The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2004

Transkript

1 Rapport The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2004 EC and National Report by Arne Andersson and Anders Jansson

2 Foto: Magnusson Produktion, Malmö Produktion: Livsmedelsverket, Box 622 SE Uppsala, Sweden Teknisk redaktör: Merethe Andersen Tryck: Livsmedelsverkets repro Uppsala Livsmedelsverkets rapportserie är avsedd för publicering av projektrapporter, metodprövningar, utredningar m m. I serien ingår även reserapporter och konferensmaterial. För innehållet svarar författarna själva. Rapporterna utges i varierande upplagor och tilltrycks i mån av efterfrågan. De kan rekvireras från Livsmedelsverkets kundtjänst (tel ) till självkostnadspris (kopieringskostnad + expeditionsavgift).

3 Rapporter som utgivits Utvärdering av Livsmedelsverkets Riksprojekt av R Lindqvist och E Hay. 2. Interkalibrering av laboratorier. Mikrobiologi Livsmedel, januari 2004 av C Normark. 3. Proficiency Testing Food Chemistry, Nutritional Components, Round 33, March-April 2004 by L Merino. 4. Examination of Residues in Live Animals Products Results of the Control 2003 by I Nordlander. 5. Proficiency Testing Food Chemistry, Trace Elements in Food, Round T 9 by C Åstrand and L Jorhem. 6. Riksprojekt Salmonella i frukt och grönsaker. 7. Projektinriktad kontroll Granskning av salmonellaförekomst i köttberedningar införda till Sverige från annat EU-land av A Brådenmark. 8. Proficiency testing. Food microbiology April 2004 by Å Rosengren and C Normark. 9. Proficiency Testing. Drinking water microbiology 2004:1, March by T Šlapokas and M Ljunge. 10. Rapportering om livsmedelstillsyn 2003 Kommunernas rapportering om livsmedelstillsyn av D Rosling. 11. Rapportering av dricksvattentillsyn 2003 Kommunernas rapportering om dricksvattentillsyn av D Rosling. 12. The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2003, EC and National Report by A Andersson, A Jansson and G A Eskhult. 13. Mat och hälsa i undervisningen skolan och lärarutbildningen av M Rosén. 14. Riksprojekt 2003 Temperaturer i storhushåll och butik av M Lindblad och M Boysen. 15. Synen på tillsyn utvärdering av tillsyn vid anläggningar med Livsmedelsverkets som tillsynsmyndighet av M Ljung. 16. Dioxins and PCBs in fish oil a survey of fish oils and fish liver oils sold on the Swedish market in February 2003 by S Wallin, P O Darnerud, R Bjerselius, A Glynn, M Aune and A Andersson. 17. Proficiency Testing Food Chemistry, Nutritional Components, Round 34, September October 2004 by L Merino. 18. Nationella mål och strategier för nutrition utvärdering av P Hagling och M Ljung. 19. Du blir var du äter studie om hur den socioekonomiska vardagsmiljön påverkar barns förhållningssätt till mat av M Jansson. 20. Proficiency Testing Food Chemistry, Vitamins in Foods, Round V-2 by H S Strandler and A Staffas. 21. Validitet av enkätfrågor om kost och fysisk aktivitet bland vuxna underlag till urval av frågor i befolkningsinriktade enkäter av H Sepp, U Ekelund och W Becker. 22. Risk profile. Virus in food and drinking water in Sweden Norovirus and Hepatitis A virus by F Lund and R Lindqvist. 23. Interkalibrering av laboratorier. Mikrobiologi Dricksvatten 2004:2, september av T Šlapokas, C Gunnarsson och A Gidlund. 24. Interkalibrering av laboratorier. Mikrobiologi Livsmedel oktober 2004 av C Normark.

4 Rapporter som utgivits Verksamhetsplan Collaborative study of method for detection of Escherichia coli O157 in food NMKL no 164, 1999, by C Normark. 3. Proficiency Testing Food Chemistry, Trace Elements in Food, Round T 10 by C Åstrand and L Jorhem. 4. Utvärdering av första etappen av projektet God livsmedelskvalitet i Västernorrland av H Nordenfors och U Fäger. 5. Lunchmat i Uppsala 2001 Undersökning av matens energi- och fettinnehåll av H Karlén Nilsson, M Arnemo och W Becker. 6. Projektinriktad kontroll Ursprung och identitet av kött infört från annat EU-land av U Evans Cederlund. 7. Interkalibrering av laboratorier. Mikrobiologi Livsmedel, januari 2005 av C Normark och C Gunnarsson. 8. Proficiency Testing Food Chemistry, Nutritional Components in Food, Round N-35, by L Merino. 9. Normerande inspektioner av storhushåll Resultat från normerande inspektioner av storhushåll i samband med kommuninspektion av U Lantz och D Rosling. 10. A Risk Assessment of Uranium in Drinking Water by K Svensson, P O Darnerud and S Skerfving. 11. The Component Aspect Identifier A Tool for Handling Food Component Information in a Food Database Management System by I Unwin and W Becker. 12. Rapportering om livsmedelstillsyn 2004 Tillsynsmyndigheternas rapportering om livsmedelstillsyn av D Rosling. 13. Interkalibrering av laboratorier. Mikrobiologi Dricksvatten 2005:1, mars av T Šlapokas och C Gunnarsson. 14. Interkalibrering av laboratorier. Mikrobiologi Livsmedel, april 2005 av C Normark, K Mykkänen och C Gunnarsson. 15. Campy-SET, Campylobacter: Smittspårning, epidemiologi och typning. 16. Examination of Residues in Live Animals Products Results of the Control 2004 by I Nordlander. 17. The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2004, EC and National Report by A Andersson, A Jansson. ISSN

