Agenda Item 2 IGE 03/2/...... -E Original: English only OSPAR CONVENTION FOR THE PROTECTION OF THE MARINE ENVIRONMENT OF THE NORTH EAST ATLANTIC MEETING OF THE INFORMAL GROUP OF DYNAMEC EXPERTS LONDON (SECRETARIAT): 21-23 OCTOBER 2003
How to further work on the OSPAR List of Substances of Possible Concern Combing-out Batch 2 (Pesticides)
Presented by WWF
Background 1. 129 substances on the OSPAR List of Substances of Possible Concern were initially selected in accordance with criteria less stringent than those for category III. These 129 substances concerned were divided in different batches which were distributed among the different IGE members for in depth- examination, with a view to their deselection. The tasks were: a. to examine the fact sheets and the underlying data for the selection focussing on the persistence criterion; b. to assess whether the persistence criterion as adopted by OSPAR 2001 (Reference Number: 2001-1) is not fulfilled; c. to write a short summary of the evaluation taking into account other parameters which would still justify a selection (occurrence in the marine environment, endocrine disruption, already prioritised, etc.) or a deselection. 2. Batch 2 was scrutinised by WWF (Ute Meyer and Andreas Ahrens, Ökopol) with ECPA (Bob Briant, Dow) as counterpart.
Approach 3. Available information on the degradability of the listed pesticides was compiled based on: a. their factsheets for further information on their degradability; b. their status with regard to Directive 91/414/EEC; c. the draft EU-PTB list; d. Classlab (EC, ecb.jrc.it/classification-labelling/); e. N-Class (Kemi, www.kemi.se/nclass/default.asp); f. PTB-Profiler (US EPA, www.pbtprofiler.net/); g. Envichem (Finnish EPA, wwwthw.vyh.fi/trip/kem/haku_eng.htm); h. PAN North America Pesticides database (Pesticides Action Network North-America, www.panna.org and www.pesticideinfo.org/Index.html); i. additional information provided by ECPA on the status of the substance in the Pesticides manual, on the producers and on inclusion in the Biocides Directive, and; j. Pesticides listed by WWF as suspected endocrine disruptors are marked in the Annex 2 (WWF ED). It was further checked whether the pesticides are listed on the EU list of suspected endocrine disruptors (Commission Communication Com(2001)262 final) (EU ED).
______1 OSPAR Commission IGE 03/2/...-E Results
Work done by OSPAR 4. The OSPAR factsheets provided degradation data supporting a DT50 < 50 d for 8 substances, 3 of which were originally selected based on these data, ie: cypermethrin, CAS 52315978 deltamethrin, CAS 52918635 alpha-cypermethrin, CAS 67375308 A proposal for deselection of two substances was already agreed by the IGE: nerolidol, CAS 7212444 (2 records suggest a DT 50 < 50 d) alpha-cypermethrin, CAS 67375308 (2 records suggest a DT 50 < 50 d, see also Annex 1) These two are existing EU pesticide active ingredients.
Available information on chemical databases 5. Only little information could be obtained from the scanned databases: None of the pesticides is considered as EU PTB. Classification. The underlying factsheet for pesticides classified as R50/53 was provided by the EC for bromophos-ethyl (DT50 soil). The PTB-Profiler gives half-lifes less than 50 days for 6 substances. Envichem provides information on one substance. The PAN Database added information on degradation on two substances. Underlying tests were not reported. More detailed information was obtained from available review reports prepared for the evaluation under 91/414 (see Annex 1). “Non-existing” pesticides 6. 6 of 18 pesticides are non-existing active pesticide ingredients in the EU, one of them is a WHO obsolete pesticides (Leptophos, CAS 21609905). Half-live data are hardly available for these substances. The PTB-Profiler suggests half-lives less than 50 d for 3 of them.
