only notified (not harmonised) classification as acute toxic 3 dermal would also be affected by a change to the directive, but it is not practical to identify exactly how many of these there would be. The names of the 10 substances identified from row 5 of the table above are set out below. These substances have harmonised classification as acute toxic 3 dermal, but not classification for other Seveso-relevant health effects and have been registered under REACH, indicating potentially large inventories at EU establishments. The table also includes details of the (harmonised) classification and labelling, as well as the acute dermal toxicity value identified in the REACH registration dossiers. Even though 7 of the 10 substances have a classification which means they may already be covered by the Seveso Directive (depending on the threshold), these are nonetheless important because, as described later in this report, consultation undertaken for this study suggests that if substances are currently included in Seveso due to environmental hazards, assessment of risks will often only be done for environmental impacts and the toxic impacts will not be covered. This would clearly need to change if the substances were also included due to their acute toxic effects.

35 22 Table 3.2 Substances classified as H311 but not other relevant health effects, and also REACH registered Substance name EC No CAS No Harmonised classification (Note 1) Acute dermal toxicity data from REACH registration (Note 2) Registered tonnage Not also classified for env. effects? No of REACH registrants Hazard class Hazard statement code Dinoseb (ISO); 6-sec-butyl- 2,4-dinitrophenol Repr. 1B Acute Tox. 3 * Acute Tox. 3 * Eye Irrit. 2 Aquatic Acute 1 Aquatic Chronic 1 H360Df H311 H301 H319 H400 H410 Rat LD50 = mg/kg bw (as active ingredient) ,000t 1 3,4-xylenol; [1] 2,5-xylenol; [2] 2,4-xylenol; [3] 2,3-xylenol; [4] 2,6-xylenol; [5] xylenol; [6] 2,4(or 2,5)-xylenol [7] [1] [2] [3] [4] [5] [6] [7] [1] [2] [3] [4] [5] [6] [7] Acute Tox. 3 * Acute Tox. 3 * Skin Corr. 1B Aquatic Chronic 2 H311 H301 H314 H411 [5] 1000 mg/kg bw (supporting study only, limited data) (Note 3) 10, ,000t [5] 1 m-cresol; [1] o-cresol; [2] p-cresol; [3] mix-cresol [4] [1] [2] [3] [4] [1] [2] [3] [4] Acute Tox. 3 * Acute Tox. 3 * Skin Corr. 1B H311 H301 H314 [1] Rabbit LD50 = 2050 mg/kg bw (single application, observed 14d) [2] Rabbit LD50 = 1380 mg/kg bw (single application, observed 14d) [3] Rabbit LD50 = 301 mg/kg bw (single application, observed 14d) [4] Same study as [3] (readacross) [1] 10, ,000t [2] 10, ,000t [3] 10, ,000t [4] ,000t 2 [1] 7 [2] 4 [3] 1 [4]

36 23 Substance name EC No CAS No Harmonised classification (Note 1) Acute dermal toxicity data from REACH registration (Note 2) Registered tonnage Not also classified for env. effects? No of REACH registrants Hazard class Hazard statement code 3,5-xylenol; 3,5-dimethylphenol Acute Tox. 3 * Acute Tox. 3 * Skin Corr. 1B H311 H301 H314 24h rat LD50 > 2400 mg/kg bw (LD0 = 2400 mg/kg bw) (single application washed at 24h, observed 14d) Intermediate only (no value given) 2 2,4-dichlorophenol Acute Tox. 3 * Skin Corr. 1B Aquatic Chronic 2 H311 H314 H411 Rat LD50 =780 mg/kg bw Intermediate only (no value given) 2 1,3-dichloropropene; [1] (Z)-1,3-dichloropropene [2] [1] [2] [1] [2] Flam. Liq. 3 Acute Tox. 3 * Acute Tox. 3 * Asp. Tox. 1 Eye Irrit. 2 STOT SE 3 Skin Irrit. 2 Skin Sens. 1 Aquatic Acute 1 Aquatic Chronic 1 H226 H311 H301 H332 H304 H319 H335 H315 H317 H400 H410 [2] Rat LD50 = 1090 mg/kg bw Intermediate only (no value given) 0 [1] 1 [2] 2-hydroxyethyl acrylate Acute Tox. 3 * Skin Corr. 1B Skin Sens. 1 Aquatic Acute 1 H311 H314 H317 H400 Rat LD50 > 1000 mg/kg bw >1000t 3 Disodium sulfide; sodium sulfide Acute Tox. 3 * Skin Corr. 1B Aquatic Acute 1 H311 H314 H400 Rabbit LD50 < 340 mg/kg bw >10,000t 5

37 24 Substance name EC No CAS No Harmonised classification (Note 1) Acute dermal toxicity data from REACH registration (Note 2) Registered tonnage Not also classified for env. effects? No of REACH registrants Hazard class Hazard statement code Lithium bis(trifluoromethylsulfonyl)imid e Acute Tox. 3 * Acute Tox. 3 * STOT RE 2 * Skin Corr. 1B Aquatic Chronic 3 H311 H301 H373** H314 H412 Rabbit LD50 < 340 mg/kg bw Confidential (NONS substance) (Note 4) 1 2-chloro-5- chloromethylthiazole Acute Tox. 3 * Skin Corr. 1B Skin Sens. 1 Aquatic Chronic 2 H311 H314 H317 H411 No data Intermediate and NONS only (no (Note 5) value given) 1 Notes: 1) Regulation (EC) No 1272/2008 as amended. 2) From ECHA REACH dissemination portal at echa.europa.eu. Data from the key study where relevant is included here. It should be noted that data used in REACH registration dossiers produced by manufacturers/importers of chemicals is not always consistent with the standard criteria for classification of substances under Regulation (EC) No 1272/2008. For example, for o-cresol, the LD50 from the key study is over 1000 mg/kg bw but a number of other studies reported on the ECHA portal have lower LD50 values. See Figure 1.1 and Figure 1.4 for details of the LD 50 values which are relevant for each hazard classification class. 3) 2,6-xylenol only. 4) NONS substance - tonnage data confidential so not necessarily > 1000t per year] 5) This is a substance that was a new rather than an existing substance under the pre-reach legislation. NONS chemicals which have a recognised notification number are regarded as registered under REACH.

38 25 The companies that registered each of the substances identified in the above table were contacted in order to provide additional information on the number of substances potentially affected. The outcomes of this consultation are described in Section Substances Potentially Affected Self-classification Table 3.1 identified a large number of substances that have harmonised classification as acute toxic 4 dermal as a minimum classification. It is therefore possible that some of these substances will be self-classified as acute toxic 3 dermal by some of the suppliers. There is also a large number of substances that have no harmonised classification but which nonetheless could have self-classification as acute toxic 3 dermal, by some (or potentially all) of the suppliers. All users of substances with harmonised classification as H311 would be aware of the classification and so include the substance under Seveso (if the Directive were amended). However, as illustrated by a review of data in the ECHA classification and labelling inventory 20, for substances with no harmonised classification as H311 but self-classification / notified classification by some companies as H311, there may (and probably will) be some establishments that would be affected by a change in the directive, but it is not possible to identify which substances will be relevant (i.e. which stocks of the substances will have notified classification as H311 and be present above the Seveso thresholds) and how many establishments would be affected for each. Based on the data in Table 3.1, it is clear that, of close to 200 substances with harmonised classification as H311, there are several 10s for which there would be at least some effect for relevant establishments (those without other 20 Searching the ECHA C&L inventory for substances classified as H311, there were 3,331 substance results if all substances are included but only 226 if only harmonised classification is selected (based on a search in ). Note that the figure of 226 is different to the 187 noted in Table 3.1 because, within the 187 substances as listed in the CLP Regulation, multiple iterations of the same/related substance but with different CAS numbers (falling under the same index number in the text of the CLP regulation) have not been counted more than once. For example, the CLP Regulation lists 4-chloroo-toluidine (CAS ) and 4-chloro-o-toluidine hydrochloride (CAS ) together under index number and these are counted as 1 of the 187 substances. The CLP inventory database lists these substances separately so they are counted as 2 of the 226 substances. It should also be noted that there are some substances that have harmonised classification for other effects (i.e. not H311) but which have a notified classification as H311 by one or more notifiers. (Previous searches of the C&L database earlier in this study i.e. late 2012, brought up a higher number of substances when searching for H311 with harmonised classification selected i.e. 350 in March It is assumed that the search function in the database has been changed so that this search no longer picks up substances without harmonised classification specifically as H311.) Of the substances that do not have harmonised classification as H311 but which have notified classification as H311, it should be noted that the number of notified classifcations as H311 is often small e.g. sodium fluoride has 254 notified classifications, only one of which includes H311. So, the companies that have registered such substances under REACH will not necessarily recognise the H311 classification. Some companies using these substances will receive a safety data sheet that includes the H311 classification while others will not and so would not consider the Seveso directive to be relevant for Seveso. Similarly, ethyl(methyl)amine (EC No ) has only 1 out of 29 notifiers which classify as H311, the others classifying in other hazard classes, mostly (acute toxic 4 dermal, without a minimum classification because the substance has no harmonised classification). So, for these groups of substances (those with no harmonised classification as H311 but with self-classification / notified classification by some companies as H311), there may (and probably will) be some establishments that would be affected by a change in the directive, but it is not possible to identify which substances will be relevant (i.e. which stocks of the substances will have notified classification as H311 and be present above the Seveso thresholds) and how many establishments would be affected for each.

39 26 acute toxic classification). Likewise, there are probably several 10s or up to a few 100s of substances with either minimum harmonised classification as acute toxic 4 dermal or without harmonised classification but which are selfclassification as H311 by at least some suppliers. It is not practicable or meaningful to extrapolate to any sort of exact figure, but what is clear is that the number of substances (and hence establishments) affected is likely to be much higher than simply the number with harmonised classification as acute toxic 3 dermal. In order to meaningfully identify substances which are, in practice, classified as acute toxic 3 dermal and which are considered to be of potential relevance by experts in the field, information was sought during the consultation process for this project (Section 4) on relevant substances not already included amongst the substances with relevant harmonised classification. Information on the substances identified by these respondents is set out in the table below. It should be noted that several of these substances are additional to the 249 substances identified in Table 3.1 that have harmonised minimum classification as acute toxic 4 dermal and which may be self-classified as acute toxic 3 dermal by some suppliers. For each of the substances in the table below, information is provided on the harmonised classification (if any); whether the substance was registered under REACH by the 2010 deadline, as well as conclusions on the classification status of the substance and information from the consultation process on the uses of the substance.

40 27 Table 3.3 Potentially relevant substances identified through stakeholder consultation Substance name EC No CAS No Harmonised classification (Note 1) REACH Registered by 2010? Notified classification Uses identified in consultation for the current project Pyrocatechol Eye Irrit. 2 Skin Irrit. 2 H319 H315 (FULL AND INTERMEDIATE) Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). REACH registration includes H311 as proposed classification. Production of dyestuffs, scents and pharmaceutical products, antioxidising agent, disinfectant, developer in photography. It is a common building block in chemical synthesis. N,N- Dibutyltrimethylen ediamine 3-Amino-1-phenylbutane #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory) #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Common building block in chemical synthesis Common building block in chemical synthesis 1,3-Dichloro-4- nitrobenzene #N/A #N/A (INTERMEDIATE) No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some notified classification as aquatic chronic 2 (ECHA C&L inventory). REACH registration includes H311 as selfclassification. Additive to extreme pressure lubricants, production of vulcanisation accelerators, disinfectants, plant protection products and colouring substances. 1,3-Dimethyl-2- imidazolidinone #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) with some also Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Cyclic urea uses as high boiling polar aprotic solvent, various applications such as detergents, dyestuffs, electronic materials and manufacture of polymers.

41 28 Substance name EC No CAS No Harmonised classification (Note 1) REACH Registered by 2010? Notified classification Uses identified in consultation for the current project n-decylamine #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Masking agent 2-(1- Methylpropyl)-4,6- dinitrophenyl acetate 1-(2- (Dimethylamino)et hyl)-4- methylpiperazine #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) and also aquatic acute 1 and chronic 1 (ECHA C&L inventory) #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some notified classification as aquatic chronic 2 (ECHA C&L inventory). Lindane Acute Tox. 3 * STOT RE 2 * Lact. Aquatic Acute 1 Aquatic Chronic 1 H301 H332 H373 ** H362 H400 H410 NO Harmonised classification as Acute Tox. 4 dermal but also classified as aquatic chronic 1 and 2. No notified classification as Acute Tox. 3 dermal (ECHA C&L inventory). Second-line pharmaceutical Methanol Flam. Liq. 2 Acute Tox. 3 * Acute Tox. 3 * Acute Tox. 3 * STOT SE 1 H225 H331 H311 H301 H370 ** (FULL AND INTERMEDIATE) Already classified as Acute Tox. 3 inhalation so already within scope of Seveso. Also, already a named substance under Seveso Annex I Part 2.

42 29 Substance name EC No CAS No Harmonised classification (Note 1) REACH Registered by 2010? Notified classification Uses identified in consultation for the current project 2,3-epoxypropyl methacrylate; glycidyl methacrylate Eye Irrit. 2 Skin Irrit. 2 Skin Sens. 1 H332 H319 H315 H317 (FULL) Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some but all notifiers as H311 also classify as STOT SE 1 (ECHA C&L inventory). REACH registration includes H311 as selfclassification. 1-vinyl-2- pyrrolidone Carc. 2 STOT RE 2 * STOT SE 3 Eye Dam. 1 H351 H332 H373 ** H335 H318 (FULL) Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but all relevant notifiers for H311 also classify as Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). REACH registration includes H311 as selfclassification. 2-methylpyridine; 2-picoline Flam. Liq. 3 Eye Irrit. 2 STOT SE 3 H226 H332 H319 H335 NO Harmonised classification as Acute Tox. 4 dermal and also Flam. Liq. 3. Notified classification as Acute Tox. 3 dermal (H311) and some but not all relevant notifiers for H311 also classify as Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Morpholine Flam. Liq. 3 Skin Corr. 1B H226 H332 H314 (FULL) Harmonised classification as Acute Tox. 4 dermal and also Flam. Liq. 3. Notified classification as Acute Tox. 3 dermal (H311) and some but not all relevant notifiers for H311 also classify as Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). REACH registration includes H311 as selfclassification.

43 30 Substance name EC No CAS No Harmonised classification (Note 1) REACH Registered by 2010? Notified classification Uses identified in consultation for the current project Calcium dipropionate #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but all relevant notifiers for H311 also classify as Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Methacrylic acid Skin Corr. 1A H314 (FULL) Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). REACH registration includes H311 as selfclassification. Sodium dodecyl sulphate #N/A #N/A (FULL) No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some but not all notified classifications also have other Seveso-relevant categories e.g. aquatic chronic 1 (ECHA C&L inventory). REACH registration does not include H311 as self-classification. Trientine Skin Corr. 1B Skin Sens. 1 Aquatic Chronic 3 H314 H317 H412 NO Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Allyl hexanoate #N/A #N/A NO No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some notified classification as aquatic chronic 2 (ECHA C&L inventory).

44 31 Substance name EC No CAS No Harmonised classification (Note 1) REACH Registered by 2010? Notified classification Uses identified in consultation for the current project Allyl heptanoate #N/A #N/A (FULL) No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331). Some notified classification as aquatic acute 1 or chronic 1, etc. (ECHA C&L inventory). REACH registration includes H311 as selfclassification. Benzene (1- methylethyl) oxidized polyphenol residue #N/A #N/A (INTERMEDIATE) No harmonised classification. Notified classification as Acute Tox. 3 dermal (but not H311). Also classified as Acute Tox. 3 inhalation (H332 not H331) (ECHA C&L inventory). Propylene diamine Flam. Liq. 3 Skin Corr. 1A H226 H314 (INTERMEDIATE) Harmonised classification as Acute Tox. 4 dermal. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). REACH registration does not include H311 as self-classification. 3,6,9- triazaundecameth ylene Skin Corr. 1B Skin Sens. 1 Aquatic Chronic 2 H314 H317 H411 NO Harmonised classification as Acute Tox. 4 dermal and also Flam. Liq. 3. Notified classification as Acute Tox. 3 dermal (H311) but not Acute Tox. 3 inhalation (H331) (ECHA C&L inventory). Tert-butyl hydroperoxide #N/A #N/A (FULL) No harmonised classification. Notified classification as Acute Tox. 3 dermal (H311) but most notified classifications also include Acute Tox. 2 inhalation (H330) (ECHA C&L inventory). REACH registration includes H311 as selfclassification.

45 Substances Identified in Previous Studies In one of the studies undertaken to support the review of the Seveso II Directive 21, information was provided on the identity of chemical substances potentially affected by the full range of changes being considered to the Directive (all areas in Figure 1.1). Specifically the French government provided information on the quantity of some substances in the inventory of 82 French industrial establishments (most of them are Seveso installations in the general chemicals sector). This includes substances identified as newly included or newly excluded from the potential scope of the Seveso directive (because of modifications to the classification through the CLP regulation). Appendix F includes the list of substances in question, it includes: 6 substances with a total inventory of 2,300t amongst the above establishments that could potentially fall out of the scope of the directive because they were classified as T under the previous legislation but acute toxic 3 dermal under the GHS (substances in Area A3 ); 97 substances with a total inventory of 31,500t that could potentially fall in the scope of the Directive if acute toxic 3 dermal substances had been included (substances classified as Xn under the previous legislation substances in Area A4 ). It should be noted, however, that there are various uncertainties in these data and they do not necessarily give a representative picture of the implications of the possible change in the Directive. For example, 2,100t of the 2,300t inventory for A3 substances is accounted for by formaldehyde, which is a named substance under the Seveso Directive. Of the 6 substances in Area A3, 4 have been added to the Directive as named substances. It should be borne in mind that this list of substances was developed at a time when there was less information available than today on the final classification of these substances. They are therefore of use as an indication as regards potential identity of substances affected, but the list is not considered to be representative. They have not therefore been analysed further, given that more specific and up-to-date information has been sought for the purposes of the current study. Nonetheless, the French study, along with information from other Member States, does provide useful additional information on the substances potentially affected and the number of establishments (considered later). 21 COWI (2010): Impact assessment study into possible options for adapting Annex 1 of the Seveso II Directive into the GHS, Final Report, February 2010.

46 33 4. Results of Stakeholder Consultation 4.1 Overview This section provides details of the key findings from the consultation of stakeholders for the purposes of the current study. It includes details of: The results of the main project consultation, undertaken through a questionnaire. Additional consultation undertaken with REACH registrants of certain chemicals, in order to attempt to identify further information on the numbers of establishments potentially affected. 4.2 Main Project Consultation Summary of response levels In total, by the end of January 2013, 21 contributions had been received to the survey and in addition, a number of organizations indicated that the survey was not relevant for them. Several contributions were collective answers from industry associations and one answer represented the experience of 40 Seveso establishments. The contributions show a good balance among the stakeholders: industry, industry associations, public authorities at national and regional level, and other categories including academic and consulting companies. Several companies (8 operators) answered directly. The level of response is satisfactory and in line with the expectations at the outset of this study, for what is a relatively niche issue (i.e. not related to a wholesale review of the Directive). This consultation aimed to reach various types of stakeholders concerned by the Directive throughout Europe. The relative complexity and level of detail of the subject means that a high response rate among the large number stakeholders consulted was not foreseen. Instead, the consultation aimed to provide additional information from various organisations likely to be aware of the specific issue of toxic category 3 substances through dermal exposure. This objective has been achieved with the involvement of representatives of industry (belonging both to multi-national companies and SMEs), representatives of industry associations (belonging to European and national associations), regional and national public authorities, agencies, associations, research and expert organisations. Thus, the idea of the consultation was not to obtain a representative sample but rather to give relevant experts in the specific field an opportunity to provide input to the study (and the net was cast widely in order to identify those experts).

47 Main findings by question area Introduction This section provides an overview of some of the key highlights of the results of the stakeholder consultation. This section is a synthesis of the answers provided by the respondents. The questionnaire was divided into the following parts: Part 0 identification of the respondent. Part 1 identification of substances within the category acute toxic 3 dermal which are considered most relevant in terms of frequency and severity of accidents. Part 2 views on significance of potential risks from acute toxic 3 dermal substances. Part 3 Available information on past accidents and near misses. Part 4 Available information on possible future accidents. Part 5 Potential number of establishments affected. Part 6 Potential costs and benefits of amending the Directive. Full details of the results are provided in Appendix D. Part 0 Identity of the respondent Most of the respondents are representatives from industry (57%, from both companies and industry associations). Most of the respondents from industry companies belong to a multi-national company operating lower tier Seveso establishments (3 respondents), upper tier establishments (3 respondents), or both (2 respondents). The other respondents are representatives of public authorities (23%, both national and regional authorities) and of other institutions such as universities, agencies and experts (19%). The figure below gives the distribution of the respondents:

48 35 Figure 4.1 Identity of respondents Part 1 Identification of substances within the category acute toxic 3 dermal which are considered most relevant in terms of frequency and severity of accidents Taking the lists of substances classified as acute toxic 3 and 4 dermal (Appendix E) as a starting point, consultees were asked to identify which other substances were considered most relevant. Most of the respondents did not know of other substances with these specific characteristics (76%). Some have underlined that many of the substances listed are also classified for their environmental hazards. The other respondents provided 24 additional substances that may be added to the list of substance identified, together with relevant information on hazards and uses in the industry (some of these substances were investigated further, as set out in Sections 3.3 and 4.3). (These substances were considered later in the project, in terms of the potential for relevant accidents.) A detail analysis of the hazard classification of these substances is provided Table of these substances have harmonised classification. 22 substances may potentially fall into the scope of this study. For 2 of the substances, other hazards relevant for Seveso have been identified. Data sources used by stakeholders for the identification of these substances are accident databases and MSDS. Key conclusions of this part of the survey are:

49 36 24% of the respondents are aware of substances (other than those on the lists provided) that are classified as acute toxic 3 dermal which are not already included in the scope of the Seveso Directive due to other properties. Several substances are listed in the survey and have been used as inputs for further analysis. Part 2 Views on significance of potential risks from acute toxic 3 dermal substances Among the 19 respondents that answered the question do acute toxic 3 dermal substances have the potential to cause major accident hazards? 3 thought that this potential exists, whereas 10 thought the contrary. 6 of the respondents thought that some of these substances have this potential. The figure below shows details of the answer. Figure 4.2 Views on whether the substances have the potential to cause major accident hazards Some respondents clearly think that including those substances in the scope of Seveso is unjustified whereas some think the contrary. Discussions are provided on possible accident scenarios that would lead to a major accident: quantities involved in the release, dispersion in river, fires (and toxic fumes) and uncontrolled runaway reaction. Another relevant point is what the best tool would be for including these substances in the scope of the Directive, if this was decided to be appropriate: as named substances for some specific chemicals (for example only gases or those that could be involved in runaway reaction), or as a generic substance group with the possibility of derogation.

50 37 When the respondents were asked to compare acute toxic 3 dermal substances with other exposure routes, their aggregated answer is that it is expected this exposure route would have less significant consequences on human health, environment and remediation costs than other exposure route (inhalation). Key outcomes of this part of the survey were: 53 % of the respondents thought that acute toxic 3 dermal substances (which do not also fall within another classification currently covered by Seveso) do not have the potential to cause major accident hazards. A suggestion was made to identify named substances when appropriate. The possible accidents involving acute toxic 3 dermal (only) substances are on average considered less significant than accidents involving other exposure routes (e.g. inhalation). Respondents rated the impact at between 1.4 and 1.6 on average out of 5). It is clear that there is disagreement on whether the substances can really cause significant accidents, so accident scenarios will be important. Part 3 - Available information on past accidents and near misses Among the 21 respondents, 7 (33%) are aware of past accidents or near misses that have involved dermal toxic effects. These respondents underline the fact that these accident scenarios are mainly linked to workplace risks. Respondents did not agree on whether these accidents could be considered as major or not. However, in the examples given, it is unclear if effects on humans are due to skin corrosion, dioxin exposure (chloracne) or dermal toxicity. A number of interesting examples are provided, which have been used as inputs to the development of accident scenarios for the present study. Part 4 Available information on possible future accidents Among the 21 respondents, 2 were aware of accident scenarios that have been considered within Seveso safety reports and that are related to dermal impacts of acute toxic substances. Scenarios identified are dispersion of product in river, uncontrolled reaction, fires and dispersion of toxic clouds (for example acetic acid anhydride and HCl). One respondent give the example of a scenario of acrylonitrile pipeline leak (acrylonitrile is already covered by the directive). This scenario has been studied in a safety report. However this scenario was not considered as major because of limited consequences (a maximum of 2 workers impacted). The most relevant scenarios are believed to be the releases with the constitution of a cloud, especially in the water, the inadvertent mixing of incompatible products (and runaway reaction), fire (and associated toxic fumes), explosion of a storage tank and the projection of product in the air. Some respondents considered that no scenario would be relevant for these substances.

51 38 Part 5 Potential number of establishments affected 5 respondents provided some estimate of the potential number of establishments that could enter into the scope of the Seveso Directive if acute toxic 3 dermal substances were to be added to Annex I. However, these answers are believed to be very uncertain by the respondents. Note that the data in the table below are simply the results of the consultation undertaken during the questionnaire process. Data provided in response to the questionnaire will be used in combination with a number of other sources of data for estimating the potential impacts of changes to the directive. Table 4.1 Questionnaire responses on potential number of establishments affected Respondent Details of response Notes University staff 6 establishments at EU-level (>50t) of which 6 not already covered by the Directive The level of confidence in this answer was rather low. Member State (FR) 25 establishments in one Member State at >50t and 8 at >200t. No details for number already covered by Seveso. Based on survey performed with support of UIC (the French Association of the Chemical Industry) in Results also presented in Appendix F of the present report. Operator of low tier establishment 8000 establishments in EU at >50t and 4000 at >200t Best estimates -Very low level of confidence. National industry association Member State (UK) 5 establishments at EU-level at >50t and 1 at >200t, of which 1 and 1 respectively not already covered by the Directive 55 establishments in one Member State at >50t (a small number at >200t), of which 55 not already covered by Seveso. Best estimate based on long experience in the chemical industry Based on survey aiming at identifying the dermal toxic substances that might have an impact on the Seveso III directive. Results were only partially complete at the time of writing. The survey focused in particular on calcium dipropionate and sodium dodecyl sulphate. The activities that are believed to be the most impacted by this measure would be: fine chemical installations, general chemical manufacture, production and storage of pesticides, biocides, fungicides, and production of basic organic chemicals and production of pharmaceuticals. The countries that were identified as being mostly impacted are: Germany, France, Italy and Spain. (However, it should be noted that this list is based on a small number of responses, from individuals/organisations that do not necessarily have an EU-overview of the potential scale of impacts. Therefore, further sources of information are needed to identify the likely geographical scale of the potential impacts.) Part 6 Potential costs and benefits of amending the Directive To the question what would be the average recurring costs and one off compliance costs per establishment in case of the inclusion of the category 3 dermal acute toxic category within the scope of the Directive (8 respondents have provided an answer), a wide variety of values was provided. The minimum and maximum values are presented in the table below.

52 39 Table 4.2 Survey responses on estimated costs of inclusion in Seveso ( per establishment) Preparation of notification and a major accident policy Prepare safety report and safety management system with emergency plans Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Not Seveso - One off compliance costs Not Seveso - Recurring costs Currently covered by Seveso One off compliance costs Currently covered by Seveso Recurring costs ,000 6, , , , ,000 12, ,000 50, ,000 12, , ,000 1, , , , ,000 1, , , ,000 Discussions were provided on the potential benefits of the inclusion of acute toxic category 3 dermal substances in the scope of Seveso. 14 respondents have provided an answer to this question. Among them, 9 clearly say that no benefit would be gained from this measure. One respondent does not see any benefit for the population but identifies some for the fire brigades and emergency services. One respondent highlights the benefit of the inclusion of Persistent Organic Pollutants, substances under the PIC scheme, chlorinated substance and organophosphorus pesticides. To the question Taking into account the costs and benefits, do you believe that these substances should be included within the scope of Seveso?, 16 respondents have provided an answer. The figure below presents these answers:

53 40 Figure 4.3 Views on whether these substances should be included in the scope of Seveso Based on a qualitative judgment, it seems that the respondents who provided the most precise answers to the questionnaire as a whole are not in favor of including these substances in the scope of Seveso Key conclusions The stakeholder consultation has enabled views and data to be collected from key stakeholders thanks to a survey that was addressed to a large number of stakeholders from industry, industry associations, public authorities, consulting companies and academics. Only a few stakeholders expressed their opinion through the questionnaire and only 21 answers were collected. However, those who are handling or using the substances addressed by the questionnaire did take the time to answer the survey. Several industry associations, industrial companies and competent authorities provided useful information for the identification of substances, definitions of scenarios and estimation of the establishments concerned and the costs to change the scope of the Seveso directive. The key findings of the survey can be summarized as follows: Generally speaking, little information is available about the potential impacts of including acute toxic 3 dermal substances in the Seveso III directive. Concerning the identification of acute toxic 3 dermal substances (Part 1 of the survey), one fourth of the respondents was aware of substances (other than those that have been already identified) that are

54 41 classified as acute toxic 3 dermal which are not already included in the scope of the Seveso Directive due to other properties. 27 substances were listed by the respondents. Concerning the significance of potential risks from acute toxic 3 dermal substances (Part 2), 53% of the respondents think that acute toxic 3 dermal substances (which do not also fall within another classifications currently covered by Seveso) have the potential to cause major accident hazards. However, the respondents view acute toxic 3 dermal substances as less significant than toxic substances where other exposure routes are relevant. Thus, possible accidents involving acute toxic 3 dermal (only) substances are on average considered less significant than accidents involving other exposure routes (e.g. inhalation). In Part 2, it was suggested to identify named substances to enter into the Seveso directive rather than the hazard categories in accordance with Regulation (EC) No 1272/2008. Regarding information on past accidents and near misses (Part 3), the survey has shown that 1/3 of the respondents are aware of past accidents or near misses that have involved dermal toxic effects. Some cases were described in details and have been used to define accident scenarios for the study. Looking at scenarios involving acute toxic 3 dermal substances (Part 4), i.e. possible future accidents, the survey only identified a few, that were regrettably not very detailed. Some answers were not fully in line with expectations since some respondents proposed scenarios involving substances that are already covered by the Seveso directive due to other properties (e.g. acrylonitrile which is also flammable). Nevertheless some ideas have been taken into account in drafting the accident scenarios. For the identification of possible establishments that might enter into the scope of the Seveso directive because of the inclusion of acute toxic 3 dermal substances, only 5 answers have been provided. Even the 2 answers that were provided by public authorities based on detailed surveys were expressed with a low level of confidence. It appears that it is difficult to answer the question. Based on the answers collected, the activities that are the most likely to be concerned by the inclusion of acute toxic 3 dermal substances in the scope of Seveso, are: - Chemical installation - other fine chemicals - General chemical manufacture (not included above) - Plastic and rubber manufacture - Production and storage of pesticides, biocides, fungicides - Production of basic organic chemicals - Production of pharmaceuticals Looking at the cost and benefit analysis (Part 6), it appears that the majority of the respondents and in particular the respondents who have provided precise answers to the questionnaire are not in favour of including acute toxic 3 dermal substances in the scope of Seveso.

55 Additional Consultation with Industry At the end of November 2012, ECHA published information on the identities of companies that had registered what are mainly high tonnage chemicals (>1000t per year) under REACH by the 2010 deadline. Other substances of lower tonnage are to be registered in May 2013 and in Because the level of information available from other sources (literature and the questionnaire) did not provide a complete picture of the number of establishments that would potentially be affected by a change in the directive, it was decided to contact a number of these companies directly (as manufacturers/importers of the chemicals, it was hoped that they would have a good idea of the number of establishments potentially involved in their supply / customer chain). Two groups of companies were approached by telephone and/or by (in February 2013): Companies that have registered under REACH substances classified as acute toxic 3 dermal which are not also classified for other Seveso-relevant toxic effects (13 substances and 21 companies). Companies that have registered substances which were identified through the questionnaire (see above and Appendix D), mainly being substances that are self-classified as acute toxic 3 dermal (8 substances and 14 companies). These companies were asked very targeted questions, specifically to provide a best estimate of the number of companies holding inventories of their chemicals above the 50t and 200t threshold in Europe and the number of these that would already be covered by Seveso due to inventories of other substances or due to other relevant effects of the substances (e.g. environmental toxicity). The table below summarises the results of the information received.

56 43 Table 4.3 Summary of responses received (up to 6 March 2013) on potential numbers of establishments relevant to REACH-registered substances Substance group Responses received Summary of responses Substances with harmonised classification as H311 Substances with notified classification as H out of 21 One company imports in the 1-10t per year band so estimates that none of their customers would be directly affected. One company sold >50t to four customers in [Note this does not necessarily imply an inventory >50t]. One company thinks that 3 of their customers have inventories >50t (of which 1 not yet covered by Seveso) and none >200t. One company estimates that 25 customers will be >50t (but highlights that most will already be Seveso installations because the substance was classified as Toxic under the previous legislation) [Note these substances/establishments could have fallen out of the scope since Seveso III was introduced.] One company, producing two of the relevant substances, indicated that (a) for one substance, none of their customers hold inventories >50t although they are likely to be already Seveso installations in any case; (b) for another substance, there is one relevant customer and they are already Seveso registered. One company only imports one of the substances at annual tonnages less than the lower (50t) threshold so its customers are unlikely to be affected. Five companies do not know or could not provide information on the number of establishments potentially affected (some citing confidentiality issues) 2 out of 8 One chemical manufacturer would move from lower tier to upper tier. Information being collected on customer implications. One company has no EU customers with annual consumption greater than lower tier threshold so estimate none of their customers would be affected. Overall, the data above provides some supplementary information but it is clearly far from a complete picture.

57 44 5. Analysis of Data on Past Accidents 5.1 Background The objectives of this section are to collect, compile and analyze data available on major accidents involving toxic substances. The analysis is focused on the identification of exposure routes involved in the accidents. The resulting data set allowed a comparison to be made between accident involving inhalation exposure and those involving dermal exposure. This following information is presented: the accident databases consulted and the compiled database used for the analysis; the analysis of this compiled database, including methodology and results. 5.2 Accident Databases Overview Details of various industrial accidents are recorded in specific databases often called accident databases. Data collection for the present study aimed to identify lessons learned from past accidents to industry and competent authorities. In the framework of this study, the accident databases consulted were as follows: e-mars; ARIA; The accident database (IChemE). The present section presents: general information on the use of these accident databases; specific information on the three databases used in this study; general information on the compiled database created from the merging of relevant information from these three databases.

58 Uses of accident databases The article development and use of a directory of accident databases involving chemicals of J.P. Pineau ( ) shows that the three most used accident databases in Europe by competent authorities, experts and industrialists in 1997 were the databases FACTS, MHIDAS and ARIA. The following table, extracted from the article, presents some of the results of this survey. It focuses on how these accidents databases are used. Table 5.1 Uses of accident databases (Pineau, 1997) Accident databases used for... Percent Accident scenario identification 79 Equipment and operator failures identification in system dealing with dangerous products 58 Emergency measures assessment 26 Safety policy design at a national/international scale 14 Policy design for insurance and finance companies 5 Dangerous phenomena consequence calculation models validation 17 Improvement of the quality/safety management 26 Reliability study and assessment of failure rates 13 Implementation of standards and regulations 17 The main use of accident databases is accident scenario identification. Quantitative analysis of such databases is a minor use. The reason is that these kinds of databases are mainly designed for providing (qualitative) lessons learned from past accidents. The quantitative analysis of such databases therefore has some limitations due to, for example, the format of the data (often based on qualitative descriptions) and the non-systematic recording of the accidents. These conclusions provide two indications relevant for the present study: it is recommended to use several databases to perform the comparison between inhalation and dermal toxic exposures during major accidents; the figures resulting from the analysis of the databases should be treated with caution: trends have to be sought and investigated instead of absolute figures. This kind of analysis is useful for comparison purposes. 22 J.P. Pineau, Development and use of a directory of accident databases involving chemicals. Proceedings of the ESREL'97, International Conference on Safety and Reliability, Vol. 3, Lisbon, Portugal (June 17 20, 1997) pp

59 46 Overall, however, the databases are of use for the current study in terms of identifying quantitative information on numbers of accidents; differences between inhalation and dermal exposure routes in past accidents; and examples of accidents that may have occurred involving substances within the scope of the current study Accident databases selected Three accident databases have been selected in the framework of this study: e-mars, ARIA and the IChemE s accident database. The following paragraphs give some details on these databases: e-mars (Major Accident Reporting System/ MAHB JRC), covering: around 700 accidents in Europe: - Coverage: e-mars collates information on major accidents in the framework of the Seveso Directive that have occurred in the European territory (and in Seveso establishments). Information on some near-misses is also collected. - Objectives: The objectives of e-mars are to centralise and broadcast lessons learned from accidents in order to prevent their occurrence in Europe. - Data collection: Competent authorities provide relevant information to the European Commission on causes and consequences of major accident when such events occur. This data is then summarised in the e-mars database. Industry operators can also willingly provide data on nearmisses. - Internet link: ARIA (Analyse, Recherche et Information sur les accidents (Analysis, Research and information on accidents)/ BARPI French ministry on environment), covering more than accidents and near-misses : - Coverage: ARIA collates data on accidents and near-misses involving dangerous substances that occurred in French classified installations for the protection of the environment ( ICPE : about 500,000 installations including about 1200 Seveso establishments). Certain large accidents that occurred in other countries are also listed in the database. The scope of the database has been recently and progressively extended to new activities such as dangerous goods transportation, gas distribution, dams, mines, careers and underground storage. - Objectives: ARIA aims to collect and broadcast a maximum of relevant data on causes, consequences and emergency measures when an accident occurs. - Data collection: The main source of data is competent authorities and industrialists records collected when an accident occurs. These data are complemented with inputs from newspapers and industrialists associations and international organisations specialized in accident prevention. - Internet link: The accident database (IChemE), covering about 15,000 accidents and near misses:

60 47 - Coverage: the accident database collates data on accidents and near-misses involving dangerous substances across the world (chemical facilities, dangerous goods transportation, etc.). - Objectives: to collect and broadcast lessons learned on accidents. - Data collection: data is provided through willing contribution of industrialists. - Internet link: These three databases have been chosen in order to provide an optimal level of information on accidents involving toxic substances: The e-mars database is the most relevant information source for studying major accidents since this is precisely its objective. However, the definition of a major accident in a Seveso establishment may be quite narrow when compared with the whole scope of accidental events that could occur in a chemical facility. With regard to this issue, and the inherent limitations of accident databases explained above, it has been concluded that it would be useful to complement this set of data with other accident database. Records from the ARIA database usefully complement the e-mars database because of its scope: it is wider because it includes more installations storing dangerous goods (establishments storing dangerous products in quantities below the Seveso threshold, but above the relevant thresholds of the French regulation). The number of accidents recorded in this database is therefore larger and provides a clearer view of the frequency and the possible consequences of toxic releases. The accident database from IChemE which, although it covers a smaller time period, usefully complements the two databases above, providing details and information on accidents that occurred in some countries less covered by the two other databases above (especially the United States of America). Examples of relevant accident scenarios are included in this database. The combination of these three databases gives a database of 55,700 accidents and near misses (redundancies have been searched and eliminated in a further step of the project) The compiled database This compiled database of 55,700 records has been analysed in two steps as described in Figure 5.1. A first filter has been used to select the following accidents: accidents which occurred between 2000 and 2012; accidents which involved toxic releases (inhalation, oral and dermal exposure routes and skin corrosion 23, involving toxicity categories 1,2,3 and 4 ); accidents which involved consequences such as injuries, death, confinement and evacuation. 23 Skin corrosion and dermal toxicity effects can be difficult to distinguish in accident descriptions provided in accident databases. As a first approach, accidents related to skin corrosion have been selected. In a second step, following a more detailed analysis, accidents related to toxic dermal effects have been distinguished.

61 48 This first filter led to the selection of 2,930 accidents involving toxic products that may have had effects on workers and local populations. A case by case analysis has then been used as a second filter to select 794 accident records relevant for the study. This process allowed redundancies to be excluded, as were accidents that did not generate any toxic effects (inhalation and dermal exposures cannot be distinguished in these cases) and accidents that involved substances and mixtures not classified for acute toxic properties under the CLP regulation (such as STOT, carcinogens, etc.) From the total of 794 accidents, 113 main substances involved have been identified. Figure 5.1 The compiled accident database The compiled database gives details for each accident (when available) on: location of the accident: country and name of town where the accident occurred; date of the accident; main activity of the establishment; main substance involved in the accident 24 (and CAS number); harmonised classification of the main substance under the CLP regulation; human consequences: number of deaths, number of injuries, number of people confined, evacuated or that asked for a medical advice; 24 During an accident more than one substance or mixture may be involved (for example because of multiple loss of containment or chemical reaction). Accident databases generally provide information only on the main substance involved: the one that produced effects on people.

62 49 the exposure route that was relevant for the product in the accident: oral, inhalation, skin corrosion, dermal (exposure characterized as confirmed or suspected ) or no exposure. Note that in a large proportion of the cases a toxic exposure involves more than one exposure route. Such accidents have been recorded in the compiled database as simultaneously involving several exposure routes. property and environmental consequences characterised on the basis of the European scale of accidents (Committee of Competent Authorities, 1994). This database is provided in the Appendix A of this report. Among the 794 selected, the distribution of the source of the descriptions used is detailed in the graphic below: Figure 5.2 Distribution of the 794 accidents selected as a function of their original database The main source of accident descriptions is the ARIA database with 672 accidents. This high proportion of the use of ARIA s records results from the larger number of accidents and a wider scope of the database. This also leads to a high proportion of the number of accidents that occurred in France. The figure and the table below provide some further details.

63 50 Figure 5.3 Distribution of the 794 accidents as a function of the continent Table 5.2 Number of accidents occurred in some countries (among the 794 accidents) Country Number of accidents Austria 1 Belgium 7 Bulgaria 1 Czech Republic 2 France 449 Germany 21 Greece 2 Hungary 2 Italy 1 The Netherlands 9 Romania 3 Sweden 1 United Kingdom 17 China 24 Japan 4 United States of America 145 More than 50% of the accidents recorded in the compiled database have occurred in France.