5 The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2004 Report concerning Directives 90/642/EEC, 86/362/EEC and Commission Recommendation 2004/74/EC By Arne Andersson and Anders Jansson Further information Information about the Swedish monitoring of pesticide in food of plant origin is available from: Arne Andersson National Food Administration Box 622, SE Uppsala, Sweden Fax:

6 2 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

7 CONTENTS Summary 5 Introduction 6 Monitoring programme 7 Sampling procedures 8 Analytical procedures 9 levels 11 Residue Limits 11 Results and discussion 11 Dietary Exposure Assessment: Short-term intake 20 References 26 Appendix 1 Analytical method codes and their sources 28 Appendix 2 Pesticides, isomers and breakdown products sought and detected 31 Appendix 3 surveillance grouped by methods used 35 Appendix 4 Appendix 5 surveillance analysed and found in per cent of MRLs enforcement analysed and found in per cent of MRLs Tables according to EU reporting format: Table A1- Part I Table A1-Part II Table A2-Part I Table A2-Part II Table B Table C Summary of numbers of analysed, sample origins and results, surveillance sampling, national and co-ordinated programme Summary of numbers of analysed, sample origins and results, enforcement sampling, national and co-ordinated programme Fruits & vegetables: Summary table of pesticides sought and found, surveillance sampling, national and co-ordinated programme Cereals: Summary table of pesticides sought and found, surveillance sampling, national and co-ordinated programme Notifications of the co-ordinated programme (specific exercise) to the European Commission Notifications of the results of Check sampling (Surveillance sampling) of the National programme to the European Commission. The results include the in the co-ordinated programme National Food Administration, Sweden Livsmedelsverkets rapport nr 17/2005 3

8 CONTENTS Table D1 Table D2 Table D3 Table D4 Table E Continue Details of exceeding EC-MRLs, surveillance sampling of fruits, vegetables and cereals, national and co-ordinated programme Details of exceeding non-harmonised MRLs including national MRLs, surveillance sampling of fruits, vegetables and cereals, national and co-ordinated programme Details of exceeding EC-MRLs, follow-up enforcement sampling of fruits, vegetables and cereals, national and co-ordinated programme Details of exceeding non-harmonised MRLs, including national MRLs, follow-up enforcement sampling of fruits, vegetables and cereals, national and co-ordinated programme Details of with multiple (>2) in single, surveillance and follow-up enforcement sampling of fruits, vegetables and cereals, national and co-ordinated programme Table F Details of the homogeneity exercise 197 Table G Laboratories: Information about laboratories involved in the monitoring exercise Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

9 The Swedish Monitoring of Pesticide Residues in Food of Plant Origin: 2004 EC and National Report Summary In 2004, a total of surveillance of fresh, frozen or processed fruits and vegetables, cereal grains and cereal products were analysed for of 239 pesticides (290 analytes). National or EU harmonised Residue Limits were exceeded by 80 (3.5 %). The violation rate has decreased compared with 2003 and amounted to 6.7 % in fresh or frozen fruits and vegetables from third countries and 4.0 % in the from EU countries except Sweden. None of the of domestic grown fruits and vegetables contained above the MRLs. Residues were found in two out of 45 from organic production. In general, from domestic Integrated Production (IP) contained less compared with from conventional production. The plant growth regulator chlormequat was found in 3 out of 62 of domestic conventional grown wheat. Although the levels were very low, chlormequat is not authorised for use in wheat. Apples, tomatoes, lettuce, strawberries, leek, orange juice, head cabbage, rye and oats, in all 513, were analysed in the 2004 EU co-ordinated programme. Eleven of these exceeded any of the EC-MRLs for the pesticides concerned. In eleven commodities (17 ) pesticide were found at levels more than 10 times the MRLs. The highest violation rate, 37 times the MRL, was found in strawberries from Egypt containing methomyl. No were found in the 92 of foods for infants and young children. A total of 232 of cereal grains were analysed. Most of the (80 %) contained no and only one sample of rice exceeded any MRLs. In the enforcement sampling of fruits and vegetables 75 were collected and 14 lots (35.8 tons) were prohibited from being sold. The homogeneity factor, calculated as the highest value found in an individual unit divided by the mean residue of individual units in a single sample, was determined for Chinese broccoli and potatoes. The stability after wok cooking was investigated for certain pesticides found in Chinese broccoli. The short-term intake was estimated for the acute toxic pesticides based on the highest residue found in a surveillance (composite) sample. The ARfDs were exceeded for toddlers in eight cases. National Food Administration, Sweden Livsmedelsverkets rapport nr 17/2005 5

10 Introduction The Swedish National Food Administration (NFA) checks foods of plant origin for pesticide. Annual reports have been published in English since The present report is our sixth combined European Commission (EC) and national report. It is aimed for the Commission, the Member States in the European Union (EU) and all other interested parties. The report contains general information about the monitoring programme, sampling procedures and analytical methods as well as detailed information about found using a format requested by the European Commission (Table A G). Certain results are also presented in percent of the MRL according to our general format for reporting found (Appendices 4 5). An assessment of the short-term intake, based on the 2004 monitoring data, has also been carried out. This report is available on NFA s web site ( together with a separate comprehensive summary report in Swedish. Since 2001 quarterly and from 2004 tertiary summary reports from the pesticide monitoring are also available in Swedish on NFA s web site. 6 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

