ANNEX to Monitoring of Pesticide Residues in Products of Plant Origin in the European Union and Norway 1998 Report

Transcription

1 EUROPEAN COMMISSION HEALTH & CONSUMER PROTECTION DIRECTORATE-GENERAL Directorate F - Food and Veterinary Office Unit 4 - Food of plant origin, plant health; processing and distribution In cooperation with JRC Ispra, IHCP, Food Products and Consumer Goods and DG SANCO E1 Annex to SANCO/2597/00-Final ANNEX to Monitoring of Pesticide Residues in Products of Plant Origin in the European Union and Norway 1998 Report

2 Table of contents 1. NATIONAL AUTHORITIES AND CONTACT POINTS FOR PESTICIDE RESIDUE MONITORING COUNTRY COMMENTS Belgium Denmark Germany Greece Spain France Ireland Italy Luxembourg Netherlands Austria Portugal Finland Sweden United Kingdom Norway

3 1. NATIONAL AUTHORITIES AND CONTACT POINTS FOR PESTICIDE RESIDUE MONITORING Authority Contact person Contact point Belgium: Ministerie van Sociale Zaken, Volksgezondheid en Leefmilieu Algemene Eetwareninspectie Ministère des Affaires Sociales, de la Santé Publique et de l'environnement, Inspection générale des denrées alimentaires Cité Administrative de l'etat Quartier Esplanade, 11 B-1010 Brussel/Bruxelles Denmark: Danish Veterinary and Food Administration Div. of Chemical Contaminants Morkhoj Bygade 19, DK-2860 Soborg Germany: Bundesministerium für Gesundheit (Federal Health Ministry) Am Propsthof 78a D Bonn Greece: R. Van Havere Tel.: Fax: ewida@health.fgov.be A. Büchert Tel.: Fax: ab@fdir.dk Dr. W. Töpner Tel.: Fax: Toepner@bmg.bund.de Ministry of Agriculture, Plant Protection Directorate 3-5 Hippokratous str. EL-10164, Athens, Greece Director Mr. Ev. Arvanitakis Tel.: Fax: Pesticide Residue Laboratory 1, S. Venizelou str. EL-14123, Lycovrissi Greece Spain: Ministerio de Agricultura, Pesca y Alimentación Dirección General de Agricultura Subdirección General de Medios de Producción Agricolas Avda. Ciudad de Barcelona, Madrid Dr. Ch. Lentza- Rizos Tel.: Fax: rizos@internet.gr Mr. A. Yague Tel.: /75 Fax: mpaniagu@mapya.es 3

4 France: Laboratoire Interregional de la Repression des Fraudes de Paris-Massy 25 Avenue de la Republique F Massy Cedex Ireland: The Pesticide Control Service Department of Agriculture, Food and Rural Development Abbotstown Castleknock Dublin 15 Italy: Ministero della Sanità, Dip. Alim., Nutrizione e Sanità Pubbl. Veterinaria Uff. V (Controllo Ufficiale Alimenti)-Roma Luxembourg: Laboratoire National de Sante BP. 1102, L-1011 Luxembourg Netherlands: Keuringsdienst van Waren (Inspectorate for Health Protection) Hoogte Kadijk 401 NL-1018 BK Amsterdam Austria: Bundesministerium für Soziale Sicherheit und Generationen, Abteilung IX/B/1 Radetzkystraße 2 A-1031 Wien Mr B. Declercq Tel.: Fax: bernard.declercq@wanadoo.fr Dr. D. O'Sullivan Tel.: Fax: Dan.osullivan@daff.irlgov.ie Dr.SSA A. Sordi Tel.: Fax: dav-u05@sanita.it Dr. A. Consolino Tel.: Fax.: dav-u05@sanita.it Dr. F. Laux Tel. : Fax: H. A. van der Schee Tel.: Fax: Henk.van.der.schee@inspectwv.nl Dr. Sylvia Frischenschlager Tel.: +43/1/ Fax.: +43/1/ jasmin.koenig@bmsg.gv.at Dr. Roland Tel.: +43/1/40490/27847 Grossgut Fax.: +43/1/40490/9278 (Bundesanstalt für grossgut@baluf.gv.at Lebensmitteluntersu chung und forschung, Kinderspitalgasse 15 A-1090 Wien) 4

5 Portugal: Direcςãao-Geral de Protecςão das Culturas Quinta do Marques PT-2780 Oeiras Finland: National Food Administration POB 5, SF Helsinki Sweden: National Food Administration Box 622, S , Uppsala United Kingdom: Pesticides Safety Directorate Mallard House, Kings Pool 3 Peaseholme Green York YO1 7PX Norway: Norwegian Food Control Authority Box 8187 Dep., N-0034 Oslo, Norway European Commission DG SANCO/ E1 200, rue de la Loi (L86/1/8) B-1049 Bruxelles European Commission Joint Research Center, Institute for Health and Consumer Protection I Ispra (Va) Italy European Commission DG SANCO, FVO/D4 Belfield Office Park Beechhill Road Clonskeagh Dublin 4 Ireland J. R. Santos Tel: Or Fax: dgpc@mail.telepac.pt Pirjo-Liisa Penttila Tel.: Fax: pirjo-liisa.penttila@ elintarvikevirasto.fi A.Andersson Tel.: Fax: slv.se S. Godson T. Ware Tel.: / Fax: t.ware@psd.maff.gsi.gov.uk s.j.godson@psd.maff.gsi.gov.uk G. Torp Varran Tel.: Fax: gesche.varran@snt.no B. Drukker Tel.: Fax: Bas.Drukker@cec.eu.int C. von Holst Tel.: Fax: christoph.vonholst@jrc.it A. Bitterhof Tel.: Fax: Almut.Bitterhof@cec.eu.int 5

