Supporting information for manuscript: Use of the Maximum Cumulative Ratio as an. approach for prioritizing aquatic co-exposure to

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1 Supporting information for manuscript: Use of the Maximum Cumulative Ratio as an approach for prioritizing aquatic co-exposure to Plant Protection Products (PPPs): A case study of a large surface water monitoring database Nathalie Vallotton*, Paul S. Price * Dow Europe GmbH, Toxicology and Environmental Research and Consulting, Bachtobelstr. 3, 8810 Horgen The Dow Chemical Company, Toxicology and Environmental Research and Consulting, 1803 Building, Midland, MI * Corresponding author Number of pages: 13 Number of figures: zero Number of Table: 8 S1

2 Supporting information The supporting information outlines the detection limit of the analytical methods (DL), as well as the benchmark for each plant protection product for fish (F), invertebrates (I), non-vascular (NVP) and vascular plants(vp) applied in the cumulative risk assessment (Table 1). Table 1: Aquatic ecotoxicity benchmark PPP Name Type of substance Fish Basis Invertebrate Basis NVP Basis VP Basis DL µg/l µg/l µg/l µg/l Trichlorophenoxy acetic acid H trichlorophenol D ,4-D H ,4-DB H ,6-Diethylaniline H, degr Hydroxycarbofuran I, degr Acetochlor H Acifluorfen H Alachlor H Aldicarb I Aldicarb sulfone I Aldicarb sulfoxide I alpha-hch I Atrazine H Azinphos-methyl I Benfluralin H Bentazon H Bromacil H S2

3 Bromoxynil H Butylate H Carbaryl I Carbofuran I Chloramben methyl ester H Chlorothalonil F Chlorpyrifos I cis-permethrin I Chloramben methyl ester H Clopyralid H Cyanazine H Dacthal (Trade Name) H Dacthal monoacid H Desethyl atrazine H, degr Diazinon I Dicamba H Dichlobenil H Dichlorprop H Dieldrinv I Dinoseb H Disulfoton I Diuron H DNOC EPTC H Ethalfluralin H Ethoprop I Fluometuron H Fonofos I γ-hch I S3

4 Linuron H Malathion I MCPA acid H MCPB H Methiocarb I Methomyl I Metolachlor H Metribuzin H Molinate H Napropamide H Norflurazon H Oryzalin H Oxamyl I p,p'-dde I , Parathion- ethyl I Parathion-methyl I Pebulate H Pendimethalin H Phorate I Picloram H Prometon H Pronamide/ Propyzamide H Propachlor H Propanil H Propargite I Propham H Propoxur I Simazine H Tebuthiuron H S4

5 Terbacil H Terbufos I Thiobencarb H Triallate H Triclopyr H Trifluralin H Codes Reference 1 Office of Pesticide Programs' Aquatic Life Benchmarks, EPA. 2 Benchmark based on assessment with PPP having a similar mode of action, see part B 3 Data on parent substance 4 Lowest benchmarks for insecticides 5 Office of Water Aquatic Life Criteria 6 Data based on US Environmental Protection Agency Office of Pesticide Programs Reregistration Eligibility Decision for Napropamide (EPA 1995) 7 Derived from (Ralston-Hooper, Hardy et al. 2009) 8 Derived from MCPA-EHE H I D Degr. Herbicide Insecticide Disinfectant Degradation product S5

6 The approach taken to select surrogate benchmarks for PPP with similar modes of action, when these were not published, is presented for each substance. Triazines: Surrogate for cyanazine The benchmark for atrazine is the lowest for invertebrates, non-vascular plants and vascular plants, therefore, atrazine s toxicity values are suggested as surrogates for cyanazine. The benchmarks are evaluated as sufficiently conservative, based on the comparative assessment of the effect of atrazine and cyanazine to aquatic plants 1, which report effect at higher concentrations than the suggested benchmark. Surrogate for deethyl-triazine The atrazine benchmark for invertebrate and fish are applied to the degradation product deethyl-triazine. A comparative assessment of the effect of atrazine and its degradation product on the unicellular algae Pseudokirchneriella subcapitata however indicates that the degradation products are less toxic to the unicellular alga by orders of magnitude 2. The extrapolation of the atrazine NVP and VP benchmark would lead to an overestimation of the effects of Deethyltriazine. In consequence, a benchmark is suggested for NVP based on the effects observed on Pseudokirchneriella subcapitata. The benchmark for non-vascular plants is extrapolated to vascular plants, even if non-vascular plants are less sensitive to triazines than vascular plants. S6

7 Table 2: Triazines F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) Atrazine Cyanazine Deethyl-triazine Prometon Simazine The aquatic ecotoxicty benchmark used for the extrapolation is in bold, while the surrogate value in italic. Chloroactetamides: Surrogate for propachlor: The acetochlor, alachlor and metolachlor benchmark for NVP and VP are in the same order of magnitude, thus extrapolation from non-vascular to vascular plants is applied to propachlor. Surrogate for 2,6-Diethylaniline: Benchmark for alachlor were applied to its degradation product 2,6-diethylaniline. Table 3: Chloroactetamides NVP (µg/l) VP (µg/l) Acetochlor Alachlor ,6-Diethylaniline Metolachlor 8 21 Propachlor The aquatic ecotoxicty benchmark used for the extrapolation is in bold, while the surrogate value in italic. S7

