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