Evaluation of monitoring data on residues of didecyldimethylammonium chloride (DDAC) and benzalkonium chloride (BAC) 1

Transcription

1 EFSA supporting publication 2013:EN-483 TECHNICAL REPORT Evaluation of monitoring data on residues of didecyldimethylammonium chloride (DDAC) and benzalkonium chloride (BAC) 1 European Food Safety Authority 2, 3 European Food Safety Authority (EFSA), Parma, Italy ABSTRACT In the framework of Article 31 of Regulation (EC) No 178/2002 4, the European Commission (EC) asked the European Food Safety Authority (EFSA) to collect monitoring data on residues of didecyldimethylmmonium chloride (DDAC) and benzalkonium chloride (BAC) in food and to provide a statistical evaluation of the collected data according to the guidelines of the Standing Committee on the Food Chain and Animal Health (section pesticides residues). The present report summarises the monitoring data on BAC and DDAC submitted to EFSA in the period November April 2013 by 16 Member States and Norway. Altogether 5472 samples were analysed in vegetables, fruits and nuts, animal products, baby food, cereals and other plant products. A total of 5168 samples (95 % of the total) did not contain quantified residues for any of the substances analysed. DDAC and the sum of BACs n=10-16 (BACs10-16) were the substances with highest number of positive detections. The highest mean values for these substances at both the Lower Bound (LB) and Upper Bound (UB) were in the categories of animal products (3.64 mg/kg) and fruits and nuts (14.4 mg/kg), respectively. The sum of BACs n=8-18(bacs8-18) was reported in a minority of samples and without any detection. European Food Safety Authority, 2013 KEY WORDS didecyldimethylammonium chloride, DDAC, benzalkonium chloride, BAC, quaternary ammonium compounds, food samples, monitoring 1 On request from the European Commission, Question No EFSA-Q , approved on 5 September Correspondence: dcm@efsa.europa.eu 3 Acknowledgement: EFSA wishes to thank the Member States for providing the data, EFSA staff Giuseppe Triacchini for the preparatory work on this output and EFSA staff Mary Gilsenan, Daniela Brocca and Hermine Reich for the support provided to this output. 4 Regulation (EC) No 178/2002 of the European Parliament and of the Council of 28 January 2002 laying down the general principles and requirements of food law, establishing the European Food Safety Authority and laying down procedures in matters of food safety. OJ L 31, , Suggested citation: European Food Safety Authority, 2013; Evaluation of monitoring data on residues of didecyldimethylammonium chloride (DDAC) and benzalkonium chloride (BAC). EFSA supporting publication 2013:EN pp. Available online: European Food Safety Authority, 2013

2 SUMMARY An ad-hoc request was received from the European Commission to collect monitoring data on residues of didecyldimethylmmonium chloride (DDAC) and benzalkonium chloride (BAC) in food samples and to provide a statistical evaluation of the collected data according to the guidelines of the Standing Committee on the Food Chain and Animal Health (section pesticides residues) and with a view to a possible future exposure assessment and setting of temporary Maximum Residue Limits (MRLs). Analytical results on the Quaternary Ammonia Compounds of interest (BACs n=10-18 and DDAC) were collected for a total of 5472 food samples in the period November April The samples were taken and analyzed by 16 Member States and Norway in the period and were collated by EFSA via the Data Collection Framework (DCF) in line with the Standard Sample Description data model (SSD). Among the 5468 samples retained after the data cleaning, 43 % corresponded to vegetables, 42 % to fruits and nuts, 6 % to animal products, 2.4 % to baby food, 2.5 % to cereals and the rest to other plant products (i.e. oilseeds, pulses, hops, spices, tea, coffee and sugar plants). The majority of the animal products and baby food samples were reported as processed foods (87 % and 70 %, respectively). Some 5168 samples (95 %) did not contain quantified residues for any of the substances analysed, while the highest number of samples with at least one positive detection was found in milk and milk products (90/239 samples with quantified results). The substances with the highest number of positive detections were DDAC with 191 positive detections (38 % of the total detections) and the sum of BACs n=10-16 (BACs10-16) with 140 positive detections (28 % of the total detections). The sum of BACs n=8-18(bacs8-18) was reported in a minority of samples and without any detection. Focusing on the most detected substances, for DDAC the highest mean value at both the Lower Bound (LB) and the Upper Bound (UB) was found in the food category of animal products (3.64 mg/kg). For the sum of BACs10-16 the highest mean value at both the LB and UB was found in the food category of Fruits and nuts (14.4 mg/kg). EFSA supporting publication 2013: EN-483 2

3 TABLE OF CONTENTS Abstract... 1 Summary... 2 Table of contents... 3 Background as provided by the European Commission... 4 Terms of reference as provided by the European Commission... 4 Data Analysis Introduction Data Collection and data management Data Cleaning Results beyond the scope of the BAC-DDAC data collection Substances and food reported as not in list Foods and substances classified incorrectly Results for the sum of BACs n= Food categories Statistical analysis Number of samples by country and by food group Frequency of left-censored data and positive detections Distribution across food groups Fruits and nuts Vegetables Animal products Baby food Cereals Other plant products Other products (incl. not classified and animal feed) Conclusions References Appendices Appendix A. Food aggregation categories and groups used in the report Appendix B. Food classification used in the report (matrix) and food groups Abbreviations EFSA supporting publication 2013: EN-483 3