64 51 This large number of accidents that occurred in France should not be considered a problem since these accidents concern Seveso establishments plus transportation of dangerous goods and also establishments storing/using dangerous products in smaller quantities than the Seveso thresholds. The analysis of these accidents is relevant in the framework of this study and brings further accuracy on accidents involving toxic products. However, some investigation has been undertaken to determine the level of representativeness of this set of data for facilities in other countries. With this aim, the data set have been split in two: accidents from France and accidents in other countries. Two parameters were then compared: the main substances involved in the accident; the main activity at the origin of the accident. The top 15 activities (among a total of 48 activities) and main substances involved in the accident for these two set of data were compared. The coherence level of activities and main substances between the two datasets is taken here as an indicator of the representativeness of the French dataset for other countries. The table below gives the results of this comparison of activities. It should be noted that, in many cases, the activity was not known. Table 5.3 Comparison of the proportion of activities linked to a major accident recorded in the compiled database for the French dataset and the dataset concerning other countries France The top 15 activities Other countries the top 15 activities Manufacture of food products and beverages 16% Production and storage of fertilizers 15% Leisure activities 9% Handling and transportation centres (ports, airports, etc.) and Transport 12% Handling and transportation centres (ports, airports, etc.) and Transport 9% Not known/applicable 10% General chemical manufacture (not included above) 8% General chemical manufacture (not included above) 8% Production of basic organic chemicals 7% Manufacture of food products and beverages 7% Processing of metals 5% Plastic and rubber manufacture 5% General engineering, manufacturing and assembly 5% Refinery 5% Waste treatment, disposal 5% Waste treatment, disposal 5% Water and sewage (collection, supply, treatment) 4% Wholesale and retail storage and distribution 4% Not know/applicable 4% Leisure activities 4% Wholesale and retail storage and distribution 3% Production of basic organic chemicals 3% Production and storage of fertilizers 3% General engineering, manufacturing and assembly 3% Textiles manufacturing treatment 3% Processing of metals 3% Electronics and electrical engineering 2% Water and sewage (collection, supply, treatment) 3% Medical, research, education (including, hospitals, university, etc.) 2% Medical, research, education (including, hospitals, university, etc.) 2%

65 52 13 activities are represented in the top 15 activities of both the French accident dataset and the other countries dataset. Activities which do not appear in both datasets in the top 15 lists are the following: plastic and rubber manufacture and refinery appears in the top 15 activities of the other countries dataset but not in the French dataset ; textiles manufacturing treatment and electronics and electrical engineering appears in the top 15 activities of the French dataset but not in the other countries dataset. Giving the number of accidents, this analysis shows a quite good representativeness of the French accident sample for the other countries sample. The table below gives the results of the comparison of main substances (these main substances are toxic for the inhalation, dermal or oral exposure routes and/or classified as skin corrosion ). Table 5.4 Comparison of the proportion of main substances involved in major accident recorded in the compiled database for the French dataset and the other countries dataset France Top 15 main substances involved Other countries Top 15 main substances involved Chlorine 22% Ammonia 15% Ammonia 17% Chlorine 15% Carbon monoxide 8% Unknown (Fumes) 12% Unknown (Fumes) 5% Unknown 10% Hydrogen sulfide 4% Hydrogen sulfide 5% Sulfur dioxide 4% Sulphuric acid 3% Unknown 4% Hydrochloric acid 3% Hydrogen chloride 4% Carbon monoxide 2% Hydrochloric acid 2% Formaldehyde 2% methylene chloride 2% Nitric acid 2% Chloropicrin 1% Hydrofluoric acid 2% Nitric acid 1% Sodium hydroxide 2% Trichloroethylene 1% Phenol 1% Bromine 1% Phosgene 1% Hydrogen cyanide 1% Styrene 1% Comparing the top 15 main substances of the two datasets, some matches occurred: for substances such as ammonia, chlorine, carbon monoxide, hydrogen sulphide, hydrochloric acid, nitric acid.

66 53 However except for these 6 substances (None of these substances are classified as toxic category 3 through dermal exposure only: these substances are all included in the actual scope of the Seveso Directive), the top 15 substances of the two datasets are different. The number of incoherent main substances in the top 15 main substances of the dataset can be explained by the great number of main substances identified for the 794 accidents of the database (113 main substances). Indeed, except for ammonia and chlorine, the presence of low proportions (below 5%) shows a wide dispersion of the samples. When the main substances are studied, the representativeness of the French dataset for the other countries dataset is then not conclusive. As a conclusion, although the representativeness of the French dataset shows some limitations, it is believed its integration into the analysis brings useful information for the purposes of this study. In order to provide a clear statement of the potential limits of the analysis, a separate analysis of the two datasets is provided in the Appendix B of this report. 5.3 Analysis of the Compiled Database Overview The purpose of the database analysis is to provide relevant information for the comparison of the frequency and the consequence of major accidents involving the dermal and inhalation exposure routes. The following subsections describe: the methodology followed for the analysis of the database; the results related to frequencies of major accidents involving the dermal and inhalation exposure routes; the results related to consequences on humans of major accident involving the dermal and inhalation exposure routes; the results related to consequences on the environment of major accidents involving dermal and inhalation exposure routes Methodology The first step of the data analysis was to define the exposure routes involved in major accidents. Six cases have been distinguished on the basis of accident descriptions: Inhalation exposure: the description clearly describes an inhalation exposure to toxic releases; Dermal exposure (confirmed): the description clearly describes a dermal exposure to the toxic release;

67 54 Skin corrosion: the description clearly describes skin corrosion effects following the exposure to the release; Dermal exposure (suspected): it is impossible to confirm the existence of toxic effects following a dermal exposure on the basis of the accident description. However, it is probable this exposure route produced effects that took part in the overall consequences of the accident; No exposure: although a release of toxic product occurred, there was no exposure of people (for example in the case of successful confinement measures); Exposure unknown. For any single accident more than one of these cases may be relevant. For example, accidents which involved both inhalation and dermal or both dermal and skin corrosion exposure routes/effects are common. Such accidents have been recorded in the compiled database as simultaneously involving several exposure routes The second step of the analysis was to identify the classification of the main substances involved. Minimum harmonised classifications of the C&L inventory have been used for this task. In some cases these data are not available and in such cases, notifications recorded in the ECHA C&L inventory database have been consulted. When these data were coherent, a classification has been retained (in the following paragraphs, this corresponds to the cases called acute tox 1-2 ). From the analysis of this database, some conclusions can be drawn concerning: the number of accidents involving dermal and inhalation toxic exposures with details on minimal classification of the main substances involved; the consequences of these accidents on humans and the environment Comparison of the number of accidents involving dermal exposure and those involving inhalation exposure The following graph gives the proportion of exposure routes (and skin corrosion) for the 794 accidents in the database:

68 55 Figure 5.4 Proportions of various exposure routes for accidents involving toxic substances Note: For some accidents, the effects of several exposure routes have been described simultaneously. The sum of the figures in the graph is then >100% Among the 794 accidents studied: 457 accidents involved inhalation exposure (for some of them other exposure routes were involved); 29 accidents involved dermal exposure (confirmed and suspected), including 18 accidents in France and 11 accidents in the other countries (for some of these 29 accidents, other exposure routes were involved). The number of accidents involving the inhalation exposure route is significantly higher than those involving dermal exposure routes. When an accident involving toxic products occurs, different types of effects and exposure routes can be simultaneously felt by exposed populations. It is impossible to determine clearly which of these exposure types produces most of the effect on the basis of accident descriptions included in the accident databases. Detailed analysis of exposed peoples clinical states is not available. This limitation of the knowledge is even more relevant when the dermal exposure route and skin corrosion effects are involved. The table below details the potential exposure routes involved for the 29 accidents involving the dermal exposure routes (confirmed or suspected):

69 56 Table 5.5 Detailed analysis of the 29 accidents potentially involving dermal exposure route Accident type Number Total accidents potentially involving dermal exposure route 29 Accidents involving dermal exposure route 18 - Dermal only (confirmed) 11 - Dermal exposure (confirmed) and skin corrosion 5 - Dermal exposure (confirmed) and inhalation 2 - Dermal exposure (confirmed) and inhalation and skin corrosion 0 Accidents for which dermal exposure route is suspected 11 - Dermal only (suspected) 1 - Dermal exposure (suspected) and skin corrosion 5 - Dermal exposure (suspected) and inhalation 3 - Dermal exposure (suspected) and inhalation and skin corrosion 2 Among the 29 accidents potentially involving dermal exposure route, 12 of them are confirmed or suspected to have generated effects on people that were related only to dermal exposure to toxic products. These first results concerning the comparative number of accidents involving dermal and inhalation toxic exposure routes have to be complemented with an analysis of the level of toxicity of the main substances involved. The table below shows the classification 25 for acute toxicity (inhalation and dermal exposure routes) of the main substances involved in accidents with toxic effects included in the database. 25 Harmonised classifications have been used in this analysis for providing a first view of the substances levels of toxicity, unless otherwise stated (where the highest class most toxic notified classifications have been used). Further analysis of the substances classifications has been performed for substances relevant for this study.

70 57 Table 5.6 Classification for acute toxicity (dermal and inhalation exposure routes) for accidents with toxic effects Exposure routes Acute tox 1 Acute tox 2 * Acute tox 3 * Acute tox 4 * Acute tox 1-2 Not classified Dermal exposure (confirmed) (classification for acute toxicity through dermal exposure route) (18 accidents) Dermal exposure (suspected) (classification for acute toxicity through dermal exposure route) (11 accidents) Inhalation exposure (classification for acute toxicity through inhalation exposure route) (457 accidents) 16.7% 0.0% 22.2% 11.1% 5.6% 44.4% 36.4% 0.0% 9.1% 9.1% 0.0% 45.5% 0.0% 12.0% 60.2% 2.4% 0.0% 25.4% For the columns with acute tox 1 to acute tox 4, data from harmonised classification was used. Harmonised classification was not available for substances in the column acute tox 1-2 and in this case all the classifications included in notifications were either acute toxic 1 or acute toxic 2. Some key elements of this table are the following: 45% of the main substances involved in major accidents with toxic dermal exposure do not have a harmonised classification. In contrast, 75% of those involved in toxic inhalation exposure have a harmonised (minimal) classification. 25% of the main substances involved in major accidents with toxic dermal exposure are classified acute toxic category 1 for dermal exposure under the CLP regulation. 60% of the main substances involved in major accidents with toxic inhalation exposure are classified acute toxic category 3 for inhalation exposure (minimum classification) under the CLP regulation. 21 main substances have been identified as being involved in the 29 accidents studied because of their dermal exposure (Appendix C gives details about these 21 main substances). In one accident, the main substance has not been identified. The two tables below gives details about the classification of these main substances (harmonised classifications have been searched for these substances): Table 5.7 Details on classification of the 21 main substances (+1) (dermal toxicity and skin corrosion hazards) Type Number Unknown substance 1 Classification unknown 1 Not classified for dermal exposure toxicity [Note 1] 5 Classified only for skin corrosion hazards 5 Classification for acute toxicity for dermal exposure (cat. 1,2,3,4) 10 [Note 1]: The study of the accident descriptions led to the conclusion of a possible dermal toxic effect. However, the substances are not classified as acute toxic for dermal exposure. The possible explanations include a misinterpretation of a skin corrosion effect or the presence of dermal toxicity not highlighted during laboratory tests.

71 58 Table 5.8 Details on classification of the 21 main substances (+1) (inhalation toxicity) Type Number Unknown substance 1 Classification Unknown 1 No classification related to inhalation toxicity 6 Harmonised classification acute toxic cat 1 inhalation 0 Harmonised classification acute toxic cat 2 inhalation 5 Harmonised classification acute toxic cat 3 inhalation 6 Harmonised classification acute toxic cat 4 inhalation 1 No harmonized classification. Notified classifications include acute toxic category 1 or 2 inhalation 2 Among these 21 main substances, only 10 are classified for acute dermal toxicity. The table below gives their classification for acute toxicity, dermal exposure (harmonised classification unless otherwise stated): Table 5.9 Detailed classification of the 10 main substances Type Number Acute tox. 1 4 Acute tox. 2 0 Acute tox. 3 2 Acute tox. 4 3 Acute tox. 1-2 [Note 1] 1 [1] Harmonised classification was not available for this substance. However, all classifications included in notifications were acute tox 1 or acute tox 2. The two main substances classified as acute toxicity category 3 dermal exposure are also classified as acute toxicity category 1,2 or 3 inhalation exposure. Among the 3 main substances classified acute toxicity category 4 dermal exposure, only one of them does not have any other classification relevant for Seveso (P-nitrophenol CAS ). The key conclusions of the comparison and the analysis of accidents involving toxic substances are the following: There have been, between 2000 and 2012, a significantly higher number of accidents that involved the inhalation exposure route than the dermal exposure route (as reported in the databases analysis, these were 57.58% for the inhalation exposure route and 3.6% for the dermal exposure route). This trend is confirmed by the analysis of the separated dataset (see Appendix B). Despite the large limits of a

72 59 quantitative analysis of accident databases, the difference between the values clearly shows a higher frequency of major accidents involving inhalation exposure compared to major accidents involving dermal exposure. Moreover, in most of the cases involving dermal exposure, several types of exposure were involved: toxic inhalation exposure, but also skin corrosion and irritant effects. 21 main substances were involved in toxic dermal accidents. According to the known classifications (see above), 11 of these substances are not classified as acute toxic for the dermal exposure route. Among the other substances, most of them are classified as acute toxic category 1 for the dermal exposure route. Only one of the substances classified as acute toxic category 3 or 4 for dermal exposure route does not have other classification relevant for Seveso. As a first indication of the consequences of such accidents, it could be added that: - among the 18 accidents involving dermal exposure route, 1 had off-site effects (injuries); and - among the 11 accidents that may have involved dermal exposure route, 2 had off-site effects (injuries) Comparison of human consequences of accidents involving dermal exposure and those involving inhalation exposure With the aim of comparing the impacts on humans of the inhalation and dermal exposure routes in case of toxic releases, two indicators have been used: The ratio of accident-death or wounded to the number of accidents. This ratio measures the proportion of accidents in which consequences were at least one death or one injured. The average number of deaths or wounded: this is an average of the number of deaths or injured per accident. The combination of these two indicators provides an insight into the consequences of accidents. The first ratio provides an answer to the question how frequent are very serious consequences when inhalation or dermal exposure to toxic substances are present during an accident? The second indicator provides an indicator of the size of these consequences. Note that, when an accident involving a toxic release occurs, more than one exposure route is likely to be involved. Also, when considering accidents potentially involving the dermal exposure route, direct contact of the product with the skin may lead to other effects, such as skin corrosion effects, irritant effects or inhalation of the toxic substance. In most cases, it is impossible to distinguish clearly which of these effects have led to the most significant damage. In those cases, accidents have been recorded in the present dataset as simultaneously producing all the relevant effects, through all the relevant exposure routes. For example, an accident where both inhalation and dermal exposure routes were involved and where death occurs, have been taken into account for both the ratio of accident-death/number of accidents for dermal and inhalation exposure routes. The table below gives the results of the calculation of the two indicators for the studied accidents.

73 60 Table 5.10 Consequences of accidents involving toxic dermal and inhalation exposure routes Dermal exposure route (29 accidents) Inhalation exposure route (457 accidents) Ratio accident- death/number of accident 17.2% 12.5% Average number of deaths/accident Ratio accident - wounded/number of accident 51.7% 72.4% Average number of wounded/accidents A larger proportion of identified accidents involving toxic dermal exposure led to one or more death (17.2%) than accidents involving toxic inhalation exposure (12.5%). However, the average number of deaths is lower for dermal exposure route accidents (0.17). A higher ratio is observed for accidents involving toxic inhalation exposure for accidents with one or more wounded people (72.4%). The average number of wounded is also clearly higher when inhalation exposure is involved (34.6). This statement is only partially confirmed by the analysis of the database in two separate datasets (see Appendix B): Contrary to the results presented in the table above, in one case (the French accidents analysis), the average number of deaths per accident involving the dermal exposure route is slightly higher than those involving the inhalation exposure route. However, the following elements have to be considered: the inherent bias of accident databases; the small difference between these two values; the statement, as explained above, that the part of the consequences attributable to the toxic dermal exposure route in an accident is unclear, in particular when the toxic inhalation exposure route and skin corrosion effects are also involved in the accident. Overall, in terms of the average number of deaths per accident, the difference between accidents involving the toxic inhalation exposure route and those involving the toxic dermal exposure route is believed to be non-conclusive. However, among the 29 accidents which involved dermal exposure, 12 accidents involved only this exposure route. For one accident among these 12, a death occurred: in France in 2006 an employee received hydrocyanic acid 26 over their whole face following the rupture of a pipe. The employee was not wearing goggles during the operation. Hydrocyanic acid is acute toxic category 1 for dermal exposure and is also classified for a number of other hazards that are relevant for Seveso. In contrast, a large number of accidents involving inhalation exposure routes (with substances with H330 or H331 hazard statements), have generated one or more deaths. 26 CAS , harmonized classification: Acute tox 1 (H310), acute tox 2 (H300, H330) aquatic acute and chronic 1 (H400, H410).

74 61 Whilst the data are not necessarily statistically significant, they suggest that accidents involving the toxic dermal exposure route lead to less severe human consequences than those involving the toxic inhalation exposure route Comparison of environment and property damages of accidents involving dermal exposures and those involving inhalation exposures A first statement is that in the three accident databases used, very few and inaccurate data are available on environment and property damages. On the basis of available data: Concerning accident involving the dermal exposure route: - None of the accidents relevant for dermal effects has generated significant environmental damage; - One accident generated some minor material damage (the first level of the European scale for property damages has been reached) 27. Concerning accidents involving the inhalation exposure route: - One has reached the first level of the European scale for environmental damage; - Six have reached the first level (and beyond) of the European scale for material damage. Considering the data scarcity, these results are not considered as conclusive, but confirm the highest consequences occur in cases relevant for the toxic inhalation exposure route. 5.4 Key Conclusions The following key elements are underlined: 55,700 accidents have been screened of which 794 have been considered relevant for the present study. There were, between 2000 and 2012, a significantly higher number of accidents which involved the inhalation exposure route than the dermal exposure route. 21 main substances were involved in the identified toxic dermal accidents. However, according to harmonised classifications (and available information on notified classifications where no harmonised classification exists), only 10 of these substances are classified as acute toxic for the dermal exposure route in Europe. Of these 10 substances, most are classified acute toxic category 1 for the dermal exposure route. Accidents involving toxic dermal exposure route led to less human consequences than those involving the toxic inhalation exposure route. 27 See decision from Committee of Competent Authorities, This scale is described at:

75 62 Considering these elements, it is considered that the risk generated by products (substances and mixtures) that are acute toxic category 3 for the inhalation exposure route is significantly higher than the risk generated by products that are acute toxic category 3 for the dermal exposure route. However, some accidents involving substances that are acute toxic category 3 for dermal exposure may have led to severe consequences. In particular, the criteria of Annex VI of the Seveso III Directive were reached for these accidents. For example, some of these accidents may have led to the death of workers at the facility. However, it has to be pointed out that, in these specific cases, the exact influence on overall dangerous effects to people of dermal toxicity is unclear because other effects were also involved in the accidents in question, such as inhalation toxicity and skin corrosion.

76 63 6. Accident Scenarios 6.1 Detailed Methodological Approach General discussion The accident databases analysis and the stakeholder consultation have provided first results on the likelihood, risks and consequences of major accidents involving acute toxic 3 dermal substances. This still only provides a partial picture, as they are exclusively based on past experience. Moreover, the lack of data and the recent evolution of the chemicals classification regime (GHS) limits the provision of clear insights into the differences of dangerous potential between dermal and inhalation exposures to acute toxic category 3 products. It is therefore proposed to complement these elements with a more analytical and illustrative approach based on the evaluation of accident scenarios. Whilst this second approach will also have weaknesses, as a complement to the first approach, it will however provide a clearer insight into the study objectives, particularly the relative importance of potential accidents involving the dermal toxic route. This task aims to provide a clearer insight into the differences of dangerous potential between dermal and inhalation exposure to acute toxic category 3 products through a comparative approach. It does not aim to assess the potential for all acute dermal toxic category 3 products to generate a major accident this objective would need far more extensive resources and a broad consensus on a precise definition of a major accident. Considering the current limitation of knowledge on vulnerability of humans to dermal toxic exposure, calculation of effects and to the variety of situations (variety of products, storage volumes, industrial establishment lay out, industrial processes, topography, possible weather, etc.), it is impossible to develop an analysis that would describe all the potential accidents. Calculation parameters such as substance, pressure, release quantities and environmental parameters will therefore be selected as realistic but not representative. The calculations will be theoretical but, since the same parameters will be used for the dermal and inhalation calculations, the results, used for comparison purposes, are expected to be valid. Three steps are necessary in terms of achieving the objectives of this analysis: scenario selection selection of the substances studied: theoretical consequence calculations.

77 Scenario selection The scenarios selected for further analysis are based on: the accident database analysis; the stakeholder consultation; experience of the contractor. 5 accident scenarios are selected for further analysis. These scenarios are designed to cover the main possibilities identified. The scenarios selected are deliberately conservative. In general, where there are many uncertainties or too many possibilities to represent them within the scenarios, worst case scenarios / conservative assumptions have been used. The scenarios have been selected to represent realistic worst cases. Some source term parameters are defined (pressure of the release, size of the vessel, etc.) to allow quantitative analysis to be undertaken. These parameters are chosen by the contractor on the basis of its experience as typical values used in risk assessments for Seveso (and similar) establishments and activities Selection of the substances studied General approach The selection of the substances to be considered in scenario assessment is a key point. As the calculations performed are theoretical, the assessment of the effects of one single substance taken alone has a limited value. However, as comparisons are performed between inhalation and dermal effects, the purpose of this approach is to compare the results for different substances classified acute toxic category 3 for dermal and/or inhalation exposure. The choice of these substances is then made in such a manner that the larger parts of the toxic category 3 dermal and inhalation are covered. Since, the dermal and inhalation toxicities are not fully comparable in medical terms, it is the upper and lower limits of these CLP categories that provide benchmarks. The figure below illustrates the objective of this selection of the substances. Note that the thresholds for inhalation vapour concentrations have been used as the basis for the comparison in the current study.

78 65 Figure 6.1 Illustration of substance selection to cover the relevant range of hazards Substance 2 Substance 1 Substance 3 Inhalation Cat 1 Cat 2 Cat 3 Cat 4 Threshold values (mg/l) Dermal Cat 1 Cat 2 Cat 3 Cat 4 Threshold values (mg/kg) Substance B Substance A Substance C The substances 1, 2 and 3 then cover a large part of the category 3 inhalation exposure route. The Substances A, B and C cover a large part of the category 3 dermal exposure route. Results from the calculations related to Substance 1 are comparable with those performed for Substance A. Results from calculations related to Substance 3 are comparable with those performed for Substance C. It has to be noted that consequence calculations are performed for one single effect: there are thus separate calculations for dermal and inhalation effects. Therefore, if one substance is used both for toxic dermal and inhalation calculations, conclusions will be still valid. A last important issue is that the level of knowledge available on the chosen substances has to be high in order to avoid errors. Consequences assessments can be considered as a simple sensitivity analysis of the potential consequences as a function of the LD 50 and LC 50. The substances of interest have been selected according to the following methodology. As a starting point, three categories of substances are used to identify substances of interest: Substances that are classified acute toxic 3 for both dermal and inhalation routes. This pool of substances is expected to enable the comparison of the relative importance of inhalation and dermal toxicity. Substances that are classified acute toxic 3 for dermal exposure and that are not covered under Seveso III for other health hazards. As above, this group should allow a comparison to be made between the

79 66 inhalation and dermal route, but in addition should underline the extent of the impact of an accidental event involving a dermal acutely toxic substance. Substances identified in the stakeholder consultation exercise. The set of substances finally selected need to cover as large a range as possible of LC 50 /LD 50 values for the category 3 inhalation and dermal exposure substances, in order to illustrate the extent of effects across the whole range covered by the category and help to achieve representative calculations. The strategy used for the selection of substances is detailed below and consists in a first step of a screening of substances from LC 50 /LD 50 values for each of the substances groups defined above. Substances that are classified Acute Toxic 3 for dermal and inhalation route In order to identify substances that could be classified acute toxic 3 for the dermal and inhalation routes, a first screening based on the lethal values (LC 50 /LD 50 ) was undertaken. Then, the quality and the completeness of data reported in REACH registration dossiers (based on ECHA s public dissemination portal) have been assessed to determine if the substance can be retained (i.e. if sufficient suitable data exists). For the substances identified, the classification of the substance in the REACH registration dossier was searched to identify substances that are classified acute toxic 3 for the dermal and inhalation routes. The methodology is presented in the following diagram.

80 67 Figure 6.2 Methodology for selecting substances acute toxic 3 for dermal and inhalation exposure routes 1 - Screening of substances according to LC 50 /LD 50 values = Acute Tox 3 (inhalation and dermal) LD 50 = 200-1,000 mg/kg and LC 50 = 2-10 mg/l (2,000-10,000 mg/m 3 ) 2 - Assessment of the quality and the completeness of data in REACh registration dossier Quality of study (Klimish criteria) and LC 50 /LD 50 well identified 3 - Selection of substances which are classified Acute Tox 3 for inhalation and dermal route Classification of the REACh registration dossier (ECHA) 1 Screening of substances according to LC50/LD50 values This screening was done based on the echemportal database with a search based on chemical property. The criteria defined for research of substances that are classified acute toxic 3 for the dermal and inhalation routes are determined as follows: Study result type: estimated by calculation ORexperimental result ORexperimental study planned Route of administration: inhalation (vapour) Effect levels, Endpoint: LC 50 Effect levels: overlapping 2-10 mg/l air OR overlapping 2-10 mg/l air (nominal) OR overlapping 2-10 mg/l air (analytical) OR overlapping 2,000-10,000 mg/m 3 air OR overlapping 2,000-10,000 mg/ m 3 air (nominal) OR overlapping 2,000-10,000 mg/ m 3 air (analytical) AND Study result type: estimated by calculation ORexperimental result ORexperimental study planned Route of administration: dermal Effect levels, Endpoint: approximate LD 50, LD 50 Effect levels: overlapping 200-1,000 mg/kg The values for effects levels correspond to the threshold of the category 3 for inhalation (vapour) and dermal route according to the CLP regulation as described in Section 1.4. The search is done in the REACH registration dossiers via the echemportal database.

81 68 2 Assessment of the quality and the completeness of data For each substance identified in the step 1, an assessment of the quality and the completeness of data in the REACH registration dossier was undertaken. The first selection step consists of excluding the studies for which the lethal values are not clearly determined, because these values cannot be used in the scenarios defined for modelling. For example, studies for which the LC 50 /LD 50 is considered to be superior or inferior to a given value (rather than a precise value), or for which the LC 50 /LD 50 is between two values are directly excluded. Indeed, in some cases, for example, for studies undertaken according to the OECD guideline 436 or for limit tests which are undertaken at threshold concentration/dose corresponding to a category, no precise value is determined. These studies are only used to classify substances according to the CLP regulation. Next, the quality of study used to determine the LC 50 /LD 50 was analysed in order to determine if the lethal value can be retained. The selection of studies takes into account the reliability based on the approach of Klimisch et al (1997) (standardized method, Good Practice of Laboratory, detailed description of the publication) 28. The reliability is related to the quality of a test protocol and report or publication relating to a standardised methodology and the way that the experimental procedure and results are described to give evidence of the clarity and 1 plausibility of the findings. The assessment of the studies is only based on the robust summaries of the registration dossiers, which are provided by the registrant (no separate assessment of experimental quality was undertaken for the present study). The main elements assessed for the selection and evaluation of data and studies are: study performed according to standardised method: Guidelines study (OECD, US EPA or comparable), study performed according to Good Laboratory Practice (GLP), species tested (rat, mice, guinea pig, rabbit, etc.), number of animals per dose and per sex, physical state of the substance, duration of exposure and observation, number of doses/concentration, analytical procedures to control concentration/dose of exposure, details on the test conditions. 28 Klimisch H.J., Andreae M. and Tillmann U. (1997) : A systematic approach for evaluating the quality of experimental toxicological and ecotoxicological data. Regulatory Toxicology and Pharmacology, 25, 1, 1-5.

82 69 3 Selection of substances (and LC 50 /LD 50 ) classified acute toxic 3 for the inhalation and dermal route For substances identified in step 2, the LC 50 /LD 50 derived from studies of best quality is retained. The substances selected are those which have a LC 50 and a LD 50 of good quality according to the different elements detailed in step 2. If a substance has a LC 50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance is not selected and vice versa. As double check, these values are compared to the classification provided in the REACH registration dossiers in order to verify the consistency of the outcome of the LC 50 /LD 50 analysis and the classification provided in the registration dossier. Substances that are classified acute toxic 3 for dermal exposure and that are not covered under Seveso III for other health hazards Two approaches have been followed to select substances that are classified acute toxic 3 for dermal exposure and that are not covered under Seveso III for other health hazards. Firstly, the substances identified in the review of CLP and REACH (Section 3) data are considered. This selection is based on harmonised and selfclassification. Secondly, the focus was on substances that are classified acute toxic 3 for dermal exposure and acute toxic 4 for inhalation exposure 29 (and excluded from the scope of Seveso for other health hazards). This second list is partially covered by the first list but the screening is primarily based on the LC 50 /LD 50 reported in the registration dossiers, and thus will complete the information given by the harmonised classification. 1 Substances identified in the review of CLP and REACH The substances identified in Section 3 are considered most likely to fall within the scope of the Directive in the event of a change to include acute toxic 3 dermal substances. These substances have been registered under REACH and have a harmonised classification as acute toxic 3 for the dermal route, but no other health hazards relevant in the context of Seveso. The studies and data related to these substances in the registration dossier are analysed in accordance with step 2 (assessment of the quality and the completeness of data) of the previous strategy and the LC50/LD50 derived from studies of best quality are retained. 2 Substances that are classified acute toxic 3 for dermal exposure and acute toxic 4 for inhalation exposure The methodology followed to identify these substances is similar to that described in the first strategy (substances that are classified acute toxic 3 for the dermal and inhalation routes). A first screening is based on the lethal values (LC 50 /LD 50 ). Then, the quality and the completeness of data in the REACH registration dossiers are assessed to determine if the substance can be retained. As double check, these results are compared to the classification provided in the REACH registration dossier in order to verify the consistency of the outcome of the LC 50 /LD 50 analysis and the classification provided in the registration dossier. This methodology is presented in the following diagram. 29 These substances would be newly included in the scope of the Directive (substances toxic category 4 for inhalation exposure are not included in the scope of the Directive except in the case of possible self-classification by some suppliers). Choosing these substances provides a basis for comparison of the significance of the exposure routes..

83 70 Figure 6.3 Methodology for selecting substances acute toxic 3 for dermal exposure routes A Screening of substances according to LC 50 /LD 50 values A screening was done on the echemportal database and the search is undertaken by chemical property. The criteria defined for research of substances that are classified acute toxic 3 for the dermal route and acute toxic 4 for the inhalation route are determined as follows: Study result type: estimated by calculation ORexperimental result ORexperimental study planned Route of administration: inhalation (vapour) Effect levels, Endpoint: LC 50 Effect levels: overlapping mg/l air OR overlapping mg/l air (nominal) OR overlapping mg/l air (analytical) OR overlapping 10,000-20,000 mg/m 3 air OR overlapping 10,000-20,000 mg/ m 3 air (nominal) OR overlapping 10,000-20,000 mg/ m 3 air (analytical) AND Study result type: estimated by calculation ORexperimental result ORexperimental study planned Route of administration: dermal Effect levels, Endpoint: approximate LD 50, LD 50 Effect levels: overlapping 200-1,000 mg/kg The values for effects levels correspond to the threshold of category 4 for inhalation (vapour) route and category 3 for the dermal route according to the CLP regulation as described in Section 1.4. The search was done in the REACH registration dossiers via the echemportal database.

84 71 B Assessment of the quality and the completeness of data For each substance identified in step A, an assessment of the quality and the completeness of data in the REACH registration dossier was undertaken. This assessment was made according to the methodology described above (using Klimisch codes). C Selection of substances (and LC 50 /LD 50 ) which are classified Acute Tox 3 for inhalation and dermal route For substances identified in step B, the LC 50 /LD 50 derived from studies of best quality was retained. The substances selected are those which have a LC 50 and a LD 50 of good quality according to the different elements detailed in step 2. If a substance had a LC 50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance was not selected and vice versa. As double check, these results were compared to the classification provided in the REACH registration dossiers in order to verify the consistency of the outcome of the LC 50 /LD 50 analysis and the classification provided in the registration dossier. Substances identified in the stakeholder consultation exercise Industrialists or public authorities have identified substances that are classified as acute toxic 3 which are not already included in the scope of the Seveso directive due to other properties. The studies and data related to these substances in the registration dossier have been analysed in accordance with step 2 (assessment of the quality and the completeness of data) of the first strategy and the LC 50 /LD 50 derived from studies of best quality have been retained. Most of these substances have notified but not harmonised classification as acute toxic 3 dermal (i.e. they are self-classified as such) Consequence calculations Once the substances are selected, consequences on human health are assessed with the aim to provide good insights into the differences between dermal and inhalation exposures routes. It was originally intended to perform a full quantitative risk assessment of the potential consequences related to toxic dermal exposure. Such assessment would require: reliable extrapolation methods from LD 50 values (based on animal exposures) for human exposures; reliable extrapolation methods for dermal exposure duration (from 24h which is the usual duration of laboratory tests to some minutes which is the usual duration of the exposure in the case of an accident); reliable extrapolation methods for adapting the skin surface exposed to the specific context of an accident (from 10% of the body in the case of laboratory tests to full body exposure in the context of an accident). Unlike the data available for inhalation exposure, the data and methods needed for the implementation of such reliable extrapolations for dermal exposure are not available. Further research and laboratory tests are needed to improve knowledge in this field. This lack of data reflects the standard practice of risk assessors for major accident

85 72 hazards, who usually neglect the toxic dermal exposure and consider this effect as covered by the inhalation toxicity effects. Taking into account this lack of data, consequence assessments has been performed using both quantitative and qualitative inputs. When physical modeling was necessary, the PHAST software 30 was used. 6.2 Scenario Selection Description of scenarios The first useful source of information for selecting the scenarios to be considered is the accident database analysis. The 29 accidents presented in Section 5 were analysed. Loss of containment events identified for acute toxic dermal exposure substances are presented in the table below: Table 6.1 Loss of containment events identified in accident database analysis Scenario (simplified) Number Leak on transfer equipment (pipes, hoses, compressors, etc.) 13 Maintenance error - leak 3 Mixing incompatible products uncontrolled reaction 2 Small vessel leak (drums, cylinder, etc.) 2 Vessel loss of containment 4 Others 2 Unknown 2 Total 29 Note: Based on data on accident scenarios relevant for the dermal route Most of these accidents are occupational accidents with consequences for workers only (i.e. on-site consequences). They are related to leaks from transfer equipment, small drums, maintenance errors, mixing products, etc. Some accidents have the potential to be significant major accidents. Most of these are related to vessel loss of containment (ruptures or major leaks). The results of the stakeholder consultation serve to confirm this assertion. Among these scenarios, vessel ruptures and pipe leaks have the most important potential for severe accidents. In case of rupture of such equipment, people may be exposed through a toxic vapour cloud (scenario 1) or through direct contact with the substance (in the liquid state scenario 2). Vessel rupture is a standard scenario in the field of risk assessment. However, the selected pressure of the rupture is usually limited. 30 Developed by DNV Copyright Det Norske Veritas (DNV) 2013.

86 73 An accident occurred in 2002 in France which involved a pneumatic rupture of a 100m 3 vessel. About ten kilograms of product were thrown into the air and fell back as rain inside and outside the facility. After the release, 6 persons were admitted to the medical service of the facility. They complained of feeling tingles after cleaning the product that lay on their cars. Taking into consideration this accident, a third scenario has been added in the analysis. This scenario has to assess the possible projection of product after a pneumatic rupture. The question of the pressurised release is also addressed through the scenario of the pipe rupture (scenario 5), which is also representative of a large number of accidents recorded in accident databases (13 accidents among the 29 accidents involving dermal toxicity). Finally, some accidents with toxic exposure, or skin corrosion effects to people, have involved an indirect exposure to the product: for instance, some leaks reached water (sea, river, etc.) with the product then spreading in the water. Nearby people were thus exposed to the diluted product. An example is the accident of LaGuaira in Venezuela in 2000 where containers were found to be leaking a toxic mix of chemicals after the containers were battered by a massive flood. As a result of this, residents of the area were evacuated. Although none of the recorded accidents involved indirect exposure to the product with dermal toxicity effects (alone and significant), this scenario has been assessed as plausible and has been added to the analysis. However, a further (quantitative) assessment of this scenario is not achievable, considering the complexity of the calculation and the number of hypotheses that would be required in order to represent the dispersion of products in water. A qualitative analysis has therefore been preferred for this scenario. Considering these elements, the following scenarios have been selected for further investigation. Table 6.2 Scenarios selected ID Scenarios Toxic exposure (dermal) 1 Vessel rupture spreading of pool and evaporation establishment of a vapor cloud Exposure to a toxic cloud 2 Vessel rupture spreading of pool Direct exposure to the product (liquid) 3 Vessel pneumatic rupture projection of product - «rain» of product Direct exposure to the product ( rain ) 4 Vessel rupture spreading of pool and dilution in water Indirect exposure (liquid diluted in water) 5 Pipe rupture release of product under pressure projection of product Direct exposure Stakeholders consulted also noticed the possibility of a toxic dispersion through fire fumes. The validity of this scenario for dermal exposure is questionable: The accident database analysis shows that this scenario may have consequences on human health, but through inhalation of the fumes;

87 74 It is questionable that the necessary toxic concentration on skin for producing lethal effects could be reached during exposure to fumes. The calculation of the concentration of toxic in fumes is a highly complex issue. It is not achievable to answer this question in the framework of the present study A first step in the quantification of the effects: basic hypothesis Other parameters related to scenarios 1, 2, 3 and 5 need to be defined in order to model accident scenarios. These values for equipment and pressure releases are considered by the authors as typical and conservative values found in the European chemical industry. Equipment: - Vessel size: 2000 m 3 most vessels containing toxic liquids are smaller than 2000 m 3 (sizes between 100 m 3 and 1000 m 3 ). This hypothesis is therefore considered as conservative; - Pipe size: 3 this size is considered as a typical diameter for transfer operations of liquids. - Duration of the leak (from both parts of the pipe): 1 hour this leak duration is representative of the case of successive failure of safety barriers. In practice, in most of the cases, safety devices may stop the leak in several minutes (10-20 minutes). Pressure of the release: - Vessel rupture (two cases: simple rupture and pneumatic rupture): simple rupture at atmospheric pressure and pneumatic rupture at 1 bar this pressure is considered as representative of a rupture pressure of an atmospheric storage tank in case of pneumatic rupture; - Pipe rupture: 3 bar this pressure is considered as a typical pressure for transfer operations. Environment: - Flat and regular surface this hypothesis is a usual hypothesis taken for consequence calculations (for simplification purposes). - No bund: most of the vessels containing toxic liquids are surrounded by bunds. However some of them are still not protected by such a measure, and moreover such a barrier may fail in case of a massive release. Although this hypothesis is very conservative, it has been considered that no bunds were present; - Atmospheric conditions: F3 this is representative of very stable weather conditions, which generate larger consequences in the case of a dispersion. Some calculations have been made on the basis of a D5 atmospheric condition for checking that F3 generates larger consequences. This hypothesis is then considered as conservative. While more stable weather conditions have been

88 75 observed in Europe (F2, F1,5), the validity of dispersion models is less known for these atmospheric conditions 31. Standard models will be used for the calculation of consequences. 6.3 Selection of Substances used for Consequence Calculations Overview The results of the substance selection (performed using the methodology described in the paragraph 6.1.3) are separated into three parts corresponding to the three different approaches: Substances that are classified as acute toxic 3 for both dermal and inhalation routes, Substances that are classified as acute toxic 3 for dermal exposure but not covered under Seveso III for other health hazards, Substances identified in the stakeholder consultation exercise Substances that are classified acute toxic 3 for dermal and inhalation route The methodology described in the step 1 of the first strategy is applied. The following substances and LC 50 /LD 50 are identified from the REACH registration dossiers. Substance Name EC Number LD 50 Values LC 50 Values 390 mg/kg bw > 4800 mg/m³ air 523 mg/kg bw 8.56 mg/l air (analytical) 1,2,3-trichloropropane mg/kg bw 850 mg/kg bw 880 mg/kg bw 900 mg/kg bw 599 mg/kg bw > 80 mg/m³ air 1,6-diisocyanatohexane mg/kg bw > 525 mg/kg bw 1-isocyanatobutane > 1000 mg/kg bw > 50 mg/m³ air 2,4,6-trichloro-1,3,5-triazine > 1000 mg/kg bw > mg/l air 31 Atmospheric conditions are usually characterised using a letter and a figure. The letter is related to Pasquill stability classes. These classes describe potential levels of atmospheric turbulences, from A very unstable to F stable. The figure represents the wind speed in metres per second. Therefore, using F3 atmospheric conditions means that it is considered that the level of atmospheric turbulence is low and the wind speed is equal to 3 metres per second.

