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Seasonal distribution of multiclass pesticide residues in the surface waters of northwest Croatia

Sanja Fingler
Sanja Fingler
, 
Gordana Mendaš
Gordana Mendaš
, 
Marija Dvoršćak
Marija Dvoršćak
, 
Sanja Stipičević
Sanja Stipičević
, 
Želimira Vasilić
Želimira Vasilić
 et 
Vlasta Drevenkar
Vlasta Drevenkar
   | 30 déc. 2021
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Article Category: Original article
Publié en ligne: 30 déc. 2021
Pages: 280 - 288
Reçu: 01 oct. 2021
Accepté: 01 nov. 2021
DOI: https://doi.org/10.2478/aiht-2021-72-3598
© 2021 Heinz-Elmar Tenorth, published by Sciendo
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Figure 1

Sampling locations of river/stream waters in northwest Croatia (https://www.google.com/maps/@45.6943072,16.0121326,9z)
Sampling locations of river/stream waters in northwest Croatia (https://www.google.com/maps/@45.6943072,16.0121326,9z)

Figure 2

Mass concentrations of individual pesticides determined in river/stream water samples collected at the beginning (March), peak (June), and end (August) of the 2015 pesticide application season. AMBA – 2-amino-4-(methylsulfonyl)benzoic acid; DEA – deethylatrazine; DET – deethylterbuthylazine; DIA – deisopropylatrazine
Mass concentrations of individual pesticides determined in river/stream water samples collected at the beginning (March), peak (June), and end (August) of the 2015 pesticide application season. AMBA – 2-amino-4-(methylsulfonyl)benzoic acid; DEA – deethylatrazine; DET – deethylterbuthylazine; DIA – deisopropylatrazine

Mass concentrations of pesticide pollutants in river/stream water samples collected in the northwest part of Croatia across application season

Pesticide compound March 2015 (N=8) June 2015 (N=8) August 2015 (N=7)
γ (ng/L) γ (ng/L) γ (ng/L)
n Rangea Medianb n Rangea Medianb n Rangea Medianb
Mesotrione 0 3 36–107 0 0
Tembotrione 0 7 51–216 77 0
AMBA 0 6 54–444 74 1 61 <LOD
Terbuthylazine 3 9–13 <LOD 8 20–419 42 5 10–26 13
DET 1 9 <LOD 4 38–200 19 2 14–45 <LOD
Atrazine 5 10–16 11 5 12–34 13 5 9–24 14
DIA 5 5–32 6 6 17–123 28 2 19–24 <LOD
DEA 4 8–11 4 7 7–24 11 5 6–32 10
Isoproturon 1 146 <LOD 0 0
Diuron 0 2 22–30 <LOD 0
Acetochlor 0 1 28 <LOD 0
Metolachlor 7 9–11 9 8 11–3015 147 6 10–63 11
Chlorpyrifos-methyl 0 1 26 <LOD 0
Chlorpyrifos-methyl-oxon 1 21 <LOD 8 23–145 64 3 34–198 <LOD
Imidacloprid 1 73 <LOD 8 12 – 34 26 0

Methods for determination of pesticides and their degradation products in natural waters by SPE and HPLC-UV(DAD) or GC-MS(ITD) analysis

Method of analysis HPLC-UV(DAD) GC-MS(ITD)
Method 1 – λ (nm) Method 2 – λ (nm) Method 3a – λ (nm) Method 4a – m/z Method 5 – m/z
Pesticide Mesotrione – 220 Terbuthylazine – 222 Atrazine – 222 Trifluralin – 264 Terbuthylazine – 214
AMBA – 220 DET – 214 DEA – 214 Atrazine – 200 Chlorpyrifosmethyl – 286
Tembotrione – 205 Malathion – 205 DIA – 214 Terbuthylazine – 214 Chlorpyrifosethyl – 314
Chlorfenvinphos – 205 Terbuthylazine – 222 Acetochlor – 223 Malathion – 173
Chlorpyrifos-methyloxon – 205 DET – 214 Alachlor – 188 Chlorfenvinphos – 267
Imidacloprid – 270 Diuron – 210, 245 Metolachlor – 162 α-Cypermethrin – 163
Linuron – 210, 245
Chlortoluron – 210, 245
Isoproturon – 202, 245
SPE OASIS HLB C18 SDB-1 C18 C18 Polar plus/ SDB-1
Activation MeOH+H2O ACN+H2O MeOH+H2O MeOH+H2O MeOH+H2O
Solvent volume (mL) 2+2 5+5 2+5 2+5 2+5
Sample volume (mL) 500 500 500 1000 500
Eluent MeOH ACN+Et.ac Ac Et.ac Et.ac
Eluent volume (mL) 10 10+5 2 2 10