11 Monitoring programme The target to be collected of each food takes into account the food's consumption rate, but fewer are taken of commodities causing few exceedances of the MRLs. The number is also based on the importance of the foodstuff in the diets of infants and young children and if the food is consumed with or the peel. In some cases, the of a specific food or a food from a particular country was increased based on found in prior. By analysis of 100 it can with 95 % confidence be predicted that the actual percentage of exceedances is less than 3 % provided that no exceedances was discerned. About 80 different commodities were included in the sampling plan for year 2004 (Table 1). Table 1. and commodities to be collected according to the monitoring programme 2004 and the outcome of the sampling. COMMODITY No. of 2004 COMMODITY No. of 2004 planned outcome planned outcome Fruits (fresh or frozen) Apples Peppers Bananas Potatoes Mandarins and similar Others Oranges Peaches and nectarines Cereal grains Pears Rice Strawberries Wheat Table grapes Others Others Processed or dried foods Vegetables (fresh or frozen) Baby foods Carrots Cereal products Cucumbers Juice, fruit drinks Lettuce Potatoe products Melons Others Tomatoes : National Food Administration, Sweden Livsmedelsverkets rapport nr 17/2005 7

12 Sampling procedures Surveillance monitoring Samples collected in accordance with the monitoring programme are defined as surveillance, i.e. there are no suspicions about excessive amounts of pesticide in the lots prior to sampling. Enforcement sampling When a surveillance sample contained a pesticide residue above the national or EC maximum residue limit (1-3), the NFA prescribed a condition for the offering for sale or other handling of the food or lot to which the food belonged. As a follow-up, next lots of the commodity from the grower/exporter were detained and enforcement were collected. The condition was cancelled either when a certain number of lots contained pesticide below the MRLs, or when other information showed that the residue problem did not exist any longer. Surveillance sampling was then once more resumed. Sample collection Fresh fruit and vegetables were sampled at wholesalers' warehouses in the first trade channel. The sampling was done according to the new EC sampling method described in Commission Directive 2002/63/EC (4). The sample was sealed and labelled with a unique sample identity. Most of the of processed or frozen fruit and vegetables, juices, fruit drinks, rice, cereal products and vegetable oils were collected in retail shops or department stores. Samples of domestic produced cereal grains were collected at the milling plants. The imported cereal grains were sampled at the port where the shipment was discharged. Usually, one bulk sample of about 3 5 kg was collected by stream sampling technique. Plant inspectors from the National Board of Agriculture collected most of the, but inspectors from the Municipal Environmental and Health Protection Committees were to some extent also involved. Quality assurance measures Trained inspectors belonging to the National Board of Agriculture collected the according to written instructions from the National Food Administration. The bags with the were sealed and a photo was taken of the box that had been sampled. 8 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

13 Analytical procedures Methods and pesticide coverage In all, by using both multi-residue methods and single residue methods, it was possible to determine 239 pesticides corresponding to 290 analytes (Appendices 2 3). This is an increase with one pesticide compared with 2003 (5). By using LC-MS/MS it has been possible to lower the limit of quantification (LOQ) to 0.01 mg/kg for a large pesticides. The analytical method codes and their sources are listed in Appendix 1. A total of about (pesticide/commodity combinations) were sought (Table A2-Part I and II). Fruit and vegetables Practically all of fruit and vegetables were analysed by the multi-residue method (MRM) code 001. By this method, the were extracted with ethyl acetate, cleaned up on an S-X3 gel permeation column and determined by capillary gas chromatography. A total of 184 pesticides (213 analytes) were covered by using this method. Depending on commodity/country combination, the unclean extract was determined by LC-MS/MS (method code 111). For acidic commodities sodium hydroxide was added in the extraction step to enable quantitative determination of 3,5-dichloroaniline, the benomyl group, thiabendazole and imazalil (method code 002 and 112). In addition to three MRMs also ten single residue methods were used, and in all 233 pesticides (282 analytes) were sought in fruits and vegetables. Of these pesticides 97 were actually found. Figure 1 shows analysed and pesticides sought and detected during the last six years. National Food Administration, Sweden Livsmedelsverkets rapport nr 17/2005 9

14 No. of No. of pesticides No. of pesticides sought No. of pesticides detected No. of Figure 1. pesticides (active substances) sought and detected, and number of of fruit and vegetables analysed, surveillance sampling Vegetable oils The were extracted using hexane and acetonitrile. After clean-up on an S-X3 gel permeation column the were determined by GC equipped with ECD, FPD or N/P-detector. A total of 32 pesticides (37 analytes) were covered by the method used (code 018). Cereal grains and cereal products All of cereal grains and cereal products were analysed using MRM code 901. This method is similar to the multi-residue method (code 001) used for analysis of fruit and vegetables. Single residue methods were used for analyses of chlormequat, mepiquat, inorganic bromide, hydrogen phosphide, glyfosate and AMPA. In all, 43 pesticides (52 analytes) were included in the control of cereals. Quality control Among other procedures, the quality control included daily checks of the instruments' sensitivity by injection of test solutions. GC-determinations were in most cases carried out using standards in matrix extracts. The EC guidelines Quality Control Procedures for Pesticide Residue Analysis (6) have been implemented as far as possible (Table G). The laboratory has participated in 16 proficiency tests. These were organised by the European Commission and FAPAS (Table G). 10 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

