Supporting Information for: Large scale risks from agricultural pesticides in small streams

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1 Supporting Information for: Large scale risks from agricultural pesticides in small streams Eduard Szöcs 1, Marvin Brinke 2, Bilgin Karaoglan 3, and Ralf B. Schäfer 1 1 Institute for Environmental Sciences, University of Koblenz-Landau, Germany 2 German Federal Institute of Hydrology (BfG), Koblenz, Germany 3 German Environment Agency (UBA), Dessau-Roÿlau, Germany Number of pages: 35 Number of gures: 11 Number of tables: 5 Corresponding author, schaefer-ralf@uni-landau.de S1

2 Contents 1 Data Cleaning S5 2 Overview of compiled data S7 3 Inuence of agricultural land use and catchment size S21 4 Eect of precipitation and season on RQ S23 5 Pesticides in small streams S28 6 Additional material S33 S2

3 List of Figures S1 Overview of data cleaning steps S6 S2 Number of sampling occasions per year and month S8 S3 Spatial distribution of the 2,301 small stream sampling sites S20 S4 S5 Raw data used for the model in Eqn. 2 and Fig. 3 of the main article... S21 Smooth and linear t S22 S6 Graphical representation of coecients from table S S26 S7 Summarised coecients (and their 95% CI) for precipitation and quarter of the year S27 S8 Cumulative distribution of the number sites exceeding RAC S30 S9 Proportion of samples with detects in small streams S31 S10 Distribution of the number of quantied compounds in the samples.... S32 S11 Relationship between catchment size and stream width S33 S3

4 List of Tables S1 Overview on chemical samples S7 S2 Overview on pesticides in the database S8 S3 S4 23 pesticides for which we modelled the relationship with precipitation and seasonality S23 Coecients and CI from per compound models S24 S5 Overview on RAC exceedances of the 78 compounds with more than 1000 measurements S28 S4

5 1 Data Cleaning Before combining into a common database, more than 30 datasets have been cleaned and homogenised separately. Cleaning steps comprised the following steps (Figure S1 gives a graphical overview): 1. Structure: Datasets have been adjusted to the database structure. 2. Coordinates: Coordinates have been transformed to a common Coordinate Reference System (DHDN / 3-Grad Gauss-Krüger Zone 3 (EPSG:31467)) and duplicates merged. 3. Chemicals: Chemical names and identiers have been unied using the webchem package ( 4. Identiers: Unique identiers have been assigned. 5. Units: All concentrations have been converted to µg/l. Values below limit of quantication were set to zero (and can be used to identify non-detects). 6. Other meta-data: meta-data has been standardised. 7. Temporal resolution: The temporal resolution of the database is 1 day. Samplings below this resolution have been aggregated by the maximum daily value. 8. Validity Checks: Simple rules for validity checks have been implemented. S5

6 Raw Data Adjust coordinates Adjust structure Assign substanceid Assign siteid and sampleid convert units adjust names validity checks Cleaned Data For each dataset merge datasets remove duplicates Figure S1: Overview of data cleaning steps. After cleaning, data have been stored in a relational spatial PostgreSQL database. S6

7 2 Overview of compiled data Table S1: Overview on chemical samples. Only data from running waters and grab sampling is shown. a : Abbreviations according to ISO :DE. b : Including metabolites name abbrv. a Begin End No. sites No.samples No. pesticides b Baden- BW Württemberg Bavaria BY Hesse HE Mecklenburg- MV Western Pomerania Lower Saxony NI North Rhine- NW Westphalia Rhineland- RP Palatinate Schleswig- SH Holstein Saarland SL Saxony SN Saxony-Anhalt ST Thuringia TH Total S7

