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. 2021 Aug 1;8:101476. doi: 10.1016/j.mex.2021.101476

Extension of an extraction method for the determination of 305 organic compounds in clay-loam soil to soils of different characteristics

Andrea Acosta-Dacal a,1, Cristian Rial-Berriel a,1, Ricardo Díaz-Díaz b, María del Mar Bernal-Suárez b, Manuel Zumbado a,c, Luis Alberto Henríquez-Hernández a,c, Ana Macías-Montes a, Octavio P Luzardo a,c,⁎
PMCID: PMC8374704  PMID: 34434875

Highlights

  • •

    These results allowed to broaden the range of soils that can be analyzed with the proposed methodology.

  • •

    In the worst case (loamy sand soil), the original methodology allowed the analysis of 180 compounds with adequate recoveries.

  • •

    For analytes outside the acceptable range in this soil and the other soil type analyzed, correction factors are proposed.

Keywords: QuEChERS, LC-MS/MS, GC-MS/MS, Pesticides, Anticoagulant Rodenticides (ARs), Pharmaceutical Active Compounds (PhACs), Persistent Organic Pollutants (POPs), Polychlorinated Biphenyls (PCBs), Polycyclic Aromatic Hydrocarbons (PAHs), Polybrominated Diphenyl Ethers (PBDEs), Organochlorine Pesticides (OCPs)

Abstract

Soil is one of the environmental compartments most affected by pollution. From this medium, the organic compounds can be emitted to the groundwater, the atmosphere, or the biota. Thus, having adequate methods of analysis of organic pollutants in this matrix is essential. However, the soil is a very complex matrix whose organic and inorganic components can determine the degree to which they are retained. Therefore, the methods must account for the various soil characteristics. In this study, the performance of an extraction method that had been already validated in clay loam soils for more than 300 organic compounds of very different nature including pesticides, PhACs, ARs, and POPs has been evaluated in four additional representative soil types of the agricultural land of the Canary archipelago: sandy loam, sandy clay, clay and loamy sand. For this purpose, recovery experiments have been performed at a single concentration (50 ng g−1) in each soil type. When there is a significant difference according to the criteria applied for a given compound, a factor has been calculated to correct the difference in performance in each soil type.

  • •

    These results allowed to broaden the range of soils that can be analyzed with the proposed methodology.

  • •

    In the worst case, which is the loamy sand soil, the original methodology allows the analysis of 180 organic contaminants with adequate recoveries. For analytes outside the acceptable range in this soil and the other soil type analyzed, correction factors are proposed.

Graphical abstract

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Specifications table

Subject Area: Chemistry
More specific subject area: Environmental Analytical Chemistry
Method name: One-Step QuEChERS method for the extraction of organic pollutants in soils
Name and reference of original method: Optimization and validation of a QuEChERS-based method for the simultaneous environmental monitoring of 218 pesticide residues in clay loam soil [1,2]
An Easy Procedure to Quantify Anticoagulant Rodenticides and Pharmaceutical Active Compounds in Soils[3]
Validation of a method scope extension for the analysis of POPs in soil and verification in organic and conventional farms of the Canary Islands[4]
Resource availability: N.A.
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Background

Soil is a well-known reservoir of organic pollutants from where they can be released to other environmental compartments such as groundwater, atmosphere, and biota [5,6]. Compounds of very different nature and usage can reach the soil through pest control in agriculture -i.e pesticides, or the sewage system -i.e anticoagulant rodenticides (ARs). In addition, pharmaceutical active compounds (PhACs), which are considered compounds of emerging concern (CECs), can reach soil through irrigation with reclaimed wastewater or the use of manure and sewage sludge as compost. Furthermore, although banned or restricted for decades, persistent organic pollutants (POPs) can end up in the soil through their historical use in agriculture -i.e organochlorine pesticides (OCPs), and industry -i.e.polybrominated diphenyl ethers (PBDEs) and polychlorinated Biphenyls (PCBs), and volatilization and deposition processes -i.e. polycyclic aromatic hydrocarbons (PAHs). Given the diversity of compounds that can end up in the soil, there is a need for methods capable of determining and quantifying them to facilitate soil surveillance in line with monitoring programs such as coordinated multi-annual plan of the European Union [7].