89 76 Substance Name EC Number LD 50 Values LC 50 Values 2,4-dichloro-1-methylbenzene > 10 mg/kg bw > 2669 mg/m³ air (analytical) 2-(diethylamino)ethanol ca. 885 mg/kg bw 7.7 mg/l air ca. 4.6 mg/l air 2-(dimethylamino)ethyl acrylate mg/kg bw > mg/l air (analytical) > 50 < 200 mg/kg bw > 0.06 mg/l air 2-[(allyloxy)methyl]oxirane mg/kg bw mg/l air 667 mg/kg bw > 4.9 mg/l air 2-butoxyethanol mg/kg bw 435 mg/kg bw 2-ethylhexanoyl chloride > 200 mg/kg bw > mg/l air 2-ethylhexyl acrylate > 177 mg/kg bw > 1.19 mg/l air (nominal) 2-methoxy-3,4-dihydro-2H-pyran > 200 mg/kg bw < mg/l air > 6.1 mg/l air (analytical) 2-sulfanylethanol ca. 112 ca. 224 mg/kg bw ca. 2 mg/l air 398 mg/kg bw 9355 mg/m³ air 5800 mg/m³ air Amines, C12-C14 tert alkyl Methyl 2-hydroxybenzoate mg/kg bw > 0.94 mg/l air < 5000 mg/kg bw 700 mg/kg bw > 400 mg/m³ air > 114 mg/m³ air N,N-dimethylethanamine > 200 mg/kg bw > 2.3 < 15.4 mg/l air N,N-dimethylpropane-1,3-diamine > 400 < 2000 mg/kg bw 4.31 mg/l air > 4.31 mg/l air N-butylbutan-1-amine mg/kg bw > 1.34 < 2.68 mg/l air (nominal) N-cyclohexylcyclohexanamine mg/kg bw > 1.4 mg/l air N-isopropylpropan-2-amine mg/kg bw 5.35 mg/l air (analytical) N-propylpropan-1-amine mg/kg bw > 8.22 mg/l air Reaction mass of 1,4-dichlorobut- 2-ene; 3,4-dichlorobut-1-ene mg/kg bw 4.1 mg/l air Reaction mass of 2-Propenoic acid and 1,2-propanediol mg/kg bw > 0.38 mg/l air (nominal) > 1000 < 1600 mg/kg bw > 1000 mg/kg bw 214 mg/kg bw

90 77 Substance Name EC Number LD 50 Values LC 50 Values > 50 < 200 mg/kg bw Reaction mass of cyclohexanol and cyclohexanone > 794 < 3160 mg/kg bw > 6.6 mg/l air > 6.2 mg/l air > 4.3 mg/l air Reaction products of propane- 1,2-diol, propoxylated by amination of the terminal hydroxyl groups ca. 890 mg/kg bw > 0.74 mg/l air (nominal) ca. 640 mg/kg bw ca mg/kg bw > 5.1 mg/l air (analytical) > 4.31 mg/l air (analytical) acrylic acid ca. 294 mg/kg bw 3.6 mg/l air 750 mg/kg bw > 3.9 < 4.8 mg/l air (analytical) 280 mg/kg bw >= 6.4 mg/l air > 6.74 mg/l air (analytical) < 200 mg/kg bw 2.03 mg/l air > 200 mg/kg bw 3.41 mg/l air acrylonitrile mg/l air 2.03 mg/l air 4 mg/l air 7.88 mg/l air benzene-1,2-diamine > 1000 mg/kg bw > 1340 mg/m³ air > 1000 mg/kg bw 3.7 mg/l air (analytical) butan-1-amine mg/kg bw 4.2 mg/l air (analytical) 4.7 mg/l air (analytical) > 4.6 mg/l air (analytical) butan-2-one oxime > 1000 mg/kg bw > 4.83 mg/l air (analytical) chloroacetyl chloride cyclohexanamine mg/kg bw < mg/l air mg/kg bw 275 mg/kg bw < mg/m³ air (analytical) > 631 < 1000 mg/kg bw 7500 mg/m³ air cyclohexanone > 794 < 3160 mg/kg bw > 6.2 mg/l air decan-1-ol > 1000 mg/kg bw > 2.05 mg/l air dimethyl phosphonate mg/kg bw > 7100 mg/m³ air (nominal) ethane-1,2-diamine ca mg/kg bw > 7 mg/l air

91 78 Substance Name EC Number LD 50 Values LC 50 Values 560 mg/kg bw 4.9 mg/l air 7.35 mg/l air 9.8 mg/l air > 17.8 mg/kg bw > 250 mg/m³ air > 20 mg/kg bw > 5000 mg/m³ air > 400 mg/kg bw > 200 mg/kg bw > 34 mg/kg bw ethaneperoxoic acid > 3 mg/kg bw > 400 mg/kg bw > 60 mg/kg bw mg/kg bw mg/kg bw mg/kg bw > 240 mg/kg bw > 184 mg/kg bw 9 mg/l air (analytical) > 2 < 3.1 mg/l air (analytical) ethyl acrylate > 6.1 mg/l air (analytical) < 165 mg/l air (nominal) > 4.1 < 8.2 mg/l air (nominal) 5.8 mg/l air > 190 mg/kg bw 6.3 mg/l air 6.5 mg/l air 6.6 mg/l air 4.5 mg/l air 5.1 mg/l air 5.9 mg/l air methyl acrylate mg/l air 2.5 mg/l air 2.7 mg/l air 5.4 mg/l air 5.7 mg/l air 6.4 mg/l air 8.7 mg/l air

92 79 Substance Name EC Number LD 50 Values LC 50 Values 9.04 mg/l air 4.6 mg/l air 5.7 mg/l air 7.36 mg/l ai 2.7 mg/l air 3.2 mg/l air 3.7 mg/l air ca. 3.6 mg/l air > 2.7 < 3.6 mg/l air (analytical) p-toluidine mg/kg bw > 0.64 mg/l air 403 mg/kg bw 6.32 mg/l air propan-1-amine mg/l air 7.87 mg/l air > 400 mg/kg bw 7.7 mg/l air (analytical) propan-2-amine mg/kg bw ca. 8.7 mg/l air (analytical) > 1000 mg/kg bw ca. 9.4 mg/l air (analytical) > 9.8 < 19.6 mg/l air From substances identified above, a first filter is applied, as described in step 2 of the first strategy, in order to exclude substances which have: LD 50 or LC 50 that are not clearly determined (for example, studies for which the LC 50 /LD 50 is considered to be superior or inferior to a given value, or for which the LC 50 /LD 50 is between two values are directly excluded); or LD 50 or LC 50 derived from studies for which no or not enough details are provided on the experimental conditions (in the REACH registration dossier). Only substances for which there are LC 50 and LD 50 clearly determined and based on sufficiently detailed studies are reported below and assessed according to the criteria of step 2. If a substance has a LC 50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance is not selected and vice versa because it is essential to have a LC 50 and a LD 50 for consequence calculation of the scenarios.

93 80 Substance Name EC Number Classification of the registration dossier (for Acute Toxicity) LD50 (mg/kg bw) CL50 (duration of exposure) (mg/l) 2-(diethylamino)ethanol Dermal : Cat 3 Inh : Cat 3 2-[(allyloxy)methyl]oxirane Dermal : NC Inh : Cat 3 2-sulfanylethanol Dermal : Cat 2 Inh : Cat 3 acrylic acid Dermal : Cat 4 Inh : Cat 4 acrylonitrile Dermal : Cat 3 Inh : Cat 3 ethane-1,2-diamine Dermal : Cat 3 Inh : Cat 4 propan-1-amine Dermal : Cat 3 Inh : Cat (4 hours) (4hours) (4 hours) 997,5 3.6 (4 hours) (4 hours) (8 hours) (4 hours) NC : Not classified ; inh : inhalation ; bw : body weight From these seven substances, only three are classified as acute toxic 3 for both dermal and inhalation routes in the REACH registration dossier and have LC 50 and LD 50 clearly determined and based on reliable studies according to the criteria of step 2: 2-(diethylamino)ethanol; acrylonitrile; and propan-1-amine. For acrylic acid, the LD 50 and LC 50 values are not consistent with the classification reported in the REACH registration dossier. This substance should be classified in category 3 for dermal and inhalation routes according to the data but this classification was not retained by the registrant. Some restrictions identified in the experimental conditions for the inhalation study (the number of animals is not specified and there are only two concentrations tested) may have led to a divergent assessment of the study. Since the raw data (in the original report) have not been reviewed for the purposes of the current study, this substance is not selected Substances that are classified Acute Toxic 3 for dermal exposure and that are not covered under Seveso III for other health hazard The results of the two approaches described in the second strategy are detailed below.

94 81 1 Substances identified in the review of CLP and REACH For all substances identified in the review of CLP and REACH (41 substances identified in section 3), a first filter was made, as described in step 2 of the first strategy, in order to exclude substances which have: no LD 50 or no LC 50 ; or, LD 50 or LC 50 that are not clearly determined (for example, studies for which the LC 50 /LD 50 is considered to be superior or inferior to a given value, or for which the LC 50 /LD 50 is between two values are directly excluded); or LD 50 or LC 50 derived from studies for which no or not enough details are provided on the experimental conditions (in the REACH registration dossier). If a substance has a LC50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance is not selected and vice versa because it is essential to have a LC 50 and a LD 50 for consequence calculation of the scenarios. For substances that pass this first filter, the studies and data related to these substances in the REACH registration dossiers were analysed in accordance with step 2 (assessment of the quality and the completeness of data) of the strategy on the basis of the information publicly available on the ECHA dissemination portal. LC 50 /LD 50 derived from the best quality studies were retained. The only substance for which there are LC 50 and LD 50 clearly determined and based on sufficiently detailed studies is (Z)-1,3-dichloropropene. The studies related to this substance in the REACH registration dossier are evaluated according to the criteria of step 2. The LC 50 and LD 50 retained and the classification in the REACH registration dossier are detailed below: Table 6.3 Toxicity data for substance identified in the review of CLP and REACH data Substance Name EC Number Classification in the registration dossier (for acute toxicity) LD 50 (mg/kg bw) LC 50 (duration of exposure) (mg/l) (Z)-1,3-dichloropropene Dermal : Cat 3 Inhalation : Cat (4 hours) The LC 50 retained is inconsistent with the classification reported in the REACH registration dossier. It appears that this substance should be classified in category 3 for the inhalation route and then included in the scope of the Seveso directive. Whilst the detailed reasons for the choice of classification have not been investigated for the current study, this substance is not selected for the comparison of the toxicity from dermal and inhalation route. However, in order to assess the impact of the dermal effects of substances identified in the review of CLP and REACH, the LD 50 of (Z)-1,3-dichloropropene is retained for determination of the distances effects for dermal exposure only. The results will be compared to the distance determined for the other substances selected.

95 82 2 Substances that are classified acute toxic 3 for dermal exposure and acute toxic 4 for inhalation exposure The methodology described in step B of the second strategy is applied. The following substances and LC 50 /LD 50 values were identified from the REACH registration dossiers. Table 6.4 Toxicity data for substances acute toxic 3 dermal and acute toxic 4 inhalation Substance Name EC Number LD50 Values LC50 Values 1,1,1-trimethyl-N- (trimethylsilyl)silanamine mg/kg bw 10.3 mg/l air 540 mg/kg bw 1,2,3-trichloropropane mg/kg bw > 4800 mg/m³ air 523 mg/kg bw mg/l air (analytical) 765 mg/kg bw 850 mg/kg bw 880 mg/kg bw 900 mg/kg bw 1,6-diisocyanatohexane mg/kg bw > 80 mg/m³ air 570 mg/kg bw > 525 mg/kg bw 1-isocyanatobutane > 1000 mg/kg bw > 50 mg/m³ air 1-nitropropane > 200 mg/kg bw mg/l air 2,4,6-trichloro-1,3,5-triazine > 1000 mg/kg bw > mg/l air 2,4-dichloro-1-methylbenzene > 10 mg/kg bw > 2669 mg/m³ air (analytical) 2,6-dimethylheptan-4-one > 16 mg/kg bw > 14.5 mg/l air (nominal) > 14.5 mg/l air (nominal) 2-(dimethylamino)ethyl acrylate mg/kg bw > mg/l air (analytical) > 50 < 200 mg/kg bw > 0.06 mg/l air 891 mg/kg bw 2-butoxyethanol mg/kg bw > 4.9 mg/l air 841 mg/kg bw 435 mg/kg bw 2-ethylhexyl acrylate > 177 mg/kg bw > 1.19 mg/l air (nominal) 2-methoxy-3,4-dihydro-2H-pyran > 200 mg/kg bw < mg/l air > 6.1 mg/l air (analytical) Amines, C12-C14 tert alkyl mg/kg bw > 0.94 mg/l air < 5000 mg/kg bw

96 83 Substance Name EC Number LD50 Values LC50 Values Methyl 2-hydroxybenzoate mg/kg bw > 400 mg/m³ air > 114 mg/m³ air > 400 mg/m³ air N,N-dimethylethanamine > 200 mg/kg bw > 2.3 < 15.4 mg/l air N,N-dimethylpropane-1,3- diamine > 400 < 2000 mg/kg bw > 4.31 mg/l air 24.8 mg/l air N-cyclohexylcyclohexanamine mg/kg bw > 1.4 mg/l air N-propylpropan-1-amine mg/kg bw > 8.22 mg/l air Reaction mass of 2-Propenoic acid and 1,2-propanediol mg/kg bw > 0.38 mg/l air (nominal) > 1000 < 1600 mg/kg bw > 1000 mg/kg bw 214 mg/kg bw > 50 < 200 mg/kg bw Reaction mass of cyclohexanol and cyclohexanone > 794 < 3160 mg/kg bw > 6.6 mg/l air > 6.2 mg/l air > 4.3 mg/l air Reaction products of propane- 1,2-diol, propoxylated by amination of the terminal hydroxyl groups ca. 890 mg/kg bw > 0.74 mg/l air (nominal) acrylic acid ca. 640 mg/kg bw > 5.1 mg/l air (analytical) ca mg/kg bw ca. 294 mg/kg bw > 4.31 mg/l air (analytical) > mg/l air 750 mg/kg bw >= 6.4 mg/l air 280 mg/kg bw > 6.74 mg/l air (analytical) benzene-1,2-diamine > 1000 mg/kg bw > 1340 mg/m³ air butan-1-amine > 1000 mg/kg bw > 4.6 mg/l air (analytical) 623 mg/kg bw butan-2-one oxime > 1000 mg/kg bw > 10.5 mg/l air > 4.83 mg/l air (analytical) chloroacetyl chloride mg/kg bw < mg/l air mg/kg bw mg/kg bw

97 84 Substance Name EC Number LD50 Values LC50 Values cyclohexanamine ca. 275 mg/kg bw < mg/m³ air (analytical) > 631 < 1000 mg/kg bw cyclohexanone > 794 < 3160 mg/kg bw > 6.2 mg/l air decan-1-ol > 1000 mg/kg bw > 2.05 mg/l air dimethyl phosphonate mg/kg bw > 7100 mg/m³ air (nominal) ethane-1,2-diamine ca mg/kg bw > mg/l air 560 mg/kg bw > 7 mg/l air 14.7 mg/l air ethaneperoxoic acid > 17.8 mg/kg bw > 250 mg/m³ air > 20 mg/kg bw > 5000 mg/m³ air > 400 mg/kg bw > 200 mg/kg bw > 34 mg/kg bw > 3 mg/kg bw > 400 mg/kg bw > 60 mg/kg bw mg/kg bw mg/kg bw mg/kg bw > 240 mg/kg bw ethyl acrylate > 184 mg/kg bw > 6.1 mg/l air (analytical) < 165 mg/l air (nominal) ca mg/l air (analytical) isobutyl acrylate ca. 793 mg/kg bw ca mg/l air > 445 < 890 mg/kg bw ca mg/l air morpholine ca. 500 mg/kg bw 18.1 mg/l air oxalaldehyde > 800 mg/kg bw > mg/l air p-toluidine mg/kg bw > 0.64 mg/l air propan-2-amine > 400 mg/kg bw > 9.8 < 19.6 mg/l air 380 mg/kg bw > 1000 mg/kg bw propionic acid mg/kg bw > 19.7 mg/l air 495 mg/kg bw

98 85 From substances identified above, a first filter is applied, as described in step B of the second strategy, in order to exclude substances which have: LD 50 or LC 50 that are not clearly determined (for example, studies for which the LC 50 /LD 50 is considered to be superior or inferior to a given value, or for which the LC 50 /LD 50 is between two values are directly excluded), or LD 50 or LC 50 derived from studies for which no or not enough details are provided on the experimental conditions (in the REACH registration dossier). Only substances for which there are LC 50 and LD 50 clearly determined and based on sufficiently detailed studies are reported below and evaluated according to the criteria of step B. If a substance has a LC 50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance is not selected and vice versa because it is essential to have a LC 50 and a LD 50 for consequence calculation of the scenarios. Table 6.5 Toxicity data for selected substances with clearly defined data Substance Name EC Number Classification of the registration dossier (for Acute Toxicity) LD 50 (mg/kg bw) LC 50 (duration of exposure) (mg/l) 1,1,1-trimethyl-N- (trimethylsilyl)silanamine Dermal : Cat 3 Inh : Cat (6 hours) acrylic acid isobutyl acrylate Dermal : Cat 4 Inh : Cat 4 Dermal : Cat 4 Inh : Cat 4 997,5 3.6 (4 hours) (4 hours) From these four substances, only one is classified as acute toxic 3 for the dermal route in the REACH registration dossier and have LC 50 and LD 50 clearly determined and based on reliable studies according to the criteria of step B and are excluded of the scope of the Seveso directive for other health hazards. This substance is 1,1,1-trimethyl-N- (trimethylsilyl)silanamine. For acrylic acid, the LD 50 and LC 50 retained are not consistent with the classification reported in the REACH registration dossier. This substance should seemingly be classified in category 3 for dermal and inhalation route according to the data but this classification was not retained by the registrant (it is outside the scope of the current study to investigate such issues). Some restrictions identified in the experimental conditions for the inhalation study (the number of animals is not specified and there are only two concentrations tested) may have led to a divergent assessment of the study. Since the raw data (original report) have not been reviewed, this substance was not selected. For isobutyl acrylate, the LD 50 retained is not consistent with the classification reported in the REACH registration dossier and so the substance is not retained.

99 Substances identified in the stakeholder consultation exercise From substances identified by industrial or public authorities that are classified as acute toxic 3 which are not already included in the scope of the Seveso directive due to other properties, substances that have a REACH registration dossier were identified. If a REACH registration dossier was available, the classification is reported in the following table: Table 6.6 Identification of whether toxicity data are available in REACH registrations for substances identified through stakeholder consultation Substance EC number Classification of the registration dossier (for Acute Toxicity) N,N-Dibutyltrimethylenediamine Not registered 3-Amino-1-phenyl-butane Not registered 1,3-Dichloro-4-nitrobenzene Dermal : Cat 3 Inh : NC 1,3-Dimethyl-2-imidazolidinone Not registered n-decylamine Not registered 2-(1-Methylpropyl)-4,6-dinitrophenyl acetate Not registered 1-(2-(Dimethylamino)ethyl)-4-methylpiperazine Not registered Lindane Not registered Methanol Dermal : Cat 3 Inh : Cat 3 2-methylpyridine; 2-picoline Not registered Calcium dipropionate Not registered Methacrylic acid Dermal : Cat 3 Inh : Cat 4 Sodium dodecyl sulphate Dermal : NC Inh : Cat 4 Trientine Not registered Allyl hexanoate Not registered Allyl heptanoate Dermal : Cat 3 Inh : NC Benzene (1-methylethyl) oxidized polyphenol residue Dermal : Cat 3 Inh : Cat 3 Propylene diamine Dermal : Cat 3 Inh : NC 3,6,9-triazaundecamethylene Not registered

100 87 Substance EC number Classification of the registration dossier (for Acute Toxicity) Tert-Butyl hydroperoxide Dermal : Cat 3 Inh : Cat 2 NC : Not classified ; inh : inhalation ; bw : body weight The studies in the registration dossier of these substances were analyzed, as described in step 2 of the first strategy, in order to exclude substances which have: no LD 50 or no LC 50, or LD 50 or LC 50 that are not clearly determined (for example, studies for which the LC 50 /LD 50 is considered to be superior or inferior to a given value, or for which the LC 50 /LD 50 is between two values are directly excluded), or LD 50 or LC 50 derived from studies for which no or not enough details are provided on the experimental conditions (in the REACH registration dossier). If a substance has a LC 50 of good quality but there is no LD 50 or a LD 50 of poor quality, the substance was not selected and vice versa because it is essential to have a LC 50 and a LD 50 for consequence calculation of the scenarios. The only substances for which there are LC 50 and a LD 50 clearly determined and based on sufficiently detailed studies are methacrylic acid and tert-butyl hydroperoxide. Tert-butyl hydroperoxide is classified as category 2 for the inhalation route. This substance is then included in the scope of the Seveso directive already and so was not selected. The studies related to methacrylic acid in the REACH registration dossier are evaluated according to the criteria of step 2. The LC 50 and a LD 50 retained and the classification in the REACH registration dossier are detailed below: Substance Name EC Number Classification of the registration dossier (for Acute Toxicity) LD50 (mg/kg bw) LC50 (duration of exposure) (mg/l) Methacrylic acid Dermal : Cat 3 Inh : Cat (4 hours) The LD 50 and LC 50 retained are not consistent with the classification reported in the REACH registration dossier. This substance should seemingly be classified in category 3 for the inhalation route. Furthermore, the experimental conditions for the dermal study do not meet the criteria used in the present study: the number of animals is too low, the exposure duration is unknown and the range of values is too wide. This substance is then not selected.

101 Summary of selected substances The following table shows the different substances identified following search strategies described in Section Table 6.7 Classification and LD 50/LC 50 values for selected substances Substance Name EC Number 2-(diethylamino)ethanol Classification of the registration LD 50 dossier (for Acute (mg/kg bw) Toxicity) Dermal : Cat 3 Inh : Cat 3 CL 50 (duration of exposure) (mg/l) 885 4,6 (4 hours) acrylonitrile Dermal : Cat 3 Inh : Cat ,05 (4 hours) Substances that are classified Acute Toxic 3 for dermal and inhalation propan-1-amine Dermal : Cat 3 Inh : Cat ,06 (4 hours) 1,1,1-trimethyl-N- (trimethylsilyl)silanamine Dermal : Cat 3 Inh : Cat (6 hours) Substances that are classified Acute Toxic 3 for dermal exposure and that are not covered under SEVESO III for other health hazard In order to assess the impact of the dermal effects of substances identified in the review of CLP and REACH, (Z)- 1,3-dichloropropene is also retained for modelling of the scenarios and the determination of distances to effects for dermal exposure only. The results will be compared to the distances determined for the other substances selected. The lethal values (LC 50 /LD 50 ) selected for these substances are used for the modelling scenarios and the consequences assessment. The substances selected that are classified acute toxic 3 for dermal and inhalation exposure will cover efficiently both category 3 for dermal and inhalation exposures as shown in the following diagram. This will provide a good insight into the relative effects of inhalation and dermal exposures.

102 89 Figure 6.4 Lethal dose values for selected substances shown against classification criteria Inhalation route (vapour) Acrylonitrile LC 50 = 2.05 mg/l Propylamine LC 50 = 7.06 mg/l CLP Regulation Cat.1 Cat.2 Cat.3 Cat.4 Directive n 67/548/EEC Threshold values (mg/l) T+ / R26 T / R23 Xn / R (diethylamino)ethanol LC 50 = 4.6 mg/l Dermal route Acrylonitrile LD 50 = 226 mg/kg 2-(diethylamino) ethanol LD 50 = 885 mg/kg CLP Regulation Cat.1 Cat.2 Cat.3 Cat.4 Directive n 67/548/EEC T+ / R27 T / R24 Xn / R21 Threshold values (mg/kg) Propylamine LD 50 = 403 mg/kg 1,1,1-trimethyl-N-(trimethylsilyl)silanamine LD 50 = 547 mg/kg 6.4 Lethal Concentrations of Products Comparison between inhalation and dermal route general consideration Accidental risk analysis has traditionally focused on the inhalation exposure pathway because it is considered to be the most important route of exposure with the exception of exposure to pesticides and certain solvents. It is

103 90 possible for hazardous substances to deposit or adsorb on to the skin directly from the air, to be transferred to the skin on contact with contaminated surfaces or by submersion of part of the body into the substance. In addition, a contaminant may be lost from the skin without being taken up into the body, either by evaporation or some other mechanism such as washing or abrasion. Finally, the presence of clothing or protective garments may modify the rate at which hazardous substances come into contact with the skin 32. Several key points are required to take into account the specificity of skin exposure Many chemicals can cross the unbroken skin (lipophilic substances). Uptake is controlled by chemical concentration, area of skin exposed, and duration of exposure. Skin site, temperature, humidity, and other chemicals can all influence dermal uptake. To know the relative impact of the dermal and inhalation routes, some authors have compared the two routes of exposure. Kezic et al. (2000) have demonstrated that dermal absorption of vapours is generally of minor importance compared to respiratory absorption 34. A comparison of the estimated whole-body skin uptake with the inhalatory uptake from the same atmosphere revealed that dermal uptake as a proportion of total uptake was from as low as 0.1% for hexane up to 1% for toluene and m-xylene (for the substances studied). In most cases, vapour absorption through the skin would not be of concern (unless a respirator is worn) because the majority of the body burden comes from inhalation. Furthermore, the skin is a good barrier, particularly to 35 hydrophilic chemicals and water. Estimating relative exposures during accidental release of a chemical substance requires the determination of the amount of chemical in contact with the skin (the dermal external dose) and the concentration in air (the inhalation external dose). An accurate estimation of external dose is a key step in the risk assessment process. In case of local effects only, the effects from the two routes of exposure cannot be added making comparison difficult. For systemic effects, the two routes can in theory be compared using an internal dose, which will allow the penetration through the skin and respiratory tract to be taken into account Although the approach seems straightforward from a theoretical point of view and is routinely applied in exposure assessment, several difficulties appear in practice when trying to compare the two routes: The test design used to determine dermal or inhalation toxicity differs by several aspects: - Exposure duration is different : Schneider T., Cherrie J.W., Vermeulen R. and Kromhout H. (2000) - Dermal exposure assessment. Ann Occup Hyg, 44, 7, Semple S. (2004) - Dermal exposure to chemicals in the workplace: just how important is skin absorption? Occup Environ Med, 61, 4, Kezic S., Monster A.C., Kruse J. and Verberk M.M. (2000) - Skin absorption of some vaporous solvents in volunteers. Int Arch Occup Environ Health, 73, 6, McDougal J.N. and Boeniger M.F. (2002) - Methods for assessing risks of dermal exposures in the workplace. Crit Rev Toxicol, 32, 4,

104 91 - Expressions of the effective concentrations are different (mg substance/cm² of skin or mg/kg body weight, versus mg substance/m 3 in the atmosphere) - Tested animals may be different (rat versus rabbit) Results are expressed as external doses. While these take into account absorption, this renders the interpretation of the results difficult as, in the case of results with apparently low toxicity results for example, it cannot be determined whether the intrinsic toxicity of a given substance is low or if the substance is weakly absorbed, without further data. An additional constraint is to adapt the results of the toxicity tests to the exposure conditions, as defined in the exposure scenario used for modelling the impact of the substances, in order to make them relevant and comparable. The different approaches discussed below for inhalation and dermal comparison must then be considered with caution Extrapolation and uncertainties Extrapolation of exposure duration Duration plays an important role in acute toxicity. Haber s Law states that the incidence and/or severity of an adverse health effect depend on the total exposure to a potentially toxic substance. This law is only valid for duration of exposure corresponding to accidental situations (a maximum of 8 hours). Total exposure is a function of the concentration (c) in the air of the substance multiplied by the duration time (t) of exposure, i.e. c t. Where the concentration varies during exposure, the average concentration is often used. Thus, c t is equivalent to the area under the exposure curve. As specified above, exposure durations usually differ in test designs used for the assessment of toxicity by the inhalation (4 hours) and the dermal (24 hours) routes. In addition, the accident scenarios are defined based on much shorter periods, representative of accidents in industrial establishments: an exposure time of one hour has been used. The toxicity levels (inhalation and dermal) must be compared taking these time periods into account. These differences have to be taken into account, and results should be extrapolated, as far as possible, but they clearly create significant uncertainties. Inhalation route Haber s Law, within constraints, is often used in setting inhalation guidelines for toxic substances 36. An adaptation of this law has been made by ten Berge et al. (1986) 37 and Bunce and Remillard (2003) 38, in order to better evaluate Gaylor D.W. (2000): The use of Haber's law in standard setting and risk assessment. Toxicology, 149, 1, ten Berge W.F. (1986): Concentration-time mortality response relationship of irritant and systemically acting vapours and gases. Journal of hazardous Materials, 13, Bunce N.J. and Remillard R.B.J. (2003): Haber s Rule: The Search for Quantitative Relationships in Toxicology. Human and Ecological Risk Assessment, 9,

105 92 toxic responses following inhalation exposure: Cn x T = dose, where C is the concentration of the substance (in ppm), n is the Haber s constant and T the exposure duration (in minutes). Haber s law is considered as valid for an extrapolation to longer durations than the exposure in laboratory tests. However, in the absence of dose-response data for different durations of exposure that would allow for the determination of a specific Haber s coefficient, the use of Haber s Law to extrapolate to shorter durations of exposure may not be sufficiently conservative. Based on the relationship between concentration and duration to produce an equal incidence of mortality for several chemicals, ten Berge et al. (1986) suggest that conservative extrapolation to shorter durations of exposure should be based on c n t, with n = 3. This equation is applied for the four substances identified above, for which the LC 50 values extrapolated for 1 hour of exposure are reported in the following table: Substance CAS No Species Exposure duration (hours) LC 50 (mg/l) Extrapolation of LC 50 for 1 hour of exposure (mg/l) 1,1,1-trimethyl-N- (trimethylsilyl)silanamine Rat (diethylamino)ethanol Rat Acrylonitrile Rat Propylamine Rat Dermal route Contrary to inhalation toxicity which has been extensively investigated, the applicability of Haber s law for dermal exposure has not been demonstrated. Hayes (1975) 39 restated Haber s rule in a form that addressed the limitation that a sufficiently high rate of detoxification can negate effects from extended exposures to low concentrations of compounds 40. For the dermal route, tests are typically performed for 24 hours of exposure. Therefore, the application of Haber s law to extrapolate to one hour of exposure for dermal exposure would not take into account the detoxification rate and then lead to underestimation of the lethal dose. Thus, in the scope of this study, Haber s law could not be used for extrapolation in the case of the dermal route. For modelling purposes, the toxicity levels (inhalation and dermal) must be compared to an exposure time of one hour, corresponding to the accidental scenario. As discussed above, the LC 50 for inhalation could be extrapolated for one hour of exposure using Haber s law, whereas this extrapolation cannot be used for LD 50 (dermal route). Without extrapolation for the dermal route, the methodology of using dermal LD 50 from experimental studies (24 hours) in accident scenarios (1 hour) is used herein although it is considered as rather conservative. 39 Hayes W.J.J. (1975): General principles: dosage and other actors influencing toxicity. In:Toxicology of Pesticides. Williams & Wilkins, Baltimore, MD, pp Miller F.J., Schlosser P.M. and Janszen D.B. (2000): Haber's rule: a special case in a family of curves relating concentration and duration of exposure to a fixed level of response for a given endpoint. Toxicology, 149, 1,

106 93 Surface area consideration For modelling, the input toxicological data in case of accidental release of chemicals into atmosphere is the LC 50 in mg/l or mg/m 3 and the exposure duration. Consequently, the raw data can be used without extrapolation. For dermal effects, in order to obtain a value that can be used for modelling, it is necessary to convert the selected LD 50 expressed in mg/kg body weight into mg/cm² of exposed skin. The conversion can be done using the following formula: Where BW = Body weight SA = Surface Area of exposure (cm²) When body weight and surface area of exposure are reported in the studies, these values can be used to determine the LD50 in mg/cm². However, in most cases, this information is not mentioned. Therefore, default data is considered according to the recommendation in the OECD guidelines (no 402). For body weight, the values for the different species are: 200 to 300g for rats, 2 to 3kg for rabbits and 350 to 450g for guinea pig (OECD, 1987). When the real weight is unknown, in order to be in the worst case, the lowest weight can be considered. The total body surface area for the different species are: 250 to 325 cm² for rats, 1270 to 3040 cm² for rabbits and 565 to 720 cm² for guinea pig41. In the OECD guidelines on acute dermal toxicity, the test substance should be applied uniformly over an area which is approximately 10 per cent of the total body surface area. As the real surface area of exposure is unknown, in order to be in the worst case, the highest area is considered. The following table summarises the body weight and the surface area of exposure for the different species using worst case assumptions: Species Body weight (kg) Total body surface area (cm²) Surface area of exposure (cm²) Rat Rabbit Guinea pig For the four substances identified earlier, the LD 50 in mg/kg are converted into LD 50 as mg/cm² as shown below. 41 SECAL (2010) - Ciencia y tecnologia del animal de laboratorio. Universidad de Alcala, Sociedad Espanola para las Ciencias del Animal de Laboratorio.

107 94 Substance CAS Species Surface Area of exposure (%) Surface area of exposure (cm²) Body wt (kg) Total Body Surface Area (cm²) Exposure duration LD 50 (mg/kg) LD 50 (mg/cm²) 1,1,1-trimethyl-N- (trimethylsilyl)silanamine Rabbit 10% h 547 3,60 2-(diethylamino)ethanol Guinea pig 10% 72 0, days 885 4,30 Acrylonitrile Rabbit 10% h 226 1,49 Propylamine Rabbit 10% h 403 2,65 (Z)-1,3-dichloropropene Rat 10% 32,5 0, h 794 4,89 * Value reported in the study For this conversion, it is considered that the absorption is independent of the area of exposure. In reality, large variations may exist as the stratum corneum varies in thickness with anatomical site and hair follicles and 42, 43 sebaceous gland can influence dermal absorption. Extrapolation to humans It is widely accepted that the extrapolation of animal toxicity data to humans involves a degree of uncertainty 44. For inhalation studies, this uncertainty is taken into account by applying numerical assessment factors to cover interspecies and intraspecies variations. The uncertainty factors are very widely used and well characterised for acute inhalation studies to extrapolate animal data to human effects. For dermal exposure, in acute situations, no widely accepted uncertainty factors have been identified to extrapolate the experimental data to humans. Furthermore, no study has allowed us to show that the uncertainty factors used for inhalation may be used for the dermal route. Indeed, for extrapolation animals to humans, the following points of uncertainty should be considered: toxicokinetic (anatomical, physiological, and/or metabolic differences between species), toxicodynamics, scenarios of exposure, etc. In this study, the results are compared for the inhalation and dermal routes based on the experimental values. No extrapolation from animals to humans has been performed for either the inhalation or dermal route. The modelling and the scenarios should therefore be used for comparative purposes (relative consideration) but not as absolute values WHO (2006) - Dermal Absorption, Environmental Health Criteria 235. World Health Organization. EFSA (2012) - Guidance on Dermal Absorption. EFSA Journal, 10, 4, VC Marshall, Implementation of the Directive on major accident hazards of certain industrial activities (82/501/EEC) - Article 19 Review of annexes I, II and III, European Commission, Contract n 84-B N, 1980.

108 Comparison of inhalation and dermal route with Mc Dougal s approach The simplest approach is to use an extrapolation to compare the two routes, adapted from Wilschut et al (1998) 45. When dermal dosing studies with comparable duration (acute for example) are available to compare to inhalation dosing studies, the extrapolation factor (EF) is the ratio between LD 50 and LC 50. This approach requires conversion of units so that the inhalation and dermal can be compared. Generally, the unit of LC 50 is mg/m 3 or mg/l and the unit of LD 50 is mg/cm 2 or mg/kg bw (body weight). In order to compare these standards, both must be converted to the same units, for example in mg/kg bw: where VR (m 3 ) is the volume of air breathed during the experiment, A (cm²) is the experimental surface area exposed, and BW (kg) is the body weight of the species of interest (adapted from Mc Dougal, et al, 2002). According to the McDougal approach, when the EF > 1, LD 50 (mg/kg) < LC 50 (converted in mg/kg) and therefore the dermal route seems to be more hazardous than the inhalation route, and vice versa. The volume of air breathed during the experiment is determined by multiplying the respiratory volume per hour by the exposure duration. For rats, the respiratory volume per hour for rat is L/h 46. In the scope of this work, the value of EF can be used to compare the two routes of extrapolation. Table 6.8 Extrapolation factors for selected substances Substance CAS Body weight (kg) Dermal exposure Exposure duration LD 50 (mg/kg) Body weight (kg) Exposure duration (hours) LC 50 (mg/l) Inhalation exposure Extrapolation of LC50 for 1 hour of exposure(mg/l) Respiratory volume per hour (L/h) LC 50 converted (mg/kg) 1,1,1-trimethyl-N- (trimethylsilyl)silanamine hours 547 0, ,17 12, ,5 2,0 2-(diethylamino)ethanol ,35 4 day 885 0,2 4 4,6 7,30 12,08 440,9 0,5 Acrylonitrile hours 226 0,2 4 2,05 3,25 12,08 196,3 0,9 Propylamine hours 403 0,2 4 7,06 11,21 12,08 677,1 1,7 EF For 1,1,1-trimethyl-N-(trimethylsilyl)silanamine, the CLP classification (acute toxic 3 for the dermal route and acute toxic 4 for inhalation route) confirms EF >1. For all three other substances, the CLP classification is category 3 for both routes (inhalation and dermal). The EF calculation shows that for propylamine, the dermal route might be more important (based on this approach) with an EF > 1, while for acrylonitrile and 2-(diethylamino)ethanol, the inhalation route is more hazardous (EF<1). 45 Wilschut A., Houben G.F. and Hakkert B.C. (1998): Evaluation of route-to-route extrapolation in health risk assessment for dermal and respiratory exposure to chemicals. TNO Report V TNO Nutrition and Food Research Institute. 46 EMA (2009): ICH Topic Q3C (R4) - Impurities: Guideline for Residual Solvents, Step 5. European Medicines Agency, Science Medicines Health.

109 96 The weakness of this approach is the requirement for appropriate and comparable toxicity studies by dermal and inhalation routes. Comparable studies are frequently not available. The dermal exposure is more likely to be a slow process, with prolonged delivery while the inhalation exposures might lead to a more rapid absorption rate. Because of metabolism, repair, or tolerance mechanisms, the rate of dose administration could have an important impact on toxicity 35. Furthermore, as previously discussed, the LC 50 can be extrapolated for one hour of exposure using Haber s law, whereas this extrapolation cannot be used for LD 50 (dermal route). Without extrapolation for the dermal route, the methodology of using dermal LD 50 from experimental studies (24 hours) in accidental scenarios (1 hour) is rather conservative. In spite of these weaknesses and limitations, the comparison using EF factors derived from the LC 50 and the LD 50 values (converted via Mc Dougal s approach) confirms the different levels of toxicity given by the classification for 1,1,1-trimethyl-N-(trimethylsilyl)silanamine. For the three substances classified in category 3 for both dermal and inhalation routes, the EF calculation shows that, for propylamine, the dermal route might be more important, while for acrylonitrile and 2-(diethylamino)ethanol, the inhalation route is more hazardous. This approach allows a comparison to be made between the hazard by inhalation and dermal routes, but does not take into account the scenarios of exposure. In case of major accidents, the dermal and inhalation exposure must be considered in order to estimate the risk. These uncertainties must be taken into account in interpreting the results Substances Selected for Analysis in Accident Scenarios From the results reported above, the data to be used for modelling are summarised in the following table. Table 6.9 Lethal dose values for substances used in modelling accident scenarios Substance CAS No Dermal LD 50 (mg/cm²) Inhalation LC 50 (mg/l) (1 hour) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine (diethylamino)ethanol Acrylonitrile Propylamine In the context of real-world accidents, the potential dermal exposure can be reduced to much lower levels as compared to inhalation exposure. For example, Marshal (1980) highlights that through the ability of humans to use personal protection, to shelter, to escape, or to receive medical treatment are all highly important. These factors, if ignored, may lead to predictions which are pessimistic by several orders of magnitude".

110 Scenario Modeling Overview Five scenarios and four substances have been selected. In order to model these scenarios, the PHAST software was used. Developed by Det Norske Veritas (DNV), this software includes models for various accidental releases. The purpose of the scenario modelling is to obtain further insights into the differences in dangerous potential between the dermal and inhalation exposure routes. In this framework, comparable effect distances for both exposure routes are provided. Some limitations of this approach, in addition to those identified in section 6.4.2, are: The exposure time used in determining LD 50 values for dermal exposure is relatively long (24h) compared to the exposure time in typical accidents (likely to be <1h) and there is also a difference between the exposure time used for inhalation exposure and that used for dermal exposure (4h is used in determining LC 50 values for inhalation exposure). LD 50 values for dermal exposure are expressed in mg/kg of animal bodyweight. Unlike the case for inhalation exposure (where exposure concentrations and LC 50 values are both typically measured in mg/l or ppm, allowing direct comparison), this unit cannot be so easily compared with the potential concentration of products that may reach humans in the context of an accident (i.e. due to the different concept/units, there is a need to translate estimated exposure from consequence assessments in mg/l for example into a predicted dose in mg/kg bw, to allow proper comparison with the LD 50 ). Additional factors that complicate such a comparison for dermal exposure include interactions between the skin and a cloud (the lower the concentration, the lower the quantity of substance absorbed) or between the skin and a liquid (the lower the total surface of the body exposed, the lower the quantity of substance absorbed). The environment and the conditions of exposure play a key role in the determining the consequences on humans and the unit of mg/kg bodyweight for dermal effects does not take this into account in the same way as the mg/l or ppm values for inhalation effects, for which exposure conditions in the event of an accident are more comparable with exposure conditions used in deriving LC 50 values. Available toxicological data are neither complete nor sufficient (especially for dermal exposure) to describe precisely and fully quantitatively the consequences of accident scenarios. The analysis is therefore based on both qualitative and quantitative inputs. Moreover, considering the lack of data, simple models are preferred. Results are provided as distances to LC 50 /LD 50 without consideration of the exposure duration Scenario 1 ID Scenarios Toxic exposure (dermal) 1 Vessel rupture spreading of pool and evaporation establishment of a vapor cloud Exposure to a toxic cloud

111 98 The first scenario to be considered is a catastrophic rupture of a 2,000 m 3 vessel. After the rupture, the liquid spreads and evaporates. The pool radius (and therefore the evaporation rate) increases until the pool reaches its minimum height which is taken to be 5mm for concrete ground in PHAST. Then the pool radius (and therefore the evaporation rate) decreases because of the decreasing volume of liquid due to evaporation. Moreover the evaporation process is endothermic so that the pool temperature decreases with time. This also contributes to the decreasing of the evaporation rate. The evaporated product forms a cloud which disperses and to which humans can be exposed. For simplification purposes, an average evaporation rate is calculated. This value is then used to calculate the resultant plume. The phenomenon is therefore stationary. Using PHAST, a field of concentration (kg/m 3 of air) is calculated. Then, the maximum distance where the concentration of the cloud is equal to LC 50 is obtained. To get the maximum distance where the concentration of the cloud is equivalent to LD 50, it is necessary to translate this LD 50 expressed in (mg/kg of animal bodyweight) into an equivalent concentration (kg/m 3 of air). This process is not straightforward. It has to be investigated from both a biological and physical point of view. It is here proposed to consider that exposure to a concentration c (kg/m 3 ) within a plume is equivalent to a dermal exposure to the quantity of product that would be contained in the volume of the target: c V where V (m 3 ) is the target volume. By dividing by the mass of the target we get an equivalent dermal value (kg/kg of animal bodyweight). A value of 1,000 kg/m 3 is retained for animal density. The air concentrations that are equivalent to LD 50 thresholds are reported in the following table: Table 6.10 Equivalent concentrations to dermal thresholds LD 50 Products Equivalent Concentration to LD 50 (mg/l) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine (diethylamino)ethanol 885 Acrylonitrile 226 Propylamine 403 The equivalent concentrations to LD 50 obtained are much larger than LC 50 (approximately by a factor of 100). Thus distances to LD 50 will necessarily be smaller than those associated with LC 50. The distances to LC 50 and equivalent concentration to LD 50 are presented in the table below. They are given from the edge of the pool. To get absolute distances the maximum radius of the pool should be added.