6 2. COUNTRY COMMENTS 2.1. BELGIUM Cereals: This report shows the results of pesticide residue monitoring on cereals on the Belgian market in In 1998, barley grains were chosen as a commodity to be monitored. The samples were taken by officials from the Food Inspection Service, e.g. in malteries. Organophosphorus pesticides were analysed by one laboratory, which had acquired accreditation for this analysis on 7 May 1997 (see annex). Table A is a list of pesticides which were included in the analytical method used. It gives the number of samples in which the pesticide is sought, the number of findings and the reporting level. The reporting level is the limit of determination of the laboratory. Table C contains the detailed results. Only pesticides that were found at least once, were listed. As no samples exceeded a MRL, no Table D is included. Ten samples contained more than one residue (Table E). Out of 8 pesticides looked for, 5 were found at least once. In decending order of number of findings, these were bromide ion, dichlorvos, pirimiphos-methyl, chlorpyrifos-methyl and malathion (see Table A and C). In 4 of the 27 samples analysed, no pesticide were found (15%). No samples contained exceeding an MRL (Table C and 1). Table 1. Number of samples analysed, number of samples in which pesticide which were looked for were not detected, number of samples in which 1 or more pesticide were detected below the MRL, number of samples in which 1 or more were detected exceeding a MRL or more specifically a EC-MRL. national programme samples analysed 27 without 4 with below MRL 23 with above MRL, 0 total with above EC-MRL 0 Fruit and vegetables: This report shows the results of pesticide residue monitoring on fresh vegetables and fruits on the Belgian market in The samples were taken by trained officials from the Food Inspection Service from the Ministry of Social Affairs, Public Health and the Environment (968 samples), or from the Service for Plant Quality and Plant Protection from the Ministry of Middle Class and Agriculture (952 samples). Sampling was done mostly according to directive 79/700/EEC, at auctions, importers, wholesalers and retail. In selecting the commodities, the methods of analysis and the number of samples, several factors were taken into account : the average consumption, the Belgian production figures, the rate of exceedences and findings of previous years, the analytical and budgetary possibilities. For less important commodities, a rolling programme is preferred. The different groups of fruits and 6

7 vegetables were included as much as possible. The co-ordinated programme of the European Commission was of course included in the national programme. A multiresidue method was performed on most samples. Dithiocarbamates and benzimidazoles were also frequently analysed. Bromide ion was measured in all commodities that are frequently grown in greenhouses. Especially on leafy vegetables and stem vegetables, a whole range of analyses were carried out, including propamocarb and N-methylcarbamates. Some single residue methods were performed on specific commodities, e.g. daminozide in apples, and propham/chlorpropham on potatoes. Acephate, methamidophos and triazophos were only measured in some commodities for the European co-ordinated programme. The two officially recognized laboratories involved in the monitoring programme acquired accreditation during 1997 for the most important analytical methods and commodities, and accreditation was gradually extended. Both laboratories participated in the European Commission s Proficiency Tests and in the the Workshop on Co-ordinated Analytical Quality Control. Results are shown in Table 1. A total of 1920 samples were analysed, of which 544 fruit, 1349 vegetable and 27 potato samples. The 787 leafy vegetable samples (lettuce, scarole and spinach) represented 41% of the total amount of samples. Out of a list of 122 different pesticide, a total of 46 were found at least once during this monitoring programme. The ten most frequently found pesticide, in descending order of number of findings, are: iprodione, bromide ion, propamocarb, dithiocarbamates, tolclofosmethyl, tolylfluanid, imazalil, vinclozolin, chlorpyrifos, carbendazim. More exceedences are related to national MRLs than to EC-MRLs. Table 1. Number of samples analysed, number of samples in which pesticide which were looked for were not detected, number of samples in which 1 or more pesticide were detected below the MRL, number of samples in which 1 or more were detected exceeding a MRL or more specifically a EC-MRL. national programme co-ordinated programme samples analysed without with below MRL with above MRL, total with above EC-MRL 49 6 Note that exceedences were counted not taking into account the uncertainty on the analytical result. 7

8 Sampling programme In selecting the commodities, the methods of analysis and the number of samples, several factors are taken into account: the average consumption, the Belgian production figures, the rate of exceedences and findings of previous years, the analytical and budgetary possibilities. The different groups of fruits and vegetables were included as much as possible. The co-ordinated programme of the European Commission was of course included in the national programme. The samples were taken by trained officials from the Food Inspection Service from the Ministry of Social Affairs, Public Health and the Environment (968 samples), or from the Service for Plant Quality and Plant Protection from the Ministry of Middle Class and Agriculture (952 samples). Sampling was done mostly according to directive 79/700/EEC, at auctions, importers, wholesalers and retail. Virtually no compliance monitoring was done, except for bromide ion in dried mushrooms (complaint of consumer organisation). Samples were refrigerated and analysed within 2-10 days. Two officially recognized laboratories were involved. A multiresidue method was performed on most samples. Dithiocarbamates and benzimidazoles were also frequently analysed. Bromide ion was measured in all commodities that are frequently grown in greenhouses. Especially on leafy vegetables and stem vegetables, a whole range of analyses were carried out, including propamocarb and N-methylcarbamates. Some single residue methods were performed on specific commodities, e.g. daminozide in apples, and propham/chlorpropham on potatoes. Acephate, methamidophos and triazophos were only measured in some commodities for the European co-ordinated programme. Analytical quality assurance The laboratories acquired a BELTEST accreditation during the year 1997 for the most important analytical methods and commodities. The situation of lab 1 in the year 1998 was the version of 4/11/1997 (extended version compared to 1/4/1997): multiresidue method for organochlorine pesticides in leafy vegetables, dithiocarbamates in leafy vegetables, berries and small fruit, bromide ion in leafy and fruiting vegetables, carbendazim and thiabendazole in leafy vegetables, bananas and citrus fruit, N-methylcarbamates in leafy vegetables and apples, imazalil in bananas, and propamocarb in lettuce. The situation of accreditation in the second lab was since 15/12/1997: dithiocarbamates with GC-ECD on fruit and vegetables and multiresidue method with GC-ECD and GC-NPD on fruit and vegetables. They prepared accreditation for the other analytical methods and commodities. In annex, copies of the accreditation documents are included. Both laboratories participated in the European Commission s proficiency tests on pesticide in fruit and vegetables in 1997 (2 tests). Both laboratories participated in the Workshop on Co-ordinated Analytical Quality Control in September 1997 in Oeiras, Portugal. The laboratories take into account the document Quality Control Procedures for Pesticide Residues Analysis. Guidelines for Residues Monitoring in the European Union. 8

