Plant protection products in agricultural soils: Do active ingredients show a comparable pattern in worms and in soil?

Plant protection products in agricultural soils: Do active ingredients show a comparable pattern in worms and in soil? Thomas Schmidt 1, Helena Viric Gasparic 2, Stefan Kimmel 1, Stefan Hoeger 1 and Renata Bazok 2 1 Innovative Environmental Services (IES Ltd), Benkenstrasse 260 4108 Witterswil Switzerland 2 Department of Agricultural Zoology University of Zagreb Faculty of Agriculture Svetosimunska 25 10000 Zagreb Croatia E-mail contact: t.schmidt@ies-ltd.ch SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk

Aim of the study Data from two sites in Croatia 2015 & 2016 Known ( ecological project ): Two fields Residues in earthworms But unknown: Residue concentrations in soil For ecotoxicological purposes: Can soil concentrations of active ingredients be reconstructed? Part 1: Compilation of field data regarding Sampling dates of worms and worm residues Use and application dates of plant protection products Part 2: Calculation method for reconstruction 2

Part 1 - Field data (1 of 8): Study sites Lukaĉ Two study sites: Lukaĉ Tovarnik Tovarnik https://www.croatiatraveller.com /Maps/CroatiaIslands.htm SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk 3

Part 1 - Field data (2 of 8): Study sites Two study sites: Lukaĉ Tovarnik https://www.croatiatraveller.com /Maps/CroatiaIslands.htm Lukaĉ Tovarnik 4

Part 1 - Field data (3 of 8): Crops Tovarnik Plot A Tovarnik Plot B Lukaĉ Plot A Lukaĉ Plot B 2015 Sugar beet 2015 Maize 2016 Maize 2016 Wheat 2015 Sugar beet 2015 Wheat 2016 Wheat 2016 Sugar beet Tovarnik Plot C Tovarnik Plot D Lukaĉ Plot C Lukaĉ Plot D 2015 Wheat 2015 Wheat 2015 Maize 2015 Oilseed rape 2016 Sugar beet 2016 Soy bean 2016 Soy bean 2015 Maize 5

Field data (4 of 8): Worm analytics - detection Worm fresh weight: 5-17 g per sample Limit of quantification: LOQ = 0.001 mg/kg fw Limit of detection (LOD): ½ LOQ = 0.0005 mg/kg fw 300 Active ingredients analysed 26 a.i. detected 621 analytical measurements 29.5 % < LOD 42.1 % between LOD and LOQ 28.3 % LOQ Thiametoxam Etofumesat Tembotrion Ciproconazole * Boskalid Azoxystrobin Clothianidin Imidacloprid Epoxiconazole Trifensulfuron-m. Triflusulfuron-m. Chloridazone Phenmedipham % detected 0 20 40 60 80 100 Thiofanat-methyl * Herbicides, Fungicides, Insecticides Desmedipham Oxasulfuron Metamitron Fenpropimorph Propiconazole Chlorpyrifos Thiacloprid Nicosulfuron Carbendazim * Flutriafol Fipronil Difenconazole % detected 0 20 40 60 80 100 * Not applied 2015/16 6

Field data (5 of 8): Worm analytics residues (n=23) Thiametoxam Tembotrion Ciproconazole * Etofumesat Boskalid Azoxystrobin Clothianidin Imidacloprid Epoxiconazole Trifensulfuron-m. Triflusulfuron-m. Chloridazone Phenmedipham % detected 0 20 40 60 80 100 mg/kg worm fw 0.0060 0.0074 0.0048 0.0037 0.0011 0.0030 0.0090 0.0509 0.0077 0.0006 0.0003 0.0025 0.0055 Herbicides, Fungicides, Insecticides Thiofanat-methyl * Desmedipham Oxasulfuron Metamitron Fenpropimorph Propiconazole Chlorpyrifos Thiacloprid Nicosulfuron Carbendazim * Flutriafol Fipronil Difenconazole % detected 0 20 40 60 80 100 * Not applied 2015/16 mg/kg worm fw 0.0046 0.0036 0.0147 0.0024 0.0057 0.0037 0.0020 0.0003 0.0002 0.0007 0.0011 0.0002 0.0007 7