8 No. samples Month Figure S2: Number of sampling occasions per year and month. Table S2: Overview on pesticides (and metabolites) in the database. a Authorized in Germany (Source: German Federal Oce of Consumer Protection and Food Safety (BVL) as at March 2015). b Authorized in the European union (Source: EU Pesticides database as at March 2015). c Regulatory Acceptable Concentration [µg/l] (Source: German Environment Agency (UBA) as at November 2015). Name CAS Group Auth. GER a Auth. EU b RAC c 1 (E)7-(Z) other x x Dodecadienylacetat 2 (Z)-9-Dodecenylacetat other x x 3 1,3-cis-Dichlorpropen other 4 1,3-trans-Dichlorpropen other 5 1-(3, metabolite Dichlorphenyl)urea 6 1-( metabolite Isopropylphenyl)urea 7 1-Decanol other x x 8 1-Methylcyclopropen other x x 9 2,4,5-T herbicide 10 2,4,6-Trichlorphenol metabolite 11 2,4-D herbicide x x ,4-DB herbicide x 13 2,4-Dichlorphenol metabolite 14 2,6-Dichlorobenzamid metabolite metabolite Hydroxydesethylatrazin 16 3-Hydroxy Carbofuran metabolite 17 4,6-Dinitro-o-Cresol insecticide S8

9 18 4-tert. Cyclobutylhexanon metabolite 19 AMPA metabolite 20 Acequinocyl insecticide x x Acetamiprid insecticide x x Acetochlor herbicide 23 Acetochlorsulfonsäure metabolite 24 Acetochlorsäure metabolite 25 Aciuorfen herbicide 26 Aclonifen herbicide x x Acrinathrin insecticide x 28 Alachlor herbicide 29 Aldicarb insecticide 30 Aldrin insecticide 31 Ametoctradin fungicide x x 32 Ametryn herbicide 33 Amidosulfuron herbicide x x 34 Aminopyralid herbicide x x 35 Amisulbrom fungicide x x 36 Anthranilsäureisopropylamid metabolite 37 Atraton herbicide 38 Atrazin herbicide 39 Atrazin, 2-Hydroxy metabolite 40 Avermectin B1a insecticide x x 41 Azadirachtin (Neem) insecticide x x 42 Azinphos-ethyl insecticide 43 Azinphos-methyl insecticide 44 Aziprotryn herbicide 45 Azoxystrobin fungicide x x Azoxystrobin-CA metabolite 47 Beubutamid herbicide x x 48 Benalaxyl fungicide x x Benazolin herbicide 50 Bensulfuron-methyl herbicide x 51 Bentazon herbicide x x Benthiavalicarb fungicide x x 53 Benzoesäure fungicide x x 54 Betacypermethrin insecticide x 55 Bifenazate insecticide x x 56 Bifenox herbicide x x 57 Bifenthrin insecticide x Bixafen fungicide x x Boscalid fungicide x x Bromacil herbicide S9

10 61 Bromadiolon other x 62 Bromocyclen insecticide 63 Bromoxynil herbicide x x Bupirimat fungicide x 65 Buturon herbicide 66 Captan fungicide x x Carbendazim fungicide Carbetamid herbicide x 69 Carbofuran insecticide 70 Carboxin fungicide x 71 Carfentrazone-ethyl herbicide x x Chloramben herbicide 73 Chlorantraniliprole insecticide x x Chlorbromuron herbicide 75 Chlordan insecticide 76 Chlorfenac herbicide 77 Chlorfenvinphos insecticide 78 Chloruazuron insecticide 79 Chloridazon herbicide x x Chlormequat other x x 81 Chloroxuron herbicide 82 Chlorpropham herbicide x x 83 Chlorpyrifos insecticide x Chlorpyriphos methyl insecticide x 85 Chlorsulfuron herbicide 86 Chlorthalonil fungicide x x 87 Chlorthalonil-SA metabolite 88 Chlortoluron herbicide x x Cinidon-ethyl herbicide 90 Clethodim herbicide x x 91 Clodinafop herbicide x x 92 Clodinafop-propargyl herbicide 93 Clofentezin insecticide x 94 Clomazon herbicide x x Clopyralid herbicide x x Cloquintocet-mexyl other x 97 Clothianidin insecticide x x Codlemone (Codlelure) other x x 99 Coumaphos insecticide 100 Crimidin other 101 Cyanazin herbicide 102 Cyazofamid fungicide x x 103 Cyclanilide other 104 Cycloat herbicide S10