8 Organophosphates: Surrogate for azinphosmethyl, chlorpyrifos, fonofos, and ethoprop. Few benchmark for non-vascular plants and vascular plants are published for the organophosphate insecticides. The lowest benchmark for plants (chlorpyrifos NVP) was used as surrogate for azinphosmethyl (NVP, VP), chlorpyrifos (VP), fonofos (NVP, VP) and ethoprop (VP). Surrogate for fonofos: Fish and invertebrate benchmark are derived from the results of standard acute toxicity testing on Bluegill and Daphnia 3. Table 4: Organophosphates F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) Azinphos-ethyl 0.18 Azinphosmethyl Chlorpyrifos Diazinon Fonofos Disulfoton Ethoprop Malathion Parathion, ethyl Parathion-methyl Phorate The aquatic ecotoxicty benchmark used for the extrapolation is in bold, while surrogate values are in italic. S8

9 Thiocarbamate: Surrogate for butylate The benchmarks for the thiocarbamates indicate a wide range of effects in fish and invertebrate and no evident ranking in the sensitivities. The lowest benchmark (thiobencarb) is not considered as a relevant surrogate for butylate based on the difference in toxicity to invertebrates, therefore the surrogate benchmarks are based on the following information: the vascular plant benchmark was derived from effects reported on the duckweed Lemna gibba 4 the non-vascular plant benchmark was derived from a Selenastrum capricornutum study published by Caux and Ménard 5 Table 5: Thiocarbamate F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) butylate (2) 1460 (1) 4600 EPTC molinate pebulate thiobencarb = benthiocarb triallate Surrogate values are in italic. S9

10 Carbamates: Surrogate for carbofuran The non-vascular plants benchmark for oxamyl is the lowest among the available benchmark for NVP. Oxamyl is however the least toxic among this group to aquatic species, therefore the carbofuran benchmark for fish is selected as a more conservative surrogate for NVP and VP. Table 6: Carbamates F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) Aldicarb Carbaryl Carbofuran Methiocarb Methomyl Oxamyl The aquatic ecotoxicty benchmark used for the extrapolation is in bold, while surrogate values are in italic. Dinitroaniline: Surrogate for benfluralin An EFSA assessment on benfluralin presents data on vascular plants, which is used as a surrogate 6. Surrogate for ethalfluralin S10

11 No similar information was found on effects of ethalfluralin to non-vascular plants, the lowest benchmark for vascular plants (pendimethalin) was used as a surrogate for ethalfluralin. Table 7 : Dinitroaniline F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) Benefin = benfluralin (1) Ethalfluralin Oryzalin Pendimethalin Trifluralin The aquatic ecotoxicty benchmark used for the extrapolation is in bold, while surrogate values are in italic. Other analytes: pp -DDE, γ-hch (lindane) and dieldrin The analytes pp -DDE, γ-hch (lindane) and dieldrin do not have any published benchmark. However, DDT, the pp -DDE parent and Dieldrin are known to be harmful to environment, based on their toxic, bioaccumulative and persistent properties (PBT). These legacy insecticides (banned respectively in 1987 and 1972) have Ambient Water Quality Criteria acute and chronic life criteria, which were applied as a benchmark for invertebrates. The benchmarks for fish, vascular and non-vascular plants were derived by selecting the lowest benchmark among all insecticides in the dataset. S11

12 Table 8: other PPP F (µg/l) I (µg/l) NVP (µg/l) VP (µg/l) Insecticide lowest BM with Azinphosmethyl Propargite Carbaryl Dieldrin pp -DDE γ -HCH S12

13 REFERENCES 1. Fairchild, J. F.; Ruessler, D. S.; Lovely, P. A.; Whites, D. A.; Heine, P. R. An Aquatic Plant Risk Assessment of Sixteen Herbicides Using Toxicity Tests with Selenastrum capricornutum and Lemna minor; Columbia, Missouri Ralston-Hooper, K.; Hardy, J.; Hahn, L.; Ochoa-Acuña, H.; Lee, L.; Mollenhauer, R.; Sepúlveda, M., Acute and chronic toxicity of atrazine and its metabolites deethylatrazine and deisopropylatrazine on aquatic organisms. Ecotoxicology 2009, 18, (7), Fairchild, J. F.; Little, E. E.; Huckins, J. N., Aquatic hazard assessment of the organophosphate insecticide fonofos. Archives of Environmental Contamination and Toxicology 1992, 22, (4), EPA, U. S. Registration Review: Ecological Risk Assessment Problem Formulatoin for: Butylate; EPA-HQ-OPP ; USEPA: Washington D.C., USA, 11/6/2009, Caux, P.-Y.; Ménard, L.; Kent, R. A., Comparative study of the effects of MCPA, butylate, atrazine, and cyanazine on Selenastrum capricornutum. Environmental Pollution 1996, 92, (2), EFSA EFSA Scientific Report: Conclusion regarding the peer review of the pesticide risk assessment of the active substance benfluralin.; European Food and Safety Agency: S13

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