European POPs Expert Team

Transcription

1 European Commission, Brussels PREPARATORY ACTIONS IN THE FIELD OF DIOXIN AND PCBs Final Report April 2002 European POPs Expert Team BiPRO Beratungsgesellschaft für integrierte Problemlösungen integrated research consulting and expertise Ökometric Bayreuther Institut für Umweltforschung

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3 This study has been funded by the European Commission. The results from this study are, in addition to other sources of information, a valuable input for future EU measures related to this topic. Nevertheless, it must be stressed that the conclusions and recommendations outlined in this study do not necessarily reflect the Commission's views.

4 Contents 1 Background, objectives and structure of the project Concept and Methodology Material flow approach Data sources Literature research Statistical data on food and feed Information request to competent institutions Information exchange with industry representatives International workshop Results from analysis Sampling plan and sampling Analysis of samples and reporting of results Estimation of weekly WHO-PCB-intake Analysis of chain of cause and effect Overview on the results of DLPCB analyses Ranges of levels for food and feedingstuffs on a Europeanwide scale Results for European Regions Overview on existing data Polychlorinated dioxins, furans and polychlorinated biphenyls (PCDD/Fs and PCBs) Overview on sources Properties and behaviour of PCDD/Fs and PCBs Environmental levels Feed and food levels Human exposure Trends Existing measures and proposals Polybrominated biphenyls...69

5 4.2.1 Overview on sources of PBBs Properties and behaviour of PBBs Environmental levels of PBBs Feed and food levels of PBBs Human exposure to PBBs Trends for PBBs Existing measures and proposals with respect to PBBs Polybrominated diphenylethers (PBDEs) Overview on PBDE sources Properties and behaviour of PBDEs Environmental levels of PBDEs Feed and food levels of PBDEs Human exposure to PBDEs Trends for PBDEs Existing measures and proposals with respect to PBDEs Polybrominated dioxins and furans (PBDD/Fs) Overview on PBDD/F sources Properties and behaviour of PBDD/Fs Environmental levels of PBDD/Fs Feed and food levels of PBDD/Fs Human exposure to PBDD/Fs Trends for PBDD/Fs Existing measures and proposals with respect to PBDD/Fs Chain of cause and effect Relations between sources and environmental compartments Relations between environmental compartments and feed/food Relations between and within feed and food Relations between food and human intake Dietary intake assessment Dietary intake assessment of WHO-PCB-TEQ as European average Average WHO-TEQ-PCB content of food...104

6 6.1.2 Average consumption of fat and cereals per citizen and day according to FAO-data Product related PCB-TEQ intake per week and kg bodyweight PCB-TEQ intake for product groups and average intake estimation Results for European regions Comparison with previous results for WHO-PCBs and WHO- PCDD/Fs Estimation: dietary intake assessment of WHO-TEQ as European average Conclusions and recommendations Conclusions Recommendations General recommendations Specific recommendations References Literature, Legislation, Proposals Overview on charts Overview on tables List of abbreviations Annexes Technical annex Classification Overview on properties and behaviour Selected physical-chemical properties (tables) Toxic equivalency factors Occurrence Levels Sampling plan, sample registration and identification Introduction to the sampling plan Representative Criterion 1: Importance of products Representative criterion 2: Regional distribution Concept to define the number of Samples Number of samples for regions and sub-regions...243

7 9.2.6 Production oriented approach and taking of individual samples Sample registration and identification Analytical methods Registration Sample Storage Pre-treatment Extraction Cleanup Matrix related analysis schemes Measurement (Identification, Quantification) Quality Assurance / Quality Control Measures Detailed results for all samples Statistical data for dietary intake assessment AUGE: Austria, Germany BENE: Belgium + Luxembourg, Netherlands FRAN: France GRIT: Greece, Italy IRUK: Ireland, United Kingdom POSP: Portugal, Spain SCAN: Denmark, Finland, Sweden International workshop, communication International Workshop...524