For this purpose, a simple and economic method was optimized and validated to extract and analyze organic compounds of diverse nature in agricultural soils that could be used in routine analysis [1], [2], [3], [4]. This method is a modification of the QuEChERS (quick, easy, cheap, effective, rugged and safe) initially introduced for the extraction of pesticides in fruit and vegetable by Anastassiades et al. [8], which has been subjected to several modification to improve the overall technique performance in other matrices and analytes [9], [10], [11], [12], [13], [14], [15]. The compounds extracted and analyzed in soil with the QuEChERS-based method constitute a large group of 305 organic compounds. These analytes are classified into 213 pesticides of current and recent use, 43 CECs 7 of which are ARs and 36 are PhACs, and 49 POPs, between PBDEs, PCBs, OCPs and PAHs. The complete list of compounds together with their group, and the technique by which they are analyzed is presented in Table 2.

Table 2.

Percentage recoveries and relative standard deviation of the 305 analytes in each soil type at the stablished concentration together with the compound number identification, group, and technique of analysis. This information is represented in figure 1 of the supplementary material.

N° Compound Group Technique Soil A
 Soil B
 Soil C
 Soil D
 Soil E
%REC %RSD %REC %RSD %REC %RSD %REC %RSD %REC %RSD
1 4,4′-Dichlorobenzophenone Pesticides, OCPs GC 164.0 12.4 138.7 27.3 87.0 12.2 95.3 12.3 126.8 18.0
2 4,4′-Dicofol Pesticides, OCPs GC 52.8 14.6 37.7 17.0 32.0 10.3 33.2 15.8 14.9 13.8
3 Abamectine Pesticides LC 67.1 8.0 31.4 9.9 60.6 13.5 58.8 0.8 57.1 5.9
4 Acephate Pesticides LC 61.3 3.2 57.3 1.2 52.8 1.3 39.8 1.5 63.8 1.2
5 Acetamiprid Pesticides LC 82.3 2.7 73.7 1.9 75.6 1.0 73.9 1.1 77.6 1.5
6 Acrinathrin Pesticides LC 83.6 8.0 39.5 25.2 76.3 6.4 77.8 5.9 72.9 2.9
7 Aldicarb Pesticides LC 83.7 3.8 71.6 1.4 76.9 1.2 80.0 0.6 77.6 1.3
8 Aldicarb sulfone Pesticides LC 85.3 2.8 77.9 2.6 78.1 1.0 77.9 2.4 75.5 1.7
9 Atrazine Pesticides LC 86.9 3.8 62.9 2.4 82.3 2.1 92.1 0.7 84.4 0.9
10 Azinphos methyl Pesticides LC 84.2 1.6 73.0 2.6 75.4 2.1 79.2 2.0 75.7 2.4
11 Azoxystrobin Pesticides LC 85.9 3.2 76.6 2.0 75.3 3.4 77.0 1.2 71.3 2.1
12 Benalaxyl Pesticides LC 87.1 2.9 71.7 4.3 85.5 1.6 88.5 1.1 84.7 1.3
13 Bendiocarb Pesticides LC 84.3 4.3 74.0 1.2 81.4 1.0 82.3 1.2 79.5 0.8
14 Bifenthrin Pesticides GC 129.6 11.6 112.7 21.3 80.4 7.8 86.2 5.8 74.4 9.9
15 Bitertanol Pesticides LC 79.5 1.9 77.4 3.0 70.4 4.1 67.8 2.8 62.5 3.9
16 Boscalid Pesticides GC 119.6 11.7 197.3 23.2 86.2 8.1 81.9 15.5 71.6 8.0