9 Reporting The results are presented in Tables A to E, in the format recommended by the Commission. Table A is a list of pesticides which were included in analytical methods used during this monitoring programme. It gives the number of samples in which the pesticide is sought, the number of findings and the reporting level. Not only the pesticides mentioned in Directive 90/642/EEC are included, but all pesticides. The reporting level is not lower than the legal limit of determination. When laboratories had a higher determination limit than that in the legislation, this higher level is the reporting level. For instance the reporting levels are higher for dithiocarbamates, iprodione, and imazalil. Table B gives the detailed results of the co-ordinated programme. Table C contains the detailed results of the national programme, including the co-ordinated programme. Only pesticides which were found at least once, are listed. Please note that the exceedences counted in Table B and C are mathematical exceedences, not taking into account the uncertainty of the analytical result. Table D gives a list of exceedences of EC harmonised MRLs, which were higher than 1.5 x MRL. Table E gives information on multiple in single samples of the Food Inspection Service. Samples from the Service for Plant Quality and Plant Protection were not included in Table E. Results A total of 1920 samples were analysed, of which 544 fruit, 1349 vegetable and 27 potato samples. The 787 leafy vegetable samples (lettuce, scarole and spinach) represented 41% of the total amount of samples. In 982 samples (51 %) no pesticide were detected. Out of a list of 122 different pesticide, a total of 46 were found at least once during this monitoring programme. The ten most frequently found pesticide, in descending order of number of findings, are: iprodione, bromide ion, propamocarb, dithiocarbamates, tolclofos-methyl, tolylfluanid, imazalil, vinclozolin, chlorpyrifos, carbendazim (see Table A). The programme was focussed on crops known to have relatively high exceedence rates such as the leafy vegetables lettuce, scarole, and spinach (exceedence rate this year 5-12%) and celery (25%), but high exceedence rates were also found in parsley, peach, mango and grapes. It can, however, be mentioned that for imported fruits and minor crops, the MRL setting is less efficace. The highest exceedence rate was found in dried mushrooms. These samples were taken as a follow up of a complaint. More exceedences are related to national MRLs than to EC MRLs (see Table C). In the coordinated programme, 5 exceedences of EC-MRLs were found (see Table B). A lot of exceedences are related to MRLs at the limit of determination. Leafy vegetables often contain more than 1 pesticide residue (see Table E). 9

10 2.2. DENMARK Pesticide Residue Monitoring of Fruits, Vegetables and Cereals in Denmark Introduction This report made for the Commission of the European Communities includes specific and harmonised monitoring results from the Danish monitoring programme The results including information about single commodities, reporting levels, violations and multiple residue determinations are presented in the text and in the Annex Table A-E. The Danish monitoring programme-1998 comprised 2164 samples including 931 samples of fruits, 1069 samples of vegetables and 164 samples of cereals. Danish produce as well as commodities imported from other member states and non-member states were examined. Sampling The nation-wide sampling plans were designed by the Danish Veterinary and Food Administration, the Institute of Food Research and Nutrition on the basis of dietary consumption pattern, production and import data, and monitoring results from previous years. The sampling plans were implemented by three regional laboratories performing the analytical work. Samples were taken at production level and at wholesalers and importers. Analysis and quality assurance The analytical methods are developed and validated by the Danish Veterinary and Food Administration and the analyses performed by three regional laboratories, which are accredited to the relevant pesticide methods. The fruit and vegetables were analysed for approximately 150 pesticides using 1) a GC multimethod based on extraction with acetone/cyclohexane/ethyl acetate 2) a HPLC method (6 fungicides) and 3) a spectrophotometric method for the sum of dithiocarbamates. The cereals were analysed for 28 pesticides using 1) a GC multimethod, 2) a LC-MS/MS method (glyphosate and AMPA). In the analytical methods 1-2 spiked samples were included in each analytical batch. The GCmultimethods included spiked samples containing 8-15 pesticides at 2 concentration levels alternating between all pesticides. Quantification was performed with a matrix-matched standard (GC-method, fruit and vegetables) or a pure solvent standard. The calibration standard was matched to the expected concentration within a factor of 2. The reporting levels entered in Table A are the general levels of quantification. However, lower quantification levels are achievable for many pesticide/crop combinations. Samples with pesticide exceeding the MRL were verified by analyses at another laboratory. 10