8 1 Background, objectives and structure of the project Polychlorinated biphenyls (PCBs), dioxins and furans are toxic substances encountered widely. Very small concentrations of these chlorine organic compounds may cause adverse environmental and health effects. The European Commission follows in its "Community Strategy for Dioxins, Furans and Polychlorinated Biphenyls" the opinion of the Scientific Committee for Food (SCF), which has established a tolerable weekly intake of 14 pg Toxic Equivalent (TEQ)/kg body weight. This recommendation is based on a thorough evaluation of all available data on various toxicological effects of dioxins and PCBs. The most effective way to reduce human exposure to dioxins and PCBs is to reduce the concentration of dioxins and dioxin-like PCBs (DLPCBs) in foodstuffs, because food consumption contributes more than 90% of total human exposure. Environmental contamination causes contamination of feedingstuffs and subsequently the contamination enters the human food chain. Consequently, lowering the environmental concentrations of dioxins and PCBs is crucial for lowering the contamination of feedingstuffs and food and thus reducing human exposure. Several studies have been performed collecting information on the presence of dioxins and dioxin-like PCBs in environment, feed and food and assessing human exposure to dioxins and PCBs. Several gaps in the current database have been identified, in particular with regard to dioxin-like PCBs. Against this background the present project was focused on closing the gaps in the current database and the collection of information on the occurrence of the mentioned contaminants in food and feed, their sources and the pathways most likely to lead to the occurrence of these compounds. Additionally polybrominated substances such as polybrominated biphenyls (PBBs), polybrominated diphenylethers (PBDEs) and polybrominated dioxins and furans (PBDDs, PBDFs) reveal similar problems. Therefore the collection of available information about these substances is included in the scope of the study. The project concerns the gathering of information to allow the Commission:! to propose legislative measures to reduce the presence of these compounds in feedingstuffs and foodstuffs;! to have at its disposal an improved inventory of releases of these compounds in order to act as a fully reliable indicator in the development of further appropriate policy for emission reduction and control. A main focus of the project was the sampling and analysis of feed and food materials across Europe in order to get an overview on the current contamination situation with dioxin-like PCBs across all Member States. Page 1

9 To follow these aims the working steps of the project can be summarized as follows: Determination and collection of representative sample for dioxin-like PCBs in key foodstuffs and feedingstuffs FWP 1/2 Overview on information and data about PBBs, PBDEs, PBDDs and PBDFs FWP 4 Taking into account available data on PCDDs, PCDFs and DLPCBs FWP 4 Analysis of samples FWP 3 Chain of cause and effect and material flows FWP 5 International Workshop FWP 6 Conclusion, Recommendations FWP = Focal working point FWP 7 chart 1-1: Working steps of the project The focal working points 1, 2 and 3 lead to new data on contamination levels based on more than 5,200 samples that have been collected in all member states of the European Community and about 2,600 of them analysed in one laboratory. An overview on the results is available in chapter 3, detailed data can be found in the annex (9.5) Focal working point 4 provides information on existing data which is summarized in chapter 4. Details are given in the annex (9.1). Focal working point 5 combines the information from the various data sources. The results of the analysis, regarding cause and effect relationships and material flows, are documented in chapter 5. Page 2

10 In chapter 6 the dietary intake of dioxin-like PCBs is assessed based on the new available data. This has been done in addition to the focal working points shown in chart 1-1 having in mind focal working point 7 which aims at the preparation of conclusions and recommendations that can be found in chapter 7. Finally the results have been presented and discussed on an international workshop (focal working point 6) in Brussels. The corresponding documentation is available in annex 9.7. The general concept and methodology of the project is described in an overview in chapter 2 on the following pages. Details and statistics related to the methodology can be found in the annex (9.2, 9.3, 9.4, 9.6). Page 3

11 2 Concept and Methodology 2.1 Material flow approach To fulfil the objective of the project it was agreed to investigate two types of material flows: 1 the flow of dioxins and PCBs 2 the flow of fat as a major basis for accumulation processes of dioxins and PCBs Obviously the material flow of dioxins and PCBs starts at the sources of these substances. Results from available literature data have been collected in order to submit the most recent data base. The results are documented in chapter 4 and 9.1. unwanted generated?? AIR Water PCBs produced Soil Plasticizers EMISSIONS Insulating & Cooling Oil Waste Feeding stuff HOT SPOTS chart 2-1: material flow: sources of PCBs The analysis of the sources is followed by an investigation of the environmental compartments, which might be affected by the sources. Literature data and data of an information request to relevant institutions show concentrations and accumulations in the material flows. The corresponding results are available in chapter 4, 5.3 and 5.4. Page 4

12 AIR Waste - WATER SOIL WATER PLANTS SEDIMENT FISH ANIMALS chart 2-2: material flow: environment, feed, food Some parts of the material flow in chart 2-2 are already points of the material flow, which is connected with feedingstuffs and food (i.e. livestock animals, fish and plants as basis for feed and food products). The chains belonging to feedingstuffs and food are complex and show various circles. For the structure of the material flow and for first quantifications a lot of data are necessary which are not available, in particular in the field of dioxin-like PCBs. Therefore a major task of the project was to generate new representative data for burdens of feedingstuffs and food with dioxin-like PCBs (DLPCB) in the European Union. In order to do this systematically the following stations of the material flows were examined. Page 5

13 Agriculture 1 (e.g. oilseed, vegetables, dry pulses, feed pees) Feedstuff Import Agriculture 2 (e.g. animals, milk, eggs) Food Industry Wholesale/ Retail Consumer chart 2-3: production and material flow orientated approach including imports The general methodological questions for the investigation were:! For which stations have samples to be taken and analysed?! Which types of feedingstuffs and food have to be analysed?! How many samples are necessary to obtain representative results?! How can regional differentiations be made? Important answers on these questions could be derived from the second investigated material flow, the product related fat flow for the European Union. Background of the chosen procedure is one important physical-chemical property of PCBs: their high fat solubility. As a consequence the thesis was derived that the occurrence of PCBs is correlated with the occurrence of fat. Analytical results confirm the thesis. Samples low in fat, such as sugar were analysed and indeed no significant PCB contamination could be detected. In addition, it could be proved that all fat containing samples contain PCB contaminations even if the concentrations found vary to a large degree. However, the question came up whether it would be reasonable to follow a top-down (production oriented) approach, which means looking at the PCB concentrations of produced fatty products, or whether it would be advantageous to follow a bottom up (consumption oriented) approach which means looking at the PCB concentrations of consumed products. The advantages of the production oriented approach can be seen in: Page 6