17 Bromopropylate Pesticides GC 128.1 15.8 113.6 15.2 90.4 5.7 93.3 4.3 83.8 9.6
18 Bromuconazole Pesticides LC 85.3 5.6 68.5 3.0 71.9 4.1 74.7 0.8 74.2 4.9
19 Bupirimate Pesticides LC 74.7 8.9 58.2 2.3 75.7 2.0 73.0 2.0 77.4 2.0
20 Cadusafos Pesticides LC 88.9 3.1 53.5 2.5 80.0 10.9 90.5 1.9 85.7 1.7
21 Carbaryl Pesticides LC 83.6 2.8 69.9 1.3 76.6 1.6 80.0 0.9 76.7 1.6
22 Carbofuran Pesticides LC 97.5 6.0 74.1 1.1 89.4 1.2 94.6 1.0 72.4 2.0
23 Carbofuran-3-hydroxy Pesticides LC 84.1 2.1 75.2 2.1 78.1 0.9 79.3 2.0 77.5 1.1
24 Chlorantraniliprole Pesticides LC 78.5 4.0 78.9 3.1 68.9 3.9 67.6 1.6 64.1 3.9
25 Chlorfenapyr Pesticides GC 111.0 4.4 96.1 29.3 76.9 13.1 73.1 13.4 57.2 3.8
26 Chlorobenzilate Pesticides GC 130.6 12.0 123.1 28.6 102.5 13.2 102.0 17.3 81.7 4.2
27 Chlorpropham Pesticides GC 152.1 19.0 143.8 31.6 106.4 16.0 100.7 9.9 96.5 8.7
28 Chlorpyrifos Pesticides GC 128.9 10.1 103.5 34.8 89.2 14.4 88.8 8.8 71.6 10.9
29 Chlorpyrifos methyl Pesticides GC 104.3 5.8 95.0 20.7 71.3 8.3 71.4 15.9 49.3 5.2
30 Chlorthal dimethyl Pesticides GC 117.8 10.5 102.3 20.0 86.1 15.6 92.6 11.2 80.3 10.2
31 Clofentezine Pesticides LC 90.4 3.6 54.1 3.0 87.1 2.2 96.7 1.5 91.0 1.6
32 Clothianidin Pesticides LC 77.5 6.0 64.5 2.9 69.8 2.5 69.9 1.2 69.2 2.9
33 Coumachlor Pesticides LC 88.4 1.6 80.7 1.2 84.4 5.3 84.3 1.4 74.6 3.2
34 Coumaphos Pesticides LC 109.1 2.4 99.2 1.5 102.3 2.8 102.3 1.9 96.2 1.5
35 Cyazofamid Pesticides LC 77.4 3.2 61.5 1.4 77.3 1.8 92.4 3.0 56.4 4.9
36 Cyflufenamid Pesticides LC 89.2 2.4 58.3 3.2 81.9 3.8 86.6 0.9 79.8 2.1
37 Cyfluthrin Pesticides GC 128.4 11.4 106.1 35.3 80.2 13.3 77.6 14.7 60.2 8.4
38 Cyhalothrin (lambda isomer) Pesticides LC 83.4 7.9 30.1 24.3 75.5 11.8 72.2 7.7 62.9 21.9
39 Cymoxanil Pesticides LC 81.5 2.3 71.2 1.3 74.4 1.7 77.2 1.2 74.1 2.0
40 Cypermethrin Pesticides GC 133.8 15.0 128.8 31.7 80.3 13.2 70.2 21.4 58.8 10.3
41 Cyproconazole Pesticides LC 85.2 2.7 80.1 1.8 78.4 2.0 78.7 1.8 76.6 2.6
42 Cyprodinil Pesticides GC 122.8 13.8 107.9 21.9 87.0 11.3 89.3 7.9 77.9 8.9
43 Deltamethrin Pesticides GC 98.6 10.1 99.1 38.7 63.5 11.1 51.2 26.0 39.5 11.9
44 Demeton-S-methyl Pesticides LC 79.5 4.2 63.0 1.4 78.5 2.3 80.6 1.6 66.7 2.1
45 Demeton-S-methyl-sulfone (Dioxydemeton) Pesticides LC 81.7 2.1 76.2 1.9 75.6 1.3 75.1 1.5 75.0 1.8
46 Diazinon Pesticides GC 125.3 8.8 118.3 19.9 96.4 10.7 96.1 7.0 77.9 8.9
47 Dichlofluanid Pesticides GC 54.6 18.4 45.3 29.4 36.1 12.5 37.0 11.2 26.5 29.2
48 Dichloran Pesticides GC 126.0 20.3 94.4 29.5 80.2 10.5 66.0 12.6 62.5 10.4
49 Diethathyl ethyl Pesticides LC 94.6 3.1 75.9 3.1 88.3 2.9 93.4 1.2 88.1 2.9