11 Results Pesticide were found in about one third of the samples of fruit, vegetables and cereals. Residues were detected in 32% and 7% of the domestically produced fruits and vegetables. In the imported fruits and vegetables were detected in 53% and 20% of the samples. Violations of maximum residue limits (MRLs) were found in 66 samples corresponding to 3.0% of the fruit, vegetables or cereals. The violations included 8 samples of Danish produce (1%); 11 samples imported from other EU member states and 47 samples imported from countries outside EU. For exceeding the MRLs or found in commodities where no MRL-value was set (open positions), a toxicological risk assessment was performed. In all cases it was concluded that the detected did not constitute any health hazard to the consumer. Results exceeding the MRL were send to the local authorities (The Municipal Food Control Units) which take actions mostly by warning the holders of the products (producers, wholesalers, and importers). For the cereals pesticide were detected by the GC-multimethod in 5% of the samples. In addition glyphosate, measured by a newly developed LC-MS/MS method were detected in 68% of 50 samples of Danish produced cereals and the degradation product of glyphosate AMPA (aminophosphonic acid) were detected in 16% of these samples. The pesticides most commonly detected in fruit, vegetables or cereals were in descending order: dithiocarbamates, thiabendazole, endosulfan, carbendazim, iprodione, procymidone, tolylfluanid, ortho-phenylphenol, vinclozolin and glyphosate. Residues of more than one pesticide were found in 10.6% of the samples. Figure 1. Summarised results from the Danish pesticide monitoring programme FRUITS Danish Imported no 68% >MRL 4% <MRL 28% no 48% >MRL 3% <MRL 49% 11

12 VEGETABLES Danish Imported >MRL 1% <MRL 6% >MRL 3% <MRL 18% no 93% no 79% CEREALS Danish Imported <MRL 3% <MRL 10% no 97% no 90% 12

13 2.3. GERMANY Pesticides Residue Monitoring in Food for the Year 1998 Summary of the Results from the Federal Republic of Germany The report contains the results of the tests carried out on food of animal origin, grain, fruit and vegetables during the 1998 survey period. It includes all of the data transmitted by 40 accredited laboratories of the food inspection services of the Laender to the Federal Institute for Health Protection of Consumers and Veterinary Medicine, BgVV. These data also comprise the results of the food monitoring carried out on a national scale, those of the official food inspection services (8843 samples) as well as of the co-ordinated monitoring programme (3077 samples). Samples were taken at the side of producers, manufacturers, wholesale and retail trade, and restaurants according a national sampling protocol published as official ordinance. The active ingredients tested for were ingredients which had already been included in the Annexes to Directives 86/362/EEC, 86/363/EEC or 90/642/EEC. In the course of the 1998 survey period, a total of 11,920 (1997: 12,362; 1996: 11,870) samples were tested for pesticide in the Federal Republic of Germany. In 6765 (57%) samples of pesticides were not determinable and in 4829 (40%) samples of pesticides were detected in compliance with official, national and EU, MRLs. Only 326 (2.7%) samples contained of pesticides exceeding MRLs. Table 1 shows the number of samples split into domestic production and import and takes into account the three Directives. No major difference can be seen between the residue situation from domestic and import food produce concerning the residue situation. Table 1 Overview of the results of the tests performed on domestic and foreign produce. domestic samples Import samples food item total without total without amount residue s up to MRL above MRL amoun t up to MRL above MRL cereals animal origin fruit/ vegetable total

14 Table 2 Top-ten of the pesticides detected as in food samples Pesticide Samples Samples with % Samples with 1 DTC det. as CS ,7 2 Procymidon ,1 3 Thiabendazol ,4 4 Endosulfan, S ,1 5 Chlorpyrifos ,0 6 Carbendazim, S ,9 7 Carbendazim ,7 8 Vinclozolin ,5 9 Iprodion ,5 10 Endosulfansulfat ,0 The food samples were analysed for overall 80 different pesticides from which 50 were detected at least in one sample. The pesticides detected most often in food samples as are shownintable2 14

15 2.4. GREECE SUMMARY OF PESTICIDE RESIDUE MONITORING RESULTS OF GREECE FOR THE YEAR EU COORDINATED PROGRAMME. 126 samples of the products specified in the 97/822/EC Commission Recommendation were examined by the coordinated laboratory. All of these were analyzed for GLC amenable pesticides (acephate, chlorpyriphos, chlorpyriphos-methyl, deltamethrin, diazinon, endosulfan, imazalil, iprodione, lambda-cyhalothrin, mecarbam, metalaxyl, methamidophos, methidathion, permethrin, pirimiphos-methyl, thiabendazole, triazophos, vinclozolin). 116 of them were also analyzed for benomyl group and 39 for maneb-group. 70 samples (55% of the total number of samples) contained not detectable of the pesticides sought. 45 samples (36%) contained detectable at or below the MRL. In 11 samples (9%) of a pesticide were detected exceeding the EU MRLs. 2. NATIONAL PROGRAMME 1164 samples were examined by 6 laboratories. 767 samples (66% of the total number of samples) contained not detectable of the pesticides sought. 224 samples (19%) contained detectable at or below the MRL. In 52 samples (5%) of one or more pesticides exceeding the EU or national MRLs were detected (50 exceeded the EU and 2 the national MRL). In 121 samples (10%) of pesticides for which no EU or national MRLs are established, were detected. In addition a. 186 samples of virgin olive oil were analyzed for organophosphorus insecticides: 107 samples contained not detectable of the pesticides sought. 65 samples contained detectable of the pesticide fenthion, 2 of which exceeded the MRL of 1 mg/kg, established by FAO/WHO (Codex Alimentarius) - since no EU MRL is established. 2 samples contained detectable of the pesticide methidathion, none of which exceeded the MRL of 2 mg/kg, established by FAO/WHO. 1 sample contained the pesticide dimethoate at 0.1 mg/kg (Codex MRL: 0.05* mg/kg (LOD)). b. One sample of carrots consisting of 15 roots - in which the analysis of the composite sample showed the presence of lindane (0.1 mg/kg) and chlorpyriphos (0.22 mg/kg), was further analysed in order to assess the variability of residue concentration. Each root was cut in half lengthwise. One half of each carrot was included in the composite sample. The remaining individual half roots were analysed separately. The concentrations of lindane determined in the individual roots ranged from to 0.15 mg/kg and those of chlorpyriphos from to 0.30 mg/kg. The total number of pesticides analyzed for is 93. The 10 most frequently pesticides found are: chlorpyriphos (156 samples), maneb group (58 samples), chlorpyriphos methyl (33 samples), phosalone (33 samples), captan (32 samples), 15