14 close relation to both, sources and endpoints possibility to identify material flows and causal chains appropriate starting points for the implementation of legislative measures The advantages of the consumption oriented approach can be seen in: direct relation to the dietary intake appropriate starting point for consumer recommendations It was agreed to follow the production oriented approach as the expected advantages of detecting a chain of cause and effect and to be able to react with legislative measures was weighted highly. These advantages occur for examples by investigating chains like shown in chart 2-4 and the possibility to compare the concentrations found with limit or action values. Green Crop Bovine Feed Grain Milk Bovine Meat Butter Cheese pg/g dry weight 2 pg/g lipid chart 2-4: selected PCB-TEQ levels in the feed and food chain Consequently only a rough calculation on dietary intake figures could be done as food prepared for consumption such as mixed consumer products like pizza, fried fish or cooked meat have not been examined. With the material flow of fat a reliable statistical basis was available to find representative samples regarding the importance of the fat content of products and the importance of the produced fat amounts in the European Union. Page 7

15 2.2 Data sources In order to give an overview on recent information on PCDD/Fs, PCBs, PBBs, PBDEs and PBDD/Fs, the information collection and evaluation was based on the following sources:! data from relevant scientific literature! statistical data on feed and food! data and information which is available from important Commission studies and reports! an information request to competent institutions at international level! individual information exchange with industry representatives! conclusions from an international workshop! new generated data resulting from the analysis of the representative food and feed samples According to the project aims the focus of the information overview was different for the various substances in question. The general objective of the overview is to compile information for these substances regarding their identity, environmental relevant physical-chemical properties, analytical aspects, possible adverse effects, transport and fate, environmental and food and feed levels, human exposure, trends and related legislation and measures. Initially, PBDEs have not been subject to the information overview, but it turned out that due to certain aspects these substances give reason for concern (see chapter 4.2) and as a consequence it was decided together with the responsible project coordinators of the Commission to include additionally an overview on PBDEs. This overview is based on recent scientific literature and to a large degree on discussions and results presented at the Second International Workshop on Brominated Flame Retardants which took place in May 2001 at Stockholm University. Page 8

16 2.2.1 Literature research According to the project aims, the relevant scientific literature for PCDD/Fs, PCBs, PBBs, PBDEs and PBDD/Fs has been identified and evaluated for the contaminants in question. The literature that is relevant for each of these POPs is cited in the corresponding chapters (see chapter 4.1 and 4.2). A comprising list referring to literature references can be found in chapter 8.1. Literature work also includes the identification and evaluation of reports, studies and background information which is available at the European Commission Statistical data on food and feed To get a representative and broad overview on the PCB-contamination of food and feedstuff the development of a sampling plan for all member states of the EU was necessary. A lot of information concerning feed and food production and consumption is available from FAO data (see chapter 9.2). Therefore FAO statistical data have been chosen as a basis for the determination of a differentiated fat material flow for all member states. These data have been cross-checked with EU data basis. The Food and Agriculture Organisation of the United Nations (FAO) publishes food balance sheets (FBS) for each country 1. In these sheets for about 20 categories of product groups (e.g. cereals, meat, vegetable oils) containing more than 100 products extensive national data is given and calculated following a consistent scheme, which is shown in the following chart. 1 Internet: Page 9

17 PRODUCTION + IMPORTS +/- STOCK CHANGES - EXPORTS = TOTAL SUPPLY Waste Seed FEED FOOD PROCESSING Other uses metric tons Consumption per capita kg/year Consumption of fat per capita gram/day = Fat content of products chart 2-5: Calculation scheme of FBS and own exploitation The amounts used for feed, food and processing were taken to determine the importance of products by calculating the fat amount related to this amounts. The production amounts were taken to determine the importance of certain regions and sub-regions for a certain product. Consumption data was the basis for the estimation of the intake. Page 10