4 BACKGROUND AS PROVIDED BY THE EUROPEAN COMMISSION Didecyldimethylammonium chloride (DDAC) is a quaternary ammonium compound, which in the EU was authorised as a plant protection product for use on ornamental crops 5 and is used as a biocide for disinfection. Benzalkonium chloride (BAC) is another compound belonging to the class of quaternary ammonium compounds which is not approved under Regulation (EC) No 1107/2009, but it is covered by the biocides review programme of Directive 98/8/EC within the product type "food and feed area disinfectants". Maximum residue levels (MRLs) for both substances have been set at the default level of 0.01 mg/kg according to Art 18(1) (b) of Regulation (EC) No 396/2005 because these uses were not expected to result in any residues in food. The Commission has been informed by food business operators and later by Member Stares that various food products may contain residue levels of DDAC and BAC higher than 0.01 mg/kg. Food business operators and Member States have been investigating the reason(s) for this unexpected presence of residues. To allow further monitoring and investigation, the Standing Committee on the Food Chain and Anima1 Health (SCoFCAH) has agreed guidelines on DDAC and BAC in July 2012, last modified on 5 October Based on statements of the German Bundesinstitut für Risikobewertung (BfR) and the results of the consumer risk assessment derived by BfR using the EFSA PRIMo 6 model, the SCoFCAH considered that the current default MRLs for DDAC and BAC are not a health standard and that it is appropriate to agree on an enforcement level of 0.5 mg/kg, as a proportionate risk management measure on a temporary basis, ensuring a high leve1 of consumer protection in the European Union. Furthermore, Member States agreed to put in place a monitoring programme to have a clear understanding of the levels of DDAC and BAC in all food and feed of plant and animal origin and to communicate the results to the Commission and to EFSA of the monitoring programmes and investigations by the end of February 2013, with a view to taking any necessary measure under Regulation (EC) No 396/2005. The Commission has been informed by EFSA during the EFSA/COM bilateral teleconference on 6 March 2013 and by e-mai1 on 18 March 2013 about the status of data submission by Member States, including the different formats in which data were submitted. The Commission considers that the data should now be analysed to allow risk managers to have an informed discussion on possible future steps. TERMS OF REFERENCE AS PROVIDED BY THE EUROPEAN COMMISSION EFSA is requested, according to Article 31 of Regulation (EC) No 178/2002, to compile and to perform a statistical evaluation of the monitoring data on residues of DDAC and BAC obtained in accordance with the SCoFCAH guidelines with a view to a possible future exposure assessment on the basis of these data and the setting of temporary MRLs. EFSA is requested to present the data in order to facilitate the possible setting of temporary MRLs. Consideration should be given to the appropriate food classification register to be created. The statistical parameters: mean, median, P90, P95, P97.5 and maximum values should be provided. If the data allow, upper bound, middle bound and lower bound values should be presented for each of the 5 It is noted that on 27 February 2013 the (EC) Regulation 175/2013 was published in which the European Commission has withdrawn approvals of didecyldimethyl ammonium chloride (DDAC) which is used as fungicide. It was approved for use as a wood preservative under the EU biocide products Directive 98/8/EC previously. Member States shall ensure that authorisations for the plant protection product didecyldimethylammonium chloride are withdrawn by 20 June 2013 and were granted a grace period of up to one year to use existing stocks. 6 PRIMo: Pesticide Residue Intake Model is a calculation model initially developed by EFSA for the risk assessment of temporary MRLs. A revised version of the model for calculating the acute and chronic consumer exposure (revision 2) with additional features for refined intake calculations is also available. A description of the EFSA PRIMo and the complete list of diets incorporated in the model is given in its reference section (EFSA, 2007). The revised PRIMo model and instructions for its use are available online: EFSA supporting publication 2013: EN-483 4

5 statistical parameters. Data should be presented separately for DDAC and BAC. Data should be presented separately, where this differentiation is possible on the basis of the information provided, for - food items (level of aggregation, e.g. food class, food group, food item, to be decided based on availability of data). - feed items, - products regulated by Commission Directive 2006/141/EC 7 on infant formulae and follow-on formulae and by Directive 2006/125/EC 8 on processed cereal-based foods and baby foods for infants and young children. 7 Commission Directive 2006/141/EC of 22 December 2006 on infant formulae and follow-on formulae and amending Directive 1999/21/EC. OJ L 401, , p Commission Directive 2006/125/EC of 5 December 2006 on processed cereal-based foods and baby foods for infants and young children. OJ L 339, , p EFSA supporting publication 2013: EN-483 5