15 Laboratory used and accreditation The analyses were carried out on a contract basis at AnalyCen Nordic AB, Lidköping. This laboratory is accredited by the Swedish accreditation authority SWEDAC for all analytical methods used for the NFA s official control of pesticide in food of plant origin. levels The majority of the pesticide were measured and reported from the limit of quantitation (determination), generally in the range of mg/kg. levels for each of the pesticides are given in Table A2-Part I-II. For certain pesticides the EC-MRLs set at the LODs (Limit of Determination) were not achievable in our routine monitoring. Residue Limits The National Food Administration's Regulations on Pesticide Residues in Food, sets MRLs for about 200 individual substances or group of substances (according to the residue definition in the regulation). Fresh, frozen and dried fruits and vegetables, cereal grains, some cereal products as well as baby foods are covered by the regulations (1-3). The MRLs, national and EC-MRLs, apply equally to domestic, EU and third country commodities, whether or not the pesticide is authorised in Sweden. When regulations concerning a certain pesticide or a certain group of food products are not given in the regulations, the NFA can decide the maximum level to be applied in each individual case. Results and discussion Surveillance monitoring In 2004, a total of surveillance of fresh, frozen or processed fruit and vegetables, cereal grains and cereal products were analysed for pesticide. Table 2 shows the surveillance analysed by country of origin. About 70 % of the originated from foods from 61 foreign countries. Most of the with unknown origin came from processed products. In 2003, the amounted to originating from 61 countries (5). National and EU harmonised Residue Limits (EC-MRLs) were exceeded by 80 (3.5 %) of the analysed. Out of of fresh or frozen fruits and vegetables 806 (45.8 %) contained at or below national and EC-MRLs and 77 National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

16 (4.4 %) exceeded these limits. One of the 232 of cereal grains exceeded the MRLs and 79.7 % contained no at all (Tables A1-Part I and D1 2). In all, analyses were carried out using 16 analytical methods. The surveillance analysed by the different analytical methods and arranged by food-groups is shown in Appendix 3. Out of the 239 pesticides (active substances) sought in all foodstuffs 100 were actually detected. The total numbers of findings of each pesticide in fruits, vegetables and cereal grains are shown in Table A2-Part I-II. Table 2. surveillance by country analysed in Country No. of Country No. of Country No. of Argentina 64 Honduras 2 Panama 8 Australia 2 Hungary 17 Peru 15 Belgium 40 India 18 Poland 24 Brazil 107 Iran 7 Portugal 1 Canada 1 Israel 32 Republic of Korea 1 Chile 32 Italy 195 Romania 2 China 30 Ivory Coast 4 Senegal 1 Colombia 42 Jordan 1 South Africa 87 Costa Rica 45 Kazakhstan 2 Spain 185 Cyprus 26 Kenya 8 Sweden 618 Czech Republic 2 Latvia 1 Taiwan 1 Denmark 8 Lebanon 5 Thailand 61 Dominica Rep. 2 Lithuania 1 Turkey 83 Ecuador 11 Makedonia 1 Ukraine 2 Egypt 19 Mauritius 2 United Kingdom 19 Finland 3 Morocco 44 United States 91 France 36 Namibia 2 Unknown country 56 German Fed.Rep. 39 Netherlands 113 Uruguay 9 Ghana 1 New Zealand 27 Venezuela 1 Greece 13 Norway 3 Vietnam 1 Guatemala 1 Pakistan 2 Zimbabwe 3 t 2280 The most commonly found pesticides in fresh or frozen fruit, vegetables and cereal grains are presented in Table 3. The fungicides imazalil and thiabendazole were among those most often found in fruits, while imidacloprid and carbendazim were most often found in the vegetable. Out of the eight different pesticides detected in cereal grain, the growth regulators chlormequat and mepiquat were most often found. 12 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

17 Table 3. Pesticides most commonly found in fruits, vegetables and cereal grains, surveillance sampling in Fruits Vegetables Cereal grains (970 ) (790 ) (232 ) No. of No. of No. of Pesticide findings Pesticide findings Pesticide findings Imazalil 157 Imidacloprid 51 Chlormequat 32 Thiabendazole 128 Carbendazim 41 Mepiquat 25 Carbendazim 84 Dithiocarbamates 33 Hydrogen phosphide 5 Dithiocarbamates 71 Endosulfan 30 Glyphosate 4 Carbaryl 62 Oxamyl 29 Pirimiphos-methyl 4 Chlorpyrifos 60 Chlorothalonil 28 Chlopyrifos-methyl 3 Orthophenylphenol 55 Procymidone 26 Bromide (inorganic) 1 Captan 50 Iprodione 20 Deltamethrin 1 Iprodion 50 Methomyl 20 Tolylfluanid 44 Imazalil 17 Comparison of from different types of production system The total analysed from organic, integrated and conventional production was 45, 175 and 2 060, respectively (Table 4). Two of the from organic growing contained. Seventeen from Integrated Production (IP) contained but none exceeded the MRLs. All the 80 exceedances came from of imported food from conventional production. In general, fewer were found in from Integrated Production compared with from the conventional production. The plant growth regulator chlormequat was found in 3 out of 62 domestic of wheat. The levels were very low, however, the use of chlormequat in wheat is not authorised in Sweden. Table 4. Comparison of found grouped by type of farming, surveillance sampling in Type of production Origin no. of No of containing No Residues< MRL Residues > MRL Organic Domestic Import IP Domestic Import Conventional Domestic Import National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

18 Fruits and vegetables - fresh or frozen A total of of fresh or frozen fruit and vegetables including potatoes were analysed for of 233 pesticides (282 analytes). About 50 % of the contained no. National or EC-MRLs were exceeded in 77 (4.4 %) of the (Figure 2). The exceedances in 2003 was 113 (6.3 %). Fruit & Vegetables ,4% Sweden ,4% EU except Sweden 599 4,0% Third countries 792 6,7% 44,9% 36,9% 51,1% 45,8% 49,8% 85,6% 56,4% Residues above national or EC-MRL:s Residues at or below national or EC-MRL:s Without Figure 2. Summary of results for fruit and vegetables, surveillance sampling Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