50 Diethofencarb Pesticides LC 89.6 3.0 82.1 2.3 82.7 2.7 86.9 1.4 78.8 1.8
51 Difenoconazole Pesticides LC 81.6 2.7 64.5 2.4 72.9 11.0 73.0 2.5 69.8 2.1
52 Diflubenzuron Pesticides LC 84.4 4.7 70.5 2.5 78.1 5.0 82.3 2.5 72.6 4.2
53 Diflufenican Pesticides LC 84.2 2.3 53.3 3.9 79.8 2.9 82.4 3.0 77.4 3.6
54 Dimethenamide Pesticides LC 82.1 2.2 68.7 2.4 78.3 2.7 82.6 1.4 75.2 0.5
55 Dimethoate Pesticides LC 83.4 3.5 72.0 2.4 76.2 1.4 75.9 0.7 76.3 1.4
56 Dimethomorph Pesticides LC 85.1 1.5 89.8 2.1 70.7 2.1 67.9 1.6 64.3 2.5
57 Diniconazole-M Pesticides LC 84.4 3.2 68.3 2.7 69.3 6.1 74.3 3.7 61.5 3.2
58 Dinocap Pesticides LC 99.1 10.0 46.0 16.1 57.0 19.1 62.6 4.9 67.1 25.4
59 Diphenylamine Pesticides LC 77.8 7.4 65.9 3.0 71.9 6.9 63.6 6.8 69.6 4.3
60 Endosulfan alfa Pesticides, OCPs GC 110.6 10.7 89.9 29.7 73.8 5.6 76.7 10.5 66.6 5.3
61 Endosulfan beta Pesticides, OCPs GC 109.6 15.1 84.9 39.0 72.8 10.7 69.1 1.6 60.4 3.7
62 EPN Pesticides LC 83.2 7.2 48.2 3.7 74.7 1.1 80.7 2.5 77.9 4.1
63 Epoxiconazole Pesticides LC 76.0 4.4 64.1 3.5 73.1 5.6 76.4 1.6 53.7 6.0
64 Esfenvalerate Pesticides GC 100.8 10.7 87.2 37.7 58.9 8.8 55.5 13.4 41.7 10.3
65 Ethion Pesticides LC 90.6 2.3 39.3 2.2 83.3 0.9 91.1 1.7 83.8 1.6
66 Ethofumesate Pesticides GC 147.1 15.6 119.4 35.5 99.8 21.0 110.3 21.6 92.4 9.8
67 Ethoprophos Pesticides LC 80.2 1.8 60.1 2.1 75.1 2.9 79.8 2.0 71.6 2.7
68 Etofenprox Pesticides LC 64.3 14.8 31.8 9.1 47.6 38.3 22.4 10.8 43.4 32.2
69 Etoxazole Pesticides LC 81.5 2.2 32.8 6.4 74.6 4.1 78.6 0.6 78.1 2.8
70 Fenamidone Pesticides LC 77.9 4.6 77.9 1.9 71.5 1.6 71.9 2.5 64.3 2.0
71 Fenamiphos Pesticides LC 92.1 2.0 76.1 2.3 86.5 2.2 86.4 1.6 77.8 2.3
72 Fenamiphos sulfone Pesticides LC 81.6 2.6 82.1 1.3 70.0 3.7 66.8 1.6 67.4 1.9
73 Fenamiphos sulfoxide Pesticides LC 72.0 2.9 72.5 1.7 62.5 3.0 52.2 0.8 67.4 2.5
74 Fenarimol Pesticides GC 120.7 10.7 110.9 24.2 79.3 10.2 76.5 5.1 73.6 8.4
75 Fenazaquin Pesticides LC 78.4 7.4 22.7 33.7 71.5 13.2 88.1 4.0 87.5 3.2
76 Fenbuconazole Pesticides LC 91.6 1.6 88.0 2.9 85.5 4.7 83.9 1.6 80.8 2.4
77 Fenbutatin oxide Pesticides LC 97.6 31.8 51.7 63.6 54.1 29.7 75.3 16.8 84.6 15.9
78 Fenitrothion Pesticides GC 110.3 16.1 103.0 32.1 79.0 18.0 72.5 18.7 51.8 9.3
79 Fenoxycarb Pesticides LC 92.8 2.6 70.9 2.1 86.7 2.1 89.1 1.4 82.4 2.1
80 Fenpropathrin Pesticides LC 85.9 4.2 28.4 14.9 72.8 3.8 74.2 1.4 68.0 1.8
81 Fenpropimorph Pesticides LC 65.7 2.3 68.3 1.8 57.8 2.4 37.9 2.7 78.3 2.2
82 Fenpyroximate Pesticides LC 84.8 4.1 26.7 36.7 78.8 1.3 78.5 0.7 73.4 2.4
83 Fenthion Pesticides LC 91.2 5.6 64.2 4.9 80.2 5.0 79.6 4.1 75.9 4.9