EU pesticides 7. 12 pesticides are or were authorised in the EU as active ingredients in plant protection products: a. 6 of the 12 pesticides are excluded from authorisation under 91/414 (decision on non-inclusion or not supported by manufacturers) 5 were not notified or supported for evaluation under 91/414/EEC (bromophos-ethyl, CAS 4824786; tridiphane CAS 58138082, also WHO obsolete pesticide, 2,4,5-T isooctyl ester, CAS 25168154, 2,4,5-T is WWF suspected endocrine disruptor, but no EU suspected endocrine disruptor (insufficient data); 4-sec-butyl-2,6-di-tert-butylphenol, CAS 17540759; cyhalothrin, CAS 68085858), and; 1 was evaluated (permethrin, CAS 52645531), but the dossier was regarded insufficient with regard to environmental fate and ecotoxicology in aquatic ecosystems (see Annex 1). The notifier withdrew its support for permethrin during the process, and a decision on non-inclusion on Annex I of 91/414 was taken (out 12/03). Permethrin is on the WWF list of suspected endocrine disruptors, however not on the EU list of suspected endocrine disruptors (insufficient data). b. 6 pesticides are authorised in EU MS: 1 was included on Annex I of Directive 91/414/EEC deltamethrin, CAS 52918635 (3 records suggesting a DT 50 < 50 d: 10-30 d, Danish EPA – selection criterion; 10-30 d, Pesticide info PANNA; DT 50 (whole system) 40-90 d,
______2 OSPAR Commission IGE 03/2/...-E RMS Sweden, see Annex 1, WWF endocrine disruptor, but no EU endocrine disruptor (insufficient data)) 3 are under evaluation dinocap, CAS 39300453 (2 records suggesting a DT 50 < 50 d: PTB-profiler: 38 d, industry data < 7 d; DT 50 (whole system) 7-15 d, RMS AU) cypermethrin, CAS 52315978 (2 records suggesting a DT 50 < 50 d: 10-30 d, Danish EPA – selection criterion; DT 50 17 d (whole system), RMS Belgium, see Annex 1; WWF endocrine disruptor, however no EU endocrine disruptor (insufficient data)) alpha-cypermethrin, CAS 67375308 (2 records suggesting a DT 50 < 50 d: DT 50 10-30 d Danish EPA – selection criterion; DT 50 (sed) 35.4, d see Annex 1; proposal for deselection agreed by the IGE) 2 are notified nerolidol, CAS 7212444 (2 records suggest a DT 50 < 50 d, proposal for deselection agreed by the IGE) bromadiolone, CAS 28772567 (notification deems unacceptable, 1 record on degradation: PTB-profiler: 38 d) Data are summarised in the Annex 2(electronic file 0215A_annex 2). Records supporting a DT 50 of less than 50 d are marked green, records indicating a DT 50 above 50 days are marked yellow.
Conclusions
8. The 6 non-existing pesticides should be flagged as “being not marketed in the EU” or put on a “set- aside” list. Too much effort on a detailed evaluation of these substances should be avoided. 9. 6 are excluded from authorisation under 91/414 (decision on non-inclusion / not supported) and 4 could also be flagged as “not marketed in the EU” or put on a “set-aside” list. Too much effort on these substances should be avoided. Permethrin is still authorised until 12/03. Although the database for permethrin is poor, the data available suggest that permethrin does not meet the persistence criteria. It is a WWF suspected endocrine disruptor, however not on the EU ED list (insufficient data). A deselection depends on the references OSPAR chooses for endocrine disruptors. 2,4,5-T is a WWF suspected endocrine disruptor, however not on the EU ED list (insufficient data). A deselection of 2,4,5-T isooctyl ester depends on the references OSPAR chooses for endocrine disruptors. 10. For the 6 pesticides still authorised in the EU: a. IGE has already agreed on the deselection of nerolidol, CAS 7212444 alpha-cypermethrin, CAS 67375308. b. Dinocap: We have some concerns with regard to the high percentage of unextractable residues and their slow mineralization in one study, however dinocap does not meet the persistence criteria as active substance, and could be deselected.
c. Cypermethrin, CAS 52315978 does not meet the persistence criteria as well. It is a WWF suspected endocrine disruptor, however not on the EU ED list (insufficient data). A deselection depends on the references OSPAR chooses for endocrine disruptors. d. For deltamethrin only one test shows a DT 50 (sed) slightly above 120 d, and includes the non- toxic isomer. The substance does not meet the persistence criteria. It is a WWF suspected endocrine disruptor, however not on the EU ED list (insufficient data). A deselection depends on the references OSPAR chooses for endocrine disruptors. e. Bromadiolone should remain on the list, but could be deselected after it is officially excluded from further authorisation.
Action Requested
______3 OSPAR Commission IGE 03/2/...-E 4. IGE is invited to: a. examine the approach on how to scrutinise the fact sheets and the underlying data for the selection focussing on the persistence criterion; b. consider whether the approach taken is consistent with that applied to other batches c. to assess whether persistence criterion as adopted by OSPAR 2001 (Reference Number: 2001-1) is not fulfilled; d. agree that certain substances are candidates for deselection
______4 OSPAR Commission IGE 03/2/...-E Annex 1 Available tests under 91/414 for the pesticides evaluated or under evaluation
1. permethrin (CAS 52645531 - out 12/03, proposed for deselection by the IGE), Extract from volume 3 of the monograph for permethrin prepared by Ireland (submitted to the European Commission in June 1998) 2. deltamethrin (CAS 52918635, Annex I), ), Annex B (Environmental Fate and behaviour) monograph for deltamethrin prepared by Sweden 3. cypermethrin, CAS 52315978, List of endpoints, Appendix 3 of monograph prepared by Belgium 4. alpha-cypermethrin, CAS 67375308 – proposed for deselection by the IGE), Appendix 3 of monograph prepared by Belgium 5. dinocap, CAS 39300453; personal communication Dr. Sonja Ecker, Austrian Agency for Health and Food Safety, Vienna ([email protected], Tel. 0043 1 73216 5327). Information accurately reflect the data submitted by Dow AgroScience in the EU review dossier.