19 In general, the imported commodities contained considerably more often than the domestic. Most (86 %) of domestic grown fruit and vegetables contained no. The corresponding figures for EU-countries (except Sweden) and third countries were 45 % and 37 %, respectively. None of the domestic grown fruits and vegetables exceeded national or EC-MRLs compared with 4.0 % of the from EU countries (except Sweden) and 6.7 % from third countries. surveillance of each fruit and vegetable and the pesticide found (in per cent of the MRL) are presented in Appendix 4. Commodities containing pesticide greater than 10 times the MRL are shown in Table 5. The ratio between the highest level found in the surveillance sampling and the MRL is given. Residues of methomyl in a sample of strawberries from Egypt amounted to 37 times the MRL. However, the high figures are partly due to cases where the MRLs are set at the limit of determination. Table 5. Commodities containing pesticide greater than 10 times the MRL, surveillance sampling in Commodity Pesticide Country No. of Max. MRL Ratio of origin with >10 times MRL residue found max. residue/ MRL mg/kg mg/kg Strawberries Methomyl Egypt 2 1,87 0,05 37 Papayas Chlorothalonil Brazil 4 0,36 0,01 36 Kumquats Imazalil Argentina 1 0,59 0,02 29 Litchis Prochloraz Israel 2 1,04 0,05 21 Kumquats Dicofol Morocco 1 0,34 0,02 17 Mandarins Bromopropylate Cyprus 1 0,84 0,05 17 Persimmons Imazalil South Africa 1 0,32 0,02 16 Spinach Dithiocarbamates Italy 1 0,80 0,05 16 Passion Fruits Chlorothalonil Kenya 1 0,14 0,01 14 Kumquats Carbendazim Morocco 1 1,31 0,10 13 Litchis Thiabendazole Mauritius 1 0,63 0,05 13 Beans, with pods Dimethoate Thailand 1 0, Passion Fruits Dithiocarbamates Kenya 1 0,55 0,05 11 Parsley Dimethoate Italy 1 0,22 0,02 11 Kumquats Thiabendazole Argentina 1 0,53 0,05 11 Lemons Bromopropylate Cyprus 1 0,53 0,05 11 Papayas Dithiocarbamates Brazil 1 0,51 0,05 10 Table grapes A total of 112 of table grapes from 12 countries have been analysed. Five (4.5 %) contained above EC or national MRLs. One sample of table grapes originating from Spain contained 0.14 mg/kg of monocroophos. The shortterm intake, calculated on this level, resulted in an exceedance of the acute reference dose with 381 % for a child (Table 10). National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

20 The EU co-ordinated programme The EU co-ordinated programme for 2004 consisted of nine commodities and 47 pesticides (7). The minimum per commodity to be analysed by each of the member states was 12 to 93 depending on the population size in the MS. In Sweden the EU co-ordinated programme is included in the national monitoring programme. In all, 513 of apples, tomatoes, lettuce, strawberries, leek, orange juice, head cabbage, rye and oats were analysed (Table B). Residues above the EC-MRLs for the pesticides listed in Table B were found in five out of the 198 of apples, one out of the 45 of lettuce, two out of the 55 of strawberries, two out of the 30 of leek and in one out of the 30 of head cabbage. None of the of tomatoes, orange juice, rye and oats contained above the EC-MRLs (Figure 3). The EU co-ordinated programme included also analysis of individual units of apples, tomatoes, lettuce, leek and head cabbage for pesticides posing an acute risk. The homogeneity factor has to be calculated based on the in the individual units. No investigations were possible to carry out as none of the taken contained for those combinations. However, the homogeneity factor has been determined for chlorpropham in potatoes and eight pesticides in Chinese broccoli. The result is shown in Table 7. Percentage of 100% 80% 60% 40% 20% 0% Apples Head Cabbage Leeks Lettuce Oats Orange Juice Rye Commodity Straberries Tomatoes No Residues below MRLs Residues above MRLs Figure 3. Summary of results for the EU co-ordinated programme, only EC-MRLs and pesticides included in Table B, surveillance sampling in Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

21 Table D1 gives detailed information about pesticide found and action taken for those 78 surveillance of fruits, vegetables and cereal grains that exceeded EU harmonised MRLs. In 21 of the, two or more pesticides exceeded the EC-MRLs in the same sample. Three of those contained even three pesticides above the limits. A total of 23 in the follow-up enforcement sampling of fruits, vegetables and cereals contained above the EC-MRLs (Table D3). Out of of fruit, vegetables and cereal grains (surveillance and compliance) 492 contained of two or more pesticides in a single sample. The highest pesticides found was eight and this was found in one sample of Chinese broccoli from Thailand and one sample of pears from Italy. None of the contained seven pesticides. Six pesticides were found in five. Detailed information is given in Table E for all with two or more pesticide in a single sample. Violation rates of pesticide The frequency of of fresh or frozen fruits and vegetables with pesticide above national or EC-MRLs is shown in Figure 4. The violation rate has decreased and amounted to 6.7 % in fresh or frozen fruits and vegetables from third countries and 4.0 % in the from EU countries except Sweden. None of the of domestic grown fruits and vegetables contained above the MRLs. Sweden EU (excl. Sweden) Exceedances 12% 11% 10% 9% 8% 7% 6% 5% 4% 3% 2% 1% 0% Third countries Figure 4. Violation rate of pesticide in of fresh or frozen fruits and vegetables, national or EC-MRLs, surveillance sampling during National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