18 The main advantages in using FBS are: + Data for basic products is available, which is required to follow the production-oriented approach. + There is data for the use of certain products available (Food, Feed, Processing, Waste, Other Use). + Data is consistent throughout all countries. + The standards how the data is accumulated and calculated can be assumed to be internationally accepted. + A weighted average fat content per product can be calculated from the consumption data per capita. Possible mistakes in the consumption data per capita (see below) are compensated because the absolute intake is not relevant for this calculation. It has to be considered that the FAO data is connected to some problems: - For some products (e.g. cereals, milk) differences to EU-statistics were found. - There is a time delay of about 3 years before data is published; therefore, numbers from 1998 had to be used 2. - There is no differentiation between intra- and extra-eu-trade in the import and export numbers. - The processing within the food-industry is partially included in the numbers for used for food. This does not affect the quality of the production oriented approach for sampling but the intake per capita might be wrong for secondary products (e.g. margarine or mayonnaise) which are processed in the local industry and exported mainly afterwards without being documented in the FBS. - There is no data for feedstuff or some final products such as cheese available. Considering that the FBS was used mainly to calculate a EU-fat material flow to define priorities for the sampling plan the advantages of using this data base are judged more important than the disadvantages. Furthermore the FBS is the only available data source, which contains data respective to the pathway of products. The second objective of using the FBS was to estimate an EU average of the weekly PCB intake. The main problem uncertainties in the intake figures per capita related to exports of the food industry is less important considering that the intra EU-trade of food is much more important than the extra EU-trade. Regional intakes can only be calculated in order to assess relative differences between the regions. 2 In the meantime data for 1999 is available Page 11

19 2.2.3 Information request to competent institutions In order to dispose of most recent information on the relevant substances and in order to be able to include the know how and the opinion of competent institutions and persons an information request has been carried during the second half of To this end more than 50 involved institutions and persons within all EU member states have been asked to provide relevant data and information. After a short introduction to the project background, the institutions have been asked for reports, publications or contact addresses related to the subject. According to the working field each person or institution has been asked for recent data that could be relevant with respect to the following questions: # Do you dispose of recent data 3 on feed/food or environmental contamination levels with PCDDs, PCDFs and in particular dioxin-like PCBs 4? # Do you furthermore dispose of recent data 5 on feed/food or environmental contamination levels with PBDDs, PBDFs, PBBs and PBDEs 6? # Is there a short overview on existing and proposed measures in your country related to the relevant substances? In order to facilitate the provision of data, a data compilation form similar to that used for the compilation of data in the SCOOP project task was used (see chapter ). The compilation form consists of an explanatory legend that explains how data can be provided by filling out one of the two alternative data input matrices. Appropriate data and information resulting from the information request has been taken into consideration in this report. 3 i.e. in particular recent information on contamination levels with PCDDs, PCDFs or PCBs which is not included in the SCOOP report (DG Health and Consumer Protection: Reports on tasks for scientific cooperation; Report of experts participating in Task 3.2.5; Assessment of dietary intake of dioxins and related PCBs by the population of EU Member States, 7 June 2000) or the SCAN report (European Commission, DG Health and Consumer Protection: Opinion of the Scientific Committee on Animal Nutrition on the dioxin contamination of feedingstuffs and their contribution to the contamination of food of animal origin, adopted on ) 4 i.e. the 12 WHO-PCBs or dioxin-like PCBs according to van den Berg, i.e. in particular recent information on contamination levels with PBDDs, PBDFs or PBBs which is not included in the relevant IPCS reports from 1998 and 1994 respectively (International Programme on Chemical Safety, Environmental Health Criteria 205: Polybrominated dibenzo-p-dioxins and dibenzofurans, WHO, Geneva, 1998 and Environmental Health Criteria 152: Polybrominated Biphenyls, WHO, Geneva, 1994) 6 i.e. information which has not been presented at the BFR Workshop 2001 in Stockholm Page 12

20 2.2.4 Information exchange with industry representatives For the consideration of existing data and information it is important to include also the opinion and data from industry representatives. To this end experts from the relevant sectors of involved industries (e.g. chemical industry, food and feed industry and in particular fisheries industry) have been contacted for an information exchange related to the subject. Thus, for this study unpublished industry data could be evaluated in order to improve the current knowledge about the relevant POPs International workshop The preliminary results of the present project have been presented at an international workshop, at Brussels 31 January 02. Recommendations and conclusions from the workshop participants have been taken into consideration with respect to the final results and conclusions of the present report. The workshop programme and a protocol with the main topics that have been discussed can be found in the annex (chapter 9.7) Results from analysis The fundamental data source for new generated data on DLPCB-contamination levels of European environmental compartments and feed and food items are the results from the analysis of samples taken all over Europe. The methodology for sampling and analysis is described in chapters 2.3 and 2.4. The results themselves can be found in chapter 9.5. Page 13

