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. 2018 Jul 6;13(7):e0199995. doi: 10.1371/journal.pone.0199995

Table 1. Summary of 73 pesticides detected in corbicular pollen loads of honeybees at three distinct agricultural production sites in South Germany during 2012–2016.

Substance Class, systemicity a) Group b) Code b) Likelihood of appearance in pollen c) [53] Appearance in pollen not expected d) [53] LOD (μg/kg) e) LOQ (μg/kg) e) Total detections f) Highest detected concentration (μg/kg) LD50oral g) MRL for apicultural products (μg/kg) h) [54] PHQmax
Acetamiprid I, s Neonicotinoids 4A x 2 5 21 42.7 14.53 50 2.94
Azoxystrobin F, s QoI 11 x 2 5 40 560.5 25 50 22.42
Benthiavalicarb isopropyl F CAA 40 x 2 5 2 8.9 100 50 0.09
Boscalid F SDHI 7 x 2 5 77 1,496.4 100 50 14.96
Chlorantraniliprole I Diamides 28 x 5 10 1 18.1 104.1 50 0.17
Clothianidin I, s Neonicotinoids 4A x 2 5 3 2.4 0.004 50 600
Coumaphos V Organophosphates 1B x 2 5 1 3.5 4.61 10 0.76
Cyflufenamid F Phenylacetamide U6 x 2 5 8 20.1 100 50 0.20
Cyproconazole F, s DMI (SBI: Class I) 3 x 2 5 1 27.7 1,000 50 0.03
Cyprodinil F, s AP 9 x 2 5 40 1,282.6 112.5 50 0.22
Difenoconazole F, s DMI (SBI: Class I) 3 x 2 5 11 147.7 177 50 0.83
Dimethoate I, s Organophosphates 1B x 2 5 2 19.7 0.12 -i) 164.41
Dimethenamid-P H Chloroacetamides K3 x 2 5 8 11.8 118.4 50 0.10
Dimethomorph F, s CAA 40 x 2 5 15 2,678.4 32.4 50 82.67
Dimoxystrobin F QoI 11 x 2 5 42 576.2 79.4 50 7.26
Epoxiconazole F DMI (SBI: Class I) 3 x 2 5 19 170.4 83 50 2.05
Etofenprox I Pyrethroids 3A x 2 5 9 7.8 0.27 50 28.89
Famoxadone F QoI 11 x 2 5 1 2.8 1,000 50 0.003
Fenhexamid F SBI: Class III 17 x 2 5 18 7,177.7 102.07 50 70.32
Fenoxycarb I Fenoxycarb 7B x 2 5 1 6.3 204 50 0.03
Fenpropimorph F, s SBI: Class II 5 x 2 5 12 17.7 95.6 50 0.19
Fluazifop-butyl H, s FOP A x 5 15 45 6,831.3 63 50 108.43
Fludioxonil F PP 12 x 5 15 32 1,085.1 100 50 10.85
Fluopicolide F Benzamides 43 x 2 5 8 23.15 241 50 0.21
Flonicamid I, s Flonicamid 29 x 2 5 1 7.3 60.5 50 0.12
Fluopyram F SDHI 7 x 2 5 25 134.3 102.3 50 1.31
Fluroxypyr-methyl H Pyridine-carboxylic acids 0 x 5 10 2 242.5 100 50 2.42
Fluoxastrobin F, s QoI 11 x 2 5 1 2 843 50 0.002
Flusilazole F, s DMI (SBI: Class I) 3 x 2 5 2 115.6 33.8 50 3.42
Fuberidazole F, s MBC 1 x 2 5 4 12.9 187.2 50 0.07
Gamma-, Lambda-Cyhalothrin I Pyrethroids 3A x 2 5 2 2.5 2.56 50 0.98
Imidacloprid I, s Neonicotinoids 4A x 2 5 1 2.1 0.0037 50 567.57
Indoxacarb I Oxadiazines 22A x 2 5 5 20 0.26 50 76.92
Iprovalicarb F, s CAA 40 x 2 5 11 974.7 199 50 4.90
Isoproturon H, s Urea C2 x 2 5 15 23.3 195 50 0.12
Kresoxim-methyl F QoI 11 x 2 5 10 106.3 110 50 0.97
Mandipropamid F CAA 40 x 2 5 8 101.8 200 50 0.51
MCPA H Phenoxy-carboxylic-acids 0 x 5 15 1 667 200 -i) 3.34
Metamitron H, s Triazines C1 x 2 5 1 6.6 97.2 -i) 0.07
Metalaxyl-M F, s PA 4 x 2 5 9 17.6 97.3 50 0.18
Metconazole F, s DMI (SBI: Class I) 3 x 2 5 20 94.4 85 50 1.11
Metolachlor H Chloroacetamides K3 x 2 5 5 6.2 110 50 0.06
Methiocarb I Carbamates 1A x 2 5 29 47.7 0.47 50 101.54
Methiocarb-sulfoxide I Carbamates 1A x 2 5 1 2.5 0.47 50 5.33
Methoxyfenozide I Diacylhydrazines 18 x 2 5 4 14.4 100 50 0.14
Metrafenone F Aryl-phenylketones U 08 x 2 5 35 368.5 114 50 3.23
Myclobutanil F, s DMI (SBI: Class I) 3 x 2 5 16 136.8 33.9 50 4.04
Nicotine I, s Nicotine 4B x 2 5 1 3 0.08 -i) 37.5
Penconazole F, s DMI (SBI: Class I) 3 x 2 5 18 35 112 50 0.31
Pencycuron F Phenylureas 20 x 2 5 2 4.5 98.5 -i) 0.04
Pendimethalin H Dinitroanilines K1 x 3 10 33 43.4 101.2 50 0.43
Picaridin IR Piperidines - x 2 5 37 412 -j) [55,56] -j) [55,56] -j)[55,56]
Picoxystrobin F QoI 11 x 2 5 1 4.2 200 50 0.02
Pirimicarb I, s Carbamates 1A x 2 5 2 14.7 4 50 3.68
Pirimicarb-desmethyl I Carbamates 1A x 2 5 1 4.1 4 50 1.03
Propiconazole F, s DMI (SBI: Class I) 3 x 2 5 2 6.5 100 50 0.07
Propamocarb F, s Carbamates 28 x 2 5 2 8 84 50 0.10
Proquinazid F Azanaphthalenes 13 x 5 10 13 110.2 125 50 0.88
Prosulfocarb H Thiocarbamates N x 2 5 38 24.2 103.4 50 0.23
Prothioconazole-desthio F, s DMI (SBI: Class I) 3 x 2 5 100 78.6 71 50 1.11
Pyraclostrobin F QoI 11 x 2 5 15 124 72.1 50 1.72
Pyrimethanil F AP 9 x 2 5 1 2.6 100 50 0.03
Quinoxyfen F, s Azanaphthalenes 13 x 5 10 10 261.4 1,000 50 0.26
Spiroxamine F, s SBI: Class II 5 x 2 5 9 132.4 100 50 1.32
Tau-Fluvalinate I Pyrethroids 3A x 2 5 2 10 12.6 50 0.80
Tebuconazole F, s DMI (SBI: Class I) 3 x 2 5 81 484.5 83.05 50 5.83
Terbuthylazine H Triazines C1 x 2 5 11 5.4 22.6 -i) 0.24
Tebufenozide I Diacylhydrazines 18 x 2 5 5 24.8 100 50 0.25
Triadimenol F DMI (SBI: Class I) 3 x 3 10 23 80.8 224.8 100 0.36
Thiacloprid I, s Neonicotinoids 4A x 2 5 145 470.4 17.32 200 27.16
Thymol V Thymus vulgaris essential oil - x 2 5 1 8 56.6 No MRL required 0.14
Trifloxystrobin F QoI 11 x 2 5 27 218.3 200 50 1.09
Zoxamide F Benzamides 22 x 2 5 1 6.6 100 50 0.07