112 99 Table 6.11 Scenario 1 Effects distances Products Distance to LC 50 (m) Distance to the concentration equivalent to LD 50 (m) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine (diethylamino)ethanol 40 0 Acrylonitrile 4,700 0 Propylamine 1,400 0 As the source of exposure is the same (the cloud), for a given exposure duration, the difference in dangerous potential between dermal and inhalation exposure only comes from the lethal dose and concentration. Therefore, the method used to translate dermal lethal doses to equivalent concentrations is an important assumption. Distances to the concentrations equivalent to LD 50 are zero because the LD 50 equivalent concentrations are large. The saturation concentrations above the pool are given in Table It represents the maximum concentration that can be reached above the pool and therefore inside the cloud. The LD 50 equivalent concentration cannot even be reached in the cloud for all products of interest except for propylamine. Distances to LC 50 range from 40m to 4,700m. This disparity of results related to inhalation exposure mostly comes from the difference of volatility between products. Table 6.12 Saturation concentration Products Saturation concentration at 15 C (mg/l) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine 99 2-(diethylamino)ethanol 101 Acrylonitrile 211 Propylamine 753 This method is based on substantial and questionable assumptions that would need further experimental validation before drawing definitive conclusions. However the results confirm the work performed by Kezic 48 that demonstrates the minor role of dermal absorption of vapours compared to respiratory absorption (the skin uptake is estimated from 1% to 0.1% of the inhalation uptake for hexane, toluene and m-xylene). 48 Kezic S., Monster A.C., Kruse J. and Verberk M.M. (2000) - Skin absorption of some vaporous solvents in volunteers. Int Arch Occup Environ Health, 73, 6,

113 Scenario 2 ID Scenarios Toxic exposure (dermal) 2 Vessel rupture spreading of pool Direct exposure to the product (liquid) This scenario is similar to scenario 1. However the direct exposure to the liquid and the dermal effects of such exposure is more specifically studied in this scenario. Distances related to inhalation exposure are equal to those calculated for scenario 1 (plus the calculated radius of the pool). The maximum distance to LD 50 is taken to be equal to the maximum radius of the pool. Provided the target is exposed to the pool, it is considered that LD 50 is reached. This is a very conservative but simple approach because when the pool depth is small this threshold is not likely to be reached. Additionally, clothes and shoes constitute a protection against dermal effects and are not taken into account in this study. The results are presented in the following table: Table 6.13 Scenario 2 Effects distances Products Distance to LC 50 (m) Maximum radius of the pool (m) Acrylonitrile 5, ,1,1-trimethyl-N-(trimethylsilyl)silanamine (diethylamino)ethanol Propylamine 1, Distances to LC 50 are larger than the maximum radius of the pool and thus than the maximum distance to LD 50. Indeed, as saturation concentrations above the pool (see Table 6.12) are greater than LC 50 for all four products, a target exposed to a pool will necessarily be exposed by inhalation to a concentration greater than LC50. The results are given without any consideration of exposure time. In fact, the target is likely to escape from the pool and to avoid a long duration of exposure to the liquid. The actual exposure time also depends on the emergency response. As such, a massive exposure to the dermal toxic substances (needed to produce lethal effects) would be more likely near the origin of the leak: in these specific cases, it would be possible that people exposed might lose consciousness due to toxic vapours or through being hit by broken equipment released during the rupture. In these cases lethal effects may be plausible.

114 Scenario 3 ID Scenarios Toxic exposure (dermal) 3 Vessel pneumatic rupture projection of product rain of product Direct exposure to the product ( rain ) This scenario is similar to scenarios 1 and 2. The maximum distance to LC 50 into the cloud will be equivalent to the maximum distances to LC 50 for scenarios 1 and 2: for all three scenarios, with regard to inhalation exposure, the scenario studied is a vessel rupture. The only parameter that changes is the rupture pressure. Because of the pressure inside the vessel, there will be projection of droplets. The maximum distance to where these droplets reach the ground is calculated (see Table 6.14). Most simple existing models consider that all the droplets touch the ground at the same point, although in practice they would be distributed on a whole surface. Table 6.14 Scenario 3 Distances to rain-out Products Distance to rain-out (m) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine 13 2-(diethylamino)ethanol 15 Acrylonitrile 40 Propylamine 13 These distances are much smaller than the pool radius and the maximum distances to LC 50 calculated for previous scenarios. Moreover, a projection phenomenon is almost instantaneous. Once exposed, the target (i.e. a person) is likely to get rid of the liquid it is exposed to. Moreover clothes protect people from an exposure incident covering a large proportion of the body. In such a case the pool and the cloud considered in previous scenarios will have more of a significant outcome than the rain. The two first scenarios would thus generate higher distances than scenario 3 for the dermal exposure Scenario 4 In the case of a vessel rupture and dilution of toxic products in water (lakes, rivers, etc.) the extent of the consequences will mainly depend of three main elements: the rapidity with which the product would reach the water (and then the possibility for an emergency team to recover the product). This mainly depends on: - The viscosity of the product (measured in poise), which is defined as the ability of a fluid to flow over the ground and to seep into the ground and underground. The more viscous a product, the slower the movement is. - The volatility of the product, which measures the ability of a product to be vaporised (i.e. to say to pass from the liquid state to the gaseous state). It is mainly measured by the vapour pressure (in

115 102 pascal or other units). The more a volatile a product, the more the product evaporates in the air and would have limited chance to reach the water. the behaviour of the product in water, i.e. whether it dissolves, floats or sinks in water. This mainly depends on: - the solubility, defined as the maximum amount of a substance than can be dissolved in a given liquid at equilibrium under given temperature and pressure (measured in mg/l); - the relative density, which determines the behaviour in an aquatic environment. This is the ratio of the densities (kg/m3) of a product compared to a solvent. In the case of freshwater, if the relative density is superior to 1, the product sinks, if it is less than 1, the product floats; - Other parameters that may be considered are the hydrophobicity polarity and stability; - the characteristics of the environment and the water where the release occur such as the flow rate (for a river), the deepness (for a lake), the topology of the body of water (slope, possible obstacles) and the wind speed. The study of a release into water would require the analysis of these parameters. It would require a description of how well the product, and its dangerous properties, transfers into the environment. In the case water body pollution, the extent of the consequences would be determined by the product s ability to be transferred to the environment as well as its inherent dangerous properties. The possible toxic exposure route of a given substance is then as important as its physical properties. In this context, it is impractical to draw general conclusions on the potential differences of effects between inhalation and dermal exposure routes. In this scenario, some category 3 substances for dermal and inhalation exposures may have significant effects on humans. The identification of the substances that may generate the more important consequences is not dependant on their LD 50 or their LC 50 but on other physicochemical parameters listed above. Some accidents recorded in accident databases illustrate the issue of the dispersion of toxic products in water bodies. For example, an accident occurred in 2007 involving the release of 130 kg of hydrazine hydrate (both H331 and H311) in a river. Despite this pollution, no direct consequences of this accident were observed for humans. Other examples include an accident in China in 2002 (release following an explosion in a facility), the aforementioned accident of La Gueira in Venezuela (release following a flood which damaged cargo containers). For both of these accidents, the substances involved in the accident are largely unknown and both dermal and inhalation toxic exposure can be suspected Scenario 5 ID Scenarios Toxic exposure (dermal) 5 Pipe rupture release of product under pressure projection of product Direct exposure

116 103 The scenario of a pipe rupture releasing a pressurised product (at 3 bar) is now considered. The liquid is projected; it rains-out and forms a pool that evaporates. In the following table, the rain-out distances are reported. It is assumed that the pipe is horizontal and located one metre above ground. Table 6.15 Scenario 5 Distances to rain-out Products Distance to rain-out (m) 1,1,1-trimethyl-N-(trimethylsilyl)silanamine 7 2-(diethylamino)ethanol 7 Acrylonitrile 10 Propylamine 8 These rain-out distances are smaller than the maximum radius pool that forms where the liquid reaches the ground. Once again, the pool and the cloud considered in scenarios 1 and 2 will have a more significant outcome than the rain. The two first scenarios would then generate higher distances than scenario 5 for the dermal exposure Synthesis In reference to the following figure (presented previously), Table 6.16 indicates which specific named substances are represented by each of the illustrative substances. Figure 6.5 Illustration of substance selection to cover the relevant range of hazards Substance 2 Substance 1 Substance 3 Inhalation Cat 1 Cat 2 Cat 3 Cat 4 Threshold values (mg/l) Dermal Cat 1 Cat 2 Cat 3 Cat 4 Threshold values (mg/kg) Substance B Substance A Substance C

117 104 Table 6.16 Substances investigated related to coverage shown in Figure 6.5 Illustrative substance Substance Inhalation exposure route 1 Acrylonitrile 2 2-(diethylamino)ethanol 3 Propylamine Dermal exposure route A B Acrylonitrile Propylamine B 1,1,1-trimethyl-N-(trimethylsilyl)silanamine C 2-(diethylamino)ethanol Thus results from the scenario assessment can be synthesised as shown in the table below. Table 6.17 Synthesis of the results of the scenario assessment Substances and maximum effect distances (metres) SCENARIO 1 Inhalation , ,400 Dermal A B B C SCENARIO 2 Inhalation Dermal A B B C SCENARIO 3 Inhalation Dermal A B B C SCENARIO 4 Not applicable see Section 6.6.5

118 105 SCENARIO 5 Inhalation Dermal A B B C Conclusions on Accident Scenarios A demonstration has been provided that toxic dermal exposure has lower 50% lethal distance effects than toxic inhalation exposure in scenarios 1,2,3 and 5. These four scenarios are the scenarios that would be more likely to occur in the context of a major accident. The differences between the distances vary significantly, with factors between 1.11 and above These results have been provided using very conservative assumptions for both inhalation and dermal exposure. However, because of a lack of knowledge and lack of recognized approaches, more conservative assumptions have been taken for the dermal exposure analysis, in particular: Duration of exposure: the duration of exposure has been neglected in the calculations. However, whilst LC 50 are based on 4 hours exposure duration (inhalation), LD 50 values are based on 24 hours or more exposure duration. As explained previously in this report, the exposure duration is a key parameter of the dermal (and inhalation) toxicity. Surface exposed: a conservative approach retained here is that any direct exposure to the toxic liquid can create a lethal risk. Also, the protection provided by clothes, shoes and personal protective equipment against dermal exposure toxicity is neglected. This approach has to be put in balance with the calculations performed for LD 50 /cm 2, which suggest that 50% lethal effects is reachable in the context of a massive exposure to toxic products. These dangerous areas are very likely to be located in the direct surroundings of the origin of a leak. These considerations, together with the analysis of the scenarios, indicate that, in order to understand the relative risk of toxic dermal and inhalation exposures, the severity of a potential accident has to be considered together with its probability. The ability of toxic effects to be transferred in the environment is then a key element. In this context, the study of scenario 1, which describes the possibility for a toxic cloud to generate effects through dermal exposure, has shown that there was no evidence that significant effects should be expected. Therefore, the simple affirmation that vapours would be more likely to reach people than liquids becomes a key element of the differences between the risks generated by toxic inhalation exposure substances and toxic dermal exposure substances. Together with the necessity of a long exposure duration and a massive exposure of the skin for reaching the 50% lethality level, it can be concluded that exposure through the dermal exposure route is less likely than exposure through the inhalation exposure route. These results are true for a large range of the LD 50 and LC 50 of the (generic) toxic categories 3 dermal and inhalation exposure. It cannot be excluded that for some specific substances (for example substances combining dermal toxicity and severe skin corrosions effects, and/or having a very rapid absorption rate) the expected effects would be greater than those assessed in this task. However, such a substance has not been found among the identified substances relevant for this study. Specific assessments would need to be used in the event that any such substance is identified in the future.

119 106 Finally, concerning the scenario 4, no significant differences between the two exposure routes have been found, either through the analysis of the scenario or through the analysis of past accidents.

120 Potential Socio-economic Impacts 7.1 Overview One of the overall aims of this report is to support the Commission s decision making on the need to cover acute toxic 3 dermal substances in Seveso from an environmental, safety and health perspective. An understanding of the potential compliance and administrative costs, and other possible socio-economic impacts (e.g. on employment), is important in understanding the overall merits of such a change. This section of the report provides estimates of the economic impacts of including these substances within the scope, in terms of possible costs for operators and for Member States/competent authorities. These have been largely estimated in quantitative terms and are estimates of the additional costs faced by establishments to comply with a possible amended Seveso directive, above-and-beyond the current (baseline) costs of their operations and compliance with other legislation. Other impacts, such as on employment, have been considered in qualitative terms, as it has not been feasible to estimate these impacts quantitatively. The assessment of these impacts has been made taking into account the Commission s guidelines on impact assessment 49. The Commission s impact assessment prepared during development of the Seveso III directive 50, as well as supporting studies 51, provided some useful estimates of the potential scale of impacts in the event of relevant changes to the directive. However, there is a need to develop more refined estimates, based on an improved understanding, to inform future decision making, particularly as regards the share of establishments that would be affected. In broad terms, the approach to estimating the potential impacts of a change to the directive was as follows: Identify how many installations and in what locations (subject to data availability) are likely to have acute toxic 3 dermal substances present above the relevant thresholds in Annex I to the directive; Of these, identify numbers and/or types of installations that will already be covered by Seveso in any case, allowing the net additional share of establishments to be calculated; Estimate the additional costs for industry and authorities of compliance with the directive per establishment, also considering the various degrees to which establishments could be affected; Combine the estimates of numbers of establishments and per-establishment costs to give an estimate of total costs to the EU; and Estimate potential benefits associated with covering these substances and installations Impact Assessment Accompanying Document to the Proposal for a Directive of the European Parliament and of the Council on the Control of Major-Accident Hazards Involving Dangerous Substances, COM(2010) 781 Final, For example: Impact assessment study into possible options for adapting Annex 1 of the Seveso II Directive into the GHS, Final Report, COWI A/S, February 2010.

121 108 Further details of the approach applied, along with the results of the analysis, are set out in the following sections of this report. 7.2 Types of establishments affected An underlying assumption in this analysis is that the qualifying quantities for inventories of acute toxic 3 dermal substances that would lead to coverage by the directive would be the same as those for other acute toxic substances already in Annex I, namely 50 tonnes for lower tier establishments and 200 tonnes for upper tier. Table 3.3 of this report provides a small sample of information on the types of uses for some of the substances that could be affected by a change in the scope of the directive. It is clear even from this small sample that there are diverse uses of the substances and it is likely that establishments in many sectors including chemicals manufacturing and various downstream uses would be affected. Not all establishments would be affected in the same way. One can envisage a number of different scenarios that would lead to establishments being affected in the event that they hold greater than the qualifying quantities of one or more relevant substances: Establishments that do not currently fall within the scope of Seveso. These could either be captured by the lower tier or upper tier requirements, depending on the quantities held. Establishments that currently fall within the scope of Seveso that would move from the lower tier to the upper tier because: - The inventories of (other types of) substances already held are insufficient to qualify for the upper tier but the inventories of acute dermal toxic 3 substances that newly fall within scope do qualify. - The substances held already fall within the scope of the directive due to other hazard properties but, because of a lower threshold for acute toxic 3 dermal substances, the establishment qualifies for the upper tier 52. Establishments that currently fall within the scope of Seveso that would not change tier but which would face additional requirements under Seveso, due either to the inclusion of new (acute toxic 3 dermal) substances or due to the additional hazard properties becoming relevant for substances that establishments are already using. In the present analysis, these three main types of situation/establishment have been used in estimating the potential economic impacts of a change in scope. There are also various other issues that will be relevant. For example, for all of the above situations, the substances in question could be either (a) subject to harmonised classification as acute toxic 3 dermal; (b) subject to harmonised minimum classification as acute toxic 4 dermal but with self-classification by some or all suppliers in 52 For example, consider a company holding over 5,000t but less than 50,000t of a substance classified as a category 2 or 3 flammable liquid under row P5c of Annex I. This company would currently qualify as a lower tier establishment. If that same substance were also classified as acute toxic 3 dermal, the establishment would become an upper tier establishment as it holds over the 200t threshold for toxic substances.

122 109 category 3; or (c) not subject to harmonised classification but nonetheless self-classified by some or all suppliers in category 3. Furthermore, establishments may come within the scope because they hold an inventory of one single substance above the qualifying quantity or because they hold inventories of several relevant substances and are affected through the summation rule How establishments would be affected Under the baseline situation, establishments affected by the directive must do a number of things to comply with the directive, most notably: For lower-tier sites: - notify basic details to the competent authority; - take all safety management measures necessary to prevent major accidents and limit their consequences to people and the environment; and - prepare a major accident prevention policy (MAPP). For upper tier establishments, the same as for lower tier sites and in addition: - prepare and update a safety report 54 ; - prepare and test an on-site emergency plan (IEP); - supply information to local authorities for off-site emergency planning purposes; and - provide certain information to the public about their activities. For each of the situations set out in the preceding section, establishments would face additional requirements in order to comply with the directive. These requirements are set out in the table below According to Note 4 to Annex I of the directive, the provisions of the directive may apply where the sum of two or more relevant substances (in the same or related category) exceeds the relevant qualifying quantity. Note that the major accident prevention policy required of lower tier operators is assumed to be included in the safety report.

123 110 Table 7.1 Additional requirements for establishments affected by possible change in the scope of the directive Type of establishment Lower tier (after change in scope) Upper tier (after change in scope) Non-Seveso becoming Seveso Lower tier moving to upper tier No change in tier NS-LT: Review substance inventories Notify authority Prepare MAPP N/A Review substance inventories Notify authority Update MAPP NS-UT: Review substance inventories Notify authority Prepare/update safety report Prepare/test IEP Provide information to authorities and public LT-UT: Review substance inventories Notify authority Prepare/update safety report Prepare/test IEP Provide information to authorities and public Review substance inventories Notify authority Update safety report (additional) Update IEP Update information to authorities and public All establishments For the substances affected: take all measures necessary to prevent major accidents and limit their consequences to people and the environment (i.e. technical or management modifications to reduce risks) The above changes have been used as the basis for estimating per-establishment costs of potential change to the directive. Note that there would also be additional requirements for the authorities associated with regulation and enforcement activities (for newly captured establishments or for those with increased requirements). 7.4 Possible number of establishments affected Data sources A number of information sources have been used to derive estimates of the potential number of establishments affected. It should be noted, however, that it is not possible to derive a fully accurate figure, a fact which has been made clear by consultation with key industry associations through the questionnaire process, as well as through information from suppliers of relevant substances 55. Key sources of data that have been used include: 55 For example, many of the suppliers of relevant substances in high volumes were unable to estimate how many of their customers held inventories above the qualifying quantities, even where they could provide such an estimate for their own operations.

124 111 Data from responses to the questionnaire applied for the present study, as well as additional consultation with manufacturers/suppliers of high-volume acute toxic 3 dermal substances. Data from France (UIC) which includes extensive data from consultation with 82 French companies in This contains information on an installation basis of substance quantities, but is mainly from establishments that are already covered by Seveso. A report for the UK authorities (ORC, ) which assessed the number of Seveso II establishments in the UK that would change classification under possible Seveso III options. This was supplemented by additional information from the UK authorities. Data from industry on the potential number of new establishments that would fall within the scope of the directive in Germany in the event of a change of scope. Data on the potential numbers of substances affected which provides some indication of the possible numbers of establishments Non-Seveso establishments coming into scope Based on information provided by industry for Germany (Cefic, 2012), around 110 establishments could come into the scope of the directive, split broadly equally between lower and upper tier establishments. This represents around 5% of the total number of establishments in Germany in 2011 (1,060 lower tier and 1,081 upper tier based on Germany s report on implementation of the Directive). Applying these percentages to the total of 9,449 establishments in the EU in 2011 (of which 4,949 were upper tier and 4,500 lower tier), a total of around 470 establishments could be affected, of which 250 could be lower tier and 220 upper tier (using the same split as for Germany). Using data from the UK authorities, provided for the current study, around 55 establishments could come into the scope of the Directive as a result of a change in scope, representing just over 5% of the 1,082 establishments in the UK in 2011 (from the UK s report on implementation of the Directive). Applying this percentage to the total of 9,449 establishments in the EU, a total of around 480 establishments could be affected, of which 240 could be lower tier and 240 upper tier (using the same split as for Germany for numbers falling into each tier, but with data rounded to the nearest 10 establishments). Taking an average of the two results above (which seem to be in reasonable agreement and are based on Member States with over a third of EU Seveso establishments combined), the estimated numbers of establishments newly coming into the scope of the directive is estimated as: 250 lower tier (uncertainty range 190 to 310 i.e. +/- 25%) 230 upper tier (170 to 290) 480 in total (360 to 600). 56 ORC (2011): HSE Seveso III Impact Assessment Final Analysis, report for HSE (UK), April 2011.

125 112 The above estimates have been used in the subsequent estimates of costs. Note that the figures have been rounded to the nearest 10 establishments Number of establishments moving from lower to upper tier Based on analysis of data collected for France (UIC, 2010) and the UK (ORC, 2011), it appears that a relatively small number of establishments would move from the lower to upper tier 57 : 2 establishments were identified based on the French data (0.36% of the 553 lower tier sites) and 2 based on the UK data (0.29% of the 687 lower tier sites). Taking an average of 0.33% and applying this to the number of lower tier sites in the EU (4,949), around 20 establishments could be affected. This figure does not take into account situations where substances are already included in Seveso but for which the qualifying threshold would be lower if the substance is also classified as acute toxic 3 dermal. Therefore, the number is more likely to be higher than lower (although it could still be lower), and a range of 15 to 30 has been used in the following analysis Number of Seveso establishments not changing tier Based on an analysis of data for France (UIC, 2010), it is estimated that the establishments surveyed reporting inventories of acute toxic 3 dermal substances in quantities above 50 tonnes represent 2.3% of all Seveso establishments in the country. Extrapolating this to the EU, around 220 establishments could be affected. Subtracting the approximately 20 establishments that could change from lower to upper tier, this leaves around 200 establishments that would be affected by a change in the scope of Seveso but which would not change tier. It is estimated that the majority of these would be upper tier establishments based on the UIC (2010) data, presumably because larger establishments are more likely to hold inventories of several different substances. An uncertainty range of 25% has been assumed in the subsequent analysis (i.e. the range assumed is 150 to 250) Summary of number affected and cross-checking The table below shows the estimated numbers of establishments affected in terms of (currently) non-seveso establishments becoming either upper or lower tier Seveso establishments, as well as numbers of lower tier Seveso establishments expected to move into the upper tier and numbers of establishments that would be affected but which would not change tier. 57 It should be noted that for both France and the UK, at least some of these establishments would be expected to move from the lower to the upper tier due to the summation rule rather than due to individual acute toxic 3 dermal substances alone. For France, the value is a minimum.

126 113 Table 7.2 Summary of estimated numbers of establishments affected by possible change in scope of the directive LT (after change in scope) UT (after change in scope) Total Non-Seveso becoming Seveso 250 ( ) 230 ( ) 480 ( ) Lower tier moving to upper tier - 20 (15-30) 20 (15-30) No change in tier 50 (38-63) 150 ( ) 200 ( ) Ranges in parentheses represent the upper and lower bounds of the estimates used in the following analysis. The actual values could still be higher or lower than these. The above data are based on survey data from a small selection of (albeit large) Member States. In order to crosscheck the validity of these estimates, particularly taking into account the fact that the CLP inventory was published after most of the underlying estimates were derived, it seems appropriate to check these against the numbers of substances affected. Based on the data in Section 3 of this report, the numbers of relevant substances that are likely to be covered by a change in scope and potentially affect establishments include: 41 substances that have harmonised classification as H311 (acute toxic 3 dermal) but not for other acute toxic hazards of which 10 were registered under REACH by Given the high volumes (>1000t), there will probably be several establishments that would be affected for each substance. In addition to this, some of the substances to be registered in 2013 (quantities on the market of t per year) could also lead to establishments being affected. Around 250 substances that have harmonised minimum classification as (acute toxic 4 dermal) but not for other acute toxic, of which around 100 were REACH-registered by 2010 and again some relevant substances are likely to be registered in Of these, some suppliers of some of the substances will include a notified (self) classification as H311. The actual number is not known. In addition to these, over 3,000 substances are self-classified as H311 (notified as such by at least one supplier), though not all of these will necessarily be actually placed on the market. Based on these data (and the lack of reliable estimates provided by companies involved in supplying the substances in question when contacted), it is not possible to derive any robust estimate of the likely numbers of establishments that would be affected from these data. However, they can be used as an additional sanity check on whether the above estimates are of a reasonable order. Assuming that there could be several 10s or perhaps 100s of substances that are placed on the market in sufficient quantities (>100t or >1,000t per year) for there to be at least some establishments holding inventories over 50t. Assuming 50 to 200 relevant substances and on average 2 to 10 establishments affected per substance, the number of establishments holding relevant inventories could be in the region of 100 to 2,000. This is purely illustrative and subject to very high uncertainty, but hopefully does serve to indicate that the estimates in the table above do not seem entirely unreasonable.

127 Per-establishment costs of amendment to Seveso Background A number of different sources of information have been used to estimate the potential scale of costs for each establishment, in each of the categories of potential effect. These are summarised below. The estimated costs do not include the costs associated with technical or management measures taken to reduce the risks. These are highly dependent upon the specific substance, establishment and processes involved. However, it should be borne in mind that the total costs would therefore be higher than those estimated in the following Sections Impact assessment for the Seveso II directive Based on the European Commission s (2010) impact assessment and supporting studies (e.g. COWI, 2010), the administrative costs for establishments newly included in the scope of the directive were estimated as 5k for those becoming lower tier and 30k for those becoming upper tier. These are annualised costs and represent the best estimates used in the analysis. Furthermore, based on these values, it can be assumed that the costs for establishments moving from the lower to the upper tier would be the difference between the two values, i.e. 25k. For existing Seveso establishments that would be affected by a change in scope but which would not change tier, the estimated costs have been derived from other data in the impact assessment. The annualised costs are estimated at around 1.5k per year for lower tier establishments (assuming notification of change and update of internal emergency plan) and 4.4k per year for upper tier establishments (including notification of change and update of the safety report) Consultation for the present study The ranges of costs estimated by respondents to the questionnaire for the current study were set out in Table 4.2. These represent the upper and lower end of the ranges provided by all respondents. It is clear from analysis of the individual responses that some of the data are outliers, with one or two respondents estimating costs that are either substantially higher or lower than other respondents. In order to dampen the effect of these outlying figures, the data used in the analysis have been derived by taking the geometric mean of the values provided by all respondents. 58 Based on data from page 85 of the impact assessment, the key cost elements (best estimates) are: notification = 3000, notification of change = 2500; safety report new = 35,000; safety report update= 17,000; IEP new = 8000; IEP update = Annualised costs were estimated using a discount rate of 4% and assuming an amortisation period of 5 years (an assumed typical period between major revisions to safety reports, etc.).

128 115 Table 7.3 Survey responses on estimated costs of additional requirements under Seveso ( per establishment) Preparation of notification and a major accident policy Prepare safety report and safety management system with emergency plans Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Not Seveso - One off compliance costs Not Seveso - Recurring costs Currently covered by Seveso One off compliance costs Currently covered by Seveso Recurring costs 4,200 34, ,000 5,100 3,200 22, ,000 4,500 2,900 17, ,000 4,800 2,900 15,000 82,000 4,800 Figures are geometric mean values of all numerical responses provided in the questionnaire for the current study. Data have been rounded to 2 significant figures. Recurring costs include, for example: ongoing updates of safety reports and safety management systems; updates of emergency plans; cooperation with inspectors; review and notification of changes in substance inventories and uses. Respondents provided estimates of recurring as well as one-off costs associated with technical modifications for example, which may reflect the fact that technical modifications are often made in stages over a period of several years (e.g. during plant downtime). In order to translate the above into estimates for each of the categories of effect for establishments, the following has been done: Technical modifications are not included in the figures, to ensure compatibility with other estimates (because these vary so much amongst establishments and substances, and are hence not possible to predict well at EU level). Lower tier establishments are assumed to review substance inventories and prepare a major accident policy. Upper tier establishments are assumed to review substance inventories, prepare a safety report and safety management system with emergency plans. For establishments newly coming into the scope of Seveso, the total additional per-installation costs of the above are assumed. For substances changing from lower to upper tier, the difference between the costs for upper tier and lower tier establishments is assumed to be the cost borne. The only additional cost for establishments already covered by Seveso is assumed to be the cost of reviewing substance inventories (one additional review).

129 116 Annualised costs are estimated using a 4% discount rate and 5 year amortisation period 59. Based on the above, equivalent annual costs for each of the categories of establishment are presented in the table below. All costs estimated here are the additional costs faced by establishments compared to the baseline (business as usual) situation. Table 7.4 Estimated costs of compliance per establishment based on survey results One-off cost ( k) One-off cost ( k) annualised Recurring cost ( k per year) Total equivalent annual costs ( k) Non-Seveso becoming Seveso LT Non-Seveso becoming Seveso UT Lower tier moving to upper tier No change in tier Cost estimates from UK authorities Data provided by the UK authorities suggest that costs for establishments newly moving into the lower tier could be 20,000 one-off costs plus 11,000 annual ongoing costs, with equivalent values for upper tier sites of 161,000 one-off costs and 56,000 per year ongoing costs. Costs for review of inventories were estimated at 125 to 1,200. Based on these data, the estimated costs per establishment in each of the categories considered in the present study are estimated as shown in the table below. Table 7.5 Estimated costs of compliance per establishment based on UK data One-off cost ( k) One-off cost ( k) annualised Recurring cost ( k per year) Total equivalent annual costs ( k) Non-Seveso becoming Seveso LT Non-Seveso becoming Seveso UT These assumptions were used in the Commission s impact assessment supporting the proposal for the Seveso III directive. They are considered appropriate for the current analysis given that: 4% discount rate is specified in the Commission s impact assessment guidelines and a 5 year amortisation period corresponds with e.g. typical frequency of updating of safety reports (and is therefore indicative of additional costs).

130 117 One-off cost ( k) One-off cost ( k) annualised Recurring cost ( k per year) Total equivalent annual costs ( k) Lower tier moving to upper tier No change in tier Notes: Data from UK authorities have been converted into Euro at an exchange rate of 1.18 per (GBP). Review of inventories is assumed to be a one-off cost and the mid-range of the value provided has been taken. Annualised one-off costs have been derived using a discount rate of 4% and an amortisation period of 5 years Chemical industry estimates Cefic (2011) estimated the costs for establishments affected by a change in the scope of the directive. These estimates include the following: For new upper tier establishments, 4 full-time-equivalents (FTE) for preparation of a new safety report and 0.5FTE for preparation of a new emergency plan. Valued at 100k per FTE, these together were costed at 450k per establishment. A one-off cost for adaptation of safety reports for establishments already covered by Seveso associated with 1FTE, valued at 100k. (In the present analysis, this value has been assumed to apply to lower tier sites becoming upper tier and for sites that do not change tier but which would have additional requirements due to the inclusion of additional substances in the relevant inventories.) Annual costs for provision of information to the public of 20k per establishment for sites with extended requirements and 15k for those with basic requirements. Annual costs of 30k per site (0.3FTE) associated with dealing with inspections for sites with extended requirements and 10k for those with basic requirements (inspections only every 3 years so a factor of 1/3 was used) In the present analysis, the costs associated with sites with basic requirements are assumed to apply to lower tier establishments and those for extended requirements to apply to upper tier establishments.

131 118 Table 7.6 Estimated costs of compliance per establishment based on Cefic data One-off cost ( k) One-off cost ( k) annualised Recurring cost ( k per year) Total equivalent annual costs ( k) Non-Seveso becoming Seveso LT Non-Seveso becoming Seveso UT Lower tier moving to upper tier No change in tier Costs for non-seveso establishments becoming UT are based on 450k per establishment for preparation of a safety report plus emergency plan, plus administrative costs of 30k for dealing with inspections and 20k for provision of information to the public. For lower tier establishments moving to upper tier and for those with no change in tier, the additional one-off costs are associated with adapting safety reports (it is recognised that this is an overestimate for lower tier establishments that do not change tier so later analysis has assumed that these costs would be only 25% of this figure for LT establishments, as they would only have to update the major accident prevention policy (MAPP), not a full safety report), with the annual administrative costs associated with information provision ( 15k) and dealing with inspections ( 30k every 3 years, undiscounted). Cefic did not provide estimates of the one-off cost for lower-tier establishments so, for the present analysis, these have been estimated by assuming the same ratio as for administrative costs. No additional administrative cost is assumed for those establishments with no change in tier. Note that no figures were given in the Cefic data that could be used in estimating recurring costs where there is no change in tier (these costs are expected to be much smaller than the other main cost elements). Unless stated otherwise, a discount rate of 4% and amortisation period of 5 years have been used Summary of cost estimates The table below summarises the cost estimates per establishment based on all of the above data sources. All of these estimates have been used in the subsequent analysis, in order to explore the range of potential costs that would be incurred. Table 7.7 Summary of cost estimates per establishment ( k, equivalent annual costs) Non-Seveso to lower tier Non-Seveso to upper tier Lower tier to upper tier No change lower tier No change upper tier 2010 impact assessment Consultation for current study UK authorities' estimates Chemical industry estimates All cost estimates are equivalent annual costs derived by adding annual recurring costs to equivalent annualised one-off costs, the latter derived using a 4% discount rate and 5 year amortisation period. For the chemical industry estimates, the costs for establishments not changing tier are assumed to be 25% of those for upper tier establishments (consultants own estimate, not included in the original data, given that these establishments would not need to update a safety report, only a major accident prevention policy).

132 Overall costs Costs to operators Based on the per-establishment costs in the preceding section (Table 7.7) and the estimates of numbers of establishments affected (Table 7.2), estimates of the total costs to operators have been derived, by multiplying the number of establishments by the per-establishment costs. The results, based on the central estimate of the number of establishments affected are shown in the table below. Table 7.8 Total EU cost estimates ( m, equivalent annual costs, central estimate of number of establishments) Data source for perestablishment costs Non-Seveso to lower tier Non-Seveso to upper tier Lower tier to upper tier No change lower tier No change upper tier Total 2010 impact assessment Consultation for current study UK authorities' estimates Chemical industry estimates These costs are also presented in the figure below, highlighting the effect of the high and low estimates of numbers of establishments affected on the overall costs.

133 120 Figure 7.1 Total EU costs using different sources for per-establishment costs ( m, equivalent annual costs) Total equivalent annual cost ( m/yr) impact assessment Consultation for current study UK authorities' estimates Chemical industry estimates 0 Note: Blue columns derived using central estimate of number of establishments; grey bars represent range using high and low estimates of number of establishments. The four data sources relate to the information used in deriving per-establishment costs, not the total EU estimates. It is worth reiterating that none of the above estimates include the costs associated with technical and management changes to address the risks of acute toxic 3 dermal substances (e.g. installing additional containment, improving equipment integrity checking, leak detection/repair or reorganisation of staff/operations amongst others). These are highly establishment and substance dependent but, by way of illustration, Cefic (2011) estimated these (one-off) costs as being in the region of 300k per establishment for infrastructure, processes and organisation. Cost estimates provided in the consultation for the current study suggested one-off costs of technical modifications to manufacturing or storage facilities to reduce risks of 140k for establishments that would newly come into the scope of Seveso and 80k for establishments already within the scope of Seveso (these estimates being specific to acute toxic 3 dermal substances). Clearly, these costs are potentially significant for the establishments concerned. However, these estimates are highly uncertain and should be treated with caution Costs to authorities In addition to the costs for operators, there would also be administrative costs to the authorities associated with a number of aspects, including, for example: Costs associated with adapting regulatory regimes to deal with an amended Annex I in general.

134 121 Costs associated with regulating (including inspecting) an increased number of establishments due to those newly coming into the scope of the directive (as well as external emergency plans for upper tier establishments). Costs associated with reviews and additional scope of substances covered for establishments already included within the scope and for developing emergency plans. To quantify these, previous assessments of administrative costs to authorities have been used: COWI (2010) estimated these costs at 10,000 per lower tier establishment and 61,000 per upper tier establishment, based on Atkins/FEA (2009). These costs apply for the first five years of an establishment and therefore apply to establishments newly coming into scope. The difference between them is taken to reflect the cost of an establishment moving from lower tier to upper tier. Additionally, the European Commission s (2010) impact assessment estimates costs of one day per establishment to review site-specific permits for all establishments affected (including those with no change in tier), with an average day cost of 350. For this assessment, it is assumed that this cost is included in the figures given above for establishments coming into scope or changing from lower to upper tier. As such, it only applies to Seveso establishments with no change in tier. Annualising these costs (over 5 years with a 4% discount rate) implies: 2,200 per year for establishments moving into scope (lower tier); 14,000 per year for establishments moving into scope (upper tier); an additional 11,000 per year for establishments moving from lower tier to upper tier 60 ; 80 per year for Seveso establishments not changing tier. These figures were applied to the numbers of affected establishments across the EU (as given in Section 7.4.5) to give the overall costs presented in Table 7.9. Table 7.9 Total administrative costs to EU competent authorities ( k, equivalent annual costs) Non-Seveso to lower tier Non-Seveso to upper tier Lower tier to upper tier No change lower tier No change upper tier Total Central estimate 540 3, ,900 Low estimate 410 2, ,900 High estimate 670 4, ,000 All cost estimates are equivalent annual costs derived using a 4% discount rate and 5 year amortisation period. Figures are based on low and high estimates of establishment numbers, not low and high cost estimates. 60 The figures presented here have been rounded to ease presentation but non-rounded data have been used in the underlying analysis.

135 122 It is of note that some Member States recover the costs of their regulatory activities from the operators. This has not been taken into account in the analysis i.e. payments to authorities are not included in the compliance costs for operators and the above cost estimates do not take into account income from operators. 7.7 Social impacts The main social impacts associated with a potential change in the scope of the directive to include these additional substances are assumed to relate to levels of employment in the affected industries. Firstly, there could potentially be an impact on business viability, especially for smaller or less profitable companies, where establishments newly come into the scope of the directive. The costs, especially in the case of new upper tier establishments, could be several tens of thousands Euros for preparation of safety reports, for example. Any effect on business viability could lead to loss of employment in the affected companies. For establishments that face new or increased requirements under Seveso as a result of a change to include acute toxic 3 dermal substances, the companies concerned would have two main options in relation to the time and associated cost needed for compliance activities (e.g. preparation of safety reports and ongoing management). Firstly, they could decide to divert existing staff time to those Seveso compliance activities, with no additional employment (or associated cost) but with potential implications for other business activities (such as reduced research and development time). Alternatively, they could decide to employ additional staff to deal with compliance activities, either directly or through contractors, which could then lead to an increase in employment levels. The option chosen is likely to depend on existing skills sets within companies and other structural aspects of the businesses concerned. 7.8 Significance of costs One way of examining whether these costs are worth imposing upon industry in order to reduce the potential impacts of major accidents is to consider the extent of harm that would need to occur to make the benefits of avoiding that harm greater than the costs imposed. The Commission s Impact Assessment guidelines suggest using a value of 1-2 million for the value of a statistical life (VOSL). This is concept does not measure the value of a life per se, instead it puts a monetary value on the willingness to accept slightly higher or lower levels of risk Note that there are various similar indicators that can be used in assessing the impacts of (avoided) safety and environmental risks. An alternative approach to use to VOSL is the value of life years lost (VLYL) which has been used extensively, for example, in impact assessments on the health impacts of air pollution (where chronic effects are concerned or where (for example) mortality is brought forward by only a relatively small number of years in people with existing health problems see for example The VOSL value has been used in the present analysis primarily because effects related to major accidents are mainly acute impacts and, in most cases, mortality related to major accidents involving acute toxic substances is not expected to be related to / dependent on any pre-existing health conditions (unlike the case of certain air pollutants, where VLYL would be more appropriate).

136 123 Taking into account the range of cost estimates set out earlier in this section, the costs for operators associated with bringing these substances into the scope of Seveso are in the region of 10 to 60 million per year using the central estimate of number of establishments affected. This is equivalent to between 5 and 60 times the VOSL estimates provided above, implying that this number of fatal accidents would need to be avoided in order for the benefits of including these substances to outweigh the risks of not imposing this additional level of regulation. Establishments are of course already obliged to manage the risks of these substances through the requirements of workplace chemicals legislation such as the Chemical Agents Directive, 98/24/EC. Given that the majority of the impacts associated with accidents involving acute toxic 3 dermal substances are likely to be on-site (affecting workers) rather than off-site, the additional safety/health benefits are likely to be modest). 7.9 Impacts on SMEs It is difficult to fully assess the overall impacts on micro organisations or SMEs of including acute toxic 3 dermal substances in Seveso, primarily due to data limitations regarding the number of SMEs currently covered by Seveso and the number of SMEs likely to come into scope. This difficulty is explicitly recognised in the European Commission s (2010) impact assessment, which states that there are limited data to support a specific assessment of the impacts on SMEs, and implicitly by COWI (2010), whose impact assessment does not address SME impacts. The main data that are available are those produced by the International Association for Soaps, Detergents and Maintenance Products (AISE) in 2010, as presented in the European Commission s (2010) impact assessment. These related to the potential number of SMEs using or storing mixtures containing sodium hypochlorite in sufficient quantities to bring them into Seveso scope. Since these data only relate to one substance in one industry (with estimates for three countries), extrapolation based on them may not provide sufficiently robust figures. While a full quantitative assessment of the scale of SME impacts is therefore not possible given currently available data, it is nonetheless possible to (a) qualitatively assess the likely impacts on SMEs; and (b) assess how significant the regulatory burden would be on affected SMEs (despite not knowing how many of these there would be). Qualitatively, it is thought that few SMEs would stand to be affected by this possible regulatory change. This is because Seveso targets companies that use or store large quantities of chemicals, which are likely to be larger companies. In addition to this, the tiered approach adopted by Seveso further limits the expected impacts on SMEs, since it is expected that affected SMEs are more likely to operate lower than upper tier sites. This is reflected in the European Commission s (2010) impact assessment. While the overall number of SMEs that stand to be affected cannot be precisely assessed, the scale of impact on those SMEs that are affected can be. The direct economic impacts of potential regulation on SMEs relates to whether an operator is able to meet the costs that are imposed on it, whether directly or indirectly. This can be assessed by comparing the compliance cost per establishment against the level of financial resources available to the operator for investment.

137 124 Information available in Eurostat Structural Business Statistics includes gross operating surplus (GOS), which is the capital available to companies which allows them to repay their creditors, to pay taxes and eventually to finance all or part of their investment. Considering that GOS can be used for financing investment, the costs per establishment (Table 7.7) were compared with GOS per operator to assess these impacts. Eurostat data were used on GOS per enterprise size category (i.e. micro, small, medium versus large-sized enterprises) in EU27 countries in 2010 for the chemical industry 62,63. For each enterprise size category, GOS was divided by the number of enterprises (as given by Eurostat Structural Business Statistics) to estimate the level of capital available at the operator level on an annual basis. This then allowed the costs per establishment (as given in Table 7.7) to be expressed as a percentage of GOS per enterprise, thus providing a measure of the likely regulatory burden for affected SMEs of bringing acute toxic 3 dermal substances into Seveso scope NACE Rev. 2 code C20: Manufacture of chemicals and chemical products. Where 2010 data were not available, 2009 data were used. Since overall GOS data for the EU27 were not available, the sum of GOS data by Member State was used instead. It should be noted that no GOS data were available for either 2010 or 2009 for Malta or Luxembourg. Data for Estonia were only available for micro (<10 employees) and small (10-49 employees) enterprises, not medium ( employees) or large (250+ employees). Employee numbers were used here to define SMEs; it should be noted that the definition also includes turnover of enterprises.. Note that the official definition of micro, small and medium enterprise as defined in Commission Recommendation 2003/361/EC is that micro enterprises have < 10 employees, small ones have < 50 and medium ones < 250. To avoid double-counting, we have adopted slightly different definitions in that we have taken micro, small and medium enterprise to be exclusive categories rather than sub-sets of one another.