21 2.3 Sampling plan and sampling Due to time and budget restrictions the following limiting factors for samples had to be followed: < 300 mixed samples < 4,000 collected samples Behind these figures stands the strategy to include a certain amount of collected samples to mixed samples which where then analysed. In this way it was possible to include a huge amount of samples and to receive average contamination levels in a very efficient way. Furthermore, this mixed sample approach enables to determine maximum contamination levels of collected samples. Mixing samples were produced by mixing equal amounts of up to 25 collected samples of one region. Consequently a theoretic maximum contamination level of every single collected sample can be calculated by assuming 24 samples with no contamination and assuming 1 sample containing the total amount of PCB. For a representative sampling, the question had to be answered how 4,000 samples should be attributed to feedingstuffs and food products in 15 member states. To answer these questions and to find representative samples the following criteria have been considered: (1) importance of products (2) quality of analysis. (3) importance of regions The consideration of these criteria defines the terms "representativity" and "reliability" for the results. Criterion (1) means that for a product with a high importance more samples have to be collected than for a product with a low importance. To determine the term importance the fat amount of product used for food, feed and processing based on FBS is followed and an ABC analysis is applied. For details see chapter 9.2. As a result the following 42 categories have been identified. They cover almost 90% of the fat amount, which is used for food, feed and processing within the EU. Due to criterion (2) quality of analysis for every collected individual sample a back up sample is necessary which leads to a limitation of 2000 individual samples. Still open is the answer to criterion (3): importance of regions. The design for the study follows 7 regions within the European Union. In addition to these regions the import (IMP) of materials will be considered as an eight region. For the 8 regions results are available for the 42 product categories (if all product categories are produced in a region). For each product (or product group) the importance of a region is generally determined by the amount of production of the product according to the FAO food balance sheet. The corresponding value for imports are extra-eu imports taken from EU-statistics. For details see Page 14

22 chapter 9.2. It would not be representative for the regions to collect samples just at one place of a country and consider the results as valid for the region. Therefore for the purpose of regional representativity the regions are structured by sub regions. Samples have been taken due to the importance of the sub regions and broadly spread over the sub regions. Region (Abbreviation) Sub-Regions Remarks Denmark, Finland, Sweden (SCAN) 3 Denmark, Finland, Sweden Austria, Germany (AUGE) 3 Austria, North Germany, South Germany Belgium, Luxembourg, Netherlands (BENE) 2 Belgium & Luxembourg, The Netherlands Ireland, United Kingdom (IRUK) 3 Ireland, North UK, South UK France (FRAN) 2 North France, South France Greece, Italy (GRIT) 3 Greece, North Italy, South Italy Portugal, Spain (POSP) 3 Portugal, North Spain, South Spain Import (IMP) 6 NAFTA 7, Mediterranean countries 8,MEEC 9, MERCOSUR 10, ACP 11, Other 12 TOTAL 25 Table 2-1: Regions and Sub-regions All the sub regions follow political and statistical borders. The number of samples within a subregion was determined due to production data (volume or value) as far as data is available. The minimum was one sample except for screening products. Following the mentioned criteria (1) to (3) the following sampling plan is resulting: product number of mixed samples number of collected individual samples 1 pig meat bovine meat USA, Canada, Mexico 8 Algeria, Cyprus, Egypt, Israel, Jordan, Lebanon, Malta, Marocco, Syria, Tunisia, Turkey, West Bank and Gaza Strip 9 Middle and Eastern Europe Countries: Poland, Czech Republic, Hungary, Slovenia, Estonia, Slovakia, Romania, Bulgaria, Latvia, Lithuania 10 Brazil, Paraguay, Argentina countries in Africa, the Caribbean and in the Pacific Area 12 There is no product specific data available for Switzerland, Norway, Russia, ASEAN, SAARC, India, China, Japan, South Africa, Australia and New Zeeland. Shares for product groups imported from these countries have been calculated by Total imports minus known country groups. Page 15

23 product number of mixed samples number of collected individual samples 3 poultry meat animal fat raw producer milk fresh milk (consumer milk) butter cream cheese soybeans soybean oil soybean oilcake rape and mustard seed rape oil rape oilcake sunflower seed sunflower seed oil sunflower oilcake olives olive oil bovine feed pig feed poultry feed wheat barley maize oats pelagic and demersal fish 7 37 Page 16

24 product number of mixed samples number of collected individual samples 29 fish oil freshwater fish eggs peas apples oranges grapes tree nuts cocoa beans vegetables bone und blood meal starchy roots sugar green crop 7 87 sum 232 2,587 Table 2-2: Number of collected and mixed samples of 42 categories The complete resulting sampling plan and the samples that have been taken can be seen in the next chart: The number of samples resulting is nearly 2,600. For each sample a back-up sample is collected which leads to a total of approximately 5,200 collected samples. The enlargement of 30% more collected samples compared to the design of the study was regarded necessary by the project team. The additional collection was done on the costs of the project team to ensure a broader representativity. Page 17

25 AUGE BENE SCAN POSP FRAN IRUK GRIT IMP Sum 001 pig meat bovine meat poultry meat animal fat raw milk (producer milk) fresh milk (consumer milk) butter cream cheese soybeans soybean oil soybean oilcake rape and mustard seed rape oil rape oilcake sunflower seed sunflower oil sunflower oilcake olives olive oil bovine feed pig feed poultry feed wheat barley maize Page 18

26 AUGE BENE SCAN POSP FRAN IRUK GRIT IMP Sum 027 oats pelagic and demersal fish fish oil freshwater fish eggs peas apples oranges grapes tree nuts cacao beans vegetables bone- and blood meal starchy roots sugar green crop SUM ,587 Table 2-3: Sampling plan Page 19