11 105 Cycloxidim herbicide x x 106 Cyufenamid fungicide x x 107 Cyuthrin (Summe Isomere) insecticide 108 Cyhalothrin (Summe insecticide x x Isomere) 109 Cymoxanil fungicide x x Cypermetryn insecticide x x Cyproconazol fungicide x x 112 Cyprodinil fungicide x x Cyromazin insecticide x 114 Daminozid other x x 115 Deiquat herbicide x x 116 Deltamethrin insecticide x x 117 Demeton-O insecticide 118 Demeton-S insecticide 119 Demeton-S-methyl insecticide 120 Demeton-Smethylsulfon insecticide 121 Desaminometribuzin metabolite 122 Desethyl metabolite hydroxyterbuthylazin 123 Desethylatrazin metabolite 124 Desethylsebuthylazin metabolite 125 Desethylsimazin metabolite 126 Desethylterbuthylazin metabolite 127 Desisopropylatrazin metabolite 128 Desmedipham herbicide x x 129 Desmethyldiuron metabolite 130 Desmethylisoproturon metabolite 131 Desmetryn herbicide 132 Desphenyl-Chloridazon metabolite 133 Diazinon insecticide 134 Dicamba herbicide x x Dichlobenil herbicide 136 Dichlouanid fungicide 137 Dichlorprop herbicide 138 Dichlorprop-P herbicide x x 139 Dichlorvos insecticide 140 Diclofop herbicide x 141 Dicofol insecticide 142 Dieldrin insecticide 143 Difenacoum other x 144 Difenoconazol fungicide x x S11

12 145 Diubenzuron insecticide x 146 Diufenican herbicide x x Dimefuron herbicide Dimethachlor herbicide x x Dimethachlor-CA metabolite 150 Dimethachlorsulfonsäure metabolite 151 Dimethachlorsäure metabolite 152 Dimethenamid herbicide 153 Dimethenamid-CA metabolite 154 Dimethenamid-P herbicide x x Dimethenamid-SA metabolite 156 Dimethenamidsulfonsäure metabolite 157 Dimethoat insecticide x x Dimethomorph fungicide x x Dimoxystrobin fungicide x x Diniconazol fungicide 161 Dinoseb herbicide 162 Dinotefuran insecticide 163 Dinoterb herbicide 164 Disulfoton insecticide 165 Dithianon fungicide x x Diuron herbicide x Dodin fungicide x x Endosulfan, alpha insecticide 169 Endosulfan, beta insecticide 170 Endosulfansulfat metabolite 171 Endrin insecticide 172 Epoxiconazol fungicide x x Esfenvalerat insecticide x x 174 Etaconazol fungicide 175 Ethidimuron herbicide 176 Ethirimol fungicide 177 Ethofenprox insecticide x x 178 Ethofumesat herbicide x x Etrimfos insecticide 180 Famoxadone fungicide x x 181 Fenamidon fungicide x x 182 Fenamiphos insecticide x 183 Fenarimol fungicide 184 Fenazaquin insecticide x x 185 Fenhexamid fungicide x x Fenitrothion insecticide 187 Fenoprop herbicide 188 Fenoxaprop herbicide S12

13 189 Fenoxaprop-p herbicide x x 190 Fenoxaprop-p-ethyl herbicide 191 Fenoxycarb insecticide x 192 Fenpropidin fungicide x x 193 Fenpropimorph fungicide x x Fenpyroximat insecticide x x 195 Fenthion insecticide 196 Fenuron herbicide 197 Fipronil insecticide x Flamprop herbicide 199 Flazasulfuron herbicide x x 200 Flonicamid insecticide x x Florasulam herbicide x x 202 Fluazifop herbicide Fluazifop-P herbicide x x Fluazifop-P-butyl herbicide Fluazifop-butyl herbicide Fluazinam fungicide x x Fluchloralin herbicide 208 Fludioxonil fungicide x x Flufenacet herbicide x x Flufenacet-SA metabolite 211 Flufenoxuron insecticide 212 Flumioxazin herbicide x x 213 Fluometuron herbicide x 214 Fluopicolide fungicide x x 215 Fluopyram fungicide x x Fluoxastrobin fungicide x x 217 Flupyrsulfuron herbicide x x 218 Fluquinconazole fungicide x x Flurochloridon herbicide x 220 Fluroxypyr herbicide x x Fluroxypyrmethylheptyl herbicide 222 Flurtamone herbicide x x Flusilazol fungicide Flutolanil fungicide x x 225 Flutriafol fungicide x 226 Fluxapyroxad fungicide x x 227 Folpet fungicide x x 228 Foramsulfuron herbicide x x Fosetyl fungicide x x 230 Fosthiazat other x x 231 Fuberidazol fungicide x x S13