84 Fenthion oxon Pesticides LC 89.0 2.4 74.9 1.6 83.0 1.7 87.3 1.1 83.0 0.6
85 Fenthion oxon sulfone Pesticides LC 76.8 2.4 70.7 2.0 69.0 2.8 67.6 2.1 67.9 2.7
86 Fenthion oxon sulfoxide Pesticides LC 70.5 3.1 66.0 2.8 61.4 1.6 52.4 1.5 69.5 2.3
87 Fenthion sulfone Pesticides LC 81.0 2.0 71.3 2.0 72.1 1.8 75.5 1.1 69.3 1.6
88 Fenthion sulfoxide Pesticides LC 82.6 1.4 79.8 1.5 71.2 3.0 70.4 1.3 69.2 2.4
89 Fenvalerate Pesticides GC 111.6 13.1 104.5 30.2 68.8 18.3 57.4 10.6 49.6 8.1
90 Fipronil Pesticides LC 80.6 4.4 85.6 3.5 69.9 4.5 72.1 2.6 68.7 1.2
91 Fipronil sulfide Pesticides GC 147.2 7.7 145.3 13.4 150.9 18.7 150.0 15.2 112.8 2.3
92 Fluazinam Pesticides LC 88.1 1.4 73.6 2.9 83.8 4.4 83.3 1.9 78.7 1.8
93 Flubendiamide Pesticides LC 82.9 2.8 69.3 2.9 79.8 1.7 80.6 3.1 75.5 1.9
94 Flucythrinate Pesticides GC 121.8 11.6 129.2 26.9 80.8 10.8 73.0 10.9 60.0 10.8
95 Fludioxonil Pesticides LC 86.0 3.0 74.7 9.0 75.2 5.4 79.7 2.6 72.5 3.9
96 Flufenoxuron Pesticides LC 80.5 3.8 45.3 1.4 71.7 4.1 74.6 2.3 70.9 2.1
97 Fluopyram Pesticides LC 81.0 1.1 66.7 2.0 69.2 3.7 71.7 1.6 67.6 0.5
98 Fluquinconazole Pesticides LC 79.5 6.3 61.9 4.6 70.1 8.0 73.5 4.5 73.2 4.6
99 Flusilazole Pesticides LC 90.7 4.9 72.6 3.2 82.7 2.8 85.6 4.0 73.7 2.3
100 Flutolanil Pesticides LC 78.4 3.5 65.2 1.4 69.7 4.1 70.5 0.9 66.6 2.1
101 Flutriafol Pesticides LC 78.5 3.7 69.1 2.3 73.5 1.7 77.9 0.7 74.5 1.0
102 Fluvalinate tau Pesticides LC 76.0 6.5 40.5 16.8 66.7 7.1 59.9 4.1 54.4 4.1
103 Fonofos Pesticides GC 126.3 9.7 117.4 24.9 93.4 11.7 97.2 8.7 79.2 6.3
104 Fosthiazate Pesticides LC 81.8 3.0 73.1 1.4 73.2 0.7 71.6 0.7 78.3 0.9
105 Hexaconazole Pesticides LC 98.4 4.8 73.0 2.0 85.5 1.5 89.5 1.9 86.1 2.4
106 Hexaflumuron Pesticides LC 71.5 3.4 73.9 3.9 60.6 5.6 56.7 3.1 51.3 5.8
107 Hexythiazox Pesticides LC 83.3 2.2 30.9 1.2 70.6 12.1 80.3 0.9 76.2 1.9
108 Imidacloprid Pesticides LC 84.5 2.6 77.2 4.3 77.2 3.0 74.5 2.2 72.8 2.7
109 Indoxacarb Pesticides LC 89.1 2.6 69.0 4.2 80.6 3.3 77.2 4.5 69.3 2.7
110 Iprodione Pesticides GC 72.9 10.9 53.2 18.6 40.4 10.2 39.3 4.4 31.7 10.9
111 Iprovalicarb Pesticides LC 79.5 1.3 69.7 1.5 73.7 0.6 76.3 0.6 72.7 1.4
112 Isocarbophos Pesticides GC 123.7 16.3 114.9 21.0 83.4 9.7 84.9 9.6 68.1 9.1
113 Isofenphos methyl Pesticides LC 83.8 3.6 60.0 3.6 76.9 4.6 82.4 2.8 77.3 3.1
114 Isoprothiolane Pesticides LC 81.2 4.3 66.0 2.9 73.4 2.0 73.7 1.4 71.6 3.6
115 Kresoxim methyl Pesticides LC 88.0 4.2 59.6 1.6 79.8 3.5 84.0 3.3 79.4 3.6
116 Linuron Pesticides LC 81.4 4.3 66.3 2.4 75.9 6.1 80.8 3.1 75.9 3.1
117 Lufenuron Pesticides LC 67.9 4.1 39.5 15.4 73.0 3.8 79.3 2.1 72.5 3.9