16 methamidophos (30 samples), benomyl group (28 samples), fluvalinate (17 samples), methidathion (16 samples) and phosmet (15 samples). The reporting levels are generally those established by the Council in the EU MRL Directives, or those indicated by FAO/WHO Codex Alimentarius. In one case (methamidophos) the EU LOD of 0.01 mg/kg could not be achieved and the limit routinely achievable (0.02 mg/kg) is reported. In some cases the reporting levels are those routinely achieved in the laboratory. QUALITY ASSURANCE The EU guidelines are followed as close as possible. The screening of samples by GLC involves the use of standard mixtures containing the most commonly encountered pesticides, including at least two pesticides with a poor or variable GC response or recovery. Bracketing calibration is used. Although most quantitations are carried out using calibration curves with 3-5 levels covering a limited concentration range, a single calibration point is sometimes used, for example for confirmation of a residue which has already been quantified on a different GC system. Routine recovery checks and blanks are carried out approximately every 20 samples rather than on the basis of batches, because of the uneven flow of samples to the laboratory. All the laboratories are in the phase of preparation for accreditation. Table 1. Οverview of the results from the Greek pesticide monitoring programme Co ordinated National Programme Programme Number % Total Number % Total Total samples analysed % % Samples with non 70 55% % detectable Samples with detectable 45 36% % at or below the MRL Samples with detectable 52 of one or more pesticides exceeding the 11 9% EU National EU or national MRLs MRLs MRLs % Samples with detectable of pesticides for whichnoeuornational MRLs are established % RESULTS FROM THE GREEK CO-ORDINATED MONITORING PROGRAMME 1998 Total number of samples: 126 <MRL 36% >MRL 9% Non Detectable 55% RESULTS FROM THE GREEK NATIONAL MONITORING PROGRAMME 1998 Total number of samples: 1164 >MRL 5% <MRL 19% No MRL established 10% Non Detectable 66% 16

17 2.5. SPAIN REPORT ON THE RESULTS OF THE EUROPEAN COMMISSION'S COORDINATED PROGRAMME 1998 INTRODUCTION Under Article 4 of Council Directive 90/642/EEC, national programmes have to be drawn up for monitoring MRLs in the Member States and, after the latter have been consulted, a recommendation is to be prepared concerning a coordinated programme of inspections for the following year. More specifically, Recommendation 97/822/EC lays down a Community programme for 1998 concerning the coordinated monitoring of of plant protection products in and on certain products of plant origin, including fruit and vegetables. The following plant products were chosen for the 1998 programme: oranges, peaches, carrots and spinach (both fresh and frozen). The number of samples was proportional to the population and the number of consumers in each Member State. In the case of Spain, 45 samples were to be taken for each vegetable product, which could come from Spain itself, from other Community countries, or be imported from third countries. The following pesticides were monitored: acephate, the benomyl group, chlorpyriphos and chlorpyriphos-methyl, deltamethrin, diazinon, endosulfan, dithiocarbamates, imazalil, iprodione, lambda-cyhalothrin, methamidophos, mecarbam, permethrin, pirmiphos-methyl, triazophos, thiabendazol, vinclozolin. For the programme, it was proposed that samples should be taken from domestic crops, given that most of the fruit and vegetables on the Spanish market are home grown. It was decided to take samples in those Autonomous Communities responsible for producing large quantities of such plant products, following the criteria laid down in Directive 79/700/EEC. The sampling distribution and the analytical laboratories are indicated in Table I. ANALYTICAL PROCEDURES As analytical methods multi-residue methods (e.g. ethylacetate method and acetone method) and single- residue methods (for dithiocarbamates and benzimidazoles) were used. QUALITY OF ANALYSIS The analyses were to a large extent carried out following the quality assurance measures proposed by the EU for residue analysis. The laboratories involved in this coordinated programme, most of which took part in Proficiency Test I organised by the EU, have all applied for accreditation, which they hope to receive once the necessary checks have taken place. RESULTS AND COMMENTS The results of the coordinated programme for 1998 are set out in tables based on the EU format. 17

18 Of the 20 pesticides monitored, analyses of the selected plant products detected 14, the highest incidence being in oranges and peaches. The pesticides found in the largest number of samples were dithiocarbamates, detected in 19 samples (11.44%) at values being close to the analytical detection limit (DL), chlropyriphos in 15 samples (9.03%) with levels in percentage terms being generally low compared with the MRLs, imazalil in 10 samples (6%) with no values exceeding 50% of the MRLs, thiabendazol in 7 samples (4.2%) mostly at the analytical DL, and methidathion in 6 samples (3.6%); no of chlorpyriphos-methyl, deltamethrin, iprodione, lambda-cyhalothrin, permethrin or triazophos were detected. Levels exceeding the relevant MRLs were detected for the benomyl group in an orange sample, with a level of 0.55 mg/kg compared with the MRL of 0.30 mg/kg, and for metalaxyl in spinach, with a level of 1.33 mg/kg compared with the MRL of 0.05 mg/kg. Six samples were found to contain two pesticide while only one sample was found to contain of three plant protection products. 18