14 232 Furalaxyl fungicide 233 Furmecyclox fungicide 234 Glufosinat herbicide x x 235 Glyphosate herbicide x x HCH, gamma (Lindan) insecticide 237 Haloxyfop herbicide 238 Haloxyfop-P herbicide x x 239 Haloxyfop-ethoxyethyl herbicide 240 Heptachlor insecticide 241 Heptachlorepoxid metabolite 242 Heptenophos insecticide 243 Hexachlorbenzen fungicide 244 Hexachlorophen other 245 Hexaconazol fungicide 246 Hexaumuron insecticide 247 Hexazinon herbicide 248 Hexythiazox insecticide x x 249 Hymexazol fungicide x x 250 Icaridinsäure metabolite 251 Imazalil fungicide x x 252 Imazamox herbicide x x 253 Imazapic herbicide 254 Imazaquin herbicide x 255 Imazethapyr herbicide 256 Imazosulfuron herbicide x x 257 Imidacloprid insecticide x x Indoxacarb insecticide x x 259 Iodosulfuron herbicide x x Iodosulfuron-methyl herbicide 261 Iodosulfuron-methylsodium herbicide 262 Ioxynil herbicide x Iprodion fungicide x x 264 Iprovalicarb fungicide x x Isodrin insecticide 266 Isophenphos insecticide 267 Isoproturon herbicide x x Isopyrazam fungicide x x 269 Isoxaben herbicide x x 270 Isoxautole herbicide x x 271 Karbutylat herbicide 272 Kresoxim-methyl fungicide x x Kresoximsäure metabolite 274 Lenacil herbicide x x S14

15 275 Linuron herbicide x 276 MCPA herbicide x x MCPB herbicide x 278 Malathion insecticide x 279 Mancozeb fungicide x x Mandipropamid fungicide x x Maneb fungicide x x 282 Mecoprop herbicide x Mefenpyr-diethyl other x 284 Mepanipyrim fungicide x x 285 Mepiquat other x x 286 Mepronil fungicide 287 Meptyldinocap fungicide x 288 Mesosulfuron herbicide x x 289 Mesotrion herbicide x x 290 Metaumizone insecticide x x 291 Metalaxyl fungicide x Metalaxyl-CA metabolite 293 Metalaxyl-CA metabolite 294 Metalaxyl-M fungicide x x Metaldehyd other x x 296 Metamitron herbicide x x Metamitron-Desamino metabolite 298 Metazachlor herbicide x x Metazachlordicarbonsäure metabolite 300 Metazachlorsulfonsäure metabolite 301 Metazachlorsäure metabolite 302 Metconazol fungicide x x 303 Methabenzthiazuron herbicide 304 Methamidophos insecticide Methidathion insecticide 306 Methiocarb insecticide x x Methobromuron herbicide x Methomyl insecticide x 309 Methoprotryn herbicide 310 Methoxychlor insecticide 311 Methoxyfenozid insecticide x x 312 Methyldesphenyl metabolite Chloridazon 313 Metiram fungicide x x 314 Metolachlor herbicide 315 Metolachlorsulfonsäure metabolite 316 Metolachlorsäure metabolite 317 Metosulam herbicide x x S15