118 Malaoxon Pesticides LC 80.0 2.3 69.3 1.4 73.7 1.0 73.5 2.1 70.5 3.1
119 Malathion Pesticides LC 81.6 3.7 68.0 2.1 71.6 2.3 73.2 2.1 69.0 2.4
120 Mandipropamid Pesticides LC 81.5 2.2 78.0 1.4 72.3 2.7 70.8 0.8 66.7 3.6
121 Mefenoxam (metalaxyl-M) Pesticides LC 75.7 2.4 68.6 1.1 69.1 0.7 67.3 0.6 69.2 0.8
122 Mepanipyrim Pesticides LC 88.7 4.6 59.4 2.2 80.8 4.2 89.1 1.8 82.6 1.6
123 Metaflumizone Pesticides LC 64.4 2.4 76.8 2.8 58.7 4.0 55.6 1.5 51.6 1.8
124 Metalaxyl Pesticides GC 124.2 9.1 108.2 32.9 82.4 11.3 86.4 14.6 76.6 7.7
125 Metaldehyde Pesticides LC 81.2 5.3 81.1 4.8 77.1 9.3 79.9 4.1 80.5 4.6
126 Metconazole Pesticides LC 85.8 2.0 67.7 1.7 82.1 1.9 80.5 1.8 75.7 0.8
127 Methamidophos Pesticides LC 44.2 6.5 47.6 1.6 52.3 0.5 41.9 1.2 46.0 2.2
128 Methidathion Pesticides LC 89.6 3.3 73.7 1.1 80.6 2.4 81.3 2.1 78.7 2.5
129 Methiocarb Pesticides LC 84.5 3.8 68.1 2.8 79.6 1.5 84.7 1.2 77.3 1.7
130 Methiocarb sulfone Pesticides LC 81.2 2.8 71.6 2.0 71.9 2.6 73.1 3.6 74.5 3.6
131 Methiocarb sulfoxide Pesticides LC 74.1 1.7 64.7 1.6 69.3 2.2 65.0 2.7 71.2 1.6
132 Methomyl Pesticides LC 89.5 4.1 77.0 1.5 77.7 0.9 76.7 0.8 80.0 2.2
133 Methomyl oxime Pesticides LC 73.2 7.8 67.4 7.1 68.5 4.3 69.6 5.8 64.9 4.6
134 Methoxyfenozide Pesticides LC 81.5 2.8 72.4 1.5 74.4 1.4 75.3 1.4 71.8 1.8
135 Metrafenone Pesticides LC 89.5 6.3 67.6 7.3 83.4 16.4 98.1 2.4 86.5 2.5
136 Mevinphos (phosdrin) Pesticides LC 77.9 2.6 72.7 1.9 75.4 0.7 75.8 0.7 75.7 0.9
137 Monocrotophos Pesticides LC 73.0 3.2 68.3 1.7 70.1 1.1 62.5 2.4 72.3 3.0
138 Myclobutanil Pesticides LC 87.7 7.5 88.7 4.0 70.7 3.2 71.8 1.5 67.1 1.8
139 N,N-Dimethyl-N'-p-tolylsulphamide (DMST) Pesticides LC 94.3 3.4 84.9 0.8 84.0 4.2 86.4 2.1 77.5 2.1
140 N,N-dimethylformamidine (DMF) Pesticides LC 102.4 6.1 76.6 1.7 95.3 4.0 101.4 3.7 82.7 3.8
141 Nuarimol Pesticides LC 78.4 8.4 73.7 3.0 71.3 3.4 73.1 3.3 67.5 2.3
142 Ofurace Pesticides LC 81.6 3.2 70.0 2.1 76.0 3.1 75.9 3.0 66.1 1.0
143 Omethoate Pesticides LC 64.3 2.7 58.5 1.2 59.6 1.0 45.4 1.0 69.1 1.6
144 Oxadixyl Pesticides LC 79.3 2.1 72.7 1.1 69.6 1.1 66.7 1.0 70.8 1.6
145 Oxamyl Pesticides LC 76.5 3.6 70.1 1.7 69.1 1.2 65.3 1.0 75.0 1.8
146 Oxamyl oxime Pesticides LC 82.2 3.3 70.7 1.9 78.1 0.5 79.8 0.8 68.0 1.4
147 Oxyfluorfen Pesticides GC 98.0 11.2 92.1 23.3 76.7 9.1 67.5 9.3 62.0 11.7
148 Paclobutrazol Pesticides LC 78.5 4.8 71.2 3.2 69.7 2.1 71.0 3.5 70.3 1.5
149 Paraoxon methyl Pesticides GC 89.4 6.3 97.2 25.1 61.9 5.5 60.8 10.6 50.7 7.6
150 Parathion ethyl Pesticides GC 105.3 13.9 92.3 16.3 79.8 14.5 65.4 8.9 57.9 15.3
151 Parathion methyl Pesticides GC 98.1 4.7 92.5 20.5 70.3 8.7 60.3 15.5 45.0 7.8