Number (N) of individual pesticide compounds, their mass concentration range, and the sum of pesticides mass concentrations (Σ) by river/stream across application season

River/Stream March 2015 June 2015 August 2015
N γ (ng/L) N γ (ng/L) N γ (ng/L)
Min Max Σ Min Max Σ Min Max Σ
Sutla 3 8 22 41 9 9 2564 3455 3 10 63 99
Krapina 7 9 146 219 10 22 3015 3992 5 6 198 248
Sava 1 2 9 73 81 11 10 242 947 4 9 45 77
Sava 2 4 6 11 35 11 7 149 498 – not analysed –
Drava 2 5 10 15 6 22 86 323 2 11 14 25
Plitvica 2 10 16 25 7 16 115 331 4 10 32 76
Bistrica 3 9 32 52 10 11 216 582 5 13 61 147
Bednja 5 7 16 56 10 12 444 867 6 11 66 161

Pesticides and pesticide degradation products analysed in this study

Class/Pesticide Chemical name Sa (mg/L) log Kowa pKaa
Dinitroaniline herbicide
Trifluralin 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)aniline 0.221 5.27 ND
s-Triazines and metabolites
Atrazine 6-chloro-N2-ethyl-N4-(1-isopropyl)-1,3,5-triazine-2,4-diamine 35 2.7 1.7
Deethylatrazine (DEA) 6-chloro-N4-isopropyl-1,3,5-triazine-2,4-diamine 2700 1.51 1.3b
Deisopropylatrazine (DIA) 6-chloro-N2-ethyl-1,3,5-triazine-2,4-diamine 980 1.15 1.2b
Terbuthylazine 6-chloro-N2-tert-buthyl-N4-ethyl-1,3,5-triazine-2,4-diamine 6.6 3.4 1.9
Deethylterbuthylazine (DET) 6-chloro-N2- tert-buthyl -1,3,5-triazine-2,4-diamine 327.1 2.3 1.35c
Phenylurea herbicides
Diuron 3-(3,4-dichlorophenyl)-1,1-dimethylurea 35.6 2.87 ND
Linuron 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea 63.8 3.0 ND
Chlortoluron 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea 76 2.5 ND
Isoproturon 3-(4-isopropylphenyl)-1,1-dimethylurea 70.2 2.5 ND
Chloroacetanilide herbicides
Acetochlor 2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl) acetamide 282 4.14 ND
Alachlor 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide 240 3.09 0.62
Metolachlor (RS)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide 530 3.4 ND
Triketone herbicides and metabolite AMBA
Mesotrione 2-[4-(methylsulfonyl)-2-nitrobenzoyl]cyclohexane-1,3-dione 1500 0.11 3.12
2-Amino-4-(methylsulfonyl) benzoic acid (AMBA) 2-amino-4-(methylsulfonyl)benzoic acid NA 0.38d 4.24d
Tembotrione 2-[2-chloro-4-methylsulfonyl-3-(2,2,2-trifluoroethoxymethyl) benzoyl]cyclohexane-1,3-dione 71000 -1.09 3.18
Organophosphorous insecticides and oxo- metabolite
Chlorpyrifos-methyl O,O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate 2.74 4.00 ND
Chlorpyrifos-ethyl O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate 1.05 4.7 ND
Chlorpyrifos-methyl-oxon Dimethyl (3,5,6-trichloropyridin-2-yl) phosphate NA 1.91e NA
Malathion Diethyl 2-[(dimethoxyphosphorothioyl)sulfanyl]butanedioate 148 2.75 ND
Chlorfenvinphos [(EZ)-2-chloro-1-(2,4-dichlorophenyl)ethenyl] diethyl phosphate 145 3.8 ND
Pyrethroid insecticide
α-Cypermethrin Racemate comprising (R) and (S) α-cyano-3-phenoxybenzyl- (1R,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane- carboxylate 0.004 5.8 ND
Neonicotinoid insecticide
Imidacloprid N-{1-[(6-chloro-3-pyridyl)methyl]-4,5-dihydroimidazol-2-yl}nitramide 610 0.57 ND
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