16 318 Metoxuron herbicide 319 Metrafenon fungicide x x 320 Metribuzin herbicide x x Metsulfuron herbicide x x 322 Metsulfuron-methyl herbicide 323 Mevinphos insecticide 324 Milbemectin insecticide x x 325 Mirex insecticide 326 Monolinuron herbicide 327 Monuron herbicide 328 Myclobutanil fungicide x x Napropamid herbicide x x Neburon herbicide 331 Nicosulfuron herbicide x x Nitenpyram insecticide 333 Nitrofen herbicide 334 Norurazon herbicide 335 Omethoat insecticide 336 Orysastrobin fungicide 337 Oxadiazon herbicide x 338 Oxadixyl fungicide 339 Oxamyl insecticide x 340 Oxydemeton-methyl insecticide Paclobutrazol other x x 342 Parathion-ethyl insecticide 343 Parathion-methyl insecticide 344 Pelargonsäure herbicide x x 345 Penconazol fungicide x x Pencycuron fungicide x x 347 Pendimethalin herbicide x x Penufen fungicide x 349 Penoxsulam herbicide x x 350 Permethrin insecticide 351 Pethoxamid herbicide x x Phenmedipham herbicide x x 353 Phoxim insecticide Picloram herbicide x x 355 Picolinafen herbicide x x Picoxystrobin fungicide x x Pinoxaden herbicide x 358 Pirimicarb insecticide x x Pirimicarb-desmethyl metabolite 360 Pirimiphos-ethyl insecticide 361 Pirimiphos-methyl insecticide x x S16

17 362 Primisulfuron-methyl herbicide 363 Prochloraz fungicide x x Procymidon fungicide 365 Profoxydim herbicide x 366 Prohexadion other x x 367 Prometryn herbicide 368 Propachlor herbicide 369 Propamocarb fungicide x x 370 Propanil herbicide 371 Propaquizafop herbicide x x 372 Propazin herbicide 373 Propetamphos insecticide 374 Propham herbicide 375 Propiconazol fungicide x x Propoxur insecticide 377 Propoxycarbazone herbicide x x 378 Propyzamid herbicide x x Proquinazid fungicide x x 380 Prosulfocarb herbicide x x Prosulfuron herbicide x x 382 Prothioconazol fungicide x x Prothioconazol-desthio metabolite 384 Pymetrozin insecticide x x 385 Pyraclostrobin fungicide x x 386 Pyraufen herbicide x x 387 Pyrazophos fungicide 388 Pyrethrum insecticide x x Pyridaben insecticide x 390 Pyridat herbicide x x 391 Pyrifenox fungicide 392 Pyrimethanil fungicide x x Pyroxsulam herbicide x x 394 Quinalphos insecticide 395 Quinmerac herbicide x x Quinoclamin herbicide x x 397 Quinoxyfen (5, fungicide x x dichloro-4-(p- uorophenoxy)quinoline) 398 Quintozen fungicide 399 Quizalofop herbicide 400 Quizalofop-ethyl herbicide 401 Rimsulfuron herbicide x x Saufenacil herbicide 403 Sebuthylazin herbicide S17

18 404 Secbumeton herbicide 405 Silthiofam fungicide x x 406 Simazin herbicide 407 Simazin, 2-Hydroxy metabolite 408 Spinosad insecticide x x Spirodiclofen insecticide x x 410 Spiromesifen insecticide x 411 Spiroxamin fungicide x x Sulcotrion herbicide x x 413 Sulfosulfuron herbicide x 414 Sulfuryluorid insecticide x x 415 Tebuconazol fungicide x x Tebufenozid insecticide x x 417 Tebufenpyrad insecticide x x 418 Tebutam herbicide 419 Teubenzuron insecticide x 420 Teuthrin insecticide x x 421 Telodrin insecticide 422 Tembotrione herbicide x x 423 Tepraloxydim herbicide x x 424 Terbumeton herbicide 425 Terbuthylazin herbicide x x Terbutryn herbicide 427 Terbutylazin-Metabolit metabolite CGA Terbutylazin-Metabolit metabolite SYN Tetraconazol fungicide x x 430 Thiabendazol fungicide x x 431 Thiacloprid insecticide x x Thiacloprid-SA metabolite 433 Thiamethoxam insecticide x x Thiencarbazon-methyl herbicide x x 435 Thifensulfuron-methyl herbicide 436 Thifenylsulfuron herbicide x x 437 Thiometon insecticide 438 Thiophanat-methyl fungicide x x 439 Thiram fungicide x x Tolclofos-methyl fungicide x x 441 Tolyluanid fungicide 442 Topramezone herbicide x Tralkoxydim herbicide x 444 Triadimefon fungicide 445 Triadimenol fungicide x x S18