Crop Part 1 - Field data (6 of 8): Use pattern of products A B C D A B C D 2015 Sugar beet Wheat Maize Oilseed rape Sugar beet Maize Wheat Wheat 2016 Wheat Sugar beet Soybean Maize Maize Wheat Sugar beet Soy bean 1 Betanal expert Hussar Harmony SX Teridox 500 g/l Pyramin WG Lontrel 300 Sekator OD Sekator OD 2 Goltix 70 SC Betanal expert Laguna 75 WG Samson Extra 6 OD Beet up trio Mustang Pyramin WG Laguna 3 Lontrel Goltix 70 SC Dicopur Max logo 300 Sekator OD Beet up trio Harmony 4 Gepard 50 SC Lontrel 300 Amistar extra Safari 50 WG Stil C logo 300 Agil 100 EC 5 Hussar Safari Thiacloprid Agil 100 EC Duett ultra Safari 50 WG Amistar Xtra 6 Amistar Xtra Amistar 250 SC Sumialfa 5 FL Laudis Karate Zeon Agil 100 EC Duett ultra 7 Bakar Prosaro 250 EC Duett ultra Amistar Xtra 8 Duett ultra Impact 25 SC Opus Team Duett ultra 9 Bravo 500 Neoram WG Amistar Xtra Karate Zeon 10 Amistar 250 SC Duett Ultra Karate Zeon Chromorel D 11 Prosaro 250 EC Bravo 500 Chromorel D Gaucho 70 WS 12 Gaucho 70 WS Karate Zeon Gaucho 70 WS Cruiser 600 FS 13 Cruiser 600 FS Gaucho 70 WS Cruiser 600 FS Force 20 SC 14 Force 20 SC Cruiser 600 FS 15 Karate Zeon Force 20 SC 16 Chromorel D Lukaĉ Tovarnik Herbicides: 2-6 products per plot Fungicides: 1-6 products per plot Insecticides: 0-4 products per plot 8

Part 1 - Field data (7 of 8): Use pattern of active ingredients Crop A B C D A B C D 2015 Sugar beet Wheat Maize Oilseed rape Sugar beet Maize Wheat Wheat 2016 Wheat Sugar beet Soybean Maize Maize Wheat Sugar beet Soy bean 1 ethofumesat iodosulfuron thifensulfuron methyl dimethachlor chloridazon clopyralid amidosulfuron Iodosulfuron 2 desmedipham mefenpyr-diethyl oxasulfuron clopyralid phenmedipham florasulam Iodosulfuron mefenpyr-diethyl 3 phenmedipham ethofumesat nicosulfuron desmedipham 2,4 D ester mefenpyr-diethyl oxasulfuron 4 metamitron desmedipham 2,4-D ethofumesat amidosulfuron chloridazon triflusulfuron-methyl 5 clopyralid phenmedipham azoxystrobin clopyralid Iodosulfuron phenmedipham propaquizafop 6 metamitron metamitron cyproconazole triflusulfuron-methyl mefenpyr-diethyl desmedipham azoxystrobin 7 quizalofop-tefuryl clopyralid thiacloprid propaquizafop propiconazole ethofumesat cyproconazole 8 iodosulfuron triflusulfuron-methyl esfenvalerat tembotrione carbendazim clopyralid epoxiconazole 9 mefenpyr-diethyl azoxystrobin epoxiconazole thiophanate-methyl triflusulfuron-methyl thiophanate-methyl 10 azoxystrobin prothioconazole thiophanate-methyl epoxiconazole propaquizafop 11 cyproconazole tebuconacole fenpropimorph lambda-cyhalothrin azoxystrobin 12 copper oxychloride flutriafol azoxystrobin cyproconazole 13 epoxiconazole copper oxychloride cyproconazole epoxiconazole 14 thiophanate-methyl epoxiconazole lambda-cyhalothrin thiophanate-methyl 15 chlorothalonil thiophanate-methyl chlorpyrifos lambda-cyhalothrin 16 prothioconazole chlorothalonil cypermethrin chlorpyrifos 17 tebuconacole flutriafol imidacloprid cypermethrin 18 imidacloprid lambda-cyhalothrin thiamethoxam imidacloprid 19 thiamethoxam imidacloprid thiamethoxam 20 teflutrin thiamethoxam teflutrin 21 lambda-cyhalothrin teflutrin 22 chlorpyrifos 23 cypermethrin Lukaĉ Tovarnik Herbicides: 2-10 active ingredients per plot Fungicides: 2-9 active ingredients per plot Insecticides: 0-6 active ingredients per plot 9

Number of products per month Part 1 - Field data (8 of 8): Worm sampling 12 10 8 6 4 2 0 Application of plant protection products & worm sampling 2015 2016 Worm 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 Month Lukaĉ Tovarnik Sampling Lukac: 16.09.2015 / 10.04.2016 / 07.09.2016 Tovarnik: 05.10.2015 / 04.05.2016 / 19.09.2016 10