19 2.6. FRANCE PESTICIDE RESIDUE MONITORING OF FRUITS, VEGETABLES AND CEREALS IN FRANCE YEAR 1998 The monitoring programme for 1998 was carried out on the basis of A.The programme recommended by the Europeen community [ commission recommendation of november 1997] B.The programme proposed by the DGCCRF to control the pesticide residue level in regard with the EU and national regulation The monitoring programme was occurring to assume that pesticides were used following good agricultural practice 4058 crops were sampling by the DGCCRF's inspectors following the sampling directive 79/700 The sampling programme was investigated on domestic and importated produce at the wholesale level. We have no rule concerning the ratio between these two sources For cereal grain the procedures were to investigate the storage situation For fruits and vegetables, the number of sampling did not only take into account the dietary intake patterns of french consumers but also some crops where residue of pestides meet some problems as lettuces and similars Limited samples of various commodities were submitted but some processed cereals were investigated as flour and bread[ not reported] Sampling crops were sent to six laboratories. Only two laboratories were accredited for some pesticides. For the accreditation it is necessary to follow only normalised methods or to validate the technics inside the laboratory. We are recognized for organo chlorinated and phosphorous compounds, dithiocarbamates, benzimidazoles and methyl carbamates. The methodology involves 1.homogenisation of samples 2.extraction with suitable solvents [ acetone or ethyl acetate] 3.clean up by partition and or by adsorbent 4.analysis by GC or HPLC using specific detectors Confirmation was investigated using GC/MS or GC/MS/MS; Laboratories participated at some ring or profienciency test with BIPEA or CHECK organisation In 40% of the samples, no were detectable and 6,6% of samples contained above MRL. This numbers of anomalies can be explained by the amount of lettuces and similars Dithiocarbamates, vinclozolin, procymidone, oxadixyl, imazalil, carbendazim were found more than 100 times in fruits and vegetables as fungicides Chlorpyriphos methyl, pyrimiphos methyl, malathion, deltamethrine, dimethoate, dicofol, endosulfan were detected as insecticides more than 50 times in fruits, vegetables and cereals. 19

20 table 1 Number of samples analysed Without detectable : With at or below MRL : With above MRL: With above national MRL: active ingredient: active ingredient: carrots radish Turnip and sweedes Food item:celeriac Others root vegetables onions garlic shallots tomatoes peppers egg plant cucumber courgette gherkin melon cauliflowers & broccolis head cabbage and cabbage lettuce and similar spinaches witloofs ciboulette, basilic parsley ginseng mint sorrel others Ginger coriander aneth Thym beans and peas mushrooms leeks celery asparagus Fennel Artichock rhubarb various vegetables potatoes oilseed 20

21 Table 2 Number of samples analysed Without detectable : With at or below MRL : With above MRL: With above national MRL: active ingredient: active ingredient: citrus nuts apples pears apricots peaches plums cherries grapes strawberries small berries bananas pineapple avocadoes tropical fruits kiwi Litchi dates figs Papayas mangoes dried fruits Number of samples analysed Without detectable : With at or below MRL : With above MRL: With above national MRL: active ingredient: active ingredient: cereals (grain) 21

22 2.7. IRELAND Irish Pesticide Monitoring Results for The Irish pesticide monitoring programme for pesticide in food is undertaken by the Department of Agriculture and Food through its Pesticide Control Service. The objectives of the programme are to ensure that - pesticides are correctly applied to food and that - consumers are not exposed to unacceptable pesticide in food. In 1998 some 608 samples were analysed for pesticide of which 285 samples were fruit and vegetables and 44 were cereals. - Fruit and Vegetables: 64 different types of fruit and vegetables were analysed as part of the monitoring programme. 40.4% of these samples were of domestic origin and the remaining 59.6% were either imported produce or of unknown origin. These samples were analysed for up to 93 different pesticides and metabolites. 56.1% of the samples analysed were found to contain some detectable pesticide residue and 4.6% contained in excess of statutory EU MRLs. Enforcement action is taken by Ireland only in respect to those pesticide MRLs which are defined in the EU residue directives, 76/895, 86/362, 86/363 and 90/642 and their amending directives. Details of the pesticide detected are provided in the attached tables. vegetables samples analysed of 37 different pesticides were detected. 31 of these pesticides and have yet to be established for the remaining 6. In the fruit and MRLs exist for The pesticides most commonly encountered in fruit and vegetables were thiabendazole (10.2% of samples), carbendazim (9.5% of samples), chlorpyriphos (9.5% of samples), iprodione (8.8% of samples), captan (5.3% of samples), chlorfenvinphos (4.9% of samples), dicofol (4.6% of samples), omethoate (4.2% of samples), dimethoate (3.9% of samples), methidathion (3.5% of samples), chlorthalonil (3.2% of samples), endosulfan (2.8% of samples) and deltamethrin, phosmet and tolcophos-me (each at 2.5% of samples). Residues of thiabendazole were primarily detected in citrus and pome fruit, of captan were detected in pome fruit, cherries and berries, of chlorfenvinphos were primarily detected in root vegetables and of dicofol were primarily detected in citrus fruit, pome fruit and berries. In all 45 samples (15.8% of samples analysed ) contained of two pesticides, 16 samples (5.6% of samples analysed) contained of three pesticides and 9 samples (3%) contained of four or more pesticides. - Cereals. Cereal samples, of which 31.8% were of domestic origin and the remainder were either imported or of unknown origin, were analysed for 69 pesticides and metabolites. Residues were detected 22