19 446 Triallat herbicide x 447 Triasulfuron herbicide x x 448 Triazophos insecticide Triazoxid fungicide x x 450 Tribenuron herbicide x x 451 Tribenuron-methyl herbicide 452 Trichlorfon insecticide 453 Triclopyr herbicide x x 454 Trioxystrobin fungicide x x Trioxystrobin-CA2 metabolite 456 Triumizol fungicide x 457 Triumuron insecticide x 458 Triuralin herbicide 459 Triusulfuron herbicide x x 460 Triforin fungicide 461 Trinexapac-ethyl other x x 462 Triticonazol fungicide x x 463 Tritosulfuron herbicide x x 464 Valifenalate fungicide x x 465 Vinclozolin fungicide 466 Warfarin other 467 Zoxamid fungicide x x 468 alpha-cypermethrin insecticide x x 469 cis-chlordan insecticide 470 gamma-cyhalothrin insecticide x x 471 o,p-dde metabolite 472 o,p-ddt insecticide 473 oxi-chlordan metabolite 474 p,p-ddd (p,p TDE) insecticide 475 p,p-dde metabolite 476 p,p-ddt insecticide 477 tau-fluvalinat insecticide x x trans-chlordan insecticide S19

20 State ER14 BW BY HE MV Lat. ER13 NI NW RP ER8 ER9 SH SL SN ST TH Lon. Figure S3: Spatial distribution of the 2,301 small stream sampling sites. Colour codes dierent federal states (see Supplemental Table S1 for abbreviations). Overlayed are ecoregions. ER4: Alps (no label), ER8: Western highlands, ER9: Central highlands, ER 13: Western plains, ER14: Central plains. S20

21 3 Inuence of agricultural land use and catchment size Agriculture [%] 50 log n(rq>1) Catchment Size [km2] Figure S4: Raw data used for the model in equation 2 and Figure 3 of the main article. Color codes the number of RAC exceedances (on a log-scale). Grey dots denote sites without any exceedance. S21

22 Agriculture [%] Catchment Size [km2] Mean no. RAC exceedances Figure S5: Smooth and linear ts for the data presented in gure 3 of the main article. S22

23 4 Eect of precipitation and season on RQ Table S3: 23 pesticides for which we modelled the relationship between RQ and precipitation and seasonality, respectively. Order is the same as in Figure 5 of the main text. See Table S4 for model coecients. Name CAS Group %>LOQ no. > LOQ total no. 1 Azoxystrobin fungicide Bentazon herbicide Boscalid fungicide Carbendazim fungicide Chlorpyrifos insecticide Clothianidin insecticide Diufenican herbicide Dimoxystrobin fungicide Diuron herbicide Ethofumesat herbicide Flufenacet herbicide Glyphosate herbicide Imidacloprid insecticide Isoproturon herbicide MCPA herbicide Mecoprop herbicide Metazachlor herbicide Nicosulfuron herbicide Propiconazol fungicide Quinmerac herbicide Tebuconazol fungicide Terbuthylazin herbicide S23