Number of products per month Part 2 - Calculation of residues in soil (1 of 5): Basics 1 12 10 8 6 4 2 0 Application of plant protection products & worm sampling 2015 2016 Needed: Soil concentration after the time period from date of application to date of worm sampling 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 Month Lukaĉ Tovarnik Available Data: Product Time of application Time between application and worm sampling 11

Part 2 - Calculation of residues in soil (2 of 6): Basics 2 Available data Unit Source Application rate of each PPP Application time of each PPP g a.i. / ha date Values of DT 0, DT 50 & DT 90 - Farmer Field dissipation studies from EC, EU, EFSA DT 0, 50 and 90 = Dissipation time when 0, 50 and 90 % of the substance has dissipated To be calculated: Dissipation Curve y = concentration at day x a = application rate at day 0 (soil concentration at day 0) b = slope x = time after application y = a * e ( b * x) 12

Part 2 - Calculation of residues in soil (3 of 6): Imidacloprid Active ingredient Imidacloprid CAS No.: 138261-41-3 Log P ow : 0.57 DT 50 soil: 129 DT 90 soil: 551 Source: EFSA 2009 Degradation curve: y = a * e (-b*x) a: 0.0605 b: 0.004 R 2 : 0.995 Rate (g a.i./ha) 130 Soil conc. (mg/kg) 0.0650 Imidacloprid DAT0 DT50 DT90 DAT 0 129 551 Conc. (mg/kg) 0.065 0.033 0.007 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 Imidacloprid (mg/kg) y = 0.0605e -0.004x R² = 0.9948 0 200 400 600 Days After Treatment (DAT) Assessment (I) 17 May 2018 13

Part 2 - Calculation of residues in soil (4 of 6): Imidacloprid mg/kg mg/kg Tovarnik/A DAT Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) Bioaccumulation factor 177 0.0298 0.0583 2.0 389 0.0128 0.0180 1.4 527 0.0073 0.0500 6.8 Imidacloprid in Tovarnik/plot A 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 177 389 527 Days after Treatment (DAT) Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) Lukač/A DAT Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) Bioaccumulation factor 160 0.0319 0.0253 0.8 367 0.0139 0.0210 1.5 517 0.0076 0.1427 18.7 SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 Imidacloprid in Lukač/plot A Soil conc. (mg/kg d.w.) 160 367 517 Days after Treatment (DAT) 14 Worm residues (mg/kg f.w.)

Part 2 - Calculation of residues in soil (5 of 6): Axoxystrobin mg/kg mg/kg Active ingredient: Azoxystrobin CAS No.: 131860-33-8 Log P ow : 2.5 DT 50 soil: 21 DT 90 soil: 261 Source: EC 1998 Dissipation curve: y = a * e (-b*x) a: 0.0641 b: 0.008 R 2 : 0.95 Rate (g a.i./ha): 160 Soil conc. (mg/kg): 0.0800 0.020 0.015 0.010 0.005 0.000 0.030 0.020 0.010 0.000 SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk Azoxystrobin in Tovarnik/plot D Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) 173 385 523 Days after Treatment (DAT) Azoxystrobin in Lukač/plot D Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) 124 331 481 Days after Treatment (DAT) 15

mg/kg mg/kg Part 2 - Calculation of residues in soil (6 of 6): Ethofumesat Active ingredient: Azoxystrobin CAS No.: 131860-33-8 Log P ow : 2.5 DT 50 soil: 129 DT 90 soil: 551 Source: EC 1998 Dissipation curve: y = a * e (-b*x) a: 0.0641 b: 0.008 R 2 : 0.95 Rate (g a.i./ha): 160 Soil conc. (mg/kg): 0.0800 0.05 0.04 0.03 0.02 0.01 0.00 0.08 0.06 0.04 0.02 0.00 SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk Ethofumesat in Tovarnik/plot A Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) 0.0015 0.0005 0.0005 173 385 523 Days after Treatment (DAT) Ethofumesat in Lukač/plot A Soil conc. (mg/kg d.w.) Worm residues (mg/kg f.w.) 0.0005 0.0005 0.0005 154 5 145 Days after Treatment (DAT) 16

Conclusions Calculation of soil residues Field dissipation curves (based on EU, EC and EFSA) reasonably predict the soil residue concentration at any time after application. Calculated residue values need to be compared to analysed ones. Calculated residue values may be helpful in risk assessments. Potential for bioaccumulation Worm residues from field studies and calculated soil residues (using application rate and date of application) can be used for assessing the potential for bioaccumulation. SETAC Europe 28 th Annual Meeting: Advances in Soil Ecotoxicology and Risk 17

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