27 2.4 Analysis of samples and reporting of results For the objectives of the project it is necessary to analytically determine levels of dioxin-like PCBs in collected food and feedingstuff samples. In detail this includes (chart 2-6): Sample registration, sample storage of ~ 2600 individual samples Preparation of 231 mixed (compound) samples and additional QA/QC samples (blanks, double analyses) Pre-treatment, extraction, clean-up and measurement of mixed samples Quality assurance and quality control measures (QA/QC) Documentation individ. sample receipt Registration Storage samples complete for mixed sample Preparation of of mixed mixed samples Pretreatment Extraction Clean-up Measurement QA / QC Measures QA / QC Measures Documentation Final Result Final Result chart 2-6: Working steps of project working point 3 Analysis of DLPCBs includes four non-ortho-substituted PCBs (PCB 77, PCB 81, PCB 126, PCB 169) and 8 mono-ortho-substituted PCBs (PCB 105, PCB 114, PCB 118, PCB 123, PCB 156, PCB 157, PCB 167, PCB 189) as recommended by the WHO (Van den Berg et al., 1998). Analysis of DLPCBs in food and feedingstuffs were executed in an accredited laboratory according to DIN EN ISO/IEC and were based on state-of-the-art methods for pretreatment, extraction, cleanup and measurement as outlined in detail in chapter 9.3 and following QA/QC requirements as listed in chapter 9.4. Measurement was based on high resolution gas chromatography / high resolution mass spectrometry (HRGC/HRMS). Usual achievable limits of quantification (instrument based) within this study were 1-5 pg absolutely and pg absolutely for non-ortho PCBs and mono-ortho PCBs, respectively. Sample based LOQ depends on the used sample amount, presence of interferences etc. Repeated analyses of total samples resulted in an average reproducibility of below 20 %. Results are presented in pg of the individual PCB congener per reference unit (fat, dry matter and for fish samples additionally fresh weight). The WHO-PCB-TEQ was calculated on basis of Page 20

28 the toxicity equivalent factors of Van den Berg et al. (1998) and is presented for both including no limit of quantification (LOQ, lower bound levels), half of the LOQ (medium bound levels) and full LOQ (upper bound levels). Results are listed in detail in chapter Estimation of weekly WHO-PCB-intake The estimation of a PCB-TEQ 13 intake was not a primary aim of the project. The dietary intake estimation is based on a limited amount of data (i.e. the analytical results from the present study) and there are several uncertainties related to the method used for dietary intake estimates (see below). It was decided on the basis of the known limitations to concentrate on an estimate of the EU average dietary intake of PCB-TEQs. However, having in mind even more important uncertainties, also regional averages have been calculated. When interpreting the results, this has to be kept in mind. The need for comparable production data and the food and feed related use of primary products led to Food-Balance-Sheets (FBS) published by the FAO on the Internet. The FBS were used as basis to establish the sampling plan (see chapter 2.3). In the FBS consumption data for each product is documented either on a total basis (kg product/year and capita) or on a fat basis (g fat/day and capita). Combining these data with the analytical results leads to a rough estimate of the European average TEQ-PCB intake. As mentioned in FBS contains mainly raw material data ( primary products e.g. wheat, produced milk, meat). The estimate is based on the concept, that burdens of PCBs remain comparatively constant during industrial processes leading to secondary (consumed) products. Some factors may lead to uncertainties of calculated intake figures: i. Waste effects during processing, trading chain, cooking and after consumption of food are higher than the waste amounts given in the FBS. PCB content of food-related waste is not included in the estimate. ii. Processing or cooking effects such as extraction of PCBs to used oil/fat iii. Surface effects, especially for processed vegetable and fruits (cereals were sampled threshed, oranges and potatoes were shelled all other fruits and vegetables washed as part of the analytic preparation). iv. In two product groups of minor importance concerning the PCB-content (vegetables, and pulses) only one product was sampled. Peas were chosen because of their high importance for feedingstuffs and sampled according to the representative criteria. For tomatoes only screening samples were taken. The directly eaten oilseeds (soybeans, rapeseed, sunflower seed and olives) were chosen because of their importance for the production of oil and oilcake. The product with the highest share of directly eaten oilseeds (shell nuts) was not selected because of its small contribution of fat to the human diet 14. In all three groups the estimation factor to calculate from the sampled products to the product group is relatively high. On the other hand the effect seems to be considerably 13 if not stated other, PCB-TEQ always means WHO-PCB-TEQ 14 For the same reason samples of offals - as single product group in the FBS - were not taken. Page 21