23 in 61% of these samples none of which exceeded an MRL. Residues of 7 pesticides were detected. MRLs have been established for five of the pesticides concerned. The pesticides encountered were pirimiphos-me (57% of samples), lindane (18% of samples) and chlorpyriphos-me (14% of samples). None of the encountered were present at a concentration greater than 10% of an established MRL. - Violations of MRLs 13 samples of fruit and vegetables were found to contain in excess of current EU MRLs. 4 of these were of Irish origin and 9 were in imported produce. 8 of the violations related to MRLs which were set at the LOD suggesting that the pesticides concerned were applied to crops illegally. The GAPs concerned have not being supported and corresponding EU MRLs have not been established. The crops affected are considered to be minor crops under current EU guidelines. These findings indicate a need to deal with the issue of MRLs in minor crops. Assessment of the consumer risk associated with the dietary intake of the pesticide / crop combinations for which the MRL was exceeded suggests that there was not a risk to consumers except in the case of chlorfenvinphos in carrots. In that instance the residue present at 0.7mg/kg was marginally in excess of the EU MRL of 0.5mg/kg and resulted in the dietary intake for adults and children approaching or being equal to the ARfD. There therfore is an urgent need to review chlorfenvinphos under Directive 91/414/EEC with a view to re-evaluating the uses of this pesticide and its associated MRLs. 23

24 2.8. ITALY Summary of the results from Italy for the year 1998 National programme concerning harmonised pesticides The report of the Ministry of Health contains the results of the tests carried out on food of vegetables origin and cereals during the 1998 survey period, concerning the pesticides listed in the Annexes II of the Directives 86/362/EEC and 90/642/EEC. 67 laboratories of the National Health Service supplied the data for the official control on pesticide but only a part is already accreditated according to the EN laboratories participated to the third EU Proficiency test in Samples were analysed using multi residual method, able to determine the presence of 100 or more pesticides. The samples were taken at random on the market and based on dietary consumption and production. Of a total of 8276 samples, in 8220 not exceeding permitted levels were found, while in 56 samples (0,7%) where found exceeding permitted levels; no were detected in 6925 samples (83,7%) Vegetables Fruit Cereals Total Nr. of samples Regular samples Irregular samples Irregular samples % 0,88 0,52 0,00 0,68 Pesticides in regular samples Vegetables Fruit Cereals Total Nr. of samples without Nr. of samples without % 90,7 76,1 92,5 83,7 Nr. of samples with within legal limits Nr. of samples with within legal limits 8,4 23,4 % 7,5 15,6 Global National Programme The results of the national programme concerning the global research or for about 280 pesticides are shown in table above. Nr. of samples Regular samples Irregular samples Irregular samples % Without With Fruit ,1 Vegetables ,4 TOTAL ,3 The total number of analysed for fruits and vegetables is The pesticides there were found most often in descending order of finding are in vegetables: cupper, procymidone, dithiocarbammates, endosulfan, dimethoato, chlorpropham, chlorpyriphos, parathion; in fruits: procymidone, dithiocarbammates, azynphos-methyl, chlorpyriphos, dimethoato, captano, chlorpyriphos methyl, parathion. 24

25 EU co-ordinate monitoring exercise (Recommendation 97/822/CE, point 1) The number of samples analysed for each compound (active substance/product) ranges between 96 and 364 for peaches, between 14 and 279 for oranges, between 20 and 195 for carrots, between 6 and 75 for spinach. No samples presented exceeding the MRL 25

26 2.9. LUXEMBOURG Pesticide monitoring in fruits and vegetables and cereals carried out in Luxembourg in 1998 Introduction This report summarizes the results of the coordinated and the national pesticide monitoring programme in fruits, vegetables and cereals on the luxembourgish market in This report has been prepared according to the recommendation of the commission as far as technically possible. It not only contains pesticides mentioned in the dir. 90/642/CEE and 86/362/CEE, but also some other pesticides. Sampling The samples were collected according to the annual sampling plan prepared from the National Food Control Administration. Samples of fresh fruits, vegetables and cereals were generally collected from the central market in Luxembourg by the local police agents. Imported products' sampling was done by the food controller in the wholesalers warehouses. Sampling is done mostly according to directive 79/700/EEC The size of a laboratory sample was at least 1 kg. The sampling plan is based on a rolling plan (the section of commodities is subject to annual variations). Analysis The samples were analysed by the division of food control which is a part of the National Health Laboratory. All the samples were analysed by a gaschromatographic multiresidue method (modified german official method DFG S19). This method consists of an acetone extraction partition with dichloromethane, and a clean-up on a biobeads S-X3 gel permeation column. The extract was analysed by GC with selective detectors (ECD, NPD and FPD). When a pesticide residue exceeded the MRL, the identity of the pesticide was confirmed by GC-MS. With this method more than 200 pesticides are covered. Dithiocarbamates were also determined on each sample by using an CS 2 evolution method. The CS 2 is determined by headspace analysing using GC with flame photometric detector (EC method, document 1729/VI/80 final 2, not published). Accreditation and quality assurance The one official laboratory involved in the monitoring pesticide residue programme is in the preparation phase for accreditation. The analytical results are governed by a quality assurance system. The laboratory take into account as far as possible the document Quality control Procedures for Pesticide Residus Analyses. Guidelines for Residus Monitoring in the European Union. 26