6 DATA ANALYSIS 1. Introduction In 2012 the Standing Committee on the Food Chain and Animal Health (SCoFCAH) was informed about the presence of residues of chemicals named benzalkoniumchloride compounds (BACs) and Didecyldimethylammonium chloride (DDAC) in food samples. BACs and DDAC are a mixture of substances belonging to the chemical group of Quaternary Ammonium Compounds (QACs) which differ in the alkyl chain length. Quaternary ammonium compounds are surface active substances containing a quaternary cationic nitrogen atom, substituted by alkyl chains of varying length. These substances are used as biocides, pesticides, herbicides, disinfectants and additives for technical applications. Benzalkonium chloride (Figure 1), also known as BAC, alkyldimethyl benzylammonium chloride and ADBAC, is a mixture of alkylbenzyldi methylammonium chlorides of various even-numbered alkyl chain lengths (C8-C18). It has three main categories of use: as a biocide, a cationic surfactant and phase transfer agent in the chemical industry. The greatest biocide activity is associated with the C12-C14 alkyl derivatives. Figure 1: benzalkoniumchloride (BAC) - (n=8,10,12,14,16,18) Didecyldimethylammonium chloride (Figure 2), also known as DDAC, is a mixture of alkylquaternary ammonium salts with typical alkyl chain lengths of C8, C10 and C12, with more than 90 % of C10 (as also defined in: EFSA 2008). DDAC is both a biocide and a pesticide active substance. Figure 2: Didecyldimethylammonium chloride (DDAC) The occurrence of residues of BAC and DDAC substances was detected by national EU laboratories in samples of fruit, vegetables and dairy products, organic and conventionally produced. Whereas the use of DDAC was registered in the EU as a plant protection product (for ornamental plants only) and mostly used as a biocide for disinfection, BACs are not registered as active substances for plant protection products (see footnote 4 on page 4 concerning the withdrawal of DDAC approval in June 2013). EFSA supporting publication 2013: EN-483 6

7 In October 2012 the SCoFCAH endorsed the Guidelines as regards measures to be taken as regards the presence of DDAC in or on food and feed (European Commission, 2012a) and Guidelines as regards measures to be taken as regards the presence of BAC in or on food and feed (European Commission, 2012b). In these two documents the Commission recommended Member States to carry out investigations on the possible causes of the BAC and DDAC contamination and to put in place a monitoring programme with a view to have a clear understanding of the levels of BAC and DDAC in all food and feed of plant and animal origin. The Member States were requested to transmit to the Commission and EFSA the results of the monitoring programmes by the end of February In agreement with the European Commission, EFSA launched an ad-hoc data collection among the Member States. At the 8 th meeting of the EFSA Networking Group on Pesticide Monitoring (Parma, October 2012), the national experts representing the 27 EU Member States and the two EFTA countries (Iceland and Norway) were provided with guidance on the transmission to EFSA of the results of the QACs residues analyses; the reporting organisations were requested to submit the monitoring data in line with the Standard Sample Description data model (SSD) (EFSA, 2010a), which is the data model used to collect and transmit to EFSA the pesticide monitoring data in the framework of Regulation (EC) No 396/2005. EFSA suggested to report food and feed items in line with the MATRIX food coding system officially in use for all the regulatory purposes concerning pesticides residues. EFSA also provided the national experts with a list of SSD codes to be used for identification and reporting of the single QACs analysed (Table 1). It was clarified that data on chlormequat, diquat, mepiquat, paraquat should not be reported, even though these substances belong to the chemical group of QACs. On 23 November, 2012 EFSA opened an ad-hoc data collection on BAC and DDAC. The data collection was closed on 04 April 2013 (extended deadline). On 10 April 2013 EFSA received a Commission mandate (M ) 9, in which EFSA was requested to perform an evaluation of monitoring data on residues of DDAC and BAC as described in the terms of reference above. The present report shows the results of the data analysis performed by EFSA in the framework of the Commission mandate. 2. Data Collection and data management A total of valid analytical results on the QACs of interest (BACs and DDAC) collected by EFSA in the period November 2012 to April 2013 were included in the present analysis. These analytical results concerned a total of 5472 food samples taken and analysed by 16 Member States and Norway during the period The resulting data were mostly transmitted to EFSA via the Data Collection Framework (DCF) in line with the Standard Sample Description data model (SSD) with the exception of a minor portion of data submitted to EFSA in Excel spreadsheet; the latter have been processed and adapted by EFSA to the SSD format. The data submitted by the reporting countries to EFSA were then checked for compliance with the SSD controlled terminology and cleaned by excluding results that are out of the scope of the BACs-DDAC data collection or that were not correctly reported. 9 EFSA supporting publication 2013: EN-483 7

8 2.1. Data Cleaning Results beyond the scope of the BAC-DDAC data collection Member States were asked to report the results of BAC and DDAC monitoring according to the PARAM codes of the SSD reported in Table 1. Originally a total of 168,151 analytical results from 5,509 food/feed samples were transmitted to EFSA in the frame of the BACs-DDAC data collection. Among these, about 150,000 results concerned substances not pertinent to the BACs-DDAC data collection; these were transmitted to EFSA by two reporting countries having the BACs-DDAC results already archived with occurrence data of other contaminants in the same analytical sample. As a consequence, the first cleaning step was to exclude all the analytical results not concerning one of the substances listed in Table 1. Table 1: PARAM codes and names requested by EFSA for the reporting of the QAC, BAC and DDAC analysis in line with the Standard Sample Description terminology. PARAM Code (SSD) Acronym Extended Name RF PPP QACs (a) Quaternary Ammonium Compounds (QACs) RF PPP DDAC Didecyldimethylammonium chloride RF PPP BAC 10 Benzalkonium Chloride (BAC) n=10 RF PPP BAC 12 Benzalkonium Chloride (BAC) n=12 RF PPP BAC 14 Benzalkonium Chloride (BAC) n=14 RF PPP BAC 16 Benzalkonium Chloride (BAC) n=16 RF PPP BAC 18 Benzalkonium Chloride (BAC) n=18 RF-XXXX-XXX-XXX Not in list NOT IN LIST (a): The category of QACs (RF PPP) is meant as parent compound of the DDAC and BACs Substances and food reported as not in list In addition, some analytical results were reported with the substance analysed labelled as Not in list with regards to the SSD controlled terminology, but described in a free-text field of the database 10. On the basis of the description of the compounds analysed and reported as not in list, EFSA created three new ad-hoc PARAM codes specific to this data collection (Table 2) aimed at recoding also these results for inclusion in the statistical evaluation. Due to time constraints, no confirmation was asked to the data providers on the recoding of PARAM not in list applied by EFSA, but the free-text description of the substances reported as not in list was explicit enough to allow a reliable interpretation (e.g. "BAC (sum of BAC 10 to BAC 16 inclusive)", "BACs (sum)", "Benzalkonium chloride (sum of BAC 10/16)", "benzyl-c8-18-alkyldimethyl chlorides", etc). 10 The SSD data model is documented in EFSA (2010). EFSA supporting publication 2013: EN-483 8