138 125 Figure 7.2 Total annual cost estimates per establishment as a proportion of gross operating surplus for SMEs in the chemical sector (based on different sources of costs, including costs to operators only) 25% 20% 15% 10% 5% 0% Non-Seveso to lower tier Non-Seveso to upper tier Lower tier to upper tier No change lower tier No change upper tier 2010 impact assessment Consultation for current study UK authorities' estimates Median Chemical industry estimates From Figure 7.2 (which covers micro, small and medium sized enterprises), it can be seen that the costs per establishment are expected to be low (as a proportion of GOS) for those SMEs that are already covered by Seveso and do not change tier. Using the per-establishment cost estimates in the European Commission s (2010) impact assessment, the burden is also expected to be manageable for SMEs newly coming into Seveso scope, as well as for those moving from lower tier to upper tier, with estimated costs consistently near or below 5% of GOS. Using the UK authorities cost estimates, this burden is also expected to be manageable for non-seveso SMEs that become lower tier, with costs representing less than 5% of GOS. However, using the UK authorities costs estimates or the chemical industry estimates, the burden is expected to be more significant for SMEs moving into the upper tier, whether from being non-seveso (costs between 17% and 23% of GOS) or from the lower tier (costs between 7% and 14% of GOS). This analysis can be further refined by considering the different size categories in more detail. The table below presents the total annualised cost estimates per establishment as a proportion of gross operating surplus for micro, small and medium enterprises in the chemical sector.

139 126 Table 7.10 Annual cost estimates per establishment as a proportion of gross operating surplus for different sizes of enterprise in the chemicals sector Size Non-Seveso to lower tier Non-Seveso to upper tier Lower tier to upper tier No change lower tier No change upper tier Micro 17% (6% - 92%) 88% (37% - 184%) 45% (31% - 110%) 2% (0.2% - 7%) 3% (0.2% - 27%) Small 3% (1% - 19%) 18% (7% - 37%) 9% (6% - 22%) 0.3% (0% - 1%) 1% (0% - 6%) Medium 1% (0.2% - 3%) 3% (1% - 6%) 1% (1% - 4%) 0.1% (0% - 0.2%) 0.1% (0% - 1%) Large 0% (0% - 0.2%) 0.2% (0.1% - 0.4%) 0.1% (0.1% - 0.2%) 0% (0% - 0%) 0% (0% - 0.1%) Figures quoted are median values with the range in parentheses. Figures have not been rounded. The figures above illustrate that the costs to operators of including acute toxic 3 dermal substances in Seveso are expected to be: under 0.5% of GOS for large enterprises, and under 0.1% of GOS for those that do not change tier; under 6% of GOS for medium enterprises, and under 1% of GOS for those that do not change tier; higher for small enterprises that do not move into the upper tier (median values all under 5% of GOS but maximum end of range estimates up to around 20% of GOS; potentially much higher for small enterprises that move into the upper tier, whether from being non- Seveso (18% of GOS as a median value but up to around 40% at the higher end of the range), or from being lower-tier (around 10% of GOS as a median value and over 20% at the upper end of the range); almost certainly problematic for micro enterprises, except those currently covered by Seveso that do not change tier, with the costs of being captured as an upper-tier establishment potentially being greater than total GOS. The main conclusion of this analysis is that, while few SMEs are expected to be affected (since most Seveso sites are thought to be owned/operated by large companies), those that would be affected by a change in scope could bear proportionately much higher costs than large companies when compared to gross operating surplus. This is especially the case for small and micro enterprises. If further changes to Seveso to include these substances are pursued, it may therefore be appropriate to consider mitigation measures, which could range from partial or complete exemptions to financial support to help the enterprises meet the new requirements (e.g. reduced fees).

140 Study Conclusions 8.1 Work undertaken In developing conclusions on the impacts of controlling acute toxic 3 dermal substances within the scope of Seveso, the project has included the following: A detailed review of past accidents has been undertaken. A number of accident scenarios have been developed and analysed in the context of the potential for acute toxic 3 dermal substances to cause major accidents, as well as to allow comparison with the exposure route.. Work has been undertaken to identify substances and number of establishments potentially affected by a change in the directive, through EU databases, consultation with industry/authorities and review of relevant literature. A wide-ranging consultation has been undertaking using a questionnaire supplemented with additional, targeted questions to individual companies. The level of response is reasonable, and in line with expectations for the project. An assessment has been made of the potential economic and social impacts of a change to the directive, though it is clear that uncertainties will remain, due to gaps in available information and knowledge amongst the affected stakeholders (industry and authorities). 8.2 Substances potentially affected A number of information sources have been used to identify the substances potentially affected by the possible change to the directive. Key information based on an analysis of these data sources includes: A total of over 4,000 substances with harmonised classification have been identified. Of these, around 420 individual substances were classified as acute toxic 3 and, of these, 187 were classified as acute toxic 3 dermal. Of these 187 substances, 41 substances were classified as acute toxic 3 dermal (H311) and not classified for other acute health hazards (dermal 1/2, oral 1/2, inhalation 1/2/3 or STOT SE 1). 10 of these had been registered under REACH in 2010, suggesting potentially high volumes. However, some were also classified for other Seveso-relevant effects, albeit with different applicable thresholds (only 15 of the 41 were not also classified for relevant environmental hazards). A similar analysis was also undertaken for substances with harmonised minimum classification as acute toxic 4 dermal, as some of these substances may be self-classified as acute toxic 3 dermal. Likewise, there are many other chemicals with no harmonised classification which will be selfclassified by at least some of the chemical suppliers as acute toxic 3 dermal. A number of such substances have been identified through the stakeholder consultation, though it is not feasible to come up with a comprehensive list of all substances affected (particularly as in many cases, only a small fraction of the chemical suppliers classify their substances as acute toxic 3 dermal).

141 Stakeholder consultation The questionnaire implemented in November 2012 to January 2013 provided some very useful insights into the substances potentially affected by a change to the directive; the relative significance of these substances; and the implications of such a change. Some of the most relevant findings were: Relatively few respondents were aware of substances other than those identified through a review of harmonised EU classifications which would be affected by a change to the directive. Around half of the respondents thought that acute toxic 3 dermal substances (which do not also fall within another classifications currently covered by Seveso) have the potential to cause major accident hazards. However, substances are viewed as less significant than toxic substances where other exposure routes are relevant, in terms of the significance of potential accidents. Some of the respondents are aware of past accidents or near misses that have involved dermal toxic effects and the survey identified a few accident scenarios that could be relevant (e.g. as considered in previous safety reports). These have been taken into account in drafting the accident scenarios within this report. Only a small number of respondents provided estimates of the number of establishments potentially affected by a change to the directive, and these varied widely. The estimates that appear to be based on more comprehensive research are related to France, Germany and the UK. The majority of the respondents and in particular the respondents who have provided precise answers to the questionnaire are not in favour of including acute toxic 3 dermal substances in the scope of Seveso. In addition to the questionnaire, additional targeted consultation was undertaken with companies that have registered relevant substances under the REACH regulation, indicating potentially high volumes/inventories within those companies and their customers. Some useful information has been received from a few companies, although in general most companies were unable to provide any reliable estimates for the number of their customers with inventories above the Seveso thresholds. 8.4 Review of accident databases An extensive review of past accidents involving toxic substances has been undertaken, based on national and international databases, in particular e-mars, ARIA and the IChemE accident database. Key conclusions from this analysis are that: Of the 55,700 accidents screened, 794 have been considered relevant for the present study (see Appendix A). Significantly more accidents in the period 2000 to 2012 involved the inhalation exposure route (57.5%) than the dermal exposure route (3.6%).

142 main substances were involved in the accidents for which toxic dermal effects were identified as relevant. However, only 10 of these have classification for the acute toxic dermal route in Europe. Of these 10, most are classified as acute toxic 1 for the dermal route. Accidents involving the toxic dermal exposure route led to lower human consequences than those involving the toxic inhalation exposure route. Overall, it is concluded that the risk generated by products that are acute toxic category 3 for inhalation exposure is higher than the risk generated by products that are acute toxic category 3 for dermal exposure, based on past accidents. Nonetheless, some accidents involving substances that are acute toxic 3 dermal exposure may have led to severe consequences (i.e. potentially major accidents). An accident may also be assessed according to the extent of its consequences that are felt outside the limits of the facility. No accident with consequences outside the establishment and involving acute toxic category 3 for dermal exposure has been found in this study. In contrast, 65 accidents with consequences outside the establishment and involving substances that are acute toxic category 3 for inhalation exposure have been found. 8.5 Development of accident scenarios A number of accident scenarios have been developed, to estimate typical consequences of accidents involving the dermal and inhalation exposure routes. The primary aim of these accident scenarios has been to compare the significance of the inhalation and dermal exposure routes. There are a number of methodological and data uncertainties associated with this approach, and in particular it is considered more challenging to extrapolate from toxicity data in animals to potential effects on humans related to industrial accidents for the dermal route than it is for the inhalation route. For 4 out of the 5 scenarios retained for the analysis, it has been demonstrated that the distances at which lethal effects are likely to be felt are greater for toxic inhalation exposure than for dermal toxic dermal exposure. Using conservative assumptions, in particular for the analysis of the dermal exposure route, the difference between the 50% lethality distances varies between a factor of 1.11 and a factor of more than These results are true for a wide range of LD 50 and LC 50 values relevant to category 3 toxicity through the dermal and inhalation exposure routes. It cannot be excluded that for some specific substances (for example substances combining dermal toxicity and severe skin corrosions effects, and/or having a very rapid absorption rates) the expected effects would be greater than those assessed in this study. However, such a substance has not been found among the identified substances relevant for this study. Specific assessments would need to be used in the event that any such substance is identified in the future. The scenario analysis has also shown that, whilst a major accident potential exists for substances classified as category 3 toxic through dermal exposure, these accidents are unlikely compared to accidents related to toxic exposure through the inhalation route. They are also unlikely to produce the same harmful/lethal consequences in the event that they do occur.

143 130 Overall, evidence from past accidents and analysis of possible accident scenarios suggest that it may be justifiable to apply a different approach to controlling major hazards related to substances classified as acute toxic 3 dermal compared to that which applies for acute toxic 3 inhalation substances. 8.6 Potential costs and benefits of a change in scope The two key elements that are of importance in assessing the economic implications of the possible change to the directive are (a) the number of establishments potentially affected, including establishments newly covered by the directive and those with increased requirements due to a change in tier or additional safety report requirements; and (b) the additional cost per establishment related to the possible changes to the directive, compared to the baseline situation. In relation to the per-establishment costs, the data used in the Commission s 2010 Impact Assessment accompanying the proposal for the (now) Seveso III directive provide a good starting point. However, additional information has been sought and analysed in the current study in order to provide a range of cost estimates, in order to help explore the sensitivity of the results to the source of information used. In terms of the number of establishments potentially affected, the current study has identified a range of information that has been used in arriving at an estimate of the likely scale of additional requirements for industry. Establishments in different situations have been considered, such as those newly coming into the scope, those changing tier and those which would only have additional requirements due to inclusion of a new substance to their existing relevant inventories. It should be understood that it is not considered possible to derive a fully accurate estimate of the number of establishments that would be affected, and this has been confirmed by the major EU trade associations and some of the largest suppliers of the relevant chemicals. Nonetheless, the analysis presented in this report is considered to have allowed reasonably accurate estimates to be derived, which are expected to be more robust than those developed in the analysis prior to the Seveso III directive s introduction (which had a much wider remit/focus). Overall, the most significant costs would be associated with establishments newly coming into the scope of the directive, particularly those that would become upper tier establishments. It is estimated that as many as 500 establishments could newly come into the scope of the directive, with some being upper tier and others lower tier 64. Only a modest number (15-30) of establishments would be expected to change tier as a result of a change in scope, based on extrapolation from data in France and the UK. There would also be a substantial number of existing establishments (estimated as around 200) which could be affected by a change in scope due to the need to address additional substances, but which would not change tier. Using data from consultation for the current study and from the Commission s previous (2010) Impact Assessment for per-establishment costs, it is estimated that the overall additional costs of the change in scope to establishments 64 This estimate is likely to be conservative i.e. relatively high, given that the total number of existing Seveso establishments was around 10,000 in 2011 (500 represents 5% of this figure).

144 131 could be around 10 million per year (as an equivalent annualised cost). Other sources of data suggest that the costs could be substantially higher (e.g. 30m per year based on data from the UK authorities or 60m based on data related to the German chemical industry). In practice, the actual costs will vary significantly by establishment and amongst Member States. Furthermore, the quantified costs do not include likely changes that would be required in terms of technical modifications to plant/equipment, which are considered too variable and uncertain to quantify. The above cost estimates are based on the central estimate of number of establishments affected and the actual range of costs could be wider. However, overall it is estimated that the costs to operators associated with a change in the directive is in the range 10 to 60 million per year. In addition to this there would be administrative costs for competent authorities associated with adapting regulatory regimes to deal with an amended Annex I in general; regulating (including inspecting) an increased number of establishments due to those newly coming into the scope of the directive (as well as external emergency plans for upper tier establishments); and costs associated with reviews and additional scope of substances covered for establishments already included within the scope and for developing emergency plans. These costs are estimated at 4 million overall ( 3-5 million range). One way of comparing these costs to the potential benefits is to ask whether incurring these costs can be justified in terms of the potential harm to humans and the environment that would be avoided. The concept of the value of a statistical life (VOSL) puts a monetary value on the willingness to accept slightly higher or lower levels of risk. The above cost estimates for operators are equivalent to between 5 and 60 times the VOSL estimates provided in the Impact Assessment guidelines, implying that this number of fatal accidents would need to be avoided in order for the benefits of including these substances to outweigh the risks of not imposing this additional level of regulation (taking into account fatalities alone). However, it should be noted that the substances affected by a change in scope could also have other effects in the event of an accident and these effects are not taken into account in the above, which relates only to acute mortality effects in humans Accidents involving the substances could, for example, cause damage to the environment as well as mortality effects on humans. For example, substances that are also classified as aquatic acute 2/3 or chronic 3/4 are not covered by Seveso but could still cause damage, even if not to the extent that this is considered a major-accident to the environment. Similarly, substances that are aquatic acute 1 or chronic 1 at establishments with inventories of t have the potential for environmental damage in the event of an accident, even if these quantities are not sufficiently high to be covered by Seveso in relation to the potential for major accidents. Bringing these substances/establishments into the scope could reduce the risks of environmental damage through improved safety management systems, and there would therefore be more benefits than simply avoided deaths (which is the only thing that the VOLY measures). Likewise, the risks of other adverse impacts for example related to injury or to property damage would potentially be reduced through the additional process controls brought in by being a Seveso establishment.

145 Conclusions on the merits of a change in scope Overall, it is clear that the costs of including acute toxic 3 dermal substances in the scope of Seveso could be significant, so it is important that there would be benefits in terms of reduced risks of death and injury to people onsite and off-site at establishments that would be affected. A review of past accidents indicates that significantly more accidents in recent years involved the inhalation exposure route than the dermal exposure route and accidents involving the toxic dermal exposure route tend to lead to lower human consequences than those involving the toxic inhalation exposure route. Likewise, consideration of a number of accident scenarios involving substances relevant for acute toxicity via the inhalation and dermal routes suggests that serious accidents involving the latter are less likely to occur and are also unlikely to produce the same harmful/lethal consequences in the event that they do occur. Nonetheless, future major accidents involving acute toxic 3 dermal substances cannot be definitively ruled out.

146 A1 Appendix A Compiled accident database The table overleaf presents the compiled database of 794 accidents referred to in Section of the main report.

147 Appendix A - Sheet 1 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 1 X X 10/11/2002 Petrochemical / Oil Refineries Valve leak Hydrogen fluoride Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A Unknown X X 07/01/2010 Not know/applicable Fall of an IBC container Hydrogen fluoride Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A Unknown during reactor load operation 3 X X 24/05/2011 Wholesale and retail storage and Drum pierced during Piperidine Acute tox 3* Acute tox 3* distribution (excluding LPG) loading activities 4 x x 03/06/2002 Plastic and rubber manufacture Valve leak Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown x x 17/03/2004 General chemical manufacture (not included Suspected inclompete Ammonia Acute tox 3* Skin Corr. 1B above) combustion of a release at the flare during emergency shut down 6 x x 04/01/2005 Wholesale and retail storage and Valve leak Ammonia Acute tox 3* Skin Corr. 1B distribution (excluding LPG) 7 x x 12/02/2005 General chemical manufacture (not included Pipe leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A above) 8 x x 22/03/2005 General chemical manufacture (not included Filter leak Unknown Unknown above) 9 x x 29/12/2005 Waste treatment, disposal Unknown Hydrogen sulfide Acute tox 2* x x 17/05/2006 Petrochemical / Oil Refineries Flange leak Mercaptan Unknown x x 24/03/2007 Processing of metals Leak from the exhaust air Chromium as trioxide Acute tox 3* Acute tox 3* Acute tox 2* 1 On site: soil contamination/ Offsite: contaminated Disposal of the contaminate sludge system of a galvanic sewage sludge hazardous waste installation 12 x x 18/06/2007 Petrochemical / Oil Refineries Failure in the flare Hydrogen sulfide Acute tox 2* system due to overpressure Nitric acid got contact 13 x x 01/01/2008 Processing of metals using electrolytic or Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B chemical processes with mettalic parts during operations - formation of nitrous gases Fire 14 x x 28/03/2008 Processing of metals using electrolytic or Potassium cyanide Acute tox 1-2 Acute tox 1-2 Acute tox chemical processes 15 x x 28/05/2009 Chemical installations - other fine chemicals Pipeline leak Hydrochloric acid Skin Corr. 1B x x 11/07/2009 Processing of metals using electrolytic or Fire Chromium trioxide Acute tox 3* Acute tox 3* Acute tox 2* Skin Corr. 1A chemical processes 17 x x 26/01/2002 General chemical manufacture (not included Decomposition process Unknown Unknown above) in a fertiliser silo 18 Spain x 17/07/2003 General chemical manufacture (not included Fire of sodium Chlorine Acute tox 3* Unknown Unknown 1 above) dichlorisocyanurate 19 Spain x 11/02/2004 General chemical manufacture (not included Rupture of a bursting Chlorine Acute tox 3* above) disk on a chlorine reactor 20 Spain Salamanca 10/09/2007 General chemical manufacture (not included Decomposition of urea in Ammonia Acute tox 3* Skin Corr. 1B above) a dryer of the NPK plant 21 x x 12/06/2001 General chemical manufacture (not included Unloading pipe leak Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B On site: soil pollution Remediation measures for polluted above) soil 22 x x 10/09/2002 Waste treatment, disposal Fire in underground Unknown (Fumes) Unknown Unknown Unknown 1 The facility have to be closed waste storage facility 23 France Le Havre 05/08/2002 General chemical manufacture (not included Transport pipe leak Acidic water Unknown On site soil pollution Remediation measures for polluted above) soil 24 x x 08/01/2003 General chemical manufacture (not included Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B above) 25 x x 14/10/2003 General chemical manufacture (not included Release during transfert Benzotrichloride Acute tox 4* 0 Acute tox 3* On site soil pollution Remediation measures for polluted above) operations soil 26 France x 12/01/2003 General chemical manufacture (not included Release from a Chlorine Acute tox 3* kg above) distillation column 27 France x 12/01/2004 General chemical manufacture (not included Fire Chlorine Acute tox 3* kg above) 28 France Feyzin 26/06/2004 Petrochemical / Oil Refineries Failure in the flare Sulfur dioxide Acute tox 3* Skin Corr. 1B kg Uknown system 29 x x 27/06/2005 Production and storage of pesticides, Fire in a nearby Unknown Unknown Suspension of business of biocides, fungicides installation kg (of one day for several various companies in the vicinity dangerous and non dangerous products) 30 x x 05/09/2006 Petrochemical / Oil Refineries Unknown Hydrogen sulfide Acute tox 2* kg (CO and H2S) 31 x x 01/01/2007 Production and storage of fertilizers Valve leak Hydrazine Acute tox 3* Acute tox 3* Acute tox 3* kg Release in the water - pollution thresholds reached Remediation measures for polluted during ten days in lagoon water 32 x x 05/01/2009 Petrochemical / Oil Refineries Unknown Hydrogen sulfide Acute tox 2* Unknown 0 33 UK x 13/01/2001 Production and storage of pesticides, Overfilling of a storage Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B kg 0 disposal of waste, cost of contractors biocides, fungicides tank to assist clean up 34 x x 29/05/2003 Petrochemical / Oil Refineries Pipe leak Hydrogen fluoride Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A kg 35 x x 02/01/2009 Production and storage of pesticides, Phosphine Acute Tox. 2 Skin Corr. 1B 0 0 Unknown kg biocides, fungicides 36 x x 10/09/2002 Petrochemical / Oil Refineries Unloading operation of Hydrogen sulfide Acute tox 2* Unknown 0 catalyst from a blinded reactor 37 x x 30/09/2005 General chemical manufacture (not included Operating error during Hydrogen fluoride Acute Tox. 2 Acute tox 1 Acute tox 2* Skin Corr. 1A Unknown above) works on pipe 38 x x 18/04/2006 Processing of metals Operating error during Blast furnace gas Unknown Unknown 0 works on pipe 39 Netherlands x 05/01/2004 General chemical manufacture (not included Operating error during Chlorine Acute tox 3* Unknown l above) maintenance works on a pipe 40 x x 28/02/2004 Petrochemical / Oil Refineries Storage tank leak Reformate Benzene m3 Hardcut (RBHC) 41 x x 05/01/2005 Processing of metals Pipe leak Carbon monoxide Acute Tox. 3 * kg 42 x x 15/03/2006 Processing of metals Valve leak Carbon monoxide Acute Tox. 3 * Unknown 43 x x 27/04/2007 General chemical manufacture (not included Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown kg Unknown above) 44 x x 14/01/2001 Ceramics (bricks, pottery, glass, cement, Valve leak Unknown Unknown m3 On site soil pollution; offsite: pollution of the sea and Minor effects on biological life Unknown etc.) 300 m of a beach 45 x x 23/08/2007 Chemical installations - ammonia Unknown Carbon monoxide Acute Tox. 3 * Unknown 46 Sweden Helsinborg 04/02/2005 General chemical manufacture (not included Rupture of a sulfuric acid Hydrochloric acid Skin Corr. 1B Unknown Heavy pollution in the harbor and in its surroundings, Unknown above) cistern - acid mixed with impacts on flore and fauna water 47 x x 16/11/2006 Processing of ferrous metals (foundries, Failure of the furnace Carbon monoxide Acute Tox. 3 * Unknown smelting, etc.) system due to loss of power 48 x x 23/12/2001 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 49 USA Sheldon 07/01/2002 Agriculture Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown Heavy pollution of the river along 32 km, all the fishes Unknown are killed 50 x x 16/01/2002 Production and manufacturing of pulp and Pipe leak Hydrogen sulfide Acute tox 2* Unknown paper 51 x x 11/04/2003 Manufacture of food products and Explosion Ammonia Acute tox 3* Skin Corr. 1B 0 Unknown Unknown beverages 52 USA Woodlawn, Ohio 14/12/2010 Not know/applicable Flange leak Hydrochloric acid Skin Corr. 1B Unknown 53 INDIA Calcultta 05/12/2000 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B unknown 1 Unknown beverages 54 USA Unknown 05/11/2000 Production of pharmaceuticals Small content spill Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 1 Unknown 0 Unknown 0 Unknown 55 USA Sonora, Texas 05/11/2000 Wholesale and retail storage and Fire Unknown (Fumes) Unknown Unknown distribution 56 CANADA Alberta 31/10/2000 General chemical manufacture (not included Burst disk Unknown (Fumes) Unknown Unknown above) 57 UK Gloucestershire 30/10/2000 General chemical manufacture (not included Drum leak Unknown Unknown Unknown Release in the river above) 58 USA Richmond 26/10/2000 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 59 Turkey Diyarbakir 19/10/2000 Water and sewage (collection, supply, Unknown Chlorine Acute tox 3* Unknown treatment) 60 USA Albany 05/10/2000 Titanium process plant Fire Chlorine Acute tox 3* Unknown 61 USA Monticello, New 04/10/2000 General chemical manufacture (not included Fire Unknown (Fumes) Unknown Unknown Release in the runoff water York above) 62 USA West Chester, Ohio 03/10/2000 Plastic and rubber manufacture Unknown (Fumes) Unknown Unknown 63 USA Bonita, Los Angeles 30/09/2000 Textiles manufacturing treatment Tank leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 64 USA New York 14/09/2000 General chemical manufacture (not included Unwaited chemical Dimethoate Acute tox 4* 0 Acute tox 4* Unknown 0 above) reaction 65 USA Bowling Green 13/09/2000 Plastic and rubber manufacture mixing Sulphuric acid Skin Corr. 1A Unknown 0 66 Mexico Salamanca 12/09/2000 Production and storage of pesticides, Explosion/fire Malathion Unknown Acute tox 4* 0 1 biocides, fungicides 67 USA Milwaukee 07/09/20000 Water and sewage (collection, supply, Fire Unknown (Fumes) Unknown Unknown treatment)

148 Appendix A - Sheet 2 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 68 USA New York 29/08/2000 Handling and transportation centres (ports, Rail tank leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 69 UK Southampton 17/08/2000 Not know/applicable fall in a chemical tank Unknown Unknown USA Honolulu 10/08/2000 Not know/applicable mixing phosphoric acid Chlorine Acute tox 3* kg 0 and bleach 71 Thailand Samut Prakarn 08/08/2000 Not know/applicable Cleaning operation of an Unknown Unknown Unknown 0 ol vessel 72 USA Temple, Texas 03/08/2000 Wholesale and retail storage and Fire Unknown (Fumes) Unknown Unknown Runoff spilled in a creek and kill fishes distribution 73 USA Bentonville 02/08/2000 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 74 USA Phoenix 02/08/2000 Wholesale and retail storage and Fire Unknown (Fumes) Unknown Unknown 100 M$ distribution 75 USA Chicago 24/07/2000 General engineering, manufacturing and Unknown Nitric acid Skin Corr. 1A Unknown assembly 76 Canada Montreal 17/07/2000 Chemical installation - inorganic acids Fire Unknown Unknown Unknown 77 USA Lancaster 10/07/2000 Manufacture of food products and Safety valve Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 78 USA Tooele 06/07/2000 Not know/applicable Pipe leak Sulphuric acid Skin Corr. 1A Unknown 0 79 USA Bayport, Texas 05/07/2000 General chemical manufacture (not included Reactor explosion Glycidol Acute tox 4* Acute tox 4* Acute tox 3* Unknown 0 above) 80 USA Columbia 02/07/2000 Not know/applicable Container leak Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 0 81 Pakistan Lahore 28/06/2000 Chemical installations - ammonia Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown 82 USA South Elgin 13/06/2000 Processing of metals Valve leak Unknown Unknown Unknown 83 Peru Choropampa 02/06/2000 Handling and transportation centres (ports, Unknown Mercury Acute Tox Unknown airports, etc.) and Transport 84 China Taizihe, Liaoning 26/05/2000 General chemical manufacture (not included Explosion of a barrel Unknown Unknown Unknown above) 85 USA St Tammany Parish 26/05/2000 Building and works of engineering Unearthed a blue Unknown (Fumes) Unknown Unknown construction container 86 USA Phoenix, Arizona 24/05/2000 Plastic and rubber manufacture Valve leak 2-ethyl-2 oxoline Unknown Unknown Cleaning cost inside the site 87 USA Orlanda, Florida 24/05/2000 Handling and transportation centres (ports, Tank truck leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 88 Ukraine Cherkassy region 20/05/2000 Handling and transportation centres (ports, Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 89 UK East Sussex 16/05/2000 Power supply and distribution Fire Unknown (Fumes) Unknown Unknown 90 USA Twin City 12/05/2000 General chemical manufacture (not included Unknown Hydrofluoric acid Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A l above) 91 USA Adrian 05/05/2000 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 92 USA Bossier city 28/04/2000 Not know/applicable Entry into confined space Naphta Unknown Unknown 93 USA Notrth Charleston 27/04/2000 Manufacture of food products and Explosion Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 94 USA Aberdeen 23/04/2000 Medical, research, education (including, Unknown Ethylene oxide Acute tox 3* Unknown hospitals, university, etc.) 95 USA San Jose 16/04/2000 Building and works of engineering Unknown Nitric acid Skin Corr. 1A Unknown construction 96 Czech Chrudim 13/04/2000 Manufacture of food products and Fire Unknown (Fumes) Unknown Unknown Republic beverages 97 USA Dothan, Alabama 11/04/2000 Production and storage of fertilizers Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 98 USA Somerset 10/04/2000 Not know/applicable Copying machine Unknown Unknown Unknown 99 Canada Scarborough, 09/04/2000 General chemical manufacture (not included Fire Hexane Unknown Ontario above) 100 USA Port Royal 06/04/2000 Not know/applicable Pressure relief valve Organophosphates Unknown Unknown (fumes) 101 USA Choudrant, Los 30/04/2000 Handling and transportation centres (ports, Tank truck collision Isobutyronitrile Acute tox2-3 Acute tox Unknown Angeles airports, etc.) and Transport 102 Canada Calgary, Alberta 28/03/2000 Handling and transportation centres (ports, Road tanker spill Sodium hydroxide Skin Corr. 1A l Spill in the sewer airports, etc.) and Transport 103 Germany Unknown 27/03/2000 Handling and transportation centres (ports, Unknwon Styrene Acute tox 4* Unknown airports, etc.) and Transport 104 USA Jackson, Mississipi 25/03/2000 Agriculture Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 105 USA Lily 23/03/2000 Not know/applicable mixing Chlorine Acute tox 3* Unknown 106 Canada Ontario 20/03/2000 Refinery Flare failure Hydrogen sulfide Acute tox 2* Unknown 107 Canada New Brunswick 14/03/2000 Medical, research, education (including, Cooler unit leak Styrene Acute tox 4* Unknown hospitals, university, etc.) 108 Singapore Rayong 08/03/2000 Plastic and rubber manufacture Pipe leak Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown 109 UK Cheschire 08/03/2000 General chemical manufacture (not included Explosion Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown above) 110 USA Clifton 01/03/2000 Not know/applicable Mixing Unknown Unknown Unknown 111 USA Unknown 29/02/2000 Not know/applicable Mixing Chlorine Acute tox 3* Unknown 112 Australia Gulgong 29/02/2000 Not know/applicable Cylinder leak Aluminium phosphide Acute Tox. 2 * Unknown 113 USA Vicksburg 23/02/2000 Handling and transportation centres (ports, Tank truck leak Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B l airports, etc.) and Transport 114 USA Texas 17/02/2000 Chemical installation - inorganic acids Pump failure Acrolein Acute tox 3* Acute tox 3* Acute tox 3* kg 115 USA Mineapolis 04/02/2000 General engineering, manufacturing and Pipe leak Hydrochloric acid Skin Corr. 1B Unknown assembly 116 USA Salt Lake City 01/02/2000 Not know/applicable Drum leak Sodium hydroxide Skin Corr. 1A l 117 USA Unknown 01/02/2000 Handling and transportation centres (ports, Road tanker leak Lead and Chromium Unknown Unknown airports, etc.) and Transport 118 Japan Fuji 30/01/2000 Handling and transportation centres (ports, Road tanker Acrylic acid Acute tox 4* Acute tox 4* Acute tox 4* Unknown airports, etc.) and Transport 119 USA Unknown 20/01/2000 Handling and transportation centres (ports, Road tanker Phosphoric acid Skin Corr. 1B Unknown airports, etc.) and Transport 120 Venezuela La Guaira 13/01/2000 Handling and transportation centres (ports, Major floods Unknown Unknown Unknown 0 1 Unknown Relase in soil and water airports, etc.) and Transport 121 Japan Tokyo 13/01/2000 General chemical manufacture (not included Unknown Sodium hydroxide Skin Corr. 1A l Unknown above) 122 USA Unknown 12/01/2000 Not know/applicable Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 123 China Bao'an 22/02/2012 Handling and transportation centres (ports, Tank truck leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 124 Thailand Karon 18/02/2012 Leisure activities Unknown Chlorine Acute tox 3* Unknown 125 Germany Brühl 17/01/2012 General engineering, manufacturing and mixing substances Chlorine Acute tox 3* Unknown assembly 126 Australia Michell 15/09/2011 Waste treatment, disposal Fire Unknown Unknown Unknown Limited pollution of the sewage and nearby rivers Limited costs due to decontamination 127 Russia Tcheliabinsk 01/09/2011 Handling and transportation centres (ports, Rail tank leak Bromine Acute tox 2* Skin Corr. 1A l airports, etc.) and Transport 128 China Guangzhou 20/07/2011 Production of basic organic chemicals Fire Sulfur trioxide Acute tox 3-0 Acute tox 3-0 Acute tox 1-0 Skin Corr. 1A Unknown 1B 129 Bulgaria Debeletts 11/07/2011 Handling and transportation centres (ports, Tank truck leak Styrene Acute tox 4* t airports, etc.) and Transport 130 Germany Müllheim 20/05/2011 Handling and transportation centres (ports, Rail tank leak Ethylene glycol Unknown airports, etc.) and Transport 131 Netherlands Moerdijk 05/01/2011 General engineering, manufacturing and Fire Unknown Unknown Unknown Release in soil and water assembly 132 Italia Paderno Dugnano 04/11/2010 Waste treatment, disposal Fire Unknown Unknown Unknown Release in soil and water 133 Hungary Kolontar 04/10/2010 Processing of metals Retention basin rupture Unknown Unknown m3 Heavy soil and water pollution High costs due to 2 ecosystem destroyed (TORNA and MARCAL) Remediation measures including remediation measures release of acid in the water for lowering the PH, construction of artificial dam in order to retain pollution) + impact on agricultural activities and water use + disposition for the waste mud 134 Germany Heilbronn 21/09/2010 General chemical manufacture (not included Runaway reaction Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 0 0 above) 135 Netherlands x 09/04/2010 Not know/applicable Unknown Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown 136 Porto Rico Bayamon 23/10/2009 Refinery Fire Unknown Unknown Unknown 137 Belgium Chastre 10/08/2009 Medical, Unknown Chlorine Unknown research, education (including, Acute tox 3* 0 1 Vegetation burnt in a limited area hospitals, university, etc.) 138 USA Joliet 07/08/2009 Refinery Pump leak Hydrofluoric acid Acute tox 2* Acute tox 1 Acute tox 2* Skin Corr. 1A Unknown 139 China Chifeng 05/08/2009 Production of pharmaceuticals Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown USA Swansea 15/07/2009 Wholesale and retail storage and pipe leak Ammonia Acute tox 3* Skin Corr. 1B l 1 Vegetation burnt (25 m2) distribution 141 USA Garner 09/06/2009 Manufacture of food products and pipe leak Ammonia Acute tox 3* Skin Corr. 1B 0 3 8,2 t Severe contamination of surroundings: soil and water High costs mainly due to the beverages explosion before the release 142 UK Stockton-on-tees 06/05/2009 Handling and transportation centres (ports, Operators in the vessel Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport Manufacture of food products 143 New Edendale 19/01/2009 and mixing substances Chlorine Acute tox 3* Unknown Zealand beverages 144 Seychelles Victoria 03/12/2009 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 145 USA Chesapeake 12/11/2008 Production and storage of fertilizers Vessel rupture Unknown (liquid Unknown m3 Pollution of soil and river (756 m3) Cleaning + dams built fertlizer) 146 USA Petrolia 11/10/2008 Production of basic organic chemicals Pump leak Sulphuric acid Skin Corr. 1A Unknown 147 China Hechi 07/10/2008 Processing of metals Floods Arsenic Unknown Acute Tox. 3 * Acute Tox. 3 * 0 1 Limited pollution of surroundings wells and ponds

149 Appendix A - Sheet 3 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 148 Belgium Anvers 02/09/2008 Refinery Failure of power supply Hydrogen sulfide Acute tox 2* kg 149 Morocco Casablanca 31/08/2008 Wholesale and retail storage and Fire Unknown (Fumes) Unknown Unknown distribution 150 USA Institute 28/08/2008 Production and storage of pesticides, Explosion Unknown (Fumes) Unknown Unknown biocides, fungicides 151 Germany Wuppertal 21/08/2008 General chemical manufacture (not included Failure of the fire Carbon dioxyde t above) protection system Failure of the fire 152 Germany Mönchengladbach 16/08/2008 General chemical manufacture (not included Carbon dioxyde t above) protection system 153 Germany Kulmbach 22/06/2008 Leisure activities Failure of a pressure Ammonia Acute tox 3* Skin Corr. 1B Unknown relief system 154 China Anning 13/06/2008 Production and storage of fertilizers Unknown Hydrogen sulfide Acute tox 2* Unknown 155 China Unknown 12/05/2008 Not know/applicable Earthquake Ammonia Acute tox 3* 0 Unknown 1 80 t Skin Corr. 1B Unknown Netherlands Rotterdam 22/04/2008 Not know/applicable Unknown Ammonia Acute tox 3* Skin Corr. 1B kg 157 USA Superior 01/11/2007 Waste treatment, disposal Unknown Hydrogen sulfide Acute tox 2* Unknown Belgium Moustier 24/10/2007 Production and storage of fertilizers Failure of the process Unknown (NPK Unknown Unknown decomposition) 159 Canada Holyrood 24/10/2007 Ceramics (bricks, pottery, glass, cement, Unknown Unknown (Fumes) Unknown Unknown etc.) 160 USA Melvindale 16/10/2007 General chemical manufacture (not included Vessel leak Hydrochloric acid Skin Corr. 1B m3 above) 161 Germany Francfort 05/10/2007 Wholesale and retail storage and mixing substances Chlorine Acute tox 3* kg distribution 162 Ukraine Unknown 16/07/2007 Handling and transportation centres (ports, Rail tank car leak Phosphorus Acute Tox. 2 * 0 Acute Tox. 2 * Skin Corr. 1A Unknown 900 kg recovered - Heavy pollution in 1km2 Agricultural prejudice = 109 airports, etc.) and Transport 000 dollars dollars for remediation + 2,4 millions de dollars for compensations to the victims 163 Czech Uhersky Brod 28/06/2007 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown republic 164 UK Preston 25/06/2007 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown 165 Belgium Stockem 08/06/2007 Processing of metals mixing substances Chlorine Acute tox 3* Unknown 166 USA El Paso 21/05/2007 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown 167 China Canghzou 11/05/2007 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 168 Spain Sama de Langreo 13/04/2007 oil/gas/coal extraction Fire Unknown (Fumes) Unknown Unknown 169 Spain Unknown 17/02/2007 Handling and transportation centres (ports, Unknown Unknown (NPK Unknown Unknown airports, etc.) and Transport decomposition) 170 UK Billingham 04/01/2007 Plastic and rubber manufacture Unknown Unknown Unknown Unknown 171 USA Tulare 19/10/2006 General engineering, manufacturing and Unknown Carbon monoxide Acute Tox. 3 * Unknown assembly 172 USA Apex 05/10/2006 Waste treatment, disposal mixing substances Unknown (Fumes) Unknown Unknown 173 Netherlands Rotterdam 15/09/2006 Refinery Heat exchanger Toluene Unknown 174 Spain Caldas de reis 01/09/2006 Production and storage of fertilizers Fire Unknown Unknown l 7 km of a river is polluted with high damage to the faune and flore 2 shell exploitation are closed, drinking water is forbidden during two days, 4 dams have to be built for limitating the pollution --> 1.6 M euros of cleaning and remediation M of compensations 175 China Unknown 27/08/2006 Handling and transportation centres (ports, Tank truck leak Sodium hydroxide Skin Corr. 1A Unknown Limited release in the river A dam have to be built airports, etc.) and Transport 176 USA Unknown 25/08/2006 Production and storage of fertilizers Rail tank car leak Styrene Acute tox 4* Unknown 177 Ivory Coast Abidjan 20/08/2006 Waste treatment, disposal Innapropriate Unknown Unknown , t Very heavy pollution of soil and water remediation = 30 M euros storage/treatment of toxic wastes 178 Hungary Budapest 09/08/2006 Medical, research, education (including, Fire Unknown (Fumes) Unknown Unknown hospitals, university, etc.) 179 Greece Laurion 26/07/2006 Production of basic organic chemicals Fire Unknown (Fumes) Unknown Unknown 180 USA Allentown 06/06/2006 oil/gas/coal extraction Unknown Hydrogen sulfide Acute tox 2* Unknown 181 Belgium Aalbeke 30/05/2006 Wholesale and retail storage and Fire Unknown (Fumes) Unknown Unknown distribution 182 Germany Wilhelmshaven 24/05/2006 Processing of ferrous metals (foundries, Unknown Nitric acid Skin Corr. 1A Unknown smelting, etc.) 183 China Miliang 30/04/2006 Mining activities (tailing and Failure of a storage basin Potassium cyanide Acute tox 1-2 Acute tox 1-2 Acute tox Unknown Unknown 1 Unknown Heavy pollution of a river (5 km) + drinking water physicochemical processes) dam forbidden in 5 cities 184 Iraq Mouqtadiya 19/03/2006 Manufacture of food products and Explosion Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 185 Germany Stuttgart 29/12/2005 Waste treatment, disposal mixing substances Hydrogen sulfide Acute tox 2* Unknown 186 China Jilin 13/11/2005 Production of basic organic chemicals Explosions Unknown Unknown Unknown Unknown 1 Unknown Heavy pollution in the river Amour ( km - China 1.2 billion of dollars during 5 and Russia), drinking water forbidden - Fishing years for remediation forbidden during 1 year in Russia measures 187 Germany Rhaderreistedt 08/11/2005 Waste treatment, disposal mixing substances Hydrogen sulfide Acute tox 2* Unknown 188 Austria Klagenfurt 21/05/2005 Wholesale and retail storage and Unknown (Fumes) Unknown Unknown distribution 189 China Unknown 29/03/2005 Handling and transportation centres (ports, Tank truck leak Chlorine Acute tox 3* t airports, etc.) and Transport 190 Kenya Unknown 18/03/2005 Handling and transportation centres (ports, Tsunami Unknown Unknown Unknown Unknown 1 Unknown airports, etc.) and Transport 191 China Hinschu 26/01/2005 Electronics and electrical engineering Unknown Arsine Acute Tox. 2 * Unknown 192 USA Graniteville 06/01/2005 Handling and transportation centres (ports, Rail tank car leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 193 Germany Rostock 04/01/2005 Production and storage of fertilizers Vessel rupture Ammonia Acute tox 3* Skin Corr. 1B t 194 USA Cumberland 05/11/2004 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 195 USA Alliance 02/10/2004 Not know/applicable Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown 196 USA Long beach 29/09/2004 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 197 USA Blair 27/09/2004 Handling and transportation centres (ports, Pipeline leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 198 Sri Lanka Unknown 27/09/2004 Handling and transportation centres (ports, Pipe leak Carbon monoxide Acute Tox. 3 * Unknown airports, etc.) and Transport 199 China Chenjiaying 26/08/2004 Production and storage of fertilizers Unknown Chlorine Acute tox 3* Unknown 200 Germany Essen 06/08/2004 Leisure activities Unknown Chlorine Acute tox 3* Unknown 201 Germany Hambourg 28/06/2004 Handling and transportation centres (ports, Tanker leak Sulphuric acid Skin Corr. 1A t release in the sea, fishes are killed airports, etc.) and Transport 202 China Fujian 16/06/2004 Medical, research, education (including, Unknown Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown hospitals, university, etc.) 203 Uruguay Montevideo 10/05/2004 Handling and transportation centres (ports, Tanker leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 204 China Chongqing 15/04/2004 Production and storage of fertilizers Unknown Chlorine Acute tox 3* Unknown 205 USA Dalton 12/04/2004 Not know/applicable Unknown Unknown Unknown Unknown 206 Germany Mülheim 18/02/2004 Plastic and rubber manufacture Fire Hydrochloric acid Skin Corr. 1B Unknown 207 Indonesia Gresik 20/01/2004 Production and storage of fertilizers Fire Unknown Unknown Unknown 208 Netherlands Delfizijl 05/01/2004 Production and storage of fertilizers Pipe leak Chlorine Acute tox 3* l Remediation measures (product recovered and diluted) 209 China Chuandongbei 23/12/2003 oil/gas/coal extraction Fuite sur puit Hydrogen sulfide Acute tox 2* Unknown soil pollution, Fauna killed 210 USA Glendale 17/11/2003 Wholesale and retail storage and mixing substances Chlorine Acute tox 3* Unknown distribution 211 Iraq Bagdad 05/09/2003 General chemical manufacture (not included Explosion Chlorine Acute tox 3* Unknown above) 212 USA Wichita 01/09/2003 Water and sewage (collection, supply, Valve leak Chlorine Acute tox 3* Unknown treatment) 213 UK Great Bridge 30/04/2003 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown USA Mill hall 25/04/2003 Production and storage of fertilizers Unknown Unknown Unknown Unknown 215 USA Norwich 22/04/2003 Agriculture Unknown Ammonia Unknown Acute tox 3* Skin Corr. 1B Switzerland Sierre 17/04/2003 Leisure activities Pipe leak Ammonia Acute tox 3* Skin Corr. 1B 0 Unknown Canada Sarnia 14/04/2003 Production and storage of fertilizers Unknown Unknown Unknown Unknown 218 USA Franklin 19/03/2003 Processing of metals Fire Unknown (Fumes) Unknown Unknown soil pollution 219 USA Gulfport 23/02/2003 Production and storage of fertilizers Unknown Ammonia Unknown Acute tox 3* Skin Corr. 1B 220 USA Harford County 05/02/2003 Production and storage of fertilizers Unknown Unknown Unknown Unknown Germany Lampertheim 25/01/2003 Production and storage of fertilizers Innapropriate Carbon monoxide Unknown Acute Tox. 3 * 0 equipments Unknown 222 New Auckland 23/01/2003 Not know/applicable Trichloroethylene Unknown Zealand 223 Netherlands Rotterdam 16/01/2003 Fuel storage (including heating, retail sale, Vessel rupture O-cresol Acute tox 3* Acute tox 3* 0 Skin Corr. 1B Unknown t of soil polluted Cleaning costs etc.) 224 USA Garyville 13/01/2003 Refinery Fire Unknown (Fumes) Unknown Unknown 225 Russia Novokuibyshevsk 08/01/2003 Production Unknown 2-methyl-1,3-butadiene Unknown of basic organic chemicals USA Houston 28/12/2002 Production and storage of fertilizers Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 227 Netherlands Pays-Bas 17/12/2002 Production and storage of fertilizers mixing substances Hydrochloric acid Skin Corr. 1B 0 12 Unknown UK Wirral 11/11/2002 Manufacture of food products and Valve leak Ammonia Skin Corr. 1B Unknown Acute tox 3* beverages 229 China Huajin 06/11/2002 Production and storage of fertilizers Vessel leak Sodium carbonate Unknown