a) F = fungicide, H = herbicide, I = insecticide, IR = insect repellent V = varroacide, s = systemic

b)For fungicides: FRAC Code List, for herbicides: HRAC, for insecticides: IRAC Classification Scheme; AP = Anilino-Pyrimidines; CAA = Carboxylic Acid Amides; DMI = DeMethylation Inhibitors; FOP = Aryloxyphenoxy-propionate, MBC = Methyl Benzimidazole Carbamates; PA = PhenylAmides; PP = PhenylPyrroles; QoI = Quinone outside Inhibitors; SBI = sterol biosynthesis inhibitors; SDHI = Succinate dehydrogenase inhibitors

c) At least one authorized plant protection product containing this active ingredient (a.i.) is classified B2 or B4. B2 = classified as hazardous to bees, except when applied after the end of the daily bee flight, B4 = classified as non-hazardous to bees

d) At least one authorized plant protection product containing this active ingredient is classified B1 or B3. B1 = classified as hazardous to bees, B3 = Due to the manner in which authorization governs application of the product, bees are not endangered. Coumaphos, nicotine, picaridin and thymol are not authorized as plant protection products.

e) LOD and LOQ from LUFA Speyer had to be chosen for better comparison of all sites.

f) Total detections after LOD and LOQ were chosen from LUFA Speyer.

g) LD50 (honeybee oral): PPDB (2017), US EPA (2017), Agritox database (2017), Dahlgren et al. (2012)

h) MRL = maximum residue limit for products of animal origin, EU pesticides database

i) No MRL data for these substances are listed in the EU pesticides database

j) No data regarding ecotoxicological analysis concerning bees are available; no tolerance levels for picaridin in food are given as residues are not expected due to its use as topical insect repellent