9 Table 2: Ad-hoc codes created for including in the statistical evaluation the substances reported as Not in list PARAM Code (ad-hoc) Acronym Extended Name new_code01 BAC (sum) Benzalkonium Chloride (sum of BACs unspecified chain lengths) new_code02 BACs10-16 Benzalkonium Chloride (sum of BACs with alkyl chain length C10-C16) new_code03 BACs8-18 Benzalkonium Chloride (sum of BACs with alkyl chain length C8-C18) With regard to the food items analysed, four samples reported as plant extract formula (a total of 24 analytical results) were disregarded because they could not be classified according to the MATRIX food catalogue of the SSD or were not considered food items. Another sample reported as fruit, cereal and nut mix together with four samples reported as Other (a total of 29 analytical determinations) were maintained in the category of not in list and were disregarded in the data analyses because they were composite food samples or unspecified food items. Finally, 197 ice cream samples (a total of 358 analytical results) reported as not in list were classified as processed Milk and cream, not concentrated, nor containing added sugar or sweetening matter, butter and other fats derived from milk, cheese and curd (SSD Matrix code: P A) that is the most appropriate food code available in the MATRIX coding system Foods and substances classified incorrectly Some 12 samples of milk based baby food were reported with a MATRIX code that is no more in use in the related SSD catalogue. The MATRIX element Infant formulae/follow-on formulae (Product code: PX100002A) was deprecated in 2012 from the SSD controlled terminology and replaced by two separate food items for milk based baby food: Follow-on formulae and Infant formulae. All the samples reported with the deprecated code were therefore split into the new SSD food categories recoding the corresponding 44 analytical results accordingly and in agreement with the data providers. The substance name and the PARAM code reported for 25 analytical results (in 25 different food samples) were corrected for inconsistency with their accompanying free-text descriptions. Another 72 results (in 72 different food samples) reported as QACs (RF PPP) and described as Didecyldimethylammonium chloride in the free text field of the SSD were disregarded from the analysis because they were considered as duplicates Results for the sum of BACs n=10-16 Data providers reported BAC results to EFSA using the proposed codes for BAC10, BAC12, BAC14, and BAC16. In addition, data for the sum of BACs10-16 and sum of BACs8-18 were reported. The European Commission expressed a specific interest in the sum of BACs n=10-16 (BACs10-16) for the statistical evaluation. After the data cleaning and recoding described above, the results reported for the sum of BACs10-16 represented 20 % of the total analytical results. The sum of BACs10-16 was then calculated for all those samples where one or more of the BACs10-16 were individually reported, without reporting the sum. All the sums reported by the data providers were checked and in nine samples the sum had to be recalculated to correct inconsistencies due to the rounding of figures in the laboratories (agreed with the data providers). The output of this processing was the creation of 42 new analytical results summing up BACs EFSA supporting publication 2013: EN-483 9

10 2.3. Food categories Evaluation of monitoring data on residues of DDAC and BACs in food According to the recommendations set out in the European Commission Guidelines (European Commission, 2012a,b), Member States were requested to take food samples belonging to the following commodity groups which correspond to commodity groups defined in Annex I of Regulation (EC) No 396/ : citrus fruit, pomes fruit, miscellaneous fruit (in particular bananas), root and tuber vegetables (in particular potatoes), fruiting vegetables, leafy vegetables and dairy products. Member States were also encouraged to collect and analyse samples of other commodity groups, such as stone fruit, berries, stem vegetables, cereals, oilseeds, tea and herbal infusions and processed products such as orange juice, flour and olive oil. Results on 143 different food (1139 food items if the food treatments are taken into account) were reported. Considering the above recommendations, EFSA carried out the data analysis at three levels of the food commodity classification. A first analysis was performed at the level of food items as reported, while additional analyses were carried out aggregating the food items on the basis of the food classification categories and groups listed in Appendix I (aggregation to seven food categories defined as Analysis level 1 and 34 food groups referred to as Analysis level 2 ). A detailed list with all the food items presents in the data set under evaluation, classified by food category and food group, is reported in Appendix II). 3. Statistical analysis Frequency tables and summary statistics were produced to describe the BACs and DDAC data by food, food group and food category. Means and percentiles were computed for each substance in food groups where sufficient data were available. Left censored data were treated by the substitution method as indicated in the EFSA scientific report Management of left-censored data in dietary exposure assessment of chemical substances (EFSA, 2010b). At the Lower Bound (LB) results below the Limit of Detection (LOD) or Limit of Quantification (LOQ) were replaced by zeros; at the Upper Bound (UB) results below the LOD or below the LOQ were replaced by the value of the LOQ. All analyses were performed using the SAS Statistical Software (SAS software, 1999) Number of samples by country and by food group The final data set obtained after applying the cleaning criteria and introducing a number of calculated results (BACs sum) included 5468 food samples (19791 analytical determinations) analysed on 143 different food items (raw and/or processed). Most of the data were submitted by Germany followed by the United Kingdom and the Netherlands. The data set covers results on samples collected from Summer 2012 to Spring 2013 with the majority of samples taken in 2012 (Table 3). The distribution of the BACs-DDAC samples across European countries per year and per food group is reported in Table Regulation (EC) NO 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. OJ L 70, , p EFSA supporting publication 2013: EN