150 Appendix A - Sheet 4 ID Country Location Date Main activity of the establishment Cause Main substance involved CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured classification - classification - Acute classification - Acute tox classification - Acute tox oral tox dermal inhalation Unknown Preventive hospitalisation /medical advice/incom modé Exposure Oral Exposure Dermal (confirmed) Exposure Dermal (suspected) Exposure Inhalation Exposure Exposure No exposure Skin corrosion Exposure Unknown Release quantity Environmental impact (scale) Proprety/economic impact (scale) Long term Environmental impact (scale) Remediation measures ( ) 230 USA Middletown 28/10/2002 Building and works of engineering Unknown Carbon monoxide Acute Tox. 3 * Unknown construction 231 China Wuhai city 27/10/2002 Production and storage of fertilizers Hose leak Chlorine Acute tox 3* Unknown 232 Vietnam Nam Kang 25/10/2002 Textiles manufacturing treatment Unknown Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 233 USA South Elgin 14/10/2002 Textiles manufacturing treatment Unknown tetrachloroethylene Unknown 234 UK Fountainbridge 27/09/2002 Manufacture of food products and Unknown Unknown Unknown Unknown beverages 235 USA Charlotte 17/09/2002 Wholesale and retail storage and Unknown aminoiminomethanesul Acute tox Acute tox Unknown distribution phinic acid 236 USA Jersey city 17/09/2002 Wholesale and retail storage and Container leak Hydrogen peroxide Acute tox 4* 0 Acute tox 4* Skin Corr. 1A Unknown distribution 237 China Guangdong 16/09/2002 General engineering, manufacturing and Unknown Unknown Unknown Unknown assembly 238 USA Freeport 13/09/2002 Textiles manufacturing treatment Explosion Cyclohexanone Acute tox 4* Unknown 239 Greece Aghioi Theodori 10/09/2002 Refinery Vessel cleaning Hydrogen sulfide Acute tox 2* Unknown 240 USA New Britain 10/09/2002 Electronics and electrical engineering inadequate protection Turpentine oil Acute tox 4* Acute tox 4* Acute tox 4* Unknown during work 241 Germany Bad Münder am 09/09/2002 Handling and transportation centres (ports, Rail tank car rupture epichlorhydrin Acute Tox. 3 * Acute Tox. 3 * Acute Tox. 3 * Skin Corr. 1B Unknown Desiter airports, etc.) and Transport 242 USA Jacksonville 07/09/2002 Handling and transportation centres (ports, Rail tank car leak Sulphuric acid Skin Corr. 1A Unknown airports, etc.) and Transport 243 USA Gainesville 19/08/2002 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 244 USA Hallowel 01/08/2002 Production and storage of fertilizers Unknown Nitric acid Skin Corr. 1A Unknown 245 UK Castleford 25/07/2002 Production and storage of fertilizers Error in mantenance p-toluidine Acute Tox. 3 * Acute Tox. 3 * Acute Tox. 3 * t prodedures 246 USA Irving 22/07/2002 General engineering, manufacturing and Unknown Carbon monoxide Acute Tox. 3 * Unknown assembly 247 USA Cosmopolis 11/07/2002 Not know/applicable Unknown Chlorine Acute tox 3* Unknown 248 USA Marlow 11/07/2002 oil/gas/coal extraction Unknown Sodium hydroxide Skin Corr. 1A Unknown 249 USA Des Moines 08/07/2002 Water and sewage (collection, supply, Unknown Hydrogen sulfide Acute tox 2* Unknown treatment) 250 Japan Kochi 02/07/2002 Production and storage of fertilizers Explosion Chlorine Acute tox 3* Unknown 251 USA Saint Cloud 26/06/2002 Leisure activities Valve leak Chlorine Acute tox 3* kg 252 Canada Kignsville 20/06/2002 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown Soil polluted 253 USA McDonald 14/06/2002 Processing of metals Vessel rupture Hydrochloric acid Skin Corr. 1B Unknown 254 Canada Montreal 13/06/2002 Textiles manufacturing treatment Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 255 Japan Kurume 10/06/2002 Waste treatment, disposal Fabrication d'articles de Hydrogen sulfide Acute tox 2* Unknown textiles, sauf habillement 256 Australia Drawin 07/06/2002 Production and storage of fertilizers mixing substances Unknown Unknown Unknown 257 Thailand Unknown 31/05/2002 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 258 Peru Lima 24/05/2002 Production and storage of fertilizers Hose leak Nitric acid Skin Corr. 1A Unknown 259 New Hornby 20/05/2002 Manufacture of food products and Failure of a pressure Ammonia Acute tox 3* Skin Corr. 1B Unknown Zealand beverages relief system 260 USA Chino 15/05/2002 Plastic and rubber manufacture Fire Unknown Unknown Unknown 261 USA Arlington 13/05/2002 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 262 USA Angels camp 22/04/2002 Waste treatment, disposal Unknown Chlorine Acute tox 3* Unknown 263 USA Burns harbor 19/04/2002 Not know/applicable Unknown Hydrochloric acid Skin Corr. 1B Unknown 264 UK Londres 04/04/2002 Not know/applicable Unknown methylene chloride Unknown 265 USA Forth Worth 03/04/2002 Production and storage of fertilizers Fire Naphtalene sulfate Unknown Unknown 266 USA Norcross 01/04/2002 Production and storage of fertilizers Drum leak Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 267 USA Claymont 18/02/2002 Production and storage of fertilizers Failure of a pressure Hexane Unknown relief system 268 China Unknown 03/02/2002 Mining activities (tailing and Unknown Carbon monoxide Acute Tox. 3 * Unknown physicochemical processes) 269 Spain Carthagene 27/01/2002 Production and storage of fertilizers Decomposition NPK Unknown (NPK Unknown Unknown decomposition) 270 USA Minot 18/01/2002 Handling and transportation centres (ports, Rail tank car leak Ammonia Acute tox 3* Skin Corr. 1B m tonnes of soil polluted, heavy pollution in a airports, etc.) and Transport pond 271 USA Holt 17/01/2002 Production and storage of fertilizers Unknown Biphenyl Unknown 272 USA Pennington 16/01/2002 Production and manufacturing of pulp and mixing substances Hydrogen sulfide Acute tox 2* Unknown paper 273 USA Madison 23/12/2001 Manufacture of food products and Vessel leak Ammonia Acute tox 3* Skin Corr. 1B l beverages 274 USA Lake Wales 17/12/2001 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 275 USA Algona 14/12/2001 Handling and transportation centres (ports, Pipe leak Ammonia Acute tox 3* Skin Corr. 1B t Heavy pollution in a river (50 km) Fish and fauna are airports, etc.) and Transport killed 276 China Pekin 22/11/2001 Production and storage of fertilizers Runaway reaction Aniline Acute Tox. 3 * Acute Tox. 3 * Acute Tox. 3 * Unknown 277 USA Keraneysville 15/11/2001 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 278 USA West Palm 12/11/2001 Manufacture of food products and mixing substances Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown beverages 279 Canada Calgary 06/11/2001 General engineering, manufacturing and Fire Unknown (Fumes) Unknown Unknown assembly 280 USA Morro bay 03/10/2001 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B l beverages 281 Switzerland Boudry 28/08/2001 Electronics and electrical engineering Unknown Hydrochloric acid Skin Corr. 1B Unknown 20 M euros dam + 4 pump have to be implemented 282 USA Phoenix 15/08/2001 Processing of metals mixing substances Chlorine Acute tox 3* Unknown 283 USA El Paso 08/08/2001 Refinery Pipe leak Sulphuric l acid 0 Skin Corr. 1A USA Anniston 30/07/2001 Not know/applicable Unknown Nitric acid Skin Corr. 1A Unknown 285 USA Manchester 26/07/2001 Wholesale and retail storage and Fire Chlorine Unknown Acute tox 3* 0 1 distribution 286 USA Delaware city 17/07/2001 Refinery Vessel rupture Sulphuric acid Skin Corr. 1A m3 Heavy pollution in the river: 2500 fishes et 250 crabs are killed 287 UK Newport 16/07/2001 Waste treatment, mixing substances Hydrogen sulfide m3 disposal Acute tox 2* USA Riverview 14/07/2001 Production and storage of fertilizers Unloading arm leak methyl mercaptan Acute tox 3* Unknown 289 USA Tulsa 11/07/2001 General chemical manufacture (not included Vessel leak Arsine Unknown Acute Tox. 2 * above) 290 USA Three rivers 09/07/2001 Refinery Explosion Hydrofluoric acid Acute tox 2* Acute tox 1 Acute tox 2* Skin Corr. 1A Unknown 291 Kuwait Kuwait city 01/07/2001 Refinery Unknown Unknown Unknown Unknown USA Beauverton 07/06/2001 Electronics Unknown Chlorine Unknown and electrical engineering Acute tox 3* South Durban 28/05/2001 Refinery Unknown Hydrofluoric Acute tox 2* 0 1 Unknown Africa acid Acute tox 2* Acute tox 1 Skin Corr. 1A keuros for remediation, 130 k for firefighter intervention costs and 10,2 M of penalty for ecological damage 294 China Zhanjiang 27/05/2001 General chemical manufacture (not included Vessel rupture Sulphuric acid Skin Corr. 1A t above) 295 Germany Ludwigshafen am 21/05/2001 General chemical manufacture (not included Fire Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B kg rhein above) 296 Pakistan Sukkur 10/05/2001 Production of basic organic chemicals Pipe explosion Ammonia Acute tox 3* Skin Corr. 1B Unknown 297 USA Milwaukee 07/05/2001 Leisure activities Drum leak Chlorine Acute tox 3* Unknown 298 USA Moody 25/02/2001 Production of basic organic chemicals Fire Unknown (Fumes) Unknown unknown 299 UK Tamworth 06/02/2001 Production and storage of fertilizers Vessel leak Hydrochloric acid Skin Corr. 1B unknown 300 Canada Red Deer 02/02/2001 Handling and transportation centres (ports, Rail tank car leak Ammonia Acute tox 3* Skin Corr. 1B unknown airports, etc.) and Transport 301 Roumania Falticeni 17/01/2001 General chemical manufacture (not included Unknown Potassium cyanide Acute tox 1-2 Acute tox 1-2 Acute tox Unknown River polluted several tonnes of fishes are killed. Ten above) sheeps are killed 302 USA Norrisville 16/01/2001 Electronics and electrical engineering Unknown Dihydrogen selenide Acute Tox Unknown 303 USA Chelsea 03/01/2001 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 304 China Jiande 17/12/2000 Handling and transportation centres (ports, Road tank leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 305 USA Oshkosh 16/12/2000 Handling and transportation centres (ports, Rail tank car leak Sodium hydrosulphite Unknown airports, etc.) and Transport 306 USA Allentown 04/12/2000 Production and storage of fertilizers Fire Unknown (Fumes) Unknown Unknown 307 USA Sheboygan 02/12/2000 Production and storage of fertilizers Unknown Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 308 Russia Ufa 24/11/2000 Production and storage of fertilizers Unknown Hydrogen sulfide Acute tox 2* Unknown 309 Germany Ludwigshafen am 23/11/2000 General chemical manufacture (not included Failure of the process Phenylphosphine Acute Tox. 3 Acute Tox. 3 Acute Tox Unknown rhein above) 310 USA Deer Park 12/11/2000 Refinery Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 311 USA Horn lake 06/11/2000 Production of pharmaceuticals Unknown Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown 312 USA Granger 05/11/2000 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown 313 USA Aberdeen 02/11/2000 Production and storage of fertilizers mixing substances Unknown (Fumes) Unknown Unknown 314 India Udumplet 01/11/2000 Production and storage of fertilizers Unknown Chlorine Acute tox 3* Unknown 315 USA Richnmond 26/10/2000 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 316 Belgium Gand 23/10/2000 Production and storage of fertilizers Failure of the process Hydrochloric acid Skin Corr. 1B Unknown 317 Turkey Diyarbakir 19/10/2000 Water and sewage (collection, supply, Unknown Chlorine Acute tox 3* Unknown treatment) 318 USA Albany 04/10/2000 Processing of non-ferrous metals (foundries, Unknown Chlorine Acute tox 3* Unknown smelting, etc.) 319 Canada Mildred Lake 03/10/2000 Not know/applicable Unknown Hydrogen sulfide Acute tox 2* Unknown 320 USA Bonita 30/09/2000 Not know/applicable Vessel leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 321 USA Stratford 30/09/2000 Production and storage of fertilizers Unknown Unknown (Fumes) Unknown Unknown 322 USA New York 14/09/2000 Production and storage of fertilizers Uncontrolled reaction Dimethoate Unknown 323 USA Bowling green 13/09/2000 Plastic and rubber manufacture Uncontrolled reaction Sulphuric acid Skin Corr. 1A Unknown

151 Appendix A - Sheet 5 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 324 Mexico Salamanca 12/09/2000 Production and storage of fertilizers Failure of the pressure Malathion Unknown relief system 325 Germany Ibbenbüren 14/08/2000 Production of basic organic chemicals Failure of the process Chlorine Acute tox 3* Unknown 326 USA Fairmont 25/07/2000 Leisure activities Unknown Chlorine Acute tox 3* m3 327 USA Lancaster 10/07/2000 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 328 USA Tooele 06/07/2000 Production and storage of explosives Pipe leak Sulphuric acid Skin Corr. 1A Unknown 329 USA Rancho Mirage 04/07/2000 Leisure activities Unknown Chlorine Acute tox 3* Unknown 330 USA Columbia 03/07/2000 Medical, research, education (including, Drum leak Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown hospitals, university, etc.) 331 Kuwait Shoubaïa 18/06/2000 Refinery Unknown Hydrogen sulfide Acute tox 2* Unknown 332 Roumania Turnu Magurele 14/06/2000 Production and storage of fertilizers Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown 333 UK Farlington 25/05/2000 Production and storage of fertilizers Fire Unknown Unknown Unknown 334 USA Twin city 12/05/2000 Production of basic organic chemicals Unknown Hydrofluoric acid Acute tox 2* Acute tox 1 Acute tox 2* Skin Corr. 1A l 335 USA Trenton 10/05/2000 Processing of metals mixing substances Unknown Unknown Unknown 336 Colombia Cali 10/05/2000 Not know/applicable Unknown Unknown Unknown Unknown 337 USA Dothan 12/04/2000 Production and storage of fertilizers Vessel leak Ammonia Acute tox 3* Skin Corr. 1B m3 338 USA Newton 11/04/2000 Medical, research, education (including, Unknown hydrochloric acid Skin Corr. 1B Unknown hospitals, university, etc.) 339 USA Two rivers 06/04/2000 Water and sewage (collection, supply, Valve leak Chlorine Acute tox 3* Unknown treatment) 340 UK Runcorn 08/03/2000 Plastic and rubber manufacture Unknown Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A t 341 Thailand Map Ta Phut 06/03/2000 Production and storage of fertilizers Hose leak Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown 342 Australia Gulcong 28/02/2000 Not know/applicable Drum leak Aluminium phosphide Acute Tox. 2 * Unknown 343 USA Pleasant hills 28/02/2000 Agriculture Valve leak Ammonia Acute tox 3* Skin Corr. 1B l 344 Germany Dresde 27/02/2000 Leisure activities Failure of a pressure Ammonia Acute tox 3* Skin Corr. 1B Unknown relief system 345 USA Vicksburg 23/02/2002 Handling and transportation centres (ports, Road tank car leak Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B l airports, etc.) and Transport 346 USA Bethel 01/02/2000 Handling and transportation centres (ports, Fire Unknown (Fumes) Unknown Unknown airports, etc.) and Transport 347 Roumania Baia Mare 30/01/2000 Mining activities (tailing and Basin of waste rupture Potassium cyanide Acute tox 1-2 Acute tox 1-2 Acute tox t Very heavy pollution of 3 river (Danube)- Impacts in physicochemical processes) Hungary, Roumania, Yougoslavia, Ukraine, Bulgaria - drinking water polluted, Thousands of animals killed, 1200 t of killed fishes 348 Belgium Bruxelles 20/01/2000 Leisure activities Erreur de dosage Chlorine Acute tox 3* Unknown 349 Brasilia Ceilanda 12/01/2000 Not know/applicable Unknown Chlorine Acute tox 3* kg Impact on flora 350 France Unknown 18/12/2003 Handling and transportation centres (ports, Rail tank car leak Ammonia Acute tox 3* Skin Corr. 1B l airports, etc.) and Transport 351 France Jarrie 18/12/2003 Chemical installation - industrial gases Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 352 France Chaumont 15/12/2003 Electronics and electrical engineering Bottle leak Nitric acid Skin Corr. 1A Unknown 353 France Billere 28/11/2003 Leisure activities Unknown Chlorine Acute tox 3* Unknown 354 France Dagneux 26/11/2003 General chemical manufacture (not included Fire Unknown (Fumes) Unknown Unknown above) 355 France Berre-l'étang 20/11/2003 Medical, research, education (including, Erreur de manipulation Ammonia Acute tox 3* Skin Corr. 1B Unknown hospitals, university, etc.) 356 France Quimper 20/11/2003 General engineering, manufacturing and Overfill Methylenediphenyl Unknown assembly diisocyanate 357 France Besançon 10/11/2003 Leisure activities Flange leak Unknown Unknown t 358 France Valence 29/10/2003 Textiles manufacturing treatment Pipe leak Biphenyl Unknown 359 France Ablis 16/10/2003 Manufacture of food products and Erreur de manipulation Phosphoric acid Skin Corr. 1B Unknown beverages 360 France Epierre 03/10/2003 Wholesale and retail storage and Joint leak Phosphorus pentoxide Skin Corr. 1A kg distribution 361 France Chasse-sur-rhone 03/10/2003 Production of pharmaceuticals Ammonia Acute tox 3* Skin Corr. 1B Unknown 362 France Marseilles 01/10/2003 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 363 France Villeneuve-la- 28/09/2003 Processing of metals Fire Unknown (Fumes) Unknown Unknown Garenne 364 France Briouze 22/09/2003 Manufacture of food products and Intervention dans une Carbon monoxide Acute Tox. 3 * Unknown beverages cuce 365 France Ferrieres-Poussarou 18/09/2003 Handling and transportation centres (ports, Road tank leak Thioglycolic acid Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B l River pollution Fishing and drinking the airports, etc.) and Transport water is forbidden during several days 366 France Ecouflant 15/09/2003 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 367 France Gardanne 11/09/2003 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 368 France Rousset 05/09/2003 Manufacture of food products and Unknown Unknown Unknown Unknown beverages 369 France Roanne 05/09/2003 General engineering, manufacturing and Hose leak Hydrochloric acid Skin Corr. 1B l assembly 370 France Sisteron 03/09/2003 Production of pharmaceuticals Unknown Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B l 371 France Fos-sur-mer 25/08/2009 Production of basic organic chemicals Process error Phosphorus trichloride Acute Tox. 2 0 Acute Tox. 2 Skin Corr. 1A Unknown 372 France Cholet 11/08/2003 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 373 France Rillieux-la-pape 29/07/2003 Waste treatment, disposal Flange leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 374 France Avignon 25/07/2003 Agriculture Process error Hexane Unknown France Ramatuelle 19/07/2003 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 376 France Custines 17/07/2003 General engineering, manufacturing and Unknown Chlorine Acute tox 3* Unknown 6 assembly 377 France Vitrolles 16/07/2003 Wholesale and retail storage and Road tanker leak Hydrochloric acid Skin Corr. 1B l distribution 378 France Champagnole 15/07/2003 Leisure activities Unknown Chlorine Acute tox 3* Unknown 379 France Juigne-sur-loire 13/07/2003 Waste treatment, Fire Unknown Unknown Unknown disposal (Fumes) France Arrabloy 13/07/2003 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown France Toucy 06/07/2003 Leisure activities Bottle Chlorine Unknown leak Acute tox 3* France Issoudun 01/07/2003 Production and storage Reactor leak Unknown Unknown m3 of fertilizers 0 1 River pollution, fishes are killed 383 France Saint-Clair-du-Rhône 30/06/2003 Production of basic organic chemicals Rejet de torchère Sulfur dioxide Unknown Acute tox 3* Skin Corr. 1B France Sorgues 27/06/2003 Agriculture Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 385 France Campbon 16/06/2003 Manufacture of food products and Vessel rupture Sulphuric Skin Corr. 1A l acid 0 1 beverages 386 France Saint-Marcel 12/06/2003 General chemical manufacture (not included Maintenance error Chlorine Acute tox 3* Unknown above) 387 France Grasse 11/06/2003 Waste treatment, disposal mixing substances Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 388 France Moirans 02/06/2003 Electronics and electrical engineering Failure of the packaging 1,2 propylene glycol l Acute Tox France Equeurdreville- 27/05/2003 Leisure activities Unknown Chlorine Acute tox 3* Unknown Hainneville 390 France Lannemezan 19/04/2003 Production of basic organic chemicals Fire Unknown (Fumes) Unknown Unknown 391 France Bordeaux 10/04/2003 Medical, research, education (including, Erreur Nitric acid Unknown de manipulation Skin Corr. 1A 1 hospitals, university, etc.) 392 France Noyelles Godault 05/04/2003 Processing of non-ferrous metals (foundries, Unknown Sulphuric acid Skin Corr. 1A Unknown smelting, etc.) 393 France Sulniac 28/03/2003 Leisure activities Bottle leak Chlorine Acute tox 3* Unknown 394 France Aurillac 21/03/2003 Plastic and rubber Erreur de manipulation Chlorine Acute tox 3* Unknown manufacture France Neuilly-sur-Marne 16/03/2003 Processing of metals Maintenance error Sodium cyanide Acute Tox. 1-2 Acute tox 1 Acute Tox Unknown 396 France Chalon sur Saone 05/03/2003 Handling and transportation centres (ports, Packaging leak Hydrofluoric acid Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * Skin Corr. 1A Unknown airports, etc.) and Transport 397 France Tergnier 24/02/2003 Handling and transportation centres (ports, Rail tank car leak Tri-methylamine Acute Tox Unknown airports, etc.) and Transport 398 France Lapeyrouse 13/02/2003 Handling and transportation centres (ports, Rail tank car leak Hydrochloric acid Skin Corr. 1B Unknown airports, etc.) and Transport 399 France Montville 11/02/2003 Textiles manufacturing treatment Unknown tetrachloroethylene Unknown 400 France Chateauneuf-degadagne beverages 27/01/2003 Manufacture of food products and Valve leak Hydrochloric acid Skin Corr. 1B Unknown 401 France Thann 25/01/2003 General chemical manufacture (not included Packaging leak Sulphuric acid Skin Corr. 1A M3 above) 402 France Heillecourt 22/01/2003 Wholesale and retail storage and Fire Chlorine Acute tox 3* Unknown distribution 403 France Le cateau- 14/01/2003 General engineering, manufacturing and Hose leak Sulphuric acid Skin Corr. 1A l Cambressis assembly 404 France Pierre Benite 16/12/2002 Production of basic organic chemicals Rejet de torchère Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A kg 405 France Unknown 21/11/2002 Handling and transportation centres (ports, Road tank leak Stannic chloride Skin Corr. 1B Unknown airports, etc.) and Transport 406 France Lucon 21/11/2002 Not know/applicable Unknown Carbon monoxide Acute Tox. 3 * Unknown 407 France Toulouse 17/10/2002 General engineering, manufacturing and Erreur de manipulation PCB Unknown assembly 408 France Aurillac 14/10/2005 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 409 France Genay 03/10/2002 Production and storage of pesticides, Hose leak Unknown Unknown Unknown biocides, fungicides 410 France La Brillanne 30/09/2002 Handling and transportation centres (ports, Road tanker leak Hydrochloric acid Skin Corr. 1B l airports, etc.) and Transport 411 France chauteauvillain 30/09/2002 Not know/applicable Bottle leak Chloropicrin Acute Tox. 4 0 Acute Tox Unknown 412 France Saint-Brieuc 28/09/2002 Wholesale and retail storage and Failure of a pressure Ammonia Acute tox 3* Skin Corr. 1B Unknown distribution relief system 413 France Rouen 27/09/2002 Medical, research, education (including, Bottle leak Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown hospitals, university, etc.)

152 Appendix A - Sheet 6 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 414 France Montoir-de- 26/09/2002 Handling and transportation centres (ports, Fire Unknown (NPK Unknown Unknown Bretagne airports, etc.) and Transport decomposition) 415 France Fismes 19/09/2002 Manufacture of food products and Unknown Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown beverages 416 France Isigny-le-Buat 15/09/2002 Processing of metals Fire Unknown Unknown Unknown 417 France Savigneux 07/09/2002 Manufacture of food products and Heat exchanger leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 418 France Roussillon 02/08/2002 General chemical manufacture (not included Vessel explosion P-nitrophenol Acute Tox. 4 Acute Tox. 4 Acute Tox kg 50 m of the road is polluted euros (product recovering above) and treatment) 419 France Le Lion d'angers 31/07/2002 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 420 France Ingersheim 29/07/2002 Processing of metals Unknown Sulphuric acid Skin Corr. 1A l 421 France Corbas 23/07/2002 Handling and transportation centres (ports, Drum leak Phosphorus trichloride Acute Tox. 2 0 Acute Tox. 2 Skin Corr. 1A m2 airports, etc.) and Transport 422 France Longvic 17/07/2002 Production and storage of pesticides, mixing substances Chlorine Acute tox 3* Unknown Treatment of soils biocides, fungicides 423 France Strasbourg 10/07/2002 Handling and transportation centres (ports, Road tanker leak Nitric acid Skin Corr. 1A l airports, etc.) and Transport 424 France Orsay 10/07/2002 Medical, research, education (including, Hose leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown hospitals, university, etc.) 425 France Colmar 02/07/2002 Handling and transportation centres (ports, Drum leak N-butyl methacrylate l airports, etc.) and Transport 426 France Chatenoy-le-royal 17/06/2002 Handling and transportation centres (ports, Drum leak Cyclohexylamine Acute Tox. 4 Acute Tox. 4 0 Skin Corr. 1B l airports, etc.) and Transport 427 France Lacq 11/06/2002 Production of basic organic chemicals Pipe leak methyl mercaptan Acute tox 3* Unknown 428 France Tartas 29/05/2002 Production and manufacturing of pulp and Valve leak Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown paper 429 France Saint-Priest 22/05/2002 Wholesale and retail storage and Drum leak Styrene oxide Acute Tox Unknown distribution 430 France Moncoutant 30/04/2002 Manufacture of food products and Erreur de manipulation Formaldehyde Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown beverages 431 France Scherwiller 18/04/2002 Waste treatment, disposal Unknown Unknown Unknown Unknown 432 France Issoire 20/03/2002 Processing of ferrous metals (foundries, mixing substances Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown smelting, etc.) 433 France Halles 15/03/2002 Not know/applicable Packaging leak Chloropicrin Acute Tox. 4 0 Acute Tox l 434 France Brive-La-Gaillarde 06/03/2002 Leisure activities Unknown Unknown Unknown Unknown 435 France Saint-Marcel 06/03/2002 General chemical manufacture (not included Process error Chlorine Acute tox 3* kg above) 436 France Givors 27/02/2002 Waste treatment, disposal mixing substances Unknown Unknown Unknown 437 France Saint-Jean-de- 13/02/2002 Processing of non-ferrous metals (foundries, Unknown Chlorine Acute tox 3* Unknown Maurienne smelting, etc.) 438 France Saint-Quentin- 08/02/2002 Handling and transportation centres (ports, Drum leak Diethylamine Acute Tox. 4 Acute Tox. 4 Acute Tox. 4 Skin Corr. 1A l Fallavier airports, etc.) and Transport 439 France Reims 05/02/2002 Medical, research, education (including, Unknown Bromine Acute tox 2* Skin Corr. 1A l hospitals, university, etc.) 440 France Persan 05/02/2002 Production of basic organic chemicals mixing substances Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 441 France Troarn 21/01/2002 Textiles manufacturing treatment mixing substances Chlorine Acute tox 3* Unknown 442 France Gresin 27/12/2001 Processing of metals Overheat of product Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown 443 France Pont-de-Claix 04/12/2001 Production of basic organic chemicals Maintenance error Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown 444 France Gresin 03/12/2001 Processing of metals Unknown Nitric acid Skin Corr. 1A l 445 France Aulnay-sous-bois 27/11/2001 Wholesale and retail storage and Drum leak Phosphoric acid Skin Corr. 1B l distribution 446 France Montigny-les-metz 10/11/2001 Handling and transportation centres (ports, Flange leak Carbon monoxide Acute Tox. 3 * Unknown airports, etc.) and Transport 447 France Mulhouse 08/11/2001 General chemical manufacture (not included Drum leak Hydrochloric acid Skin Corr. 1B Unknown above) 448 France Saint-Symphorien 06/11/2001 Processing of metals Erreur de manipulation methylene chloride Unknown 449 France Macon 05/11/2001 Leisure activities Unknown Unknown Unknown Unknown 450 France Nancy 26/10/2001 Electronics and electrical engineering Fire Unknown (Fumes) Unknown Unknown 451 France Lacq 24/10/2001 General chemical manufacture (not included Rejet de torchère Sulfur trioxide Unknown Acute tox 3-0 Acute tox 3-0 Acute tox 1-0 Skin Corr. 1A - above) 1B 452 France Colleville 11/10/2001 Manufacture of food products and Process error Carbon monoxide Acute Tox. 3 * Unknown beverages 453 France Miramas 03/10/2001 Handling and transportation centres (ports, Pipe leak Ammonia Acute tox 3* Skin Corr. 1B t Pollution of the river airports, etc.) and Transport 454 France La-Voulte-sur-Rhone 01/10/2001 Not know/applicable Unknown Iso-butanol kg 455 France Saint-Saviol 29/08/2001 Manufacture of food products and Maintenance error Ammonia Acute tox 3* Skin Corr. 1B kg beverages 456 France Le Grand-Quevilly 08/08/2001 Production and storage of fertilizers Sulfur dioxide Acute tox 3* Skin Corr. 1B t 457 France Marseille 01/08/2001 Handling and transportation centres (ports, Road tank leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 458 France Venissieux 31/07/2001 Not know/applicable Overheat of product Trichloroethylene Unknown 459 France Lanslebourg-Mont- 25/07/2001 Not know/applicable Pump leak Carbon monoxide Acute Tox. 3 * Unknown Cenis 460 France Moyenmoutier 22/07/2001 Not know/applicable Unknown Chloropicrin Acute Tox. 4 0 Acute Tox Unknown 461 France Harnes 17/07/2001 Manufacture of food products and Maintenance error Ammonia Acute tox 3* Skin Corr. 1B l beverages 462 France Toulon 04/07/2001 Leisure activities Unknown Tetrachloromethane Acute Tox. 3 Acute Tox. 3 Acute Tox Unknown 463 France Lorient 04/07/2001 Waste treatment, disposal Road tank leak Nitric acid Skin Corr. 1A Unknown 464 France Le Cheylard 21/06/2001 General engineering, manufacturing and mixing substances Chlorine Acute tox 3* Unknown assembly 465 France Bar-le-duc 31/05/2001 Textiles manufacturing treatment Unknown Unknown Unknown Unknown 466 France Gresy-le-Duc 30/05/2001 Agriculture Road tank leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 467 France Trilport 18/05/2001 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown 468 France Maizey 11/05/2001 Manufacture of food products and Unknown Chlorine Acute tox 3* Unknown beverages 469 France Saint-Privat-La- 09/04/2001 Not know/applicable Unknown Carbon monoxide Acute Tox. 3 * Unknown Montage 470 France Toulouse 02/04/2001 Production and storage of explosives Valve leak Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown 471 France Thann 30/03/2001 General chemical manufacture (not included Pipe leak Chlorine Acute tox 3* Unknown above) 472 France Lieu Saint 06/03/2001 Handling and transportation centres (ports, Unknown Pyridine Acute Tox. 4 Acute Tox. 4 Acute Tox Unknown airports, etc.) and Transport 473 France Baupte 15/02/2001 Manufacture of food products and Maintenance error Hydrogen sulfide Acute tox 2* Unknown beverages 474 France La Mole 08/02/2001 Water and sewage (collection, supply, Pipe leak Chlorine Acute tox 3* kg treatment) 475 France Schwindratzheim 06/06/2001 Handling and transportation centres (ports, Road tank leak Ethyl acrylate Acute Tox. 4 Acute Tox. 4 Acute Tox Unknown airports, etc.) and Transport 476 France Feuquieres 29/01/2001 Ceramics (bricks, pottery, glass, cement, Process error Carbon monoxide Acute Tox. 3 * Unknown etc.) 477 France Unknown 15/01/2001 Not know/applicable Unknown Carbon monoxide Acute Tox. 3 * Unknown 478 France Wisches 09/01/2001 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 479 France Quincieux 01/01/2001 Leisure activities Unknown Carbon monoxide Acute Tox. 3 * Unknown 480 France Voreppe 22/12/2000 Electronics and electrical engineering Process error Trichloroethylene Unknown 481 France Plouguiel 15/12/2000 Water and sewage (collection, supply, Process error Chlorine Acute tox 3* l treatment) 482 France Haguenau 08/12/2000 General chemical manufacture (not included Fire Unknown (Fumes) Unknown Unknown above) 483 France VOREPPE 05/01/2000 Electronics and electrical engineering Unknown Trichloroethylene l 484 France HARBONNIERES 06/01/2000 General chemical manufacture (not included Explosion Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown above) 485 France EPIERRE 14/01/2000 Production of basic organic chemicals Process failure Phosphorus pentoxide Skin Corr. 1A l 486 France CHAULNES 27/01/2000 Handling and transportation centres (ports, Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 487 France SCIONZIER 09/02/2000 Processing of metals Process error Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 488 France AUNAY-SOUS-CRECY 22/02/2000 Production and storage of fertilizers Fire Sulfur Unknown France CHAUMONT 23/02/2000 Water and sewage (collection, supply, Erreur de manipulation Chloropicrin Acute Tox. 4 0 Acute Tox Unknown treatment) 490 France SAINT-GALMIER 21/03/2000 Handling and transportation centres (ports, Rail tank car leak Nitric acid Skin Corr. 1A Unknown 800 m2 of polluted soil 2000 m2 of soil recovered and airports, etc.) and Transport cleared 491 France CHALAMPE 29/03/2000 Production of basic organic chemicals Explosion Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * kg 492 France ARGENTEUIL 11/04/2000 Leisure activities Unknown Chlorine Acute tox 3* France ALLONZIER-LA- 05/05/2000 Agriculture Erreur de Hydrogen Acute tox 2* 0 0 manipulation sulfide 1 1 Unknown CAILLE 494 France SAINT-VULBAS 18/05/2000 Production of pharmaceuticals Hose leak Phenylacetyl chloride Unknown 495 France EBLANGE 18/05/2000 Processing of ferrous metals (foundries, Overfill Ammonia t Acute tox 3* Skin Corr. 1B 1 smelting, etc.) 496 France LE GRAND-QUEVILLY 09/06/2000 Production and storage of fertilizers Valve leak Ammonia Acute tox 3* Skin Corr. 1B kg 497 France GRENOBLE 13/06/2000 Electronics and electrical engineering mixing substances Chlorine Acute tox 3* Unknown 498 France SAINT-QUAY- 14/06/2000 Textiles manufacturing treatment mixing substances Chlorine Acute tox 3* Unknown 1 PORTRIEUX 499 France GRENOBLE 23/06/2000 Electronics and electrical engineering Unknown Unknown Unknown Unknown 500 France TOULOUSE 05/07/2000 Production of basic organic chemicals Maintenance Chloroformate Unknown kg error 4 1