27 Reporting levels./. The lowest residue levels are the same as the limits of determination (generally in the range of 0,01-0,1 mg/kg). The limits of determination are determined by recovery tests. Results A total of 230 samples were analysed out of which 90 fruits, 120 vegetables and 20 cereals. Luxembourgish products were concerned for 21.4 % of the analysed samples and 78.6 % came from EU or third countries. Out of a list of 94 different pesticide a total of 31 were found at least once during the monitoring programme. The ten most frequently found pesticide, in descending order of number of findings are iprodione, procymidon, imazalil, endosulfan, folpet, captan, chlorpyriphos, maneb group, methidation and pyrimiphosmethyl. In 156 samples no pesticide were detected. Eigt samples contained a residue level higher than the maximum EU level Summary of results are shown in the following table: Total no. of samples analysed No. of samples without No. of samples with at or below the MRL No. of exceedings of EC-MRLs No. of exeedings of N-MRLs Co-ordinated programme fruits an vegetables National * programme fruits and végétables National programme cereals * In the national programme of fruits and vegetables the co-ordinated programme is included. 27

28 2.10. NETHERLANDS SUMMARY During 1998 about 5000 samples were analysed, both Dutch and foreign production. During the last 10 years the import fraction was increased according to the importance on the market. Import products in general show higher percentages of MRL-violations. Both import and local production show above the limit of detection in about 50 % of the samples. In 1998 higher violation rates were observed than in the years before. Probably this not caused by worse agricultural practice only, but also by better analytical possibilities. 1 INTRODUCTION Pesticide residue control has been a task of the Dutch Inspectorate for Health Protection for many years. Therefore, a suitable infrastructure was present for the EU-monitoring as required by directives 90/642/EEC (products of plant origin), 86/362/EEC (cereals) and Recommendation 97/822/EU (the harmonised specific program 1998). 2 SAMPLING During 1998 the Inspectorate for Health Protection was under reorganisation. In September the number of inspectorates was reduced from 13 to 5. In the new system samples are analysed by one centralised laboratory and taken by the 5 inspectorates at auctions, importers, wholesale trade and industries processing agricultural products. Due to the reorganisation considerably less samples were analysed than in the past. Especially from August to the end of the year the activity was lower. The samples are taken without prior information about the sample and represent the situation in the market for the product at that time. However, sampling is directed to products that need attention because of the violation rate. The number of items of a lot is regulated by the Dutch Food and Commodity Law. This regulation is the implementation of the EC-directive 79/700/EEC. 3 ANALYSIS AND QUALITY CONTROL The general strategy is obtaining as much information as possible by using Multi-Residu- Methods (MRMs). These methods consist of an extraction of into an organic solvent followed by a chromatographic separation and selective detection of. The four main methods are: - Gas chromatography (GC) with Electron Capture Detection (ECD) - Gas chromatography with Nitrogen/Phosphorus Detection (NPD) - Gas chromatography with ITD Detection - High Pressure Liquid Chromatography (HPLC) with post-column derivatisation and fluorimetric detection of N-methylcarbamates Along with these MRMs a total-sum method is used for the of the dithiocarbamate group. In the centralised laboratory GC-ITD is the leading system, with additional use of NPD/ECD in cases of low sensitivity. The MRMs detect about 275 analytes of the 450 substances that have an MRL. The remainder must be controlled by Single-Residue-Methods (SRM's), which are not performed in routine but on a survey base. Only the dithiocarbamates and carbendazim are analysed as routine SRM's. Annex I gives information about the scope of the MRMs, as published in the Dutch method collection. Details of the methods used are described in this manual, which is a result of cooperation of governmental and private institutes. In 1996 a new edition of this manual was presented (6.1). 28

29 The validity of the analytical results is governed by a quality assurance system complying EN To avoid the risk of false negatives a series of standard mixtures that contain frequent occurring are available to check system performance. The centralised laboratory implemented the EU Guideline on Quality Control (6.2) to a considerable extent. 4 REGISTRATION AND COMPILATION The inspectorates for health protection have a data-system for the storage of sample data and analytical results. The applied MRMs and SRM's are recorded and the results are stored. Because of the registration of MRMs also the absence of a residue can be established. The data of the regional inspectorates were collected for the report using a data-extraction procedure. 5 MONITORING RESULTS During 1998 about 5000 samples were analysed, both Dutch production and import. During the last 10 years the import fraction was increased according to the importance on the market (Figure 1). Import products in general show higher percentages of MRL-violations (Figure 2). In 1998 higher violation rates were observed than in the years before. Probably this is not caused by worse agricultural practice only, but also by better analytical possibilities. Import samples show above the limit of detection in about 50 % of the samples. Local production gives more samples without detectable (Figure 3 and 4). Number samples avg '87/90 avg '91/93 avg '94/96 '97 '98 %>MRL avg '87/90 avg '91/93 avg '94/96 '97 '98 Import Figure 1. Total number of samples. NL Import Figure 2. Violation percentage. NL No residue Res. <MRL Res. >MRL No residue Res. <MRL Res. >MRL Figure 3. Pesticides in import products. Figure 4. Pesticides in Dutch products. Tables A.1 and A.2 show summarised statistical data on both and products. The pesticides giving rise to violations of MRLs show considerable changes in Frequently found pesticides that show more violations are: - diethofencarb, pyrimethanil, cyprodinil, fludioxonil, oxamyl, endosulfan, bifenthrin, chlorprofam, thiabendazole Pesticides becoming less important are: - metalaxyl, bupirimaat, methiocarb, parathion. Also products violating MRLs show variations. More violations are encountered in: - pear, beans, tangerine, lemon, grape, kiwi fruit, broccoli, mango and raspberry. Considerably fewer violations were found in: 29