29 minor due to the estimate that these groups contribute less than 1% to the estimated total TEQ-PCB intake (see chapter 6.1). v. statistical deficiencies of FAO Food-Balance-Sheets (see chapter 2.2). The calculation leading to the estimate is done in 5 Steps: 1) Calculating a weighted EU-average PCB-TEQ content of each product based on analytical results and FAO-production data. 2) Calculating an EU-average consumption of fat or product (cereals, fruits, vegetable and starchy roots) per day, capita and product based on FAO-Data. This average was calculated weighted by the population of each country and region. 3) Calculating consumption of PCB-TEQ per product, day and capita by multiplying the results of 1) and 2) 4) Estimation of the intake of PCB-TEQ of product groups by calculating the share of products within a product group, which have not been sampled and analysed, assuming the same average content of PCB-TEQ like in analysed products within the same group. The share was calculated based on the consumption of product or the consumption of fat related to the product respectively. 5) Estimation of the EU-average PCB-TEQ intake per week and kg bodyweight by addition of the product groups. Estimates for the regions have been made following the same scheme. Instead of the EUaverages described in step 1) and 2) regional averages were calculated and the important uncertainties which are described below have to be considered. The detailed description of the calculation is following: 1) Calculating an EU-average PCB-TEQ content of each product based on analytical results and FAO-production data. Σ P R * TEQ R TEQ Avg = [pg/g fat or dry matter] (1) P T P R Production amount of a product in a region or imported amount (extra-eu) 15 ; 15 R= AUGE, BENE, France, GRIT, IRUK, POSP, SCAN and IMP Page 22

30 P T TEQ R Total production of a product (Extra-EU imports included); Analytical result of TEQ-PCB for the mixing sample originated from this region; TEQ Avg Average contamination of a product with TEQ-PCB To get an idea about the range of contamination the lowest and highest WHO-TEQ-PCB value found in regional mixing samples for a product are important indicators. They are named TEQ max and TEQ min in the following. 2) Calculating an EU-average consumption of fat per day, capita and product based on FAO- Data. The consumption values per citizen were calculated according to the analytical data either on a fat basis or on a product intake basis, depending whether a TEQ in pg/gram fat or a TEQ in pg/gram dry matter was measured. The latter is only relevant for cereals. Due to the low contamination of cereals (the share of cereals to the total intake can be estimated less than 1% of the total TEQ intake) the difference between total weight and dry matter was not taken into account. Page 23

31 The average EU-consumption was calculated as follows Σ C R * IN R IN Avg = [g fat or cereal/day] (2) C T C R C T IN R IN Avg Citizens in a region; Citizens within the EU; Regional consumption of fat related to product (or cereal) per citizen and day in g fat/day or g product/day for cereals according to FBS; Average consumption of fat or product related to product per EU-Citizen and day The statistical problems related to FBS that are described above (see chapter 2.2) are compensated very well by the calculation of the average of the EU-average (fat) consumption. The absolute numbers of regional consumption may be not accurate because of processing steps, which are for many products between the market supply of a product and the real intake by the consumer (e.g. cereals bread, meat sausage). The regional values seem to be reasonable too and show plausible differences in regional diet habits. Nevertheless, the relations between the regional consumption numbers are giving useful hints to understand and describe different regional consumption habits. Another uncertainty belonging to products, which are used in the food industry and not directly consumed is, that The FBS takes exports and imports of such secondary products not into account. That does not matter calculating EU-averages because all the intra-eu trading is covered. On a regional basis this factor (exporting of products of the regional food industry) has to be considered especially for products, which are only produced in few plants located in single countries. In spite of this the calculated regional fat consumption per capita and day seems to be reasonable, even considering that imports and exports of secondary products are not taken into account Waste effects seem to be more important Page 24

32 3) Calculating consumption of PCB-TEQ per product, week and kg bodyweight TEQ Avg * IN Avg *7 IP TEQ = [pg PCB-TEQ/week and kg bodyweight] (3) 70 IN Avg Average consumption of fat related to product per EU-Citizen and day TEQ Avg Average contamination of a product with TEQ-PCB 7 Number of day per week 70 Estimated average bodyweight per citizen IP TEQ Estimated intake of PCB-TEQ per product, week and kg bodyweight The TEQ-PCB intake per Citizen related to a single product was estimated by multiplying equation (1) and (2). The result was divided by 70 to get the intake per kg body weight and multiplied with 7 to calculate an intake per week. To be able to estimate a range of the intake the minimum and maximum level of TEQ-PCB for a product within all regions was used in equation (3) instead of TEQ Avg. The estimation of regional intakes per product is not possible accurately using the FBS as a data base for the following reasons: a) The influence of the PCB-TEQ of imported products is not calculated. The analysed samples have a clear and documented origin within the region where the sample was taken. b) The influence of imports and exports of secondary products. Estimating PCB-intake per capita related to products leads to the problem described above especially uncertainties due to the high PCB-TEQ contents of fish and fish oil. These products deliver only 1 2% of the fat intake per capita. Because of the high contamination of fish and fish oil compared with other food the share of the PCB intake can be estimated in a range of ~40% - ~80%. Especially fish oil is not consumed directly but processed to up to ~70% for secondary products like margarine or mayonnaise in a few countries (mainly Spain, UK, Denmark, Germany). According to the systematic of the calculation done by the FAO in the FBS the amounts of processed fish oil are included in the intake per citizen, which leads to obvious wrong numbers with national peaks in the countries that are processing a lot of fish and especially fish oil. Another factor of uncertainty is that fish oil if used e.g. in margarine or mayonnaise undergoes processes (e.g. hydrogenation, hardening) which reduces significantly the dioxin content and very probably also the PCB content. Regional intake values were calculated too but the main goal of this calculation was not to generate information about absolute values but to show relations between the regions. Especially the influence of regional consumption habits on the contribution of PCB-TEQs from food seems to be important in order to be able to identify regions and products, which need more specific investigations. Most important results are the shares of fish and meat to the total Page 25