153 Appendix A - Sheet 7 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 501 France MONTPELLIER 25/07/2000 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* kg treatment) 502 France QUIMPERLE 26/07/2000 Wholesale and retail storage and Joint leak Ammonia Acute tox 3* Skin Corr. 1B l distribution 503 France PORT-DE-BOUC 29/07/2000 Production of basic organic chemicals Pump leak Bromine Acute tox 2* Skin Corr. 1A Unknown 504 France REDING 08/08/2000 Processing of metals Hose leak Hydrochloric acid Skin Corr. 1B l 505 France PARTHENAY 08/08/2000 Manufacture of food products and Fire Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 506 France VENISSIEUX 08/08/2000 General engineering, manufacturing and Bottle leak Phosphorus trichloride Acute Tox. 2 0 Acute Tox. 2 Skin Corr. 1A l assembly 507 France TREVOUX 10/08/2000 Leisure activities Maintenance error Chlorine Acute tox 3* Unknown 508 France BRIVE-LA- 21/08/2000 Leisure activities Unknown Carbon monoxide Acute Tox. 3 * Unknown GAILLARDE 509 France SAINT-MARCEL 22/08/2000 General chemical manufacture (not included Process error Chlorine Acute tox 3* kg above) 510 France CHALAMPE 23/08/2000 Production of basic organic chemicals Rejet de torchère Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown 511 France CAUDEBEC-LES- 26/08/2000 General engineering, manufacturing and Valve leak Unknown Unknown l ELBEUF assembly 512 France ILLKIRCH- 31/08/2000 Manufacture of food products and Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B kg GRAFFENSTADEN beverages leak 513 France ISSOIRE 22/09/2000 Electronics and electrical engineering Bottle leak Chlorine Acute tox 3* Unknown 514 France CHALAMPE 29/09/2000 Production of basic organic chemicals Overfill Unknown Unknown kg 515 France CLERMONT- 05/10/2000 Not know/applicable Unknown Carbon monoxide Acute Tox. 3 * Unknown FERRAND 516 France FEYTIAT 15/10/2000 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 517 France CHALAMPE 18/10/2000 Production of basic organic chemicals Loading arm leak Hydrochloric acid Skin Corr. 1B Unknown 518 France BEUVRY-LA-FORET 20/10/2000 Production of basic organic chemicals mixing substances Hydrochloric acid Skin Corr. 1B Unknown 519 France BROGLIE 23/10/2000 Handling and transportation centres (ports, Drum leak Allethrin Acute Tox. 4 0 Acute Tox Unknown airports, etc.) and Transport 520 France PIERRELATTE 08/11/2000 General chemical manufacture (not included Overfill Hydrofluoric acid Acute tox 2* Acute tox 1 Acute tox 2* Skin Corr. 1A kg above) 521 France MONTIGNY-LES- 16/11/2000 Handling and transportation centres (ports, Unknown Ethyl acrylate Acute Tox. 4 Acute Tox. 4 Acute Tox Unknown METZ airports, etc.) and Transport 522 France TARASCON 20/11/2000 Production and manufacturing of pulp and mixing substances Chlorine dioxide Acute Tox. 2 Skin Corr. 1B Unknown paper 523 France PROUILLY 28/11/2000 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 524 France VITRY-LE-FRANCOIS 06/01/2004 Manufacture of food products and Maintenance error Ammonia Acute tox 3* Skin Corr. 1B kg beverages 525 France LA CHAMBRE 12/01/2004 General chemical manufacture (not included Fire Chlorine Acute tox 3* kg above) 526 France VIEUX-THANN 13/01/2004 General chemical manufacture (not included Pipe leak Chlorine Acute tox 3* kg above) 527 France TAVAUX 03/02/2004 General chemical manufacture (not included Valve leak Vinyl chloride kg above) 528 France LE PONT-DE-CLAIX 03/02/2004 Production of basic organic chemicals Maintenance error Phosgene Acute Tox. 2 * 0 Skin Corr. 1B Unknown 529 France AMBERIEU-EN- 11/02/2004 Handling and transportation centres (ports, Flange leak Ammonia Acute tox 3* Skin Corr. 1B Unknown BUGEY airports, etc.) and Transport 530 France STRASBOURG 13/03/2004 Waste treatment, disposal Drum leak Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * l 531 France GONFREVILLE- 16/03/2004 Refinery Vessel rupture Butanone Unknown L'ORCHER 532 France THANN 30/03/2004 General chemical manufacture (not included Rejet de torchère Sulfur trioxide Acute tox 3-0 Acute tox 3-0 Acute tox 1-0 Skin Corr. 1A kg above) 1B 533 France SAINT-GENIS- 01/04/2004 Water and sewage (collection, supply, mixing substances Chlorine Acute tox 3* Unknown POUILLY treatment) 534 France GRANDPUITS-BAILLY- 02/04/2004 Production and storage of fertilizers Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 535 France SAINT-VULBAS 02/04/2004 Waste treatment, disposal mixing substances Hydrogen bromine Skin Corr. 1A Unknown 536 France LA WANTZENAU 13/04/2004 Plastic and rubber manufacture Flange leak Ammonia Acute tox 3* Skin Corr. 1B l 537 France ODIVAL 20/04/2004 Processing of ferrous metals (foundries, Failure of an hoven Carbon monoxide Acute Tox. 3 * Unknown smelting, etc.) 538 France SIAUGUES-SAINTE- 29/04/2004 Processing of metals mixing substances Chlorine dioxide Acute Tox. 2 Skin Corr. 1B Unknown MARIE 539 France TREVOUX 04/05/2004 General engineering, manufacturing and Bottle leak Chlorine Acute tox 3* Unknown assembly 540 France SANDOUVILLE 06/05/2004 Processing of non-ferrous metals (foundries, Unknown Chlorine Acute tox 3* Unknown smelting, etc.) 541 France LE PECHEREAU 18/05/2004 General engineering, manufacturing and mixing substances Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown assembly 542 France FOS-SUR-MER 25/05/2004 Production of basic organic chemicals Joint leak Acrylonitrile Acute Tox. 3 Acute Tox. 3 Acute Tox Unknown 543 France FOS-SUR-MER 28/05/2004 Production of basic organic chemicals Pipe leak Chlorine Acute tox 3* kg 544 France FLORANGE 02/06/2004 Processing of ferrous metals (foundries, Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B Unknown smelting, etc.) leak 545 France METZ 15/06/2004 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 546 France FEYZIN 26/06/2004 Refinery Fire Sulfur dioxide Acute tox 3* Skin Corr. 1B t 547 France MUIZON 05/07/2004 Textiles manufacturing treatment mixing substances Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 548 France LOOS 15/07/2004 General chemical manufacture (not included Process error Ammonia Acute tox 3* Skin Corr. 1B Unknown above) 549 France YAINVILLE 19/07/2004 General chemical manufacture (not included Unknown Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown above) 550 France LA TOUR-D'AIGUES 20/07/2004 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 551 France PIERRELATTE 23/07/2004 Power supply and distribution Drum leak Hydrogen fluoride Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A g 552 France LE HAVRE 26/07/2004 Manufacture of food products and Unknown methylene chloride Unknown beverages 553 France BOURDAINVILLE 28/07/2004 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 554 France LE PONTET 03/08/2004 Handling and transportation centres (ports, Process error Chlorine Acute tox 3* Unknown airports, etc.) and Transport 555 France LIMOGES 19/08/2004 General engineering, manufacturing and Bottle leak Ammonia Acute tox 3* Skin Corr. 1B Unknown assembly 556 France LONS 30/08/2004 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 557 France BESANCON 03/09/2004 Medical, research, education (including, Unknown Bromine Acute tox 2* Skin Corr. 1A ml hospitals, university, etc.) 558 France THANN 09/09/2004 Production of basic organic chemicals Unknown Hydrochloric acid Skin Corr. 1B Unknown 559 France FLOGNY-LA- 13/09/2004 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown CHAPELLE beverages 560 France TREGUNC 19/09/2004 Manufacture of food products and Vessel leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 561 France LIGNY-LE-CHATEL 21/09/2004 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 562 France GENAY 22/09/2004 Production of basic organic chemicals Maintenance error Ethyl acrylate Acute Tox. 4 Acute Tox. 4 Acute Tox Unknown 563 France HOERDT 27/09/2004 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 564 France LA FLECHE 27/09/2004 Leisure activities Process error Chlorine Acute tox 3* Unknown 565 France MONTARDON 02/10/2004 Waste treatment, disposal Fire Unknown (Fumes) Unknown Unknown 566 France MARSEILLE 06/10/2004 General engineering, manufacturing and Unknown Hydrogen sulfide Acute tox 2* Unknown assembly 567 France LA BOHALLE 12/10/2004 General chemical manufacture (not included Unknown methylene chloride Unknown above) 568 France MARTIGUES 13/10/2004 Not know/applicable Valve leak Chlorine Acute tox 3* Unknown 569 France MAUBEUGE 23/10/2004 General engineering, manufacturing and Unknown Carbon monoxide Acute Tox. 3 * Unknown assembly 570 France LANNEMEZAN 25/10/2004 Production of basic organic chemicals Fire Ammonia Acute tox 3* Skin Corr. 1B kg 571 France THANN 07/11/2004 General chemical manufacture (not included Unknown Hydrogen sulfide Acute tox 2* kg above) 572 France AJACCIO 10/11/2004 Power supply and distribution Fire Unknown (Fumes) Unknown Unknown 573 France VAULX-EN-VELIN 16/11/2004 Processing of metals mixing substances Unknown Unknown Unknown 574 France VITRE 28/11/2004 Manufacture of food products and Fire Ammonia Acute tox 3* Skin Corr. 1B 0 1 Unknown beverages 575 France TRELAZE 01/12/2004 Not know/applicable Fire Unknown (Fumes) Unknown Unknown 576 France BERNAY 10/12/2004 Processing of metals Process error Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 577 France BELLEGARDE 13/12/2004 Handling and transportation centres (ports, Drum leak Glutaral Acute Tox. 3 0 Acute Tox. 3 Skin Corr. 1B Unknown airports, etc.) and Transport 578 France LOON-PLAGE 18/12/2004 Refinery Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 579 France LES 20/12/2004 Manufacture of food products and Joint leak Ammonia Acute tox 3* Skin Corr. 1B Unknown CERQUEUX-DE- beverages MAULEVRIER 580 France MILLY-LA-FORET 05/01/2005 Manufacture of food products and Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B kg beverages leak 581 France OLLAINVILLE 07/01/2005 Not know/applicable mixing substances Unknown Unknown Unknown 582 France TORCE 12/01/2005 Manufacture of food products and Hoven failure Carbon monoxide Acute Tox. 3 * Unknown beverages 583 France MONTIGNY-LES- 15/01/2005 Handling and transportation centres (ports, Valve leak Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown METZ airports, etc.) and Transport 584 France THYEZ 26/01/2005 Processing of metals mixing substances Chlorine Acute tox 3* Unknown

154 Appendix A - Sheet 8 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 585 France MARTIGUES 31/01/2005 General chemical manufacture (not included Process error Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A t above) 586 France VIRIAT 25/02/2005 Manufacture of food products and Flange leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 587 France SANDOUVILLE 06/03/2005 Plastic and rubber manufacture Fire Unknown (Fumes) Unknown Unknown 588 France MORNAC 16/03/2005 Waste treatment, disposal Maintenance error Hydrogen sulfide Acute tox 2* Unknown 589 France DOULLENS 23/03/2005 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 590 France SAINT-JUST-SAINT- 31/03/2005 General chemical manufacture (not included Fire Chlorine Acute tox 3* Unknown RAMBE above) RT 591 France GAILLON 15/04/2005 General chemical manufacture (not included mixing substances Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A kg above) 592 France MORNAC 20/04/2005 Textiles manufacturing treatment Fire Unknown (Fumes) Unknown Unknown 593 France NEMOURS 23/04/2005 Wholesale and retail storage and Drum leak Ammonia Acute tox 3* Skin Corr. 1B Unknown distribution 594 France BRUGUIERES 11/05/2005 Production of basic organic chemicals mixing substances methylene chloride l 595 France LOUDEAC 17/05/2005 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 596 France PARIS 19/05/2005 Leisure activities Unknown Chlorine Acute tox 3* Unknown 597 France MACON 25/05/2005 Manufacture of food products and mixing substances Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 598 France PARIS 26/05/2005 Leisure activities Unknown Chlorine Acute tox 3* Unknown 599 France HOUDAN 27/05/2005 Water and sewage (collection, supply, Unknown Hydrogen sulfide Acute tox 2* Unknown treatment) 600 France TOULOUSE 29/05/2005 Production of pharmaceuticals Joint leak Bromine Acute tox 2* Skin Corr. 1A l 601 France BEZONS 30/05/2005 Leisure activities Unknown Chlorine Acute tox 3* Unknown 602 France DAUMERAY 30/05/2005 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 603 France EVREUX 01/06/2005 Production of pharmaceuticals mixing substances Methyl methacrylate Unknown 604 France MONTREUIL-JUIGNE 22/06/2005 Processing of metals Bottle leak Chlorine Acute tox 3* Unknown 605 France SAINT-AVOLD 24/06/2005 Plastic and rubber manufacture Torchère Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 606 France BEZIERS 27/06/2005 Production and storage of pesticides, Fire Unknown (Fumes) Unknown Unknown biocides, fungicides 607 France SAINT-QUENTIN- 29/06/2005 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown FALLAVIE beverages R 608 France SAUMUR 01/07/2005 Leisure activities Bottle leak Chlorine Acute tox 3* Unknown 609 France ROUBION 05/07/2005 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 610 France SAINT-AMAND-LES- 07/08/2005 Leisure activities Valve leak Chlorine Acute tox 3* Unknown EAUX 611 France LES MARTRES- 15/08/2005 Medical, research, education (including, Fire Unknown (Fumes) Unknown Unknown D'ARTIERE hospitals, university, etc.) 612 France PIERRE-BENITE 25/08/2005 General chemical manufacture (not included Valve leak Bromine Acute tox 2* Skin Corr. 1A Unknown above) 613 France HAUTMONT 31/08/2005 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 614 France COULOUNIEIX- 15/09/2005 Handling and transportation centres (ports, Drum leak methylene chloride l CHAMIERS airports, etc.) and Transport 615 France JARRIE 29/09/2005 General chemical manufacture (not included Maintenance error Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown above) 616 France ROGNAC 11/10/2005 Chemical installation - industrial gases Bottle leak Hydrogen sulfide Acute tox 2* Unknown 617 France FRANOIS 11/10/2005 Waste treatment, disposal Process error Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 618 France TAVERNY 26/10/2005 General engineering, manufacturing and Unknown Unknown Unknown Unknown assembly 619 France GRAND-FOUGERAY 16/11/2005 Production and storage of pesticides, Malathion Acute tox 4* m3 Pollution of the river (4 km) Hundred of fishes killed Dams + absorbent products + pumps biocides, fungicides 620 France FOS-SUR-MER 22/11/2005 Processing of ferrous metals (foundries, Fire Unknown (Fumes) Unknown Unknown smelting, etc.) 621 France LE PONT-DE-CLAIX 01/12/2005 Production of basic organic chemicals Pipe leak Phosgene Acute Tox. 2 * 0 Skin Corr. 1B g 622 France VIRY-CHATILLON 03/12/2005 Leisure activities Unknown Chlorine Acute tox 3* Unknown 623 France CHARTRES 09/12/2005 General chemical manufacture (not included mixing substances Hydrogen sulfide Acute tox 2* Unknown above) 624 France SANDOUVILLE 13/12/2005 Processing of non-ferrous metals (foundries, Small bore fittings leak Chlorine Acute tox 3* kg smelting, etc.) 625 France VITRE 06/01/2006 Manufacture of food products and Failure of pressure relief Ammonia Acute tox 3* Skin Corr. 1B l Several fishes are killed beverages system 626 France BREAU 09/01/2006 Not know/applicable Process error Ammonia Acute tox 3* Skin Corr. 1B Unknown 627 France EVREUX 16/01/2006 Production and manufacturing of pulp and Unknown Carbon monoxide Acute Tox. 3 * Unknown paper 628 France CHERISY 17/01/2006 Processing of metals Maintenance error Carbon monoxide Acute Tox. 3 * Unknown 629 France MARIGNANE 24/01/2006 General engineering, manufacturing and Pipe leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown assembly 630 France DEUIL-LA-BARRE 26/03/2006 Leisure activities Unknown Carbon monoxide Acute Tox. 3 * Unknown 631 France AMIENS 08/04/2006 General engineering, manufacturing and Maintenance error Trichloroethylene Unknown assembly 632 France CORMENON 23/04/2006 Processing of metals Fire Unknown (Fumes) Unknown Unknown 633 France CATENOY 26/04/2006 Production of basic organic chemicals Pipe leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown 634 France MONTAUBAN 30/04/2006 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 635 France RAMBURELLES 05/05/2006 Wholesale and retail storage and Bottle leak Chloropicrin Acute Tox. 4 0 Acute Tox Unknown distribution 636 France VIVIEZ 12/05/2006 Processing of ferrous metals (foundries, mixing substances Ammonia Acute tox 3* Skin Corr. 1B Unknown smelting, etc.) 637 France BEZIERS 17/05/2006 General engineering, manufacturing and Pipe leak Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * Unknown assembly 638 France FOS-SUR-MER 17/05/2006 Production of basic organic chemicals Fire Chlorine Acute tox 3* Unknown 639 France THIONVILLE 18/05/2006 Water and sewage (collection, supply, Unknown Chlorine Acute tox 3* Unknown treatment) 640 France PARIS 03/06/2006 Leisure activities Unknown Chlorine Acute tox 3* Unknown 641 France POISSY 12/06/2006 Waste treatment, disposal Unknown Hydrogen sulfide Acute tox 2* Unknown 642 France SAINT-AVOLD 25/06/2006 Production of basic organic chemicals mixing substances Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * Unknown 643 France TANINGES 09/08/2006 Manufacture of food products and Compressor leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 644 France MAULEVRIER- 20/08/2006 Handling and transportation centres (ports, Road tank leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown SAINTE-GERT airports, etc.) and Transport RUDE 645 France DIJON 25/08/2006 Leisure activities Bottle leak Chlorine Acute tox 3* Unknown 646 France SAYAT 30/08/2006 Electronics and electrical engineering Fire Carbon monoxide Acute Tox. 3 * Unknown 647 France GONFREVILLE- 05/09/2006 Refinery Process error Hydrogen sulfide Acute tox 2* kg L'ORCHER 648 France SOLEYMIEU 08/09/2006 Textiles manufacturing treatment Fire Unknown (Fumes) Unknown Unknown 649 France LIMAS 21/09/2006 Production and storage of pesticides, mixing substances Carbon disulphide Unknown biocides, fungicides 650 France PARIS 11/10/2006 Leisure activities Unknown Chlorine Acute tox 3* Unknown 651 France QUIMPER 12/10/2006 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 652 France DIJON 13/10/2006 Medical, research, education (including, Erreur de manipulation Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown hospitals, university, etc.) 653 France CALAIS 16/10/2006 General chemical manufacture (not included Process error Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown above) 654 France GRANDPUITS-BAILLY- 02/11/2006 Production and storage of fertilizers Rail tank car leak Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 655 France GRANDPUITS-BAILLY- 08/11/2006 Production and storage of fertilizers Valve failure Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 656 France HALLUIN 15/11/2006 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 657 France CHALLERANGE 28/11/2006 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 658 France SERRIS 29/11/2006 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 659 France PERSAN 05/12/2006 Production of basic organic chemicals Bottle leak Boron trifluoride Acute Tox. 2 0 Skin Corr. 1A Unknown 660 France JARRIE 10/01/2007 Processing of non-ferrous metals (foundries, Pipe leak Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown smelting, etc.) 661 France DOURGES 01/02/2007 Wholesale and retail storage and Road tank leak Ethyl acrylate Acute Tox. 4 Acute Tox. 4 Acute Tox l distribution 662 France SAINT-ANDRE-LEZ- 21/02/2007 Production of basic organic chemicals Vessel leak Hydrochloric acid Skin Corr. 1B Unknown LILLE 663 France MALISSARD 17/04/2007 General chemical manufacture (not included Fire Chlorine Acute tox 3* Unknown above) 664 France LE PONT-DE-CLAIX 19/04/2007 Production of basic organic chemicals Valve leak Phosgene Acute Tox. 2 * 0 Skin Corr. 1B g 665 France CHIGNY-LES-ROSES 21/05/2007 Manufacture of food products and Process error Carbon monoxide Acute Tox. 3 * Unknown beverages 666 France LEVES 07/06/2007 Water and sewage (collection, supply, Unknown Chlorine dioxide Acute Tox. 2 Skin Corr. 1B Unknown treatment) 667 France CORBEIL-ESSONNES 28/06/2007 Processing of metals mixing substances Unknown Unknown Unknown 668 France SAINT-REMY-DE- 03/07/2007 Wholesale and retail storage and Fire Chlorine Acute tox 3* Unknown PROVENCE distribution 669 France LE PASSAGE 19/07/2007 Production of pharmaceuticals Unknown Carbon monoxide Acute Tox. 3 * Unknown

155 Appendix A - Sheet 9 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 670 France LE TREPORT 03/09/2007 Production and storage of fertilizers Process error Hydrogen sulfide Acute tox 2* Unknown 671 France CHOREY 03/09/2007 Not know/applicable Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 672 France FLERS-EN- 04/09/2007 General engineering, manufacturing and Unknown Carbon monoxide Acute Tox. 3 * Unknown ESCREBIEUX assembly 673 France CAMPBON 28/09/2007 Manufacture of food products and Compressor leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 674 France GALLARGUES-LE- 02/10/2007 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown MONTUEUX beverages 675 France BAR-LE-DUC 05/10/2007 Waste treatment, disposal Unknown Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 676 France LE HAVRE 12/10/2007 General chemical manufacture (not included Process error Sulfur dioxide Acute tox 3* Skin Corr. 1B kg above) 677 France PARIS 19/10/2007 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 678 France ANTONY 09/11/2007 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 679 France BUROSSE- 15/11/2007 oil/gas/coal extraction Pipe leak Hydrogen sulfide Acute tox 2* Unknown MENDOUSSE 680 France BOZOULS 19/11/2007 Waste treatment, disposal Packaging leak Chloropicrin Acute Tox. 4 0 Acute Tox Unknown 681 France BULGNEVILLE 03/12/2007 Manufacture of food products and Compressor leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 682 France LILLE 12/12/2007 Handling and transportation centres (ports, Rail tank car leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 683 France LANEUVEVILLE- 20/12/2007 Processing of non-ferrous metals (foundries, mixing substances Ammonia Acute tox 3* Skin Corr. 1B Unknown DEVANT-NA smelting, etc.) NCY 684 France CHAMBRETAUD 17/01/2008 General engineering, manufacturing and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown assembly 685 France RAON-L'ETAPE 25/01/2008 Not know/applicable Unknown Carbon monoxide Acute Tox. 3 * Unknown 686 France BREST 07/02/2008 Handling and transportation centres (ports, Unknown Phosphine Acute Tox. 2 Skin Corr. 1B Unknown airports, etc.) and Transport 687 France MIREBEAU 10/02/2008 Manufacture of food products and Maintenance error Ammonia Acute tox 3* Skin Corr. 1B kg beverages 688 France CHATEAU-ARNOUX- 14/02/2008 Production of basic organic chemicals Joint leak Chlorine Acute tox 3* kg SAINT-A UBAN 689 France SERVON-SUR- 28/02/2008 Manufacture of food products and Flange leak Ammonia Acute tox 3* Skin Corr. 1B Unknown VILAINE beverages 690 France LANESTER 05/03/2008 Production of pharmaceuticals Overfill Sulfur dioxide Acute tox 3* Skin Corr. 1B l 691 France BROONS 19/03/2008 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 692 France AVIGNON 16/04/2008 Leisure activities Pump failure Chlorine Acute tox 3* Unknown 693 France FOS-SUR-MER 22/04/2008 Refinery Torchère Hydrogen sulfide Acute tox 2* Unknown 694 France DIJON 10/05/2008 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 695 France LOUDEAC 13/05/2008 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 696 France LA TREMBLADE 19/05/2008 General engineering, manufacturing and Road tank leak Hydrofluoric acid Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A Unknown Limited soil pollution Dam + dilution + absorption assembly 697 France CHASSE-SUR-RHONE 05/06/2008 Manufacture of food products and mixing substances Chlorine Acute tox 3* Unknown beverages 698 France CHATILLON-LE-DUC 20/06/2008 Water and sewage (collection, supply, Vessel leak Chlorine Acute tox 3* Unknown Limited river pollution treatment) 699 France VILLENEUVE-LA- 24/06/2008 Not know/applicable Pipe leak Hydrogen sulfide Acute tox 2* Unknown GARENNE 700 France VEDENE 25/07/2008 Handling and transportation centres (ports, Packaging leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 701 France MARCIGNY 29/07/2008 Leisure activities Unknown Chlorine Acute tox 3* Unknown 702 France SENS 30/07/2008 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown treatment) 703 France VIRIAT 10/09/2008 Waste treatment, disposal Maintenance error Hydrogen sulfide Acute tox 2* Unknown 704 France LAVAL 15/09/2008 Manufacture of food products and Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages leak 705 France SAINT-NICOLAS-DE- 18/09/2008 Not know/applicable Unknown Phosphorus Acute Tox. 2 * 0 Acute Tox. 2 * Skin Corr. 1A Unknown LA-TA ILLE 706 France BRIVE-LA- 19/09/2008 Processing of metals mixing substances Nitrogen dioxide Acute Tox. 2 * Skin Corr. 1B Unknown GAILLARDE 707 France PARIS 19/09/2008 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 708 France RUEIL-MALMAISON 16/10/2008 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 709 France DIJON 18/10/2008 Leisure activities Compressor leak Ammonia Acute tox 3* Skin Corr. 1B Unknown 710 France BALARUC-LES-BAINS 28/10/2008 Manufacture of food products and Fire Unknown Unknown Unknown (Fumes) 0 6 beverages 711 France DECINES-CHARPIEU 29/10/2008 Leisure activities Mixing substances Chlorine Acute tox 3* Unknown 712 France LILLE 28/11/2008 Leisure activities Process error Chlorine Acute tox 3* Unknown 713 France LA SELLE-EN-LUITRE 12/12/2008 Processing of metals Process error Unknown Unknown Unknown France CLICHY 18/12/2008 Medical, research, education (including, mixing substances Hydrobromic acid Unknown Skin Corr. 1B Unknown hospitals, university, etc.) 715 France CHATEAUNEUF-LES- 05/01/2009 Refinery Unknown Hydrogen sulfide Acute tox 2* Unknown MARTIG UES 716 France FRESNES 05/01/2009 Processing of metals Maintenance error Trichloroethylene Unknown 717 France GONFREVILLE- 14/01/2009 Waste treatment, disposal mixing substances Unknown Unknown Unknown L'ORCHER 718 France MONCHY-LE-PREUX 16/01/2009 Production and manufacturing of pulp and Unknown Carbon monoxide Acute Tox. 3 * Unknown paper 719 France CHATEAU-THIERRY 16/01/2009 Plastic and rubber manufacture Fire Chlorine Acute tox 3* Unknown 720 France FROIDMONT- 28/01/2009 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* Unknown COHARTILLE treatment) 721 France GONFREVILLE- 06/02/2009 Refinery Unknown Carbon monoxide Acute Tox. 3 * Unknown L'ORCHER 722 France RENAGE 07/02/2009 Handling and transportation centres (ports, Road tank leak Ammonia Acute tox 3* Skin Corr. 1B Unknown airports, etc.) and Transport 723 France MESNIL-SAINT- 17/02/2009 Manufacture of food products and Process error Ammonia Acute tox 3* Skin Corr. 1B Unknown NICAISE beverages 724 France TORCE 23/02/2009 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 725 France DIEPPE 16/03/2009 Leisure activities Process error Chlorine Acute tox 3* Unknown 726 France DUNKERQUE 21/03/2009 Wholesale and retail storage and Fire Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown distribution 727 France OUDALLE 17/04/2009 General chemical manufacture (not included Process error Hydrogen sulfide Acute tox 2* Unknown above) 728 France OUDALLE 07/05/2009 General chemical manufacture (not included Process error Hydrogen sulfide Acute tox 2* Unknown above) 729 France LAXOU 20/05/2009 Leisure activities mixing substances Chlorine Acute tox 3* Unknown 730 France LA 25/05/2009 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown CHAUSSEE-SAINT- beverages VICTOR 731 France SAINT-SEVER 02/06/2009 Manufacture of food products and Bottle leak Ammonia Acute tox 3* Skin Corr. 1B kg beverages 732 France LUGOS 04/06/2009 Handling and transportation centres (ports, Road tank leak Ammonia Acute tox 3* Skin Corr. 1B m3 8 ha of flora brunt airports, etc.) and Transport 733 France SAINT-LEU- 10/06/2009 Production of pharmaceuticals Process error Hydrogen chloride Acute Tox. 3 * Skin Corr. 1A Unknown D'ESSERENT 734 France DUNKERQUE 19/06/2009 Electronics and electrical engineering Unknown Carbon monoxide Acute Tox. 3 * Unknown 735 France ROUSSILLON 26/06/2009 Production of basic organic chemicals Fire Cumene hydroperoxide Acute Tox. 4 Acute Tox. 4 Acute Tox. 3 Skin Corr. 1B Unknown 736 France MALISSARD 02/07/2009 General chemical manufacture (not included Fire Chlorine Acute tox 3* Unknown above) 737 France RIVECOURT 10/07/2009 Not know/applicable Unknown Unknown Unknown Unknown 738 France SALAISE-SUR-SANNE 15/07/2009 Waste treatment, disposal Fire Unknown Unknown Unknown (Fumes) France GRANDPUITS-BAILLY- 22/07/2009 Production and storage of fertilizers Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR leak OIS 740 France GRANDPUITS-BAILLY- 13/08/2009 Production and storage of fertilizers Process error Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 741 France L'ISLE-SUR-LA- 10/09/2009 Wholesale and retail storage and Fire Chlorine Acute tox 3* Unknown SORGUE distribution Processing of 742 France FRIVILLE- 16/09/2009 metals Unknown Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1 Acute Tox. 2 * Unknown ESCARBOTIN 743 France DONGES 25/09/2009 Refinery Valve leak Hydrogen fluoride Acute Tox. 2 Acute Tox. 1 Acute Tox. 2 Skin Corr. 1A Unknown 744 France FLAUCOURT 16/10/2009 Manufacture of food products and Unknown Carbon monoxide Acute Tox Unknown 0 0 * 0 1 beverages 745 France MENTON 24/11/2009 Water and sewage (collection, supply, mixing substances Chlorine Acute tox 3* Unknown treatment) 746 France VINCENNES 16/12/2009 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages

156 Appendix A - Sheet 10 ID Country Location Date Main activity of the establishment Cause Main substance CAS Harmonized Harmonized Harmonized Skin Corrosion Harmonized Death Injured Preventive Exposure Oral Exposure Exposure Exposure Exposure Exposure No exposure Exposure Release Environmental impact (scale) Proprety/economic impact Long term Environmental impact (scale) Remediation measures ( ) involved classification - classification - Acute classification - Acute tox classification - hospitalisation Dermal Dermal Inhalation Skin Unknown quantity (scale) Acute tox oral tox dermal inhalation Unknown /medical (confirmed) (suspected) corrosion advice/incom modé 747 France LES 24/12/2009 General chemical manufacture (not included Maintenance error methylene chloride Unknown PAVILLONS-SOUS- above) BOIS 748 France SAINT-MARCELLIN 06/01/2010 Plastic and rubber manufacture Failure of the flare Carbon monoxide Acute Tox. 3 * Unknown 749 France MITRY-MORY 03/02/2010 Wholesale and retail storage and Unknown Chlorine Acute tox 3* Unknown distribution 750 France BERNAY 24/04/2010 Water and sewage (collection, supply, Bottle leak Chlorine Acute tox 3* kg treatment) 751 France BRIE-COMTE- 06/05/2010 Textiles manufacturing treatment Unknown Carbon monoxide Acute Tox. 3 * Unknown ROBERT 752 France SANDOUVILLE 02/06/2010 Handling and transportation centres (ports, Process error Phenol Acute tox 3* 0 1 Unknown Acute tox 3* Acute tox 3* Skin Corr. 1B 1 1 airports, etc.) and Transport 753 France DOUCHY-LES-MINES 21/06/2010 Waste treatment, disposal Packaging leak Mercury Acute Tox Unknown 754 France GRANDPUITS-BAILLY- 01/07/2010 Production and storage of fertilizers Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 755 France SARROUX 12/08/2010 Water and sewage (collection, supply, mixing substances Chlorine Acute tox 3* Unknown treatment) 756 France ARDON 20/08/2010 Handling and transportation centres (ports, Drum leak methylene chloride Unknown airports, etc.) and Transport 757 France MAURY 26/08/2010 Manufacture of food products and Fire Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown beverages 758 France BRUGUIERES 22/09/2010 Handling and transportation centres (ports, Packaging leak Potassium cyanide Acute tox 1-2 Acute tox 1-2 Acute tox Unknown airports, etc.) and Transport 759 France MARTIGUES 12/10/2010 Power supply and distribution Natural release Hydrogen sulfide Acute tox 2* Unknown 760 France MONTCEAU-LES- 19/10/2010 Power supply and distribution Fire Carbon monoxide Acute Tox. 3 * Unknown MINES 761 France SAINT-MARCEL 29/10/2010 Chemical installation - chlorine Pipe leak Chlorine Acute tox 3* Unknown 762 France MARSEILLE 29/10/2010 Production of basic organic Hose leak Ammonia Acute tox 3* 0 1 Unknown chemicals Skin Corr. 1B France BOURG-EN-BRESSE 03/11/2010 Textiles manufacturing treatment mixing substances Chlorine Acute tox 3* 0 4 Unknown France WISCHES 16/02/2011 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 765 France LE PONT-DE-CLAIX 16/03/2011 General chemical manufacture (not included Valve rupture Toluene-2,6-diisocyanate Acute Tox l above) 766 France LONS 28/03/2011 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 767 France NUEIL-LES-AUBIERS 24/06/2011 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 768 France PERPIGNAN 28/06/2011 Handling and transportation centres (ports, Bottle leak Chlorine Acute tox 3* Unknown airports, etc.) and Transport 769 France VITTEL 05/07/2011 Manufacture of food products and Unknown Carbon monoxide Acute Tox. 3 * Unknown beverages 770 France STRASBOURG 12/07/2011 Water and sewage (collection, supply, Packaging leak Chlorine Acute tox 3* Unknown treatment) 771 France TREVE 27/07/2011 Manufacture of food products and Compressor leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 772 France MANTES-LA-JOLIE 01/08/2011 Plastic and rubber manufacture Hose leak Toluene-2,6-diisocyanate Acute Tox Unknown 773 France LA TALAUDIERE 01/08/2011 General engineering, manufacturing and Vessel leak Ethylene glycol Unknown assembly 774 France PORCHEVILLE 03/08/2011 Medical, research, education (including, Packaging leak 3-Bromopropene Acute tox Acute tox 2-0 Skin Corr. 1B Unknown hospitals, university, etc.) 775 France BOUCHAIN 14/09/2011 Power supply and distribution Fire Carbon monoxide Acute Tox. 3 * Unknown 776 France BERRE-L'ETANG 05/10/2011 Textiles manufacturing treatment Process error Sodium bisulphite Acute tox 4* Unknown 777 France THONON-LES-BAINS 13/10/2011 Water and sewage (collection, supply, Process error Chlorine Acute tox 3* Unknown treatment) 778 France VALENCE 18/10/2011 Processing of metals mixing substances Sulfur dioxide Acute tox 3* Skin Corr. 1B Unknown 779 France FLORANGE 31/10/2011 Processing of ferrous metals (foundries, Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown smelting, etc.) 780 France ANGERS 17/11/2011 Manufacture of food products and Unknown Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 781 France GRANDPUITS-BAILLY- 19/11/2011 Production and storage of fertilizers Overfill Ammonia Acute tox 3* Skin Corr. 1B Unknown CARR OIS 782 France ROUEN 13/12/2011 Handling and transportation centres (ports, Fire Aluminium phosphide Acute Tox. 2 * Unknown airports, etc.) and Transport 783 France MIRIBEL 14/12/2011 Textiles manufacturing treatment mixing substances Chlorine Acute tox 3* Unknown 784 France BORDERES-SUR- 29/12/2011 Manufacture of food products and Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B kg L'ECHEZ beverages leak 785 France SAINT-LAURENT-DU- 10/02/2012 Processing of metals Explosion Unknown (Fumes) Unknown Unknown PONT 786 France MONTLUCON 07/03/2012 Leisure activities Unknown Trichloroethylene Unknown 787 France DUNKERQUE 20/04/2012 Refinery Hose leak 2-furaldehyde Acute Tox. 3 Acute Tox. 4 Acute Tox Unknown 788 France AMNEVILLE 15/06/2012 Waste treatment, disposal Packaging leak Unknown Unknown Unknown 789 France MIONS 22/06/2012 Handling and transportation centres (ports, Packaging leak Pyridine Acute tox 4* Acute tox 4* Acute tox 4* l airports, etc.) and Transport 790 France CONCARNEAU 08/07/2012 Manufacture of food products and Valve leak Ammonia Acute tox 3* Skin Corr. 1B l beverages 791 France ESTREES-MONS 27/07/2012 Manufacture of food products and Pressure relief system Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages leak 792 France LE COTEAU 30/08/2012 Manufacture of food products and Pipe leak Ammonia Acute tox 3* Skin Corr. 1B Unknown beverages 793 France FESSENHEIM 05/09/2012 Power supply and distribution mixing substances Hydrazine Acute tox 3* Acute tox 3* Acute tox 3* Unknown 794 France SAINT-ELOY-LES- 12/09/2012 Handling and transportation centres (ports, Road tank leak Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B Unknown MINES airports, etc.) and Transport

157 B1 Appendix B Results of analysis of accident database France versus other countries Overview This analysis has been conducted because of the limits of representativeness of the compiled accident database accidents. It is intended to provide a clear insight of the difference between the datasets that concern accidents which occurred in France (449 accidents) and accidents which occurred in all other countries (345 accidents). The methodology and the indicators calculated for this analysis are the same than the one described in Sections and Comparison of the number of accidents involving toxic dermal exposures and those involving toxic inhalation exposures in France The following graph gives the proportion of exposure routes (and skin corrosion) for the 449 accidents occurred in France: Proportions of various exposure routes for accidents involving toxic substances Note: For some accidents, the effects of several exposure routes have been described simultaneously. The sum of the figures in the graph is then >100%

158 B2 Of the total of 449 accidents that occurred in France: 290 accidents involved inhalation exposure; 18 accidents involved dermal exposure. A detailed analysis of the exposure routes and type of effects involved in the 18 dermal exposure accidents is provided in the table below: Detailed analysis of the 18 accidents potentially involving dermal exposure route Accident type Number Total accidents potentially involving dermal exposure route 18 Accidents involving dermal exposure route 15 - Dermal only (confirmed) 10 - Dermal exposure (confirmed) and skin corrosion 4 - Dermal exposure (confirmed) and inhalation 1 - Dermal exposure (confirmed) and inhalation and skin corrosion 0 Accidents for which dermal exposure route is suspected 13 - Dermal only (suspected) 1 - Dermal exposure (suspected) and skin corrosion 1 - Dermal exposure (suspected) and inhalation 1 - Dermal exposure (suspected) and inhalation and skin corrosion 0 The table below shows the classification for acute toxicity (inhalation and dermal exposure routes) of the main substances involved in accidents with toxic effects includes in the dataset. Classification for acute toxicity (dermal and inhalation exposure routes) for accidents with toxic effects Exposure routes Acute tox 1* Acute tox 2 * Acute tox 3 * Acute tox 4 * Acute tox Not classifi ed Dermal exposure (confirmed) (classification for acute toxicity through dermal exposure route) (15 accidents) Dermal exposure (suspected) (classification for acute toxicity through dermal exposure route) (3 accidents) 13.3% 0.0% 20.0% 13.3% 6.7% 46.7% 33.3% 0.0% 0.0% 33.3% 0.0% 33.3% Inhalation exposure (classification for acute toxicity through inhalation exposure route) (290 accidents) 0.0% 12.1% 66.6% 2.1% 0.0% 19.3% These results confirm the results of the analysis of the whole database presented in the main report. 66 Minimal classification was not available for these substances. However, all the classification proposed in notifications were acute tox 1 or acute tox 2.

159 B3 Comparison of the number of accidents involving dermal exposures and those involving inhalation exposures in other countries The following graph gives the proportion of exposure routes (and skin corrosion) for the 3345 accidents occurred in the other countries: Proportions of various exposure routes for accidents involving toxic substances Note: For some accidents, the effects of several exposure routes have been described simultaneously. The sum of the figures in the graph is then >100% A detailed analysis of the exposure routes and type of effects involved in the 11 dermal exposure accidents is provided in the table below: Detailed analysis of the 11 accidents potentially involving dermal exposure route Accident type Number Total accidents potentially involving dermal exposure route 11 Accidents involving dermal exposure route 3 - Dermal only (confirmed) 1 - Dermal exposure (confirmed) and skin corrosion 1 - Dermal exposure (confirmed) and inhalation 1 - Dermal exposure (confirmed) and inhalation and skin corrosion 0 Accidents for which dermal exposure route is suspected 8 - Dermal only (suspected) 0

160 B4 Accident type Number - Dermal exposure (suspected) and skin corrosion 4 - Dermal exposure (suspected) and inhalation 2 - Dermal exposure (suspected) and inhalation and skin corrosion 2 The table below shows the classification for acute toxicity (inhalation and dermal exposure routes) of the main substances involved in accidents with toxic effects includes in the dataset. Classification for acute toxicity (dermal and inhalation exposure routes) for accidents with toxic effects Exposure routes Acute tox 1* Acute tox 2 * Acute tox 3 * Acute tox 4 * Acute tox Not classifi ed Dermal exposure (confirmed) (classification for acute toxicity through dermal exposure route) (3 accidents) Dermal exposure (suspected) (classification for acute toxicity through dermal exposure route) (8 accidents) Inhalation exposure (classification for acute toxicity through inhalation exposure route) (167 accidents) 33.3% 0.0% 33.3% 0.0% 0.0% 33.3% 37.5% 0.0% 12.5% 0.0% 0.0% 50.0% 0.0% 12.0% 49.1% 3.0% 0.0% 35.9% These results confirm the results of the analysis of the whole database presented in the main report. Comparison of human consequences of accidents involving dermal exposures and those involving inhalation exposures in France The table below gives the results of the calculation of the two indicators for consequences analysis: Consequences of accidents involving toxic dermal and inhalation exposure routes Dermal exposure route Inhalation exposure route Ratio accident- death/number of accident 11.1% 4.8% Average number of deaths/accident Ratio accident - wounded/number of accident 33.3% 62.8% Average number of wounded/accidents In contrast to results presented in the main report, the average number of deaths per accident is lower in the cases of accident involving the inhalation exposure route than for those involving the dermal exposure route. 67 Minimal classification was not available for these substances. However, all the classification proposed in notifications were acute tox 1 or acute tox 2.

161 B5 Comparison of human consequences of accidents involving dermal exposures and those involving inhalation exposures in other countries The table below gives the results of the calculation of the two indicators for consequences analysis: Consequences of accidents involving toxic dermal and inhalation exposure routes Dermal exposure route Inhalation exposure route Ratio accident- death/number of accident 27.3% 25.7% Average number of deaths/accident Ratio accident - wounded/number of accident 81.8% 89.2% Average number of wounded/accidents These results confirm the results of the analysis of the whole database presented in the main report.

162 C1 Appendix C Details of main substances involved in dermalrelevant accidents from accident databases

163 C2 Main substance involved CAS No Harmonised classification Harmonised classification - Acute tox oral Harmonised classification - Acute tox dermal Harmonized classification - Acute tox inhalation Skin Corrosion Number of accidents confirmed Number of accidents suspected Total number of accident Other classification relevant for Seveso (based on harmonized classification Sodium cyanide NO Acute Tox. 1-2 Acute tox 1 Acute Tox X Potassium cyanide NO Acute tox 1-2 Acute tox 1-2 Acute tox X Hydrogen cyanide Acute Tox. 2 * Acute Tox. 1* Acute tox 2* Flam. Liq. 1; Aquatic Acute 1; Aquatic Chronic 1 Hydrogen fluoride Acute Tox. 2 * Acute Tox. 1* Acute Tox. 2 * Skin Corr. 1A No Hydrofluoric acid Acute tox 2* Acute Tox. 1* Acute tox 2* Skin Corr. 1A 1 1 No Toluene-2,6-di-isocyanate Acute tox 2* Bromine Acute tox 2* Skin Corr. 1A 1 1 Named substance Named substance 2-furaldehyde Acute tox 3* Acute Tox. 4* Acute tox 3* No Ammonia Acute tox 3* Skin Corr. 1B 1 1 Hydrazine Acute tox 3* Acute tox 3* Acute tox 3* Named substance Flam. Liq. 3, Aquatic Acute 1, Aquatic Chronic 1 Phenol Acute tox 3* Acute tox 3* Acute tox 3* Skin Corr. 1B No Cumene hydroperoxide Acute Tox. 4* Acute Tox. 4* Acute tox 3* Skin Corr. 1B 1 1 Aquatic Chronic 2; Org. Perox. E

164 C3 Main substance involved CAS No Harmonised classification Harmonised classification - Acute tox oral Harmonised classification - Acute tox dermal Harmonized classification - Acute tox inhalation Skin Corrosion Number of accidents confirmed Number of accidents suspected Total number of accident Other classification relevant for Seveso (based on harmonized classification Chlorine dioxide Acute tox 3* Skin Corr. 1B 1 1 Aquatic Acute 1 P-nitrophenol Acute Tox. 4* Acute Tox. 4* Acute Tox. 4* No Nitric acid Skin Corr. 1A 1 1 Ox. Liq. 3 Sulphuric acid Skin Corr. 1A 1 1 No Sodium carbonate No Toluene Flam. Liq. 2 Ethylene glycol No Butanone Flam liquid.2 Chloroformate Unknown NO X X X X 1 1 X Unknown Unknown NO X X X X 1 1 X

165 D1 Appendix D Detailed results of questionnaire responses The following pages contain details of the responses received to the questionnaire launched in November 2012 to January The full text of each question is included, along with either the full text of responses (numbered to avoid disclosing the identity of the organisations) or an analysis of the responses provided. At the end of each of the main sections, a summary of key conclusions is provided.