24 Table S4: Coecients and CI from per compound models. Bold values denote coecients where the CI for precipitation encompasses zero. Coecients are on the link scale (log for µ and logit for ν). Compound eect log precip 0 log precip 1 Quarter 1 Quarter 2 Quarter 3 Quarter 4 1 Azoxystrobin µ 0.23 ( ) 2 Bentazon µ ( ) 3 Boscalid µ 0.06 ( ) 4 Carbendazim µ -0.1 ( ) 5 Chlorpyrifos µ 0.08 ( ) 6 Clothianidin µ 0.08 ( ) 7 Diufenican µ ( ) 8 Dimoxystrobin µ 0.35 ( ) 9 Diuron µ 0 ( ) 10 Ethofumesat µ 0.12 ( ) 11 Flufenacet µ 0.03 ( ) 12 Glyphosate µ ( ) 13 Imidacloprid µ 0 ( ) 14 Isoproturon µ 0.02 ( ) 15 MCPA µ 0.04 ( ) 16 Mecoprop µ 0.04 ( ) 17 Metazachlor µ ( ) 18 Nicosulfuron µ 0.23 ( ) 19 Propiconazol µ 0.08 ( ) 20 Quinmerac µ 0.02 ( ) 21 Tebuconazol µ ( ) 22 Terbuthylazin µ 0.09 ( ) 23 Azoxystrobin ν 0 ( ) 24 Bentazon ν 0 ( ) 25 Boscalid ν ( ) 26 Carbendazim ν 0.09 ( ) 27 Chlorpyrifos ν 0.11 ( ) 0.04 ( ) 0.02 ( ) 0.1 ( ) 0.16 ( ) ( ) -0.1 ( ) 0.05 ( ) 0.02 ( ) 0.07 ( ) 0.01 ( ) 0.05 ( ) 0.14 ( ) ( ) 0.21 ( ) 0.09 ( ) 0.05 ( ) 0.09 ( ) ( ) 0.01 ( ) 0.05 ( ) 0.09 ( ) 0.11 ( ) 0.24 ( ) 0.05 ( ) 0.45 ( ) 0.19 ( ) 0.1 (0-0.19) ( ) ( ) ( ) ( ) 0.85 ( ) 0.94 ( ) ( ) ( ) ( ) ( ) ( ) -6.3 ( ) 0.61 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -3.5 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 1 ( ) 0.67 ( ) ( ) ( ) ( ) ( ) -3.7 ( ) ( ) 1.15 ( ) ( ) ( ) ( ) ( ) -0.2 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 0.9 ( ) 1.02 ( ) ( ) ( ) ( ) ( ) ( ) ( ) 1.4 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -2.2 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 0.94 ( ) 1.55 ( ) ( ) ( ) ( ) -6.1 ( ) ( ) ( ) 1.24 ( ) ( ) -4.7 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -3.2 ( ) ( ) ( ) ( ) ( ) S24

25 28 Clothianidin ν ( ) 29 Diufenican ν 0.06 ( ) 30 Dimoxystrobin ν 0.19 ( ) 31 Diuron ν 0.05 ( ) 32 Ethofumesat ν 0.09 ( ) 33 Flufenacet ν 0.16 ( ) 34 Glyphosate ν 0.11 (0-0.23) 35 Imidacloprid ν ( ) 36 Isoproturon ν 0.04 ( ) 37 MCPA ν ( ) 38 Mecoprop ν 0.07 ( ) 39 Metazachlor ν 0.06 ( ) 40 Nicosulfuron ν 0.2 ( ) 41 Propiconazol ν ( ) 42 Quinmerac ν ( ) 43 Tebuconazol ν 0.1 ( ) 44 Terbuthylazin ν 0.06 ( ) 0.19 ( ) 0.26 ( ) 0.23 ( ) 0.28 ( ) 0.21 ( ) 0.59 ( ) 0.29 ( ) -0.1 ( ) 0.31 ( ) 0.35 ( ) 0.35 ( ) 0.21 ( ) 0.26 ( ) 0.39 ( ) 0.32 ( ) 0.3 ( ) 0.28 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -3.8 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 0.34 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -2.9 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) -0.8 ( ) ( ) ( ) ( ) ( ) ( ) -1.2 ( ) ( ) ( ) S25

26 µ ν log prec 1 log prec µ ν Quarter Q4 Quarter Q3 Quarter Q2 Quarter Q Coefficient Figure S6: Graphical representation of coecients from table S4. Top row: Eect of precipitation at the day before sampling and at day of sampling. Bottom row: estimates for the four quarters of the year. Each dot represents one compound (in the order described in table S3). Coecients where the CI encompasses zero are shown in grey colour. Coecients are shown on the link scale (log for µ and logit for ν). S26