22 Foods intended for infants and young children In total, 92 of baby foods e.g. cereal based product, juices, fruit drinks, canned fruits and vegetables were analysed. No detectable were found in any of the. Photo: Harriet Böckman-Superti Juices and fruit drinks (excluding baby food ) A total of 41 of juices and fruit drinks were analysed. Three out of six of grape juice contained. The pesticides found were: carbaryl (0.04 mg/kg), carbendazim (0.01 mg/kg) and pyrimethanil (0.08 mg/kg). Fruits and vegetables processed or dried (excluding baby food ) 43 of dried fruits and canned or processed vegetables were analysed. Ten out of the 16 of dried grapes contained pesticide. The highest residue found was 0.31 mg/kg of carbendazim. The sprout inhibitor chlorpropham was found in 8 out of 35 of fried potato products. Two exceeded the national MRL and the highest residue was 2.7 mg/kg. Detailed information is given in Table C. Vegetable oils Olive oil, 22 in all, were analysed for of 32 pesticides (method code 018). Endosulfan was detected in 14 of the and the highest residue found was 0.07 mg/kg (Table C). Cereal products A total of 44 of pasta, were analysed. None of the contained (Table C). Cereal grains A total of 232 of cereal grains, mainly wheat, rice and rye, were analysed. Most of the (80 %) contained no at all (Figure 5). One sample of rice contained 0.15 mg/kg of hydrogen phosphide, which is above the limit of 0.1 mg/kg. The growth regulators chlormequat and mepiquat were most frequently found (Table 3). Chlormequat was found in 3 out of 62 of domestic wheat. The use of chlormequat in Sweden is authorised for rye but not for wheat (Table C). 18 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

23 Cereal grains 232 Sweden 153 EU except Sweden 12 Third countries 67 19,8% 0,4% 20,3% 25,0% 17,9% 1,5% 79,7% 75,0% 80,6% Residues above national or EC-MRL:s 79,7% Residues at or below national or EC-MRL:s Without Figure 5. Summary of results for cereal grains, national or EC-MRLs, surveillance sampling in Enforcement Enforcement were collected as a follow-up, when excessive amounts of pesticide were found in surveillance. EC-MRLs were exceeded in 23 out of 75 enforcement (Tables A1-Part II, Tables D3-4). A total of 14 lots (35.8 tons) of foods were prohibited for sale in 2004 (Table 6), compared with 23 lots (42.3 tons) in 2003 (5). These lots had either to be destroyed or returned to the supplier. A re-export is accepted only when the competent authority in the receiving country gives its approval. The analysed, grouped by food commodity, country of origin and found, expressed in per cent of the MRL, are shown in Appendix 5. Table 6. Lots prohibited for sale in 2004 Food Country No. of lots Weight, ton Carambole Malaysia Kumquats Argentina Papayas Brazil Parsley Italy Passion fruits Kenya Pepper, white Hungary Spinach Italy Table grapes Turkey National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

24 Rapid Alert System The Rapid Alert System for Foodstuffs (RASFF) was established by Council Directive 92/59/ECC on General Product Safety. Products entailing a serious health risk to the consumer are classified as Alert notifications. The notifying Member State (MS) informs the Commission, which then notifies the other Member States. Sweden has during 2004 sent three food-alarms concerning high pesticide to the Commission. The notifications were for one consignment of table grapes from Spain containing monocrotophos and two consignments of Chinese broccoli from Thailand containing dicrototophos and methamidophos, chlorpyrifos and dicrotophos, respectively. Dietary Exposure Assessment Homogeneity (variability) factor The homogeneity (variability) factor is defined as the quotient between the maximum and the mean residue of individual units in a sample. This factor was determined for chlorpropham in potatoes and for eight different pesticides in Chinese broccoli. In the calculations, units containing no were assigned a figure corresponding to half of the limit of determination. The homogeneity factor varied from 1.6 to 4.9 (Table 7). Table 7. Homogeneity factors for pesticides/commodities investigated in Pesticide Commodity No. of units Homogeneity Max Mean residue, residue, factor mg/kg mg/kg Sample Reference Chlorothalonil Chinese broccoli S401 Chlorpyrifos Cypermethrin Dicrotophos Iprodione Metalaxyl Metamidophos Chlorothalonil Chinese broccoli 5 1) G201 Dicrotophos ) Myclobutanil ) Chlorpropham Potatoes H507 1) Plastic bags containing 5-6 units of small broccoli, plant weight about 15 gram. 20 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

25 Study of stability of pesticides after wok cooking Two studies have been done to investigate the stability after wok cooking of pesticides found in Chinese broccoli. The broccoli with the incurred was divided in two equal portions, one part was analysed as raw (unprepared) and the second part was analysed after frying in a hot wok for about two minutes according to recipe. Two spoons of vegetable oils were added in the pan before frying. No significant reduction of the was obtained for the organophosphorous pesticides chlorpyriphos, dicrotophos and methamidophos. These pesticides are classified as acute toxic compounds (Table 8). Table 8. Studies of the stability after wok cooking of some pesticides found in Chinese broccoli. Pesticide Study Raw broccoli After cooking 1) Remaining mg/kg % Chlorpyriphos Dicrotophos Dicrotophos Metahmidophos Chlorothalonil Chlorothalonil < Cypermetrin Iprodione Metalaxyl Myklobutanil ) The are re-calculated taking into account the lost of water due to the wook cooking Short-term Intake The acute dietary intake or short-term exposure has to be considered for those pesticides that are classified as acute toxic. This area is relatively new and approaches how to estimate the acute intake has been put forward by WHO (8-11) and UK (12). The aim of the WHO and EU is to evaluate pesticides and establish acute reference doses (ARfD) for pesticides that possibly impose an acute health risk (13-14). The acute reference dose of a chemical is an estimate of the amount a consumer can ingest during one meal or during one day any health risk. In this study the national estimated short-term intake (NESTI) has been calculated for each pesticide found and for which EU, JMPR, JECFA or US-EPA (15) have established a reference dose. The type of foodstuffs of most concern when estimating the acute exposure are those where the entire commodity (including peel) is consumed at one occasion, i.e. nectarines, apples or table grapes. National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