11 Table 3: Number of food samples by reporting country per year. Sampling Year Member State / Norway Total samples reported AT BE CY CZ DE ES FI FR GB HU IE IT NL NO PL SE SK Total Most of the results concerned DDAC and the sum of BAC10-16 (25 % and 20 % of the total number of analytical determinations, respectively) while results for the single BACs (C10-C16) accounted for 15 % of the analytical determinations each. The remaining compounds were less represented (from 1 % to 5 % of the entire set of analytical determinations) (Table 6). The most frequently reported food categories among the 5468 samples retained after the data cleaning were vegetables (43 %) and fruits and nuts (42 %) followed by animal products (6 %), baby food (2.4 %) and cereals (2.5 %) The remaining minor percentages are distributed on the other plant products (i.e. oilseeds, pulses, hops, spices, tea, coffee and sugar plants) (Table 4). Table 4: Distribution of samples analysed per food category. Food Category (Level 1) No Samples % Samples % Processed Vegetables % 1 % Fruits and nuts % 5 % Animal products % 87 % Other plant products % 44 % Cereals % 18 % Baby food % 70 % Other products (incl. not classified and animal feed) % 57 % TOTAL % - Food groups were not evenly sampled in the reporting countries; furthermore, the monitoring was more focused on leafy vegetables and fresh herbs, tropical and sub-tropical fruit and solanacea followed by fruits (pomes fruit, citrus fruit, stone fruit, table and wine grapes) and on milk and milk products. The number of samples by country and food group is illustrated in Table 5. EFSA supporting publication 2013: EN

12 Table 5: Number of samples analysed per food group (analysis level 2) and per reporting country (ND=results below the LOQ). Food group (Analysis level 2) No Samples No of samples above the ND ND % AT BE CY CZ FI FR DE HU IE IT NL NO PL SK ES SE UK LOQ (a) Cucurbits % Leafy vegetables & fresh herbs % Sweet corn % Legume vegetables (fresh) % Stem vegetables % Brassica vegetables % Potatoes % Root and tuber vegetables (except tropical) % Solanacea (e.g. tomatoes, peppers) % Fungi % Bulb vegetables % Tropical root and tuber vegetables % Other vegetable samples % Tropical and sub-tropical fruit % Table and wine grapes % Citrus fruit % Strawberries % Stone fruit % Pome fruit % Cane fruit, small fruit and berries % Other fruit and nuts samples % Table olives % Oilseeds and oilfruits % EFSA supporting publication 2013: EN

13 Food group (Analysis level 2) No Samples No of samples above the ND ND % AT BE CY CZ FI FR DE HU IE IT NL NO PL SK ES SE UK LOQ (a) Pulses % Spices % Hops % Tea, coffee, herbal infusions and cocoa % Sugar plants % Eggs % Milk and milk products % Meat (swine, bovine, sheep, goat, poultry) % Baby food % Cereals % Other products (incl. not classified % and animal feed) (a): This table is a synthesis at sample level; as a consequence, the number of samples above the LOQ refers to the samples where at least one positive result was found. EFSA supporting publication 2013: EN