152 Penconazole Pesticides LC 84.6 1.7 63.6 3.5 78.0 1.5 81.5 2.8 77.7 3.5
153 Pencycuron Pesticides LC 81.8 3.7 52.1 2.7 69.7 5.7 78.1 3.2 58.7 1.6
154 Pendimethalin Pesticides LC 86.6 3.3 38.4 4.4 79.3 2.6 79.5 3.4 76.7 1.5
155 Permethrin Pesticides GC 126.3 14.2 128.8 30.4 93.0 9.2 92.7 17.4 71.2 6.2
156 Phosalone Pesticides LC 86.3 2.0 60.6 4.1 82.2 2.0 87.4 1.0 81.1 2.6
157 Phosmet Pesticides LC 86.9 3.6 76.5 2.7 77.1 2.9 78.3 1.7 72.6 2.6
158 Phosmet oxon Pesticides LC 79.0 2.8 70.5 1.5 70.0 0.7 69.3 0.9 71.4 0.9
159 Phthalimide (Folpet deg) Pesticides GC 131.6 5.2 131.3 23.3 109.7 4.2 104.9 5.3 115.0 3.6
160 Pirimicarb Pesticides LC 56.0 8.8 61.9 1.1 67.3 1.3 59.4 1.3 71.6 0.9
161 Pirimiphos ethyl Pesticides LC 81.3 3.6 37.1 2.4 79.6 1.1 86.9 0.6 81.3 1.1
162 Pirimiphos methyl Pesticides LC 90.4 4.5 54.5 2.0 83.3 2.5 91.7 0.9 85.3 1.3
163 Prochloraz Pesticides LC 95.3 4.5 69.3 3.8 90.2 1.5 88.6 1.9 86.9 4.8
164 Procymidone Pesticides GC 139.6 19.3 108.9 19.9 98.8 10.3 104.0 12.6 87.8 4.9
165 Profenofos Pesticides LC 87.4 3.0 44.6 1.9 77.0 2.9 81.6 2.1 73.9 1.9
166 Propargite Pesticides LC 82.2 3.1 30.0 8.7 74.6 5.8 81.7 2.1 77.6 1.6
167 Propoxur Pesticides LC 86.3 2.8 73.1 2.2 80.3 0.9 82.5 1.6 80.9 1.3
168 Propyzamide (pronamide) Pesticides LC 83.4 6.3 62.4 0.8 73.8 1.9 79.9 3.6 75.5 4.2
169 Proquinazid Pesticides LC 78.6 2.6 21.0 51.3 71.9 8.5 76.7 3.4 70.6 1.0
170 Prothioconazole-desthio Pesticides LC 76.3 5.3 55.9 3.1 74.0 4.6 84.6 3.5 59.4 3.3
171 Prothiophos Pesticides GC 129.3 11.0 105.7 40.2 84.8 11.7 87.2 14.0 69.5 5.1
172 Pyraclostrobin Pesticides LC 85.4 3.0 59.2 2.4 77.2 3.0 81.0 1.9 75.1 1.2
173 Pyrazophos Pesticides LC 84.5 2.6 76.1 2.1 75.4 2.7 72.7 1.3 67.1 3.4
174 Pyridaben Pesticides LC 81.6 1.9 27.5 35.1 75.2 5.9 84.2 0.9 80.8 0.9
175 Pyridaphenthion Pesticides LC 79.3 7.4 72.0 2.9 61.6 3.0 62.0 2.1 55.8 1.8
176 Pyrimethanil Pesticides GC 129.0 11.8 119.3 26.3 94.2 12.7 95.0 5.7 80.5 11.5
177 Pyriproxifen Pesticides LC 82.0 2.3 32.3 3.2 76.4 0.9 81.4 1.4 78.6 1.8
178 Quinalphos Pesticides LC 91.9 2.3 74.2 3.6 89.5 1.6 93.9 3.7 89.6 1.8
179 Quinoxyfen Pesticides LC 78.8 7.1 22.6 2.9 70.4 8.5 88.7 2.1 88.7 2.1
180 Rotenone Pesticides LC 89.4 2.6 79.7 4.1 78.7 7.1 80.7 1.0 66.9 4.5
181 Simazine Pesticides LC 78.4 5.2 56.7 2.7 75.9 2.9 76.0 2.4 76.0 2.0
182 Spirodiclofen Pesticides LC 86.9 4.3 27.0 39.3 79.8 2.3 87.0 1.1 79.0 1.4
183 Spiromesifen Pesticides LC 82.8 4.5 31.5 3.3 71.2 6.1 73.6 3.8 68.0 1.3
184 Spirotetramat Pesticides LC 78.8 4.2 106.1 3.2 71.5 4.4 66.0 3.2 61.8 3.1
185 Spirotetramat-enol Pesticides LC 77.7 5.7 109.3 1.0 70.6 3.6 67.2 3.6 61.9 6.4