26 Calculation of the national estimated short-term intake The national estimated short-term intake was calculated using the formulae shown in Figure 6. These formulae (case 2) are used when the meal-sized portion, as a single fruit or piece of vegetable (unit weight of the whole portion is > 25 g) might have a higher concentration of residue than the composite sample due to variability of in individual units. When the residue data reflect residue levels in the food as consumed (case 1), no variability factor is considered (i.e. cereals, juices). The consumption figures used when calculating the national estimated short-term intake (NESTI) are based on the 97.5 th percentile consumption of eaters only, which reflects the largest portion consumed during one meal or during one day. In this study consumption data from United Kingdom have been used (Table 9). Monitoring data reflect residue levels found in the products on the market. The observed residue (OR comp ) is the highest residue found in a composite sample. In order to refine the intake estimates, correction factors (when available) were applied to foodstuffs that normally are peeled or prepared, e.g. boiled or fried (12). OR comp is multiplied with a variability (homogeneity) factor (V). For commodities with unit weights between g a default factor of 7 (10 for leafy vegetables) is used. A factor of 5 is used for unit weights above 250 g. Known variability factors or in individual units should be used for more refined estimates. Table 9. Consumption figures and unit sizes for foods used in the short-term intake calculations (UK data). Commodity Large portion size Unit size Toddlers Adults (kg) (kg) (kg) Chinese Broccoli 1) Cucumbers ) Lettuce Melons Potatoes 3) Table grapes Zucchini ) Consumption data not availably. One unit for toddlers and three units for adults used in the intake calculation 2) A slice of one inch 3) Baked/roasted 22 Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

27 Case 1: The composite residue data reflect residue levels in the food as consumed NESTI = LP ORcomp bw Case 2a: The unit weight of the whole commodity (U) is smaller than the large portion (LP) NESTI U = ORcomp V ( + LP U bw ) ORcomp Case 2b: The unit weight of the whole commodity (U) is larger than the large portion (LP) NESTI LP ORcomp = bw V NESTI = National estimated short-term intake U = Median unit weight of the edible portion (kg) OR comp V = = Highest observed residue in a composite sample of edible portion incorporation processing factors if available Variability factor; 1 to 10 depending on unit weight and commodity LP = Highest large portion provided (97.5th percentile of eaters) in kg of food per day bw = Body weight (kg) Figure 6. The formulae used for calculating the national estimated short-term intake. National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

28 Results of the assessment of the national estimated short-term intake Children, with low body weight relative to their consumption of fruits and vegetables, compose a risk group of approaching the acute reference dose when the products contain high levels of acute toxic pesticides. In this study the estimated short-term intake has been calculated for a large pesticides/commodity combinations but the results are shown only when the intake for a child is above 50 % of the acute reference dose (Table 10 and Figure 7). The estimated short-term intake for a child (body weight 14.5 kg) exceeded the ARfD for aldicarb in potatoes, dicrotophos in Chinese broccoli, endosulfan in melons, lambda-cyhalothrin in lettuce, monocrotophos in table grapes and oxamyl in zucchini and cucumber (Figure 7). The intake of dicrotophos from Chinese broccoli reached 18 times the acute reference dose for a child and four times the ARfD for an adult (Table 10). 200% 1 763% 381% Per cent of ARfD 150% 100% 50% Aldicarb Deltamethrin Dicrotophos Endosulfan 0% Lambda-Cyhalothrin Chinese broccoli Cucumber Lettuce Melons Potatoes, Baked Table grapes Zucchini Monocrotophos Oxamyl Figure 7. Estimated short-term intake for a child, surveillance sampling in Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

29 Table 10. The estimated short-term intake of certain pesticides based on the highest residue found in composite in Only intakes above 50 % of the ARfD for a toddler are shown. Pesticide Commodity ARfD mg/kg bw Highest residue Correction factor Homogeneity factor Intake % of ARfD toddlers adults Aldicarb Potatoes, Baked Potatoes, Baked Deltamethrin Table grapes Dicrotophos Chinese broccoli Endosulfan Melons Melons Lambda-Cyhalothrin Lettuce Monocrotophos Table grapes Oxamyl Zucchini Cucumber National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

30 References 1. The National Food Administration's regulations on pesticide in food, SLVFS 2002:43, amendment 2003:27. National Food Administration, Uppsala, Sweden. 2. The National Food Administration's regulations on pesticide in food, SLVFS 2004:14, amendment 2004:24. National Food Administration, Uppsala, Sweden. 3. Commission Directive 2003/13/EC amending Directive 96/5/EC on processed cereal-based foods and baby foods for infants and young children. 4. Commission Directive 2002/63/EC of 11 July 2002 establishing Community methods of sampling for the official control of pesticide in and on products of plant and animal origin and repealing Directive 79/700/EEC. OJ L187, , Andersson A, Jansson A, Eskhult A G. The Swedish monitoring of pesticide in food of plant origin: Rapport nr 12, National Food Administration, Uppsala, Sweden. 6. Quality control procedures for pesticide analysis. Guidelines for monitoring in the European Union, third edition, Document no. SANCO/10476/ Commission recommendation of 9 January 2004 concerning a co-ordinated community monitoring programme for 2004 to ensure compliance with maximum levels of pesticide in and on cereals and certain products of plant origin. (2004/74/EC). OJ L16, , Guidelines for predicting dietary intake of pesticide (revised). GEMS/Food, WHO/FSF/FOS/97.7, World Health Organization, Geneva. 9. FAO/WHO. Pesticide Residues in food Report of the joint meeting of the FAO panel of experts on pesticide in food and the environment and the WHO core assessment group on pesticide. Rome, Italy, September FAO/WHO. Pesticide in food Report of the joint meeting of the FAO panel of experts on pesticide in food and the environment and the WHO core assessment group on pesticide. Geneva, Switzerland, September FAO/WHO. Pesticide Residue in food Report of the joint meeting of the FAO panel of experts on pesticide in food and the environment and the WHO core assessment group on pesticide. Rome, Italy, September New UK technical policy on the estimation of acute dietary intakes of pesticides. PSD, York, UK, 13 January Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