14 3.2. Frequency of left-censored data and positive detections Some 97.5 % of the observations across the 10 compounds/groups of compounds analysed were below the LOQ. The substances with the highest number of quantified results were DDAC with 191 positive detections (38 % of the total results above the LOQ) and the sum of BAC10-16 with 140 positive detections (28 % of the total results above the LOQ) (Table 6). The sum of BAC10-18 was reported in a limited number of samples; while there were more analytical determinations for BAC 18, there was not a single detection in more than 1000 determinations. Table 6: Number of analytical determinations per compound and frequency of positive detections. QAC name Obs (a) % Obs (a) No Positive detections % detected % non detected DDAC % % 96.1 % BAC % % 96.6 % BAC % % 97.4 % BAC % % 98.2 % BAC % % 99.8 % BAC % % % BAC % % % BAC (sum) % % 88.3 % Quaternary Ammonium Compounds (QACs) % % 98.8 % BAC % % % Total Analytical Determinations % % 97.5 % (a): Obs: analytical determinations. Across food groups, the frequency of samples which don t contain measurable residues of the compounds under consideration ranged from 70 to 100 %. In total 5168 samples (95 %) did not contain quantified results for any of the substances analysed, while the highest number of samples with at least one positive detection was found in samples classified as milk and milk products (90 samples with detections out of 329 samples). The majority of animal products and baby food samples were reported as processed foods (87 % and 70 %, respectively) Distribution across food groups Across food groups, BACs and DDAC were mostly found in Milk and milk products (12 % of positive results in the food group), followed by leafy vegetables and fresh herbs (6 %) and baby food (5 %). The frequencies of positive results in Animal feed, Legume vegetables (fresh), Fungi, Citrus fruit and Tropical and subtropical fruit ranged from 3 to 4 % of the total determinations of the respective food groups. In the remaining food groups, BACs and DDAC were detected with lower frequencies (ranging from 1 to 2 % in their food groups). No quantifiable results were obtained for any of the compounds analysed in "Sweet corn", "Bulb vegetables", "Tropical root and tuber vegetables", "Vegetables", "Strawberries", "Fruits and nuts", "Table olives", "Oilseeds and oil fruits", "Spices", "Hops", "Tea, coffee, herbal infusions and cocoa", EFSA supporting publication 2013: EN

15 "Sugar plants", "Eggs", "Meat (swine, bovine, sheep, goat, poultry)", "Cereals" (Table 7). However, a high percentage of results below the LOQ in certain food groups (except for "Sweet corn", "Strawberries", "Oilseeds and oil fruits" and "Cereals") should be interpreted taking into account that the significance of these findings is limited due to the limited number of samples analysed. The number of quantified results as well as the maximum and average level of BACs and DDAC at the lower bound (LB) and upper bound (UB) by food category (analysis level 1) are presented in Table 8. The 95 th, 97.5 th and 99 th percentiles are also calculated where enough observations were reported 12. The same statistical analyses were performed at analysis level 2 (food groups) and at the individual food level. Due to the large volume of data, more detailed statistics at the detail of food group and individual food level are presented in an Excel file accompanying this report, which has been delivered to the Commission. The discussion of the results presented in the next sections ( ) is based on the statistics presented in the Excel file. Table 7: Total number of analytical determinations and frequency of positive detections of BACs and DDAC Food Group (Analysis level 2) No Analytical determinations No Detected % detected Milk and milk products % Leafy vegetables & fresh herbs % Baby food % Other products (incl. not classified and animal feed) % Legume vegetables (fresh) % Fungi % Citrus fruit % Tropical and subtropical fruit % Pulses % Table and wine grapes % Root and tuber vegetables (except tropical) % Pome fruit % Cucurbits % Brassica vegetables % Stone fruit % Solanacea (e.g. tomatoes, peppers) % Potatoes % Cane fruit, small fruit and berries % Stem vegetables % Bulb vegetables % Cereals % Eggs % Fruits and nuts % Hops % 12 In accordance with the specifications of the EFSA Guidance on the use of the Comprehensive database (EFSA, 2011), percentile estimates with insufficient observations are not considered since they may not be statistically robust (60 observations are considered sufficient for the 95 th percentile, while for the 97.5 th 160 observations are needed and for the 99 th the minimum number of observations is 300). EFSA supporting publication 2013: EN

16 Food Group (Analysis level 2) No Analytical determinations No Detected % detected Meat (swine, bovine, sheep, goat, poultry) % Oilseeds and oil fruits % Spices % Strawberries % Sugar plants % Sweet corn % Table olives % Tea, coffee, herbal infusions and cocoa % Tropical root and tuber vegetables % Vegetables % Grand Total % EFSA supporting publication 2013: EN

17 Food Category (Analysis level 1) Fruits and nuts Vegetables Animal products Baby food Cereals Table 8: Distribution of BACs and DDAC (mg/kg) by food category (Analysis level 1). No Obs (d) No Detected Lower bound Upper bound min mean p95 (a) p97.5 (b) p99 (c) max min mean p95 (a) p97.5 (b) p99 (c) max BAC10-BAC DDAC BAC10-BAC DDAC BAC10-BAC DDAC BAC10-BAC DDAC BAC10-BAC DDAC Other plant BAC10-BAC products DDAC Other products (incl. not BAC10-BAC classified and animal feed) DDAC (a): 95 th percentile estimates are not shown with less than 60 observations as they may not be statistically robust (EFSA, 2011) (b): 97.5 th percentile estimates are not shown with less than 160 observations as they may not be statistically robust (EFSA, 2011) (c): 99 th percentile estimates are not shown with less than 300 observations as they may not be statistically robust (EFSA, 2011) (d): Obs: analytical determinations. EFSA supporting publication 2013: EN