Permethrin (IR, non-inclusion)
not readily biodegradable Water/sediment distribution of 14C -cyclopropane labelled permethrin shows: - rapid disappearance from water phase, increase in sediment residues - 23 d : total removal from water phase, - 36-82 % in sediments (mainly as permethrin; 17.7% identified metabolites; 15.2 % unidentified metabolite) - 57 d: 26% permethrin; 22% unextractable residues; metabolites partially readily biodegradable – percentage not given) no DT 50 (whole system) presented report concludes that there might a concern for dwelling organism because of persistence of residues in sediments
=> Metabolites not identified. However data suggest that permethrin as active substance does not meet the persistence criteria.
Deltamethrin (S, Annex I)
not readily biodegradable Water/sediment distribution of 14C (14C -benzyl labelled deltamethrin) in two sediment/water systems:
Day 0 Day 4 Day 28 Day 56 Day 84 Water 37-38% 10-20% 0-0.25% 0% 0.15-0.2% Sed 60-63% 75-89% 65-82% 62-77% 51-66% As 82-84% 76-90% 39-70% 37-66% 28-53% deltamethrin Unextractable 0.1-1% 1.1-2.4% 6.4-17% 5.2-19% 7.8-17% Other <2% 3-8% 2.5-4% 4.5-5% 4-4.5% -R-isomer of deltamethrin constituted part of the percentages deltamethrin presented in the tables (HPLC analysis). In both systems the amount of the -R-isomer increased from about 2-5% at the beginning, to about 21-24% after 1-2 weeks, and decreased to about 13-14% at the end of the test. The -R-isomer, thus formed in substantial amounts, was further degraded through ester cleavage. As the -
______5 OSPAR Commission IGE 03/2/...-E R-isomer shows no insecticidal activity, the amounts identified as this isomer were withdrawn from the percentages of deltamethrin found, and the DT 50 was calculated accordingly: DT50 (whole system) of deltamethrin (including its -R-isomer) 51 - 53 d (TNO system), and 116 and 124 days (Kromme Rijn system). DT50 (whole system) of deltamethrin (excluding its -R-isomer) 40 – 90 d.
Only one test results in a DT 50 (whole system) slightly above 120 d, but includes the non-toxic isomer. Other data suggest that deltamethrin does not meet the persistence criterion.
Cypermethrin (B, pending) not readily biodegradable Distribution in water / sediment systems (active substance) up to 42% in sediment at d 2 DT50 (active substance, whole system) 17d Metabolites: 3 phenoxybenzoic acid (up to 30% at d 7 in whole system), DT 50 3 d (whole system); unidentified metabolite (up to 25% at d 14) (DT 50 37 d whole system)
=> DT 50 of active substance and metabolites do not meet persistence criteria. alpha-Cypermethrin (B, pending)
not readily biodegradable Distribution in water / sediment systems (active substance) up to 62-55% in sediment at d 2 DT 50 DT water 0,4-2,1 d DT sed 6.4 –35.4 d Non-extractable residues up to 37.1% at d 105 Metabolites (no insecticidal activity): - 3 phenoxybenzoic acid: DT 50 3 d (whole system), distribution in water / sediment systems (up to 23% at d 7 in whole system) - dimethylcyclopropane carboxylic acid DT 50 37 d (whole system), distribution water /sediment systems up to 47% at d 14 in water phase and up to 19.5% at d 14 in sediment
=> DT 50 of active substance and metabolites do not meet persistence criteria.
Dinocap (Austria, pending) The 2,4-isomer and 2,6 isomer were studied separately DT 50 (whole system) 2,4 isomer 4.1-7.3 d; 2,6 isomer 1.38-15.5 d. Fate of dinocap in water/sediment systems (14C - labelled dinocap) Quick metabolisation already in water phase, remaining parent substance and metabolites adsorb to sediments. Parent substance degrade in sediments, further metabolisation of metabolites and formation of unextractable residues. Mineralization of unextractable residues. Maximum percentage of unextractable residues: 2,4 isomer: 49.5 % after 61 d; 69.5 % after 100 d 2,6 isomer: 47.1-73.2 % after 59 d; 36.8 - 66.6 % after 100 d.
CO2-production after 100 d: 7.8-13.4 % (2,4-isomer) und 30.2-58.6 % (2,6-isomer).
______6 OSPAR Commission IGE 03/2/...-E (see also deselection proposal submitted by Dow AgroScience)
DT 50 of active substance does not meet persistence criteria. Rather slow mineralization of unextractable residues in clay loam system.
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