31 13. Inventory of IPCS and other WHO pesticide evaluations and summary of toxicological evaluations performed by the Joint Meeting on Pesticide Residues (JMPR) through WHO/PCS/02.3. World Health Organization, Geneva. 14. Legislation, the status of active substances under EU review (document 3010, updated 04/11/2004). 15. US-EPA interim registration eligibility decision for dicrotophos. Case No 0145, April 3, National Food Administration, Sweden Livsmedelsverkets rapport nr 17/

32 Appendix 1. Analytical method codes and their sources Code 001: GC-Multimethod Andersson A, Pålsheden H. Multi-residue method for analysis of pesticides in fruit and vegetables using ethyl acetate extraction, GPC clean-up and GC determination. In: Pesticide analytical methods in Sweden, part 1. Uppsala, Sweden: National Food Administration, Rapport 1998;17:9 41. Code 002: GC-Multimethod (alkaline extraction) Wåglund T, Elgerud C. A multi-residue procedure applied to the analysis of 3,5- dichloroaniline in some vegetables by use of gas chromatography. In: Pesticide analytical methods in Sweden, part 1. Uppsala, Sweden: National Food Administration, Rapport 1998;17: Ohlin B, Jansson C. Determination of benzimidazoles and some other pesticides in agricultural crops with HPLC. In: Pesticide analytical methods in Sweden, part 1. Uppsala, Sweden: National Food Administration, Rapport 1998;17: Code 008: Dithiocarbamates Pihlström T. Determination of dithiocarbamates in fruits and vegetables using GC/FPD. Not published, National Food Administration, Uppsala, Sweden. Harrington P. Analysis of dithiocarbamates by quantification of CS 2 using 2,2,4-trimethyl pentane method. Central Science Laboratory, York, UK. Keppel G E. Collaborative study of the determination of dithiocarbamate by a modified carbon disulphide evolution method. J. Ass. Offic. Anal. Chem. 1971;54: Winell B. Residues of dithiocarbamates in fruit, berries, vegetables and potatoes (in Swedish). Vår Föda 1975;27: Code 009: Diquat Kirsten W J. The determination of diquat in potato tubers. Analyst 1966;91: Åkerblom M. Second derivative scanning in spectrophotometric determination of pesticide. Fourth International Congress of Pesticide Chemistry (IUPAC), Zürich, Abstract volume VI 701. Code 010: Bromide, inorganic Rocklin R D, Johnsson E L. Determination of cyanide, sulfide, iodide, and bromide by ion chromatography with electrochemical detection. Analytical Chemistry 1983;55:4 7. Modified by the Swedish University of Agricultural Sciences, Department of Environmental Assessment, Uppsala, Sweden. Lindgren B, Berglöf T, Ramberg Å, Stepinska A, and Åkerblom M. Liquid chromatographic determination of bromide ion in cereals, fruit, vegetables, and blood with a Silver electrode in an electrochemical detector system. JAOAC International 1995,78: Livsmedelsverkets rapport nr 17/2005 National Food Administration, Sweden

33 Appendix 1. Cont. Code 018: GC-Multimethod for vegetable oils and oil seeds Pihlström T, Isaac G, Waldebäck M, Österdahl, B-G, Markides K. Pressurised fluid extraction (PFE) as an alternative general method for the determination of pesticide in rape seed. Analyst, 2002;127: Pihlström T, Isaac G, Waldebäck M, Österdahl, B-G, Markides K. Some preliminary results of the use of pressurised liquid extraction for the determination of pesticide in rape seed. Poster presented at the 3 rd European Pesticide Residue Workshop, July 3-5, York, UK. Pihlström T. Determination of pesticides in vegetable oils and oil seeds. Not published, National Food Administration, Uppsala, Sweden. Code 019: Ethoxyquin Blomkvist G. Some examples of the use of GC/MS in the Swedish pesticide monitoring programme. (Determination of ethoxyquin and diphenylamine in apples and pears). Poster presented at the 7 th Annual California Pesticide Residue Workshop, March 12 17,1995. Sacramento, California. Code 021: Tin organic pesticides (code 014) incl. fenbutatin oxide Wåglund T. Determination of tin organic pesticides, including fenbutatin oxide. Not published, National Food Administration, Uppsala, Sweden. Code 022: Maleic hydrazide Wåglund T, Elgerud C. A liquid chromatographic method for the determination of maleic hydrazide in potatoes. Not published, National Food Administration, Uppsala, Sweden. Code 025: Abamectin Wåglund T. A liquid chromatographic method for the determination of abamectin in tomatoes. Not published, National Food Administration, Uppsala, Sweden. Code 030: Chlormequat and mepiquat Ohlin B. Determination of chlormequat and mepiquat in fruit and vegetables using LC- MS/MS. Not published, National Food Administration,Uppsala, Sweden. Alder L et al. Non fatty foods determination of chlormequat and mepiquat- LC-MS/MS method. Proposed method for European Standard: CEN TC 275 WG 4, Doc N 146. Code 106: Benzoylphenylurea insecticides Jansson C, Kajrup B. Determination of benzoylphenylurea insecticides in fruit and vegetbles by liquid chromatography-mass spectrometry. Poster presented at the 3 rd European Pesticide Residue Workshop, July 3-5, York, UK. Code 111: LC-MS/MS Multimethod Jansson C, Pihlström T, Österdahl B-G, Markides K. A new multi-residue method for analysis of pesticide in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection. J. Chromatogr. A 1023 (2004) National Food Administration, Sweden Livsmedelsverkets rapport nr 17/