33 intake of PCB-TEQs within a region. The interpretation of the regional results is described in chapter 6.1. These effects do not affect the estimation of EU-averages significantly because all uncertainties due to EU-internal trade are compensated by the calculation of weighted averages and the external imports are taken into account. The remaining uncertainties are extra-eu exports.. 4) Estimation of the consumption of PCB-TEQ of product groups by calculating the share of products within a product group, which have not been sampled and analysed. F G IPG TEQ = ΣIP TEQ * [pg PCB-TEQ/week and kg bodyweight] (4) F S ΣIP TEQ Total estimated intake of PCB-TEQ week and kg bodyweight for all products within a product group (addition of the values from equation (3)). F G F S IPG TEQ Total consumption or total fat consumption related to a product group respectively Total consumption or total fat consumption related to products within the product group that have been sampled and analysed respectively. Estimated intake of PCB-TEQ related to a product group. In this step, the coverage of the mixing sample according to the total consumption of the product group was taken into account. For example the product group meat consists of pig meat, bovine meat, poultry meat, mutton & goat meat and other meat. The first three products have been sampled and analysed. They are covering 93% of the total fat consumption related to the total meat consumption within the EU. Therefore, the intake values of the sampled products were multiplied with a correction factor, estimating that the non-analysed products show the same average contamination like the analysed products. In many product groups this correction was not necessary due to the fact that all the products within a group are sampled (e.g. animal fats) or that product groups and products are identical (e.g. eggs, tree nuts). The calculation was done in same way for the minimum and maximum values. Page 26

34 5) Estimation of the EU-average PCB-TEQ intake per week and kg bodyweight by addition of the product groups. eint TEQ = ΣIPG TEQ [ng PCB-TEQ/week and kg bodyweight] (5) ΣIP TEQ Total estimated intake of PCB-TEQ week and kg bodyweight for all product groups (addition of the values from equation (4)). eint TEQ Estimated average intake of PCB-TEQ per kg bodyweight and week for a EU-citizen The calculation was done in the same way for the minimum and maximum values. All WHO-PCB-TEQ values used in this chapter are upper bound levels (including the full limit of quantification). However, for most of the samples no significant differences could be observed between lower bound and upper bound levels as to be seen from the detailed analytical results as presented in chapter 9.5. It has to be pointed out, that results refer exclusively to the tested samples. Therefore, extrapolation or comparison to other results must consider details of the samples tested (e.g. species etc.). Page 27

35 2.6 Analysis of chain of cause and effect The intention of this investigation is to find out whether rules or causal connections can be established for the relations between the various steps of the material flow. To follow this aim all available information (already existing and new generated by analysis of samples) is used. The investigation is done by a two step approach: first a "top down analysis" starting at the sources, focussing always at the "input side" of a material flow station and ending at the intake of European citizens. second a "bottom up analysis" starting at the citizen and asking for reasons for contamination levels that are at present focused in the environment, feed, food and consumers. The investigation is usually done by qualitative means as a complete quantification for all flows is not available. Rules and causal connections are formulated as "theses" for which evidence seems to be available. In some aspects these theses also have the function to serve as an input for the scientific discussion. Page 28

36 3 Overview on the results of DLPCB analyses To summarise the results of the DLPCB analyses, first an overview on ranges of DLPCB levels are given on a European-wide scale for individual sample matrices of food and feedingstuffs. Following this, results are described on a regional level. Import samples are considered separately from the European samples. It is the objective of this overview to present a survey on typical levels and on ranges of levels found in the analytical part of this study. Therefore, minimum, maximum and median values are presented on basis of the WHO-PCB-TEQ (chart 3-1). As the maximum number of regional samples contributing to one sample matrix is seven (excluding import samples) and as the number contributing is varying between matrices no further statistical evaluation has been made Maximum 7 6 UNIT 5 4 Median Minimum 0 chart 3-1: Matrix Chart format for European-wide survey on analytical results All WHO-PCB-TEQ values used in this chapter are upper bound levels (including the full limit of quantification). However, for most of the samples no significant differences could be observed between lower bound and upper bound levels as to be seen from the detailed analytical results as presented in chapter 9.5. It has to be pointed out, that results refer exclusively to the tested samples. Therefore, extrapolation or comparison to other results must consider details of the samples tested (e.g. species etc.). Page 29