27 µ (RQ) ν (LOQ) log precip 1 log precip Quarter Q4 Quarter Q3 Quarter Q2 Quarter Q Coefficient Figure S7: Summarised coecients (and their 95% CI) for precipitation (top row) and quarter of the year (bottom row) from a meta-analysis of the 22 modelled compounds (see Figure S6). Left: coecients for mean RQ (µ), right: coecients for probability of exceeding LOQ (ν). Coecients are shown on the link scale. Single compound coecients are provided in Supplemental Table S4 and Figure S7. S27

28 5 Pesticides in small streams Table S5: Overview on RAC exceedances of the 78 compounds with more than 1000 measurements. No. = number of measurements; % RQ >1 = RAC exceedances; % RQ >1 >LOQ= RAC exceedances as fraction of detects. Name No. No. >LOQ % >LOQ No. RQ >1 % RQ >1 % RQ >1 >LOQ 2,4-D Aclonifen Azoxystrobin Benalaxyl Bentazon Bifenthrin Boscalid Bromoxynil Carbendazim Chloridazon Chlorpyrifos Chlortoluron Clomazon Clopyralid Clothianidin Cypermetryn Cyprodinil Dicamba Difenoconazol Diufenican Dimefuron Dimethachlor Dimethoat Dimethomorph Dimoxystrobin Diuron Epoxiconazol Ethofumesat Fenhexamid S28

29 Fenpropimorph Fluazifop Fluazifop-P Fluazifop-P-butyl Fluazifop-butyl Fludioxonil Flufenacet Fluquinconazole Fluroxypyr Flurtamone Flusilazol Glyphosate Imidacloprid Ioxynil Isoproturon Kresoxim-methyl Lenacil MCPA Mecoprop Metalaxyl Metamitron Metazachlor Methamidophos Methobromuron Metribuzin Napropamid Nicosulfuron Penconazol Pendimethalin Pethoxamid Phoxim Picolinafen Picoxystrobin Pirimicarb Prochloraz Propiconazol Propyzamid Prosulfocarb Pyrimethanil Quinmerac Rimsulfuron Spiroxamin Tebuconazol Terbuthylazin S29

30 Thiacloprid Thiamethoxam Triadimenol Triazophos Trioxystrobin Fraction of sites max(rq) Figure S8: Cumulative distribution of sites exceeding RAC. Dotted lines indicate fraction of sites exceeding a RQ of 1 and 0.1, respectively. 23% of the sites showed no detection of compounds with available RAC values and are not shown due to logarithmic x-axis. S30

31 Metazachlorsulfonsäure Metazachlorsäure AMPA Dimethachlorsulfonsäure Metolachlorsulfonsäure Desphenyl Chloridazon Chlorthalonil SA Icaridinsäure Glyphosate Methyldesphenyl Chloridazon Simazin, 2 Hydroxy Metolachlorsäure Dimethenamidsulfonsäure Group Fungicide Herbicide Metabolite # samples Boscalid Isoproturon Bentazon Kresoximsäure Carbendazim Atrazin, 2 Hydroxy % detects Figure S9: Proportion of samples with detects in small streams. Only Compounds with more than 100 samples and 15% of detects are shown. S31

32 7500 No. samples No. compounds Figure S10: Distribution of the number of quantied compounds in the samples. S32

33 6 Additional material 50.0 Width = 0.33 Size^0.57 Stream width [m] Dataset TH Voss 2015 Fernandez Catchment Size [km 2 ] Figure S11: Relationship between catchment size and stream width. A power function was tted to each dataset separately (colored dashed lines) and the combined dataset (black line and equation). The grey rectangle marks the estimated catchment size for a width of 1 m (=7 km 2 ). Data was compiled from three dierent sources: Fernández et al. (1), Voss et al. (2) and the federal state of Thuringia. S33

34 References [1] Diego Fernández, Katharina Voss, Mirco Bundschuh, Jochen P. Zubrod, and Ralf B. Schäfer. Eects of fungicides on decomposer communities and litter decomposition in vineyard streams. Sci. Total Environ., 533:4048, [2] K. Voss, D. Fernández, and R.B. Schäfer. Organic matter breakdown in streams in a region of contrasting anthropogenic land use. Sci. Total Environ., :179184, S34