18 Fruits and nuts The category of fruits and nuts has been analysed for almost all the substances listed in table 1 (total obs = 8232) with a total number of positive results (pos) less than 2 % (pos =148). The compounds found were mostly detected in the food groups "Citrus fruit", "Tropical and subtropical fruit", "Pome fruit", "Table and wine grapes", "Stone fruit", "Cane fruit, small fruit and berries". For the sum of BAC10-BAC16 the highest mean value within this food category at both the LB and UB was found in samples of unprocessed grape fruits (14.4 mg/kg). The highest mean value of DDAC at both the LB and the UB was found in samples of bananas (0.95 mg/kg) followed by apples, pears, grapefruit and citrus fruits (ranging from 0.2 to 0.7 mg/kg) Vegetables Vegetables samples have been analysed for almost all the substances listed in table 1 (obs = 8802) with a number of positive results around 2 % (pos = 193). The compounds found were mostly detected in the food groups Leafy vegetables & fresh herbs, Legume vegetables (fresh), Solanacea (e.g. tomatoes, peppers). For the sum of BAC10-16 the highest mean value within this food category at both the LB and UB was found in samples of Carrots (0.48 mg/kg) followed by Leaf vegetables and Fresh herbs (0.3 mg/kg). The highest mean value of DDAC at both the LB and the UB was found in samples of Fresh Herbs (0.92 mg/kg) followed by Rhubarb (0.39 mg/kg) and Cultivated fungi (0.32 mg/kg) Animal products Animal products have been analysed for almost all the substances listed in table 1. The number of observations was lower with respect to those available for fruits and vegetables (obs = 988) but with 12 % of positive results (n=117). There were no positive detections in the few samples taken of poultry meat (10 samples) and eggs (4 samples). The analysed compounds were only detected in the food group Milk and milk products which includes processed and unprocessed products. In order to better interpret the data reported in the food group Milk and milk products, table 9 shows also the product treatment and the free-text food description reported by the data providers. On the basis of the treatment and the additional food description it was possible to identify the samples of ice cream, unprocessed milk, and butter. The highest mean value of DDAC at both the LB and the UB was found in samples of ice cream (3.64 mg/kg). DDAC was also detected at lower concentrations in samples of butter and other churned milk products where the highest means at the UB ranged from 0.01 to 0.3 mg/kg. DDAC was also detected in unprocessed milk samples (obs=348) with mean value at both the LB and the UB ranging from 0.01 to 0.03 mg/kg. The highest mean value of the sum BAC10-16 at both the LB and UB was found in the same ice cream samples (1.74 mg/kg), but also in processed milk product reported as churned dairy products - cattle, presumably butter (1.1 mg/kg). The remaining detections of the sum of BAC10-BAC16 were in samples of cheese and other dairy products of goat and sheep milk with the highest mean values at LB and UB ranging from 0.01 to 0.07 mg/kg. EFSA supporting publication 2013: EN

19 Table 9: Number of analytical determinations in milk and milk products. The Milk product type was identified on the basis of the reported product name, treatment and prodtext (free text description of the food sample). Food Item Treatment PRODTEXT Obs (a) Milk product type Dairy products Cattle Dairy products Goat Dairy products Sheep Milk and cream, not concentrated, nor containing added sugar or sweetening matter, butter and other fats derived from milk, cheese and curd Churning BUTTER 30 Churning DAIRY PRODUCTS CATTLE 10 Processed Processed MRAZENÝ SMOTANOVÝ KRÉM COKOLÁDOVÝ S KÚSKAMI COKOLÁDY 1 LITER RUSKÁ ZMRZLINA OD MRAZÍKA, MRAZENÝ SMOTANOVÝ KRÉM S OBLÁTKOU, 845 ML Butter and other churned milk products Butter and other churned milk products 6 Ice cream 6 Ice cream Unprocessed DAIRY PRODUCTS CATTLE 2 Milk Churning DAIRY PRODUCTS GOAT 16 Butter and other churned milk products Churning DAIRY PRODUCTS SHEEP 8 Butter and other churned milk products Churning FORMAGGIO 16 Butter and other churned milk products Churning MILK AND CREAM, NOT CONCENTRATED, NOR CONTAINING ADDED SUGAR OR SWEETENING MATTER, BUTTER AND OTHER FATS DERIVED FROM MILK, CHEESE AND CURD Churning PANNA PASTORIZZATA 4 Milk pasteurisation Milk pasteurisation Milk pasteurisation Milk pasteurisation Milk pasteurisation - 18 Milk LATTE PASTORIZZATO 20 Milk LATTE UHT 16 Milk MILK AND CREAM, NOT CONCENTRATED, NOR CONTAINING ADDED SUGAR OR SWEETENING MATTER, BUTTER AND OTHER FATS DERIVED FROM MILK, CHEESE AND CURD SMOTANA NA ŠLAHANIE VYSOKOPASTERIZOVANÁ 33 % TORTOVÁ SMOTANA NA ŠLAHANIE 36 % EFSA supporting publication 2013: EN Milk Milk pasteurisation 6 Processed ICE CREAM 346 Ice cream MILK AND CREAM, NOT Processed CONCENTRATED, NOR CONTAINING ADDED 126 SUGAR OR SWEETENING 6 Butter and other churned milk products Butter and other churned milk products Other processed milk products Other processed milk products Other processed milk products

20 Food Item Treatment PRODTEXT Obs (a) Milk product type MATTER, BUTTER AND OTHER FATS DERIVED FROM MILK, CHEESE AND CURD Unprocessed - 36 Milk Unprocessed MILK AND CREAM, NOT CONCENTRATED, NOR CONTAINING ADDED SUGAR OR SWEETENING MATTER, BUTTER AND 106 Milk OTHER FATS DERIVED FROM MILK, CHEESE AND CURD (a): Obs: analytical determinations. EFSA supporting publication 2013: EN