166 D1 Part 0 - Identity of the respondent Analysis of the questionnaire will require us to know if you are from industry or from the authorities, or another stakeholder group, and if you answer for your company or for a group of companies or an association. However, please be assured that details of your organization s response to the questionnaire will not be mentioned in our reporting and the data will be treated in confidence. Please be assured that all information provided will only be used for the purposes of the survey. 1. Category of the respondent Total respondents for this question 21 of 21 (100%) Option No of answers Percent Industry - Petrochemical 2 9 % Industry - Pesticides, pharmaceuticals 1 5 % Industry - General chemicals manufacture 4 19 % Industry Association - European 1 5 % Industry Association - National 4 19 % Public authorities National 3 14 % Public authorities Regional or local 2 9 % Other, please specify EU Agency / Institute Chemical University - Evaluating Safety Reports under the Seveso Directive for the Catalan Government. University 4 19 %

167 D2 2. In case of enterprises, information on the size of the company / enterprise Total respondents for this question 21 of 21 (100%) Option No of answers Percent belong to a multi-national company 7 30 % SME (less than 42 M of turn-over and 250 employees) 2 9 % independent but not an SME 1 5 % If other, please specify: EU Agency / Institute Association National competent authority Any size, from SMEs to big multinational companies, is represented in CEFIC Port Authority The BCF is an industry trade association representing 150 enterprises and some employees More than 4000 employees As we are an Industry Association, we only represents enterprises that are of all dimensions (small, medium, big, multinational). Authorities %

168 D3

169 D4 3. In case of enterprises, please select if the company / enterprise is: Total respondents for this question 21 of 21 (100%) Option No of answers Percent Operator of a Seveso upper tier establishment/site 3 15 Operator of a Seveso lower tier establishment/site 3 15 Operator of multiple Seveso sites (both upper and lower tiers) 2 10 If other, please specify: EU Agency / Institute Association National competent authority Not operating Seveso establishments Consulting company for managing the Seveso responsibilities of more than 40 sites not relevant (Industry association) Port Authority The BCF is an industry trade association University Not relevant (Industry Association)

170 D5 Part 1 - Identification of substances within the category acute toxic 3 dermal which are considered most relevant in terms of frequency and severity of accidents AMEC and INERIS have carried out a preliminary analysis of the Classification and Labelling Inventory, which is a database which contains classification and labelling information on substances notified under Regulation (EC) No 1272/2008 (the CLP Regulation) and registered under Regulation (EC) No 1907/2006 (the REACH Regulation), and also contains the list of legally binding harmonised classifications (Annex VI to the CLP Regulation). It is established and maintained by the European Chemicals Agency. ( It follows from this analysis that there are a large number of substances that are classified as acute toxic category 3, both substances subject to harmonised classification and self-classified substances. However, many of these substances are also classified in one or more other chemicals categories, some of which are covered by the Seveso directive, assuming that the relevant thresholds in Annex I are met (for tier 1 and tier 2 establishments). AMEC and INERIS have drawn up a list of substances currently classified as acute toxic 3 dermal (harmonized classification only), but not also classified under one or more of the other categories covered by Seveso. The list has been spilt in two parts that are accessible at list1 & list2. Since the list is based on harmonized classification only, the actual list of potentially affected substances could be larger, as it could also include substances self-classified as acute toxic 3 dermal. The following questions will help to further refine the list of potentially affected substances. 4. Are you aware of any substances (other than those on the list linked to above) that are classified as acute toxic 3 dermal which are not already included in the scope of the Seveso Directive due to other properties? Total respondents for this question 21 of 21 (100%) 5. If yes, for each substance that you would like to mention, please provide the following details: e.g. Substance XYZ:

171 D6 substance name, EC number, CAS number. the industrial sectors in which it is used (if known). the potential for major accident hazards (if known). Please use separate paragraphs for each substance/sector combination. Please note we are aware that you may not be able to provide an answer for each question. If so, please answer to the best of your knowledge. Total answers for this question 6 of 21 (29%) Answers: (5) Many of the substances included within List 1 would still be covered within the Seveso III Directive scope due to their Environmental Hazards, however I feel that their potential of being a Health Hazard also needs to be considered and taken into consideration. My expereince with reviewing COMAH safety reports in the UK is that if a substances falls within the Seveso Directive because it is dangerous to the environment then the number of Major Accident Scenarios involving that substances that will result in ill health are minimum since the report will focus more on the environmental requirements. Pyrocatechol EC number: CAS number: This susbatnce is used for the productiuon of dyestuffs, scents and pharmaceutical products. In addition it is also used as an antioxidising agent, disinfectant and developer in photography. It is a common building block in chemical synthesis. Risk of explosion when in contact with Oxidising agents. Will decompose with heat to form 1,3-Butadiene, ether, methane, carbon monoxide, aromatics. N,N-Dibutyltrimethylenediamine EC number: CAS number: It is a common building block in chemical synthesis. Combustible liquid. Thermal decomposition products include toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2). Can also result in Hydrogen Cyanide vapours. Forms explosive mixtures with air on intense heating. 3-Amino-1-phenyl-butane EC number: CAS number: It is a common building block in chemical synthesis. Combustibe liquid. Thermal decomposition products include toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2). 1,3-Dichloro-4-nitrobenzene EC number: CAS number: Used as additive to extreme pressure lubricants. It is also used in the production of vulcanisation accelerators, disinfectants, plant protection products and clouring substances. Combustible solid. Thermal decomposition products include nitrogen oxides (NO, NO2) and Hydrogen Chloride. 1,3-Dimethyl-2-imidazolidinone EC number: CAS number: is a cyclic urea used as a high-boiling polar aprotic solvent. It is used in a variety of applications including detergents, dyestuffs, electronic materials and in the manufacture of polymers. Combustible liquid. Thermal decomposition products include toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2). n-decylamine EC number: CAS number: Most widely used as a masking agent. Combustible liquid. Thermal decomposition products include toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2). Heating will cause a rise in pressure in container which could result in risk of explosion. 2-(1-Methylpropyl)-4,6-dinitrophenyl acetate EC number: CAS number: Risk of explosion if heated under confinement. Thermal decomposition products include toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2).

172 D7 1-(2-(Dimethylamino)ethyl)-4-methylpiperazine EC number: CAS number: Decomposition products are toxic carbon oxides (CO, CO 2) and nitrogen oxides (NO, NO2). Lindane EC number: CAS number: Under the CLP classification, Lindane is acute toxic cat 3 oral and cat 4 inhalation and dermal. If my understanding of the Seveso III Directive is correct then Lindane would not fall in the scope of the directive because it has an acute inhalation and dermal toxicity classification. Lindane is a forbidden persistent organic pollutant however there is a specific exemption to that ban which allows it to be used as a second-line pharmaceutical. Furthermore the HSE in the UK use Lindane as their toxic exemplar for a toxic solids warehouse fire using the FIREPEST model. A fire involving any Lindane used or stored onsite could result in Phosgene or Hydrogen Chloride being produced. Should Lindane no fall within the scope of the Directive? (6) not applicable (9) méthanol (n CAS ) (10) Name CAS 2,3-epoxypropyl methacrylate; glycidyl methacrylate vinyl-2-pyrrolidone methylpyridine; 2-picoline Morpholine (15) see answer to Q 4 (21) All the substances below are believed to be in area A4, i.e. they have potential to bring new sites into scope of Seveso, but have little or no major accident hazard potential as a result of the acute toxicity cat 3 dermal classification. Calcium dipropionate CAS Food processing sector (mould inhibitor for bakery products, processed cheeses etc) No major accident hazard potential (powdered solid) Calcium dipropionate CAS Agriculture sector (mould inhibitor for livestock and poultry feeds) No major accident hazard potential (powdered solid) Methacrylic acid CAS Chemicals/ plastics sector No major accident hazard potential. (Low volatility liquid stored at atmospheric pressure.) Sodium dodecyl sulphate CAS (Note: some ECHA notifications suggest Seveso-relevant environmental classification) Personal care products (toothpaste, bubble bath, shaving foam) No major accident hazard potential (solid crystals/ solutions in water stored at atmospheric pressure) Trientine CAS Pharmaceuticals sector No major accident potential low volatility liquid stored at atmospheric pressure Allyl hexanoate CAS Fragrances/ cosmetics No major accident potential low volatility liquid stored at atmospheric pressure Allyl heptanoate CAS

173 D8 Fragrances/ cosmetics No major accident potential low volatility liquid stored at atmospheric pressure Benzene (1-methylethyl) oxidized polyphenol residue CAS Chemicals sector No major accident potential low volatility liquid stored at atmospheric pressure Propylene diamine CAS Chemicals sector No major accident potential low volatility liquid stored at atmospheric pressure 3,6,9-triazaundecamethylene CAS Chemicals sector No major accident potential low volatility liquid stored at atmospheric pressure Tert-Butyl hydroperoxide CAS Chemicals sector No major accident potential in terms of dermal toxicity low volatility liquid stored at atmospheric pressure. Major accident potential due to phys chem. 6. Please provide details of any known references which indicate the potential for major accident hazards associated with these substances Total answers for this question 9 of 21 (29%) Answers: (5) The following databases were used to identify accidents involving the substances in List 1 and also those mentioned above: FACTS Hazardous Materials Accident Knowledge Base: The ARIA Database: (6) not applicable (9) MSDS (15) To our knowledge there are no references which indicate the potential for major accident hazards associated with acute toxic category 3 dermal (20) We are not aware of any reference wich indicates the potential for major accident hazards associated with acute toxic category 3 dermal (21) Major accident hazard potential assessed by expert judgment. See also response to Part 2. Outcomes of Part 1: 24% of the respondents are aware of substances (other than those on the list linked to above) that are classified as acute toxic 3 dermal which are not already included in the scope of the Seveso Directive due to other properties Several substances (27) were listed in the survey and will be used as inputs for the analysis done in Task 2

174 D9 Part 2 Views on significance of potential risks from acute toxic 3 dermal substances 7. In your opinion, do acute toxic 3 dermal substances (which do not also fall within another classifications currently covered by Seveso) have the potential to cause major accident hazards? Total respondents for this question 19 of 21 (90%) Option No of answers Percent Some 6 32 All 3 16 None If some or all please provide a justification for this. If some, please provide an indicative proportion. Total answers for this question 11 of 21 (52%) Answers: (5) Within the Directive a major accident is defined as: an occurrence such as emission, fire or explosion resulting from uncontrolled developments in the course of the operation of any establishment covered by the directive, leading to serious danger to human health or the environment, immediate or delayed, inside or outside the establishment, and involving one or more dangerous substances. A release of a toxic substances, even if the exposure route is dermal (the majority of the substances in list 1 are also acute toxic 3 oral which would not be included in the scope) would result in danger to human health and as such would fall under the definition of a Major Accident. In addition, a fire involving one of these substances would result in toxic gases, vapour or smoke due to heat decomposition e.g. Kelevan will decompose and emit toxic vapours of Chlorine. It therefore seems appropriate that this category/group of substances are included within the Seveso III Directive. The first driver for any amendments to the Seveso II Directive is lessons learned from past accidents. It seems that the review process has not identified the need to modify Annex I due to accidents with specific substances. The second

175 D10 driver however, is to adapt the scope due to technical progress, especially concerning new technologies, new energy carriers, emerging risks, - and also whether specific categories or substances are appropriately covered by the scope of Seveso. Looking at the substances in List 1 and the ones I have mentioned, these are all acute toxic 3 dermal substances that will fall out the scope of the new directive, however they all have the potential to cause a major accident hazard. Even with the existing Seveso II Directive there are not that many Acute Toxic 3 (dermal) relevant substances, for example if we consider Formaldehyde: Formaldehyde is included in the directive (as a named substance) due to it being an Acute Toxic 3 substance based on dermal toxicity. However, formaldehyde is used in large quantities in the phenol-formaldehyde process that produces a common industrial binder (resin). The phenol-formaldehyde process has a long track record of run-away incidents, in which an extremely rapid temperature and pressure excursion leads to a violent explosion of the reaction vessel. The accidents are reported to have had consequences for the general public. The formaldehyde clearly has a major accident potential, the concern being its reactivity rather than its toxicity. Since there is no generic Seveso II category for "reactivity hazards", formaldehyde is included in the directive for its toxic dermal properties. If the reason for the exclusion of acute toxic 3 dermal category is because not many have been found to be within the Seveso II relevant substances then the ones that would be included/relevant will have to be managed by named substances. There are two ways to ensure that these dangerous substances do not fall out the scope of the directive: 1. The Seveso III Directive should introduce some new named substances with specific thresholds to make up for those "lost" in the acute toxic 3 dermal category. 2. If no new named substances are introduced, the review should ensure that this category of substances are appropriately covered by the scope of Seveso even if they are not seen as having the potential to cause a major accident. Considering the information above, it seems appropriate that acute toxic cat 3 dermal substances are included within the Seveso III Directive with some additional notes (in Notes to Annex I) allowing for justified exclusions. (6) not applicable (7) If amount is relevant, major accident hazard can be not negligible for the population (11) Just those effects related to full scale spills contaminating large extensions with those substances. (13) Well, taking into account that a release of a substance acute toxic 3 dermal must be controlled by physical measure or by human intervention, it is clear that a major accident can be generated. But, at the same time, it is not normal that the only property of a substance is toxic dermal, probably have inhalation consequence too. Then, it is necessary to generate a relation list of toxic properties of the interest substance. (15) not relevant (18) If there is a release to the river or the sea the population swimming in the water or just using the water for domestic uses would be affected. (19) i.e. those substances which may undergo to runaway / uncontrolled reactions and/or have a relevant risk potential for workplace safety (21) Only a small percentage of dermal cat 3 substances would be expected to have major accident potential. These are most likely to be liquids, particularly any pressure liquefied gases since these would be stored under pressure. However none of the substances identified in list 1, list 2 or the additional substances in Part 1 of this questionnaire appears to be gases or potential pressure liquefied gases. By expert judgment, the proportion would be expected to be less than 1%. 9. Do you think that possible accidents involving acute toxic 3 dermal (only) substances are as significant as accidents involving other exposure routes (e.g. inhalation) in terms of potential for damage to health, environment and property? (From 0 to 5) Total answers for this question 21 of 21 (100%)

176 D11 To health (for human) To environment (including fauna) Remediation costs Significance of potential damage of accidents involving acute toxic 3 dermal substances relative to other exposure routes- MIN Significance of potential damage of accidents involving acute toxic 3 dermal substances relative to other exposure routes-avg Significance of potential damage of accidents involving acute toxic 3 dermal substances relative to other exposure routes-max Outcomes of Part 2: 53 % of the respondents think that acute toxic 3 dermal substances (which do not also fall within another classifications currently covered by Seveso) have the potential to cause major accident hazards The average figure here is of most relevance. Because the average is less than 2.5, the main conclusion is that respondents view acute toxic 3 dermal substances as less significant than toxic substances with other exposure routes. Some respondents also suggested to identify named substances when appropriate The possible accidents involving acute toxic 3 dermal (only) substances are on average considered less significant than accidents involving other exposure routes (e.g. inhalation). The average of the impact is between 1.4 and 1.6 out of 5) From Q7/Q8, it is clear that there is uncertainty on whether the substances can really cause significant accidents, so accident scenarios will be important.

177 D12 Part 3 - Available information on past accidents and near misses 10. Are you aware of any past accidents or near misses that have involved dermal toxic effects? Total respondents for this question 21 of 21 (100%) 11.. If yes please provide details of the following (if known). Total answers for this question 10 of 21 (48%) Answers: (5) I have used the FACTS Hazardous Materials Accident Knowledge Base ( and found the following accidents that involved acute toxic cat 3 dermal substances: 21 accidents involving Sodium Sulfide 3 accidents involving 2,4 Dichlorophenols 7 accidents involving Lindane 1 accident involving Pyrocatechol Tetramethylammonium Hydorxide - An engineer was accidentally drenched with concentrated TMAH solution (25%) whiles conducting a routine examination of the pipe system in a plant manufacturing thin film transistor liquid crystal displays. He was wearing a clean room suit with plastic goggles, but not a mask. TMAH sprayed all over his head. He closed the release valve and took a shower at the nearby emergency shower facility. 30 min after the accident the paramedic team arrived and found the injured person loosing consciousness. He suffered second degree burns on 24% of his total body surface area and third degree burns on 5% of his total body surface area. He passed away 8 days later. (6) Please note that no major accidents are known involving acute toxic dermal cat. 3 substances (7) SEVESO for chloracne (9) Some FA/accident but not major accident as SEVESO definition. (10) An accident was reported in the French data-base ARIA, which happened in the Netherland, in Rotterdam, and involved orthocresol (reported in List 1). The references of this accident are the following : ARIA /01/2003.

178 D13 (11) Accidents and near misses of this type are obviously contemplated in all Occupational and Safety Risk Evaluations. However, known cases involving population (i. e. Seveso) are usually associated to substances included in other lists of the Seveso Directive. (13) I am really not sure that the last answer is "yes" cause in some accident tha main consequence is not the dermal toxicity of the substance. But, at least, is one of the problems that you find to solve the emergency situation. For example, in accident that has big consequence for the environment, it is quite sure that for dermal contact will not be good too. (15) This question should be answered by the Competent Authorities of the Member State (see also answer to Q 29) (19) Workplace near misses with chemical burns e.g. phenols (20) This question should be answered by the Competent Authorities of Member States (see answer to Q29) Outcomes of Part 3: One third (33 %) of the respondents are aware of past accidents or near misses that have involved dermal toxic effects Some interesting examples are provided. They will be used as inputs for the Task 2 of the study Part 4 Available information on possible future accidents 12. Are you aware of any accident scenarios that have been considered within Seveso Safety Reports (or similar assessments) that relate to dermal impacts of acute toxic substances? Total respondents for this question 21 of 21 (100%) If Yes, please explain your choice: (5) SEVESO Safety Report (6) No accident scenarios involving acute toxic dermal cat. 3

179 D14 (14) A large gas cloud involving acetic acid anhydride and also HCL gas cloud can potential cause a major accident (15) see answer to Q If yes, please provide details of: - The substance involved (name, EC number, CAS number) - The installation type - A description of the accident scenario - If readily available, a copy of the relevant parts of the Safety Report or other documentation. Total answers for this question 5 of 21 (24%) Answers: (5) Acrylonitrile EC number: CAS number: The site primarily manufactures products used to enhance industrial processing in various industries such as papermaking, mining, oil extraction, wastewater treatment and textile processing. It also manufactures ingredients that are used in home and personal care products such as thickening agents. This site operates a continuous process. The report considered a leak in the transfer pipeline connecting the bulk storage tank in the tank farm to the reactor vessel in the manufacturing area. The report had considered other major accident scenarios such as catastrophic tank failure and unloading of the wrong materials into the acylonitrile tank. These other scenarios resulted in fatalities whilst the accident scenario considering the pipeline leak would only affect a small number of workers (worst case was considered to be 2)and it would be within the confinement of a bund. Considering the leak detection system in place and also the characteristic pungent smell of Acrylonitrile this scenario was not considered to be a representative major accident scenario. (6) see answer to question 1 (14) The scenario listed in our Safety report is gas-clouds that reach our surroundings and neighbors. (15) see answer to Q11 (20) see answer to Q In your opinion, what are the most credible scenarios for major accident hazards involving acute toxic 3 dermal substances? Please provide a description Total answers for this question 12 of 21 (57%) Answers: (2) --- (3) Release to the environment, rivers, lakes etc. (5) From my experience acute toxic 3 dermal substances are mainly stored in moveable containers and stored in warehouse therefore the most credible scenarios would be: - Inadvertent mixing of incompatible chemicals An acute 3 toxic dermal substances such as Pyrocatechol (1,2-Bensenediol) can explode when it comes into contact with an oxidising agent. - Warehouse fire involivng stored acute 3 toxic dermal substances The major accident hazard from such a fire is that dangerous substances could be entrained into the smoke plume giving rise to a hazard from toxic smoke. There is also the potential for a fire to cause loss of containment of dangerous substances and the potential for mixing of non-compatible substances. Many of the cute 3 toxic dermal substances considered are combustible. Spillages / Leaks

180 D15 This could be either on a storage tank, moveable container (IBC), pipelines etc. The consequences and severity would be low due to the fact that they can occur within a bund or because the number of people exposed are low. Scenarios caused by other dangerous substances There may be other major accident scenarios as a result of other dangerous substances held at the site. Once a site qualifies as coming under COMAH, all dangerous substances, regardless of the quantities held, must be considered for their potential to give rise to a major accident (Either directly or through escalation of events). (6) None (7) Large release in case of large amount with dispersion and downwind exposure for worker and population (9) For industrial tank in chemical plant, no major hazards. Some leaks but contain in retention. In case of explosion, could be project with different piece but important is surpression in this case not some drop of this kind of product... Perhaps during transport of for citern of methanol on road but no SEVESO major accident. (11) Explosions or runaway reactions spreading those substances at medium distances. I. e. rupture of a bursting disk through an open pipe. HOWEVER, it is easy designing prevention and protection measures against such scenarios. So their frequencies must be very, very low. They could be considered in a Quantitative Analisys of Risk, but they are not really relevant for public emergency response planning. (13) It is not a matter of the most credible accident. The main problem is the trainning of the emergency services in order to manage the release of the acute toxic 3 dermal substances. The scenario is any scenario that generate a loss of containment not confined. (15) None. (These scenarios are not relevant in the context of the Seveso Directive. See note under Q 29) (18) In general the most credible scenarios would be the release of toxic substances to the river or the sea. (19) Unintended release into workplace involving several people. Escape from air emission treatment devices e.g. filters which dispersion of toxic cloud (20) None. (These scenarios are not relevant in the context of the Seveso Directive. See note under Q29) 15. In your opinion, what is the worst-case consequence/impact possible through major accidents involving these substances? Total answers for this question 12 of 21 (57%) Answers: (2) --- (3) Environmental damage with sanitation and restoring costs as a consequence. (5) Most of the cute toxic 3 dermal substances have other hazard classification such as flammable or toxic via inhalation which could result in major accident scenarios with greater consequences. In my opinion the worst consequence scenario would be a warehouse fire involving stored acute 3 toxic dermal substances. The reasons for this are: 1. Some acute 3 toxic dermal substances will decompose to produce toxic substances such as nitrous oxides, carbon monoxide or Hydrogen Cyanide. In some cases high temperatures can result in explosion. 2. A large fire in such a warehouse not only causes the usual damage to stock and property but can threaten both people on site and those living downwind of the fire who may be exposed to smoke containing significant amounts of unburned toxic materials. An example of why a warehouse fire is the worst case consequence is the use of Lindane as a toxic exemplar by the HSE in the UK when using the FIREPEST model. The FIREPEST model was developed because warehouses were storing large quantities of pesticides or other toxic chemicals and there had been several major fires which posed a considerable hazard. (6) None

181 D16 (7) Large release in case of large amount with dispersion and downwind exposure for worker and population (9) Road risk accident (11) Direct contact due to accidental spreading as indicated above. (15) None. (see answer to Q 14) (17) Short-term health effects on those involved in the emergency (18) Dermal affection to the people in contact with the contaminated water. Inhaling the powder dispersed in the air when an accident occurs. (19) Severe injuries / deaths in heavy populated context e.g. due to air dispersion (20) None (see answer to Q14) 16. Are you aware of any other information on the potential for accidents involving acute toxic 3 dermal substances? Total respondents for this question 19 of 12 (95%) Outcomes of Part 4: Not so many scenarios are provided or not detailed enough Some substances evoked, e.g. Acrylonitrile are also flammable and already covered by the Seveso 2 directive Some ideas have been taken into account to draft the scenarios in Task 1 and 2.

182 D17 Part 5 Potential number of establishments affected 17. Roughly, in how many establishments do you estimate acute toxic 3 dermal substances are present in quantities over 50 tonnes and in quantities over 200 tonnes? Total answers for this question 5 of 21 (24%) Below the 5 tables presenting the answers collected, some remarks about the confidence of the estimations are proposed. These remarks have been obtained thanks to a personal correspondence with the respondent, either by or by telephone. These remarks help to perceive the overall confidence of the results of this question. The remarks apply for question 17 and for question 18. Over 50 tonnes Over 200 tonnes In the EU-27 6 In a specific Member State In a specific region In a specific sector of industry NB: This answer was provided by a representative from a large university. The level of confidence in this answer was rather low.

183 D18 Over 50 tonnes Over 200 tonnes In the EU-27 In a specific Member State (FRANCE) 25 8 In a specific region In a specific sector of industry NB: This answer was provided by the French public authorities and it is based on a survey which has been performed with the support of UIC (the French Association of the Chemical Industry). During this survey that took place in 2008 at the time COWI was preparing a report for the European Commission, 87 answers were collected and the numbers presented derive from this survey. Over 50 tonnes Over 200 tonnes In the EU In a specific Member State France: In a specific region Aquitaine: In a specific sector of industry Chimie EU27: NB: This answer was provided by an operator of a chemical low tier site belonging to a multi-national company. The level of confidence is very low and the respondent did not provide more information on the assumptions used to derive the estimated figures.

184 D19 Over 50 tonnes Over 200 tonnes In the EU In a specific Member State 1 In a specific region 1 In a specific sector of industry 1 NB: This answer was provided by the representative of a national industry association related to the chemical and plastic industry. The respondent was rather vague about the assumptions taken, and wrote: I looked at the list of substances involved and used my experience of 35 years in the Chemical Industry to make a best estimate related to the various questions. It is my opinion that the dermal toxicity is of minor importance since the dominant route to toxic effect is through the lungs. Over 50 tonnes Over 200 tonnes In the EU-27 In a specific Member State (United Kingdom) 55? (small number) In a specific region In a specific sector of industry NB: This answer was provided by the British public authorities and it is based on a survey aiming at identifying the dermal toxic substances that might have an impact on the Seveso III directive. The survey focuses in particular on calcium dipropionate and sodium dodecyl sulphate. The analysis of the results was not completed when the present report was prepared, and this is the reason why the confidence of the estimation is rather low.

185 D Of the above, how many of these installations are not already covered by the Seveso Directive (i.e. how many installations do not handle/store other substances falling under Seveso and/or only handle acute toxic 3 dermal substances that do not also pertain to another hazard category falling in Seveso). Total answers for this question 3 of 21 (14%) Over 50 tonnes Over 200 tonnes In the EU-27 6 In a specific Member State In a specific region In a specific sector of industry Over 50 tonnes Over 200 tonnes In the EU-27 1 In a specific Member State 1 In a specific region 1 In a specific sector of industry 1 Over 50 tonnes Over 200 tonnes In the EU-27

186 D21 In a specific Member State 55? (small number) In a specific region In a specific sector of industry As written above, the same remarks made for question 17 apply also for question What is your level of confidence in the estimations provided in the two previous questions? Total answers for this question 21 of 21 (100%) Ranking-MIN Ranking-AVG Ranking-MAX Level of confidence for the estimations Outcomes of Part 5/Q17, Q18 and Q 19: Only 5 answers were collected among the 21 respondents for Q17 and 3 for Q18 2 of the answers collected have been provided by public authorities in charge of the Seveso directive. Their estimations are based on survey that they have launched in their country to address the question of the impact of the inclusion of the dermal toxic 3 substances in the scope of the Seveso directive. The level of confidence is low: it shows that it is difficult to answer the questions 17 and 18, even after having performed a survey.

187 D If the Seveso Directive were amended to include these substances, what activities are undertaken by establishments that would come into the scope of Seveso (i.e. activities that use these substances but are not already covered by Seveso)? Please tick all that apply Total respondents for this question 6 of 20 (30%) Answers from industries (13): Option No of answers Agriculture 1 Chemical installation - ammonia 1 Chemical installation - carbon oxides 1 Chemical installation - chlorine 1 Chemical installation - fluorine or hydrogen fluoride 1 Chemical installation - hydrogen 1 Chemical installation - industrial gases 1 Chemical installation - inorganic acids 1 Chemical installation - nitrogen oxides 1 Chemical installation - other fine chemicals 2 Chemical installation - sulphur oxides, oleum 1 General chemical manufacture (not included above) 2 Handling and transportation centres (ports, airports, etc.) 1 Manufacture of glass 1 Plastic and rubber manufacture 2 Processing of metals 1 Production and manufacturing of pulp and paper 1 Production and storage of explosives 1 Production and storage of fertilizers 1 Production and storage of fireworks 1 Production and storage of pesticides, biocides, fungicides 2 Production of basic organic chemicals 2 Production of pharmaceuticals 3 Textiles manufacturing treatment 1 Waste treatment, disposal 1 Wood treatment and furniture 1 Not applicable / not known 2

188 D23 Answers universities (2): Option No of answers Agriculture 1 Chemical installation - other fine chemicals 1 Handling and transportation centres (ports, airports, etc.) 1 Production and storage of fertilizers 1 Production and storage of pesticides, biocides, fungicides 1

189 D24 Answers from Authorities (6): Option No of answers Ceramics (bricks, pottery, glass, cement, etc.) 1 Chemical installation - ammonia 1 Chemical installation - carbon oxides 1 Chemical installation - chlorine 1 Chemical installation - fluorine or hydrogen fluoride 1 Chemical installation - hydrogen 1 Chemical installation - industrial gases 1 Chemical installation - inorganic acids 1 Chemical installation - nitrogen oxides 1 Chemical installation - other fine chemicals 2 Chemical installation - sulphur oxides, oleum 1 General chemical manufacture (not included above) 2 Manufacture of food products and beverages 1 Mining activities (tailing and physicochemical processes) 1 Power supply and distribution 1 Production and storage of pesticides, biocides, fungicides 1 Production of basic organic chemicals 1 Production of pharmaceuticals 1

190 D25 Answers from all categories (21): Option No of answers Agriculture 2 Ceramics (bricks, pottery, glass, cement, etc.) 1 Chemical installation - ammonia 2 Chemical installation - carbon oxides 2 Chemical installation - chlorine 2 Chemical installation - fluorine or hydrogen fluoride 2 Chemical installation - hydrogen 2 Chemical installation - industrial gases 2 Chemical installation - inorganic acids 2 Chemical installation - nitrogen oxides 2 Chemical installation - other fine chemicals 5 Chemical installation - sulphur oxides, oleum 2 General chemical manufacture (not included above) 4 Handling and transportation centres (ports, airports, etc.) 2 Manufacture of food products and beverages 1 Manufacture of glass 1 Mining activities (tailing and physicochemical processes) 1 Plastic and rubber manufacture 2

191 D26 Power supply and distribution 1 Processing of metals 1 Production and manufacturing of pulp and paper 1 Production and storage of explosives 1 Production and storage of fertilizers 2 Production and storage of fireworks 1 Production and storage of pesticides, biocides, fungicides 4 Production of basic organic chemicals 3 Production of pharmaceuticals 4 Textiles manufacturing treatment 1 Waste treatment, disposal 1 Wood treatment and furniture 1 Not applicable / not known 2

192 D27 Outcomes of Part 5/Q20: The table hereunder presents the activities that were cited more than 3 times from all categories, and at least twice for one category of respondent: Activities Total Industry Universities Authorities Chemical installation - other fine chemicals General chemical manufacture (not included above) Plastic and rubber manufacture 2 2 Production and storage of pesticides, biocides, fungicides Production of basic organic chemicals Production of pharmaceuticals In which Member States are these establishments mostly located? Total respondents for this question 5 of 21 (24%) Belgium 2 50 Bulgaria 1 25 France 3 75 Germany 3 75 Italy Netherlands 2 50 Poland 1 25 Romania 1 25 Spain United Kingdom 2 50 Belgium 2 50 Bulgaria 1 25 France 3 75

193 D28 Part 6 Potential costs and benefits of amending the Directive The European Commission s Impact Assessment estimated that, on average, the annual costs for upper tier establishments newly coming under the scope of Seveso are around 30,000 EUR and for lower tier establishments around 5,000 EUR as average annual administrative costs (p. 90 IA full report These cost estimates are taken to arise from the following cost elements: One-off compliance costs, for example: Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc. Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories. Recurring administrative costs, based on: o o o Written update of safety report (one every five years). Written update of internal emergency plan (updated every three years). Cooperation with inspectors (frequency not indicated). Notification of presence or changes in presence of dangerous substances (5-10% of establishments every year). 22. If acute toxic 3 dermal substances were included within the Seveso Directive (in Annex I Part 1, with the same thresholds as for other H2 toxic substances 50t for lower tier and 200t for upper tier), what do you estimate the average costs would be, per establishment, for establishments which are not currently covered by the Seveso Directive? One-off compliance costs Total answers for this question 8 of 21 (38%) Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 1000

194 D29 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc. Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories 100 Cost estimate ( ) Preparation of notification and a major accident prevention policy 5000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 6000 Cost estimate ( )

195 D30 Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks. unknown Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 3000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 5000

196 D31 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks to Reviewing substance inventories 5000 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 200 Preparation of extensive safety report and a safety management system with emergency plans etc

197 D32 Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories Other, please specify: (4) new planning consents (6) Please see the cost estimation elaborated by CEFIC 2011 (will be send by ) (11) Increasing of taxes and fees related to major accidents (11) Increasing of taxes and fees related to major accidents (15) no elements for a reliable answer (depending on the specific situation and starting point); in 2011 a CEFIC cost estimate was provided. (19) The estimate costs should reflect the average values above indicated respectively for upper and lower tier levels for new establishments (20) We don't believe there are elements for a reliable answer (that depends on the specific situation and starting point of the involded site). (21) HSE does not have separate estimates for the above cost categories. However, most recent available and published estimates for the one off compliance costs for establishments not currently covered by the Seveso Directive are as follows: FOR THOSE MOVING INTO TOP TIER = 161,000 per establishment one off costs FOR THOSE MOVING INTO LOW TIER = 20, 000 per establishment one off costs Please note, these estimates do not include cost estimates for technical modifications to manufacturing or storage sites to reduce risks. Such costs are difficult to quantify because there is so much variability between sites, and any proportionate sample testing would not enable a robust estimate to be made. HSE initial IA estimated that to review all inventories, the total time per site for the Seveso III Directive could range from half a day to 5 days of time (i.e. between 125 and 1,200). If the scope of Seveso III is further changed to include Acute toxic 3 dermal, then another review of inventories will be required. This will probably take less time than that estimated for Seveso III, but it is not possible to quantify this with any reasonable accuracy. It is reasonable to say however that 125-1,200 is probably the top end of the estimate of cost per site to review inventories for this specific issue.

198 D If acute toxic 3 dermal substances were included within the Seveso Directive (in Annex I Part 1, with the same thresholds as for other H2 toxic substances 50t for lower tier and 200t for upper tier), what do you estimate the average costs would be, per establishment, for establishments which are not currently covered by the Seveso Directive? Recurring costs Total answers for this question 8 of 21 (38%) Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 1000 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc. Technical modifications to manufacturing or storage facilities to reduce risks.

199 D34 Reviewing substance inventories 100 Cost estimate ( ) Preparation of notification and a major accident prevention policy 2000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks. Not possible to specify Reviewing substance inventories 2000 Cost estimate ( ) Preparation of notification and a major accident prevention policy 6000/Y Preparation of extensive safety report and a safety management system with emergency plans etc. 6000/Y Technical modifications to manufacturing or storage facilities to reduce risks. Unknown Reviewing substance inventories 20000/Y

200 D35 Cost estimate ( ) Preparation of notification and a major accident prevention policy 3000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 5000 Cost estimate ( )

201 D36 Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 200 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories Other, please specify: (6) see answer to question 1 (11) Increasing of taxes and fees related to major accidents (15) no elements for a reliable answer (depending on the specific situation and starting point); in 2011 a CEFIC cost estimate was provided. (20) We don't believe there are elements for a reliable answer (that depends on the specific situation and starting point of the involded site).

202 D37 (21) HSE does not have separate estimates for the above cost categories. However, most recent available published estimates for the recurring compliance costs for establishments not currently covered by the Seveso Directive are: FOR THOSE MOVING INTO TOP TIER = 56,000 per establishment per year. FOR THOSE MOVING INTO LOW TIER = 11, 000 per establishment per year. Please note, these estimates do not include cost estimates for technical modifications to manufacturing or storage sites to reduce risks. Such costs are difficult to quantify because there is so much variability between sites, and any proportionate sample testing would not enable a robust estimate to be made. HSE initial IA estimated that to review all inventories, the total time per site for the Seveso III Directive could range from half a day to 5 days of time (i.e. between 125 and 1,200). If the scope of Seveso III is further changed to include Acute toxic 3 dermal, then another review of inventories will be required. This will probably take less time than that estimated for Seveso III, but it is not possible to quantify this with any reasonable accuracy. It is reasonable to say however that 125-1,200 is probably the top end of the estimate of cost per site to review inventories for this specific issue 24. If acute toxic 3 dermal substances were included within the Seveso Directive (in Annex I Part 1, with the same thresholds as for other toxic substances), what do you estimate the average costs would be, per establishment, for establishments which are already covered by Seveso but which would require additional measures to also cover the possible risks of acute toxic 3 dermal substances by the Seveso Directive? One-off compliance costs Total answers for this question 8 of 21 (38%) Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 1000

203 D38 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc. Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories 100 Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 3000 Cost estimate ( )

204 D39 Preparation of notification and a major accident prevention policy 6000/Y Preparation of extensive safety report and a safety management system with emergency plans etc. 6000/Y Technical modifications to manufacturing or storage facilities to reduce risks. Unknown Reviewing substance inventories 20000/Y Cost estimate ( ) Preparation of notification and a major accident prevention policy 0 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 0 Cost estimate ( ) Preparation of notification and a major accident prevention policy 10000

205 D40 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 5000 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 0 Preparation of extensive safety report and a safety management system with emergency plans etc. 6000

206 D41 Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories Other, please specify: (6) see answer to question 1 (11) same as above (15) see note to Q 22 (20) see note to Q22 (21) Preparation of notification and a major accident prevention policy Not possible to quantify at this stage Preparation of extensive safety report and a safety management system with emergency plans etc. It is not possible to quantify at this stage the additional costs of making sure the safety report and safety management system cover the new substances proposed. It is not expected these costs would be as significant as for establishments not currently covered by the Seveso Directive. Technical modifications to manufacturing or storage facilities to reduce risks. This cannot be quantified. There will be a great variability in experience between sites, so some may have to make only minor changes, and some much more significant changes. Greater understanding of which sites would be affected, and their current safety measures would be required to understand the impact on these sites. It may be that if the sites are in scope for other substances, then only minor modifications will be required for the new substances. Reviewing substance inventories HSE initial IA estimated that the total time per site for the Seveso III Directive could range from half a day to 5 days of time to review all inventories for the current proposed Seveso III Directive (monetised as between 125 and 1,200). If the scope of Seveso III is further changed to include Acute toxic 3 dermal, then another review of inventories will be required. This will probably take less time than that estimated for Seveso III, but it is not possible to quantify this with any reasonable accuracy. It is reasonable to say however that 125-1,200 is probably the top end of the estimate of cost per site to review inventories for this specific issue. 25. If acute toxic 3 dermal substances were included within the Seveso Directive (in Annex I Part 1, with the same thresholds as for other toxic substances), what do you estimate the average costs would be, per establishment, for establishments which are already covered by Seveso but which would require additional measures to also cover the possible risks of acute toxic 3 dermal substances by the Seveso Directive? Recurring costs Total answers for this question 8 of 21 (38%) Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000

207 D42 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 1000 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc. Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories 100 Cost estimate ( ) Preparation of notification and a major accident prevention policy 1000 Preparation of extensive safety report and a safety management system with emergency plans etc

208 D43 Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 3000 Cost estimate ( ) Preparation of notification and a major accident prevention policy 6000/Y Preparation of extensive safety report and a safety management system with emergency plans etc. 6000/Y Technical modifications to manufacturing or storage facilities to reduce risks. Unknown Reviewing substance inventories 20000/Y Cost estimate ( ) Preparation of notification and a major accident prevention policy 0 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks

209 D44 Reviewing substance inventories 0 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks Reviewing substance inventories 5000 Cost estimate ( ) Preparation of notification and a major accident prevention policy Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks

210 D45 Reviewing substance inventories Cost estimate ( ) Preparation of notification and a major accident prevention policy 0 Preparation of extensive safety report and a safety management system with emergency plans etc Technical modifications to manufacturing or storage facilities to reduce risks. Reviewing substance inventories Other, please specify: (6) see answer to question 1 (11) same as bove (21) As in question Please describe the source of information and basis of the figures for the above cost estimates. Total answers for this question 6 of 12 (50%) Answers: (2) our experience in preparing safety report (3) My 35 years of experience in the Chemical Industry (4) Recent additional Seveso site due to reclassification (6) CEFIC Issue Team Process and plant safety (9) experiences (11) Just an estimation of the cost for preparing and evaluating Safety Reports of SME. (13) It is based on the expirience after 10 years working on Seveso Directive and as a Process Safety Group Leader in Spain. (15) CEFIC ISSUE TEAM "Process and Plant Safety"

211 D46 (17) Estimate of average cost to review substance and mixture database to identify H311 substances and calculate amounts of raw materials, product in process and finished stocks. (18) The experience of working in this area for several years, preparing safety reports and other documents for several companies. (20) Federation ad hoc working group, in coordination with European Association (CEFIC) (21) One off compliance cost estimates have been taken from a report: Safety report regime - evaluating the impact on new entrants to COMAH. Prepared by Entec UK Ltd for the HSE, These estimates were then compared to previous estimates in another research report: Impact evaluation of the Control of Major Accident Hazards (COMAH) Regulations Which was delivered to HSE in The conclusion of this report was that the ENTEC study was reasonable. On-going compliance cost estimates have been taken from a survey of all COMAH sites, which received a 25% response rate, dating from Understanding around compliance costs has also increased via a series of small focus groups in If these substances were included within the Seveso Directive, what do you think would be the main benefits? Total answers for this question 14 of 21 (67%) Answers: (2) I do not see any clear benefit. (3) None, it would just make things more complicated and costly for no real reason. It is much more relevant to make the current legislation work efficiently first before we implement rules that are not relevant. (4) Unclear (5) The main benefit would be that Persistent Organic Pollutants, substances under the PIC scheme and substances such as chlorinated and organophosphorus pesticides with a high potential for human intoxication would be included within the scope of the SEVESO Directive. Also we need to consider the example of formaldehyde that clearly has a major accident potential due to its reactivity rather than its toxicity but since there is no generic Seveso II category for "reactivity hazards", formaldehyde is included in the directive for its toxic dermal properties. What would happen to other substances with similar properties under the new scope? (6) none (9) no benefits (11) None. (13) Not clear benefits for the population. Clear benefits for the emergency services and fire brigade to learn how to work with this substances. (15) NONE (17) None as I do not think any new establishments in the coatings and inks manufacturing industry would be brought within scope. (18) SAfety would improve and better prevention of chemical hazards and major accidents. (19) Improved control of major hazard potential (20) None (21) No clear benefits, existing regulation already covers the substances. The key disadvantage would be to dilute the regulatory effect of Seveso.

212 D Taking into account the costs and benefits, do you believe that these substances should be included within the scope of Seveso? Total respondents for this question 16 of 21 (76%) Option No of answers Percent Yes 4 25 No Uncertain Please provide any additional comments in relation to your response to this questionnaire. Total answers for this question 9 of 21 (43%) Answers: (3) I think this is an example where the cost benefit argument should have been used before we put too much energy down a path that is not really relevant (5) In my opinion the first driver for any amendments to the Seveso II Directive is lessons learned from past accidents. It seems that the review process has not identified the need to modify Annex I due to accidents with specific substances. The second driver however, is to adapt the scope due to technical progress, especially concerning new technologies, new energy carriers, emerging risks, - and also whether specific categories or substances are appropriately covered by the scope of Seveso. Looking at the substances in List 1, these are all acute toxic 3 dermal substances that will fall out the scope of the new directive. Many of the substances in List 1 would still be covered in the Seveso III directive due to their potential to be an Environmental Hazard but not for their potential of being a Health Hazard and this does not seem right. If the reason for the exclusion of acute toxic 3 dermal category is because not many have been found to be within the Seveso II relevant substances then the ones that would be included/relevant will have to be managed by named substances. There are two ways to ensure that these dangerous substances do not fall out the scope of the directive: 1. The Seveso III