21 Table 10: Distribution of BACs and DDAC (mg/kg) by milk product type. Milk product type (e) Butter and other churned milk products Ice cream Milk BAC10- BAC16 No Obs (d) No Detected Lower bound Upper bound min mean p95 (a) p97.5 (b) p99 (c) max min mean p95 (a) p97.5 (b) p99 (c) max DDAC BAC10- BAC DDAC BAC10- BAC DDAC Other processed milk DDAC products (a): 95 th percentile estimates are not shown with less than 60 observations as they may not be statistically robust (EFSA, 2011) (b): 97.5 th percentile estimates are not shown with less than 160 observations as they may not be statistically robust (EFSA, 2011) (c): 99 th percentile estimates are not shown with less than 300 observations as they may not be statistically robust (EFSA, 2011) (d): Obs: analytical determinations. (e): Categories defined in table EFSA supporting publication 2013: EN

22 Baby food The category of Baby food (including milk based and cereal based baby food) has been analysed for almost all the substances listed in table 1 (obs = 640) with 5 % of positive results (pos=31) distributed among all the foods included in this category. The mean value of DDAC detected in baby food for infants and young children and Follow-on formulae ranged from to 0.12 mg/kg at both the LB and the UB. The mean value of BAC10-16 detected in baby food for infants and young children and Follow-on formulae, Infant formulae and Processed cereal-based baby food ranged from to 0.13 mg/kg at both the LB and the UB Cereals The category of Cereals includes samples of unprocessed Barley, Buckwheat, Maize, Millet, Oats, Rice, Rye, Sorghum, Wheat and other cereals. Samples of Buckwheat, Rye and Wheat flour are also included. All these foods have been analysed for all the BACs-DDAC but the entire set of analytical determinations (obs=486) did not contain any positive detection of BACs-DDAC Other plant products This broad category classifies samples of dry beans, cocoa, coffee, ginger, dried herbal infusions, dried hops, dry lentils, linseed, olives for oil production, soya bean, sugar beet, sunflower seed, tea and turmeric (curcuma). All these plant products have been analysed for almost all the substances listed in table 1 (obs= 432) and only one positive detection of the sum BAC10-16 was found in dry beans with a mean value at LB and UB of 0.73 mg/kg Other products (incl. not classified and animal feed) This category includes mostly Crops exclusively used for animal feed (obs=182) together with other samples where the food was not specified or broadly defined as fruit, cereal and nut mix or other (obs=29). All these products have been analysed for almost all the substances listed in table 1 and only two positive detections of the sum BAC10-16 and two positive detections of DDAC were found in the crops exclusively used for animal feed, leading to mean values at LB and UB ranging from to mg/kg. EFSA supporting publication 2013: EN

23 CONCLUSIONS - Analytical results on a set of Quaternary Ammonia Compounds of interest (BACs10-18 and DDAC) from 5472 food samples were submitted to EFSA during the period November April Some 5168 of 5472 samples (95 %) did not report quantified values for any of the substances analysed. - The substances with the highest number of positive detections are the DDAC (38% of the total detections) and the sum of BACs10-16 (28 % of the total detections). The sum of BACs8-18 was reported in a minority of samples all of which were below detection limits. - The highest mean value of DDAC concentration at both the Lower Bound (LB) and the Upper Bound (UB), across the entire data set, was found in ice cream samples (3.64 mg/kg) while for the sum of BACs the highest mean value was found in samples of unprocessed grape fruits (14.4 mg/kg). - Considering the most sampled food categories, the highest mean value of DDAC in vegetables at both the LB and UB was found in fresh herb samples (0.92 mg/kg) while for the sum BACs the highest mean value was found in samples of carrots (0.48 mg/kg). For fruits and nuts the highest mean value of DDAC at both the LB and UB was found in samples of bananas (0.95 mg/kg). EFSA supporting publication 2013: EN

24 REFERENCES European Commission, 2012a. Guidelines as regards measures to be taken as regards the presence of Didecyl Dimethyl Ammonium Chloride (DDAC) in or on food and feed agreed by the Standing Committee of the Food Chain and Animal Health (SCoFCAH) on 13 July 2012 and modified on 5 October 2012 European Commission, 2012b. Guidelines as regards measures to be taken as regards the presence of Benzalkonium Chloride (BAC) in or on food and feed agreed by the Standing Committee of the Food Chain and Animal Health (SCoFCAH) on 25 July 2012 and modified on 5 October 2012 EFSA (European Food Safety Authority), Reasoned opinion on the potential chronic and acute risk to consumers health arising from proposed temporary EU MRLs. EFSA (European Food Safety Authority), Conclusion on pesticide peer review regarding the risk assessment of the active substance didecyldimethylammonium chloride. EFSA Scientific Report (2008) 214, EFSA (European Food Safety Authority), 2010a. Standard sample description for food and feed. EFSA Journal; 8(1):1457, 54 pp. doi: /j.efsa EFSA (European Food Safety Authority), 2010b. Scientific report of EFSA: Management of left censored data in dietary exposure assessment of chemical substances. EFSA Journal, 8(3):1557, 96 pp. doi: /j.efsa EFSA (European Food Safety Authority), Guidance of EFSA. Use of the EFSA Comprehensive European Food Consumption Database in Exposure Assessment. EFSA Journal, 9(3):2097, 34 pp. doi: /j.efsa EFSA supporting publication 2013: EN