186 Spiroxamine Pesticides GC 62.7 12.0 105.0 19.1 37.9 8.5 17.7 5.4 86.3 4.9
187 Tebuconazole Pesticides LC 81.1 3.1 63.3 1.4 77.3 2.5 78.6 6.2 77.0 5.4
188 Tebufenocide Pesticides LC 80.7 2.6 65.4 1.2 73.5 2.9 74.6 2.3 70.4 2.6
189 Tebufenpyrad Pesticides LC 101.5 2.6 48.0 2.1 91.9 2.3 97.1 3.1 88.9 2.3
190 Teflubenzuron (artifact 3) Pesticides GC 153.4 8.7 131.7 21.4 103.5 10.5 93.9 9.9 96.6 7.7
191 Tefluthrin Pesticides GC 137.2 19.3 138.0 31.2 102.0 13.2 98.8 12.6 86.7 4.4
192 Telodrin Pesticides GC 130.4 13.9 101.1 24.7 83.1 16.7 85.5 15.2 76.0 12.5
193 Terbufos Pesticides GC 135.6 7.0 125.2 25.5 96.8 6.5 100.2 11.1 79.3 3.5
194 Terbuthylazine Pesticides LC 81.3 2.6 55.8 1.9 72.6 2.6 78.6 1.1 71.8 2.1
195 Tetrachlorvinphos Pesticides LC 100.8 3.4 80.2 2.6 96.6 1.2 100.6 2.2 95.6 4.1
196 Tetraconazole Pesticides LC 78.6 3.6 63.5 5.8 70.3 2.4 72.5 2.3 67.8 3.6
197 Tetradifon Pesticides GC 135.8 12.0 116.3 26.5 82.3 8.0 84.9 14.3 68.9 3.6
198 Tetramethrin Pesticides GC 113.5 14.6 102.7 28.5 57.9 7.2 60.0 5.4 48.9 10.6
199 Thiacloprid Pesticides LC 78.3 3.1 71.6 2.0 69.2 0.6 67.5 0.2 73.5 1.4
200 Thiamethoxam Pesticides LC 76.1 3.7 62.1 3.6 66.0 3.2 62.6 1.6 61.3 2.3
201 Thiodicarb Pesticides LC 72.0 3.0 74.0 1.9 61.8 1.3 58.6 0.6 71.9 1.6
202 Tolclofos methyl Pesticides GC 129.7 9.0 115.7 28.1 90.7 13.7 97.1 16.7 68.3 5.0
203 Tolylfluanid Pesticides GC 70.1 13.7 56.9 33.9 42.9 12.8 40.9 10.5 31.2 24.3
204 Triadimefon Pesticides LC 84.1 2.4 84.4 1.9 77.7 0.9 75.5 3.1 71.4 4.9
205 Triadimenol Pesticides LC 81.0 1.1 99.6 1.8 78.6 2.0 76.0 4.3 72.5 2.8
206 Triazophos (hostathion) Pesticides LC 81.4 3.1 70.8 1.7 74.1 0.5 77.9 1.9 74.0 1.5
207 Trichlorfon Pesticides LC 79.6 3.5 65.6 2.4 70.6 2.5 71.4 3.0 68.9 3.0
208 Trifloxystrobin Pesticides LC 83.5 3.2 49.5 3.1 77.6 1.7 82.9 0.7 77.5 1.8
209 Triflumizole Pesticides LC 77.2 6.0 45.8 2.2 78.3 1.7 81.7 2.9 82.1 1.3
210 Triflumuron Pesticides LC 93.7 3.2 63.2 2.2 84.5 2.3 85.6 3.3 81.7 5.0
211 Trifluralin Pesticides GC 114.2 28.5 134.2 33.4 100.5 8.9 80.7 5.1 78.3 12.0
212 Triticonazole Pesticides LC 82.9 2.5 82.3 3.9 76.9 1.8 73.3 2.8 72.2 3.8
213 Vinclozolin Pesticides GC 150.3 5.8 130.5 27.2 99.3 13.8 105.7 22.1 89.3 6.2
214 Aldrin OCPs GC 115.2 10.2 100.7 18.0 83.0 9.0 91.6 10.9 78.6 8.2
215 Dichlorodiphenyldichloroethane (p,p’ DDD) OCPs GC 113.5 17.7 88.4 36.9 83.1 20.7 73.9 9.7 112.3 4.2
216 Dichlorodiphenyldichloroethylene (p,p’ DDE) OCPs GC 121.2 9.6 96.8 30.6 116.0 36.2 90.6 16.0 110.7 30.6
217 Dieldrin OCPs GC 102.7 9.7 80.7 25.1 127.1 26.1 75.5 13.9 53.7 12.1
218 Endrin OCPs GC 90.8 13.1 73.4 31.1 66.5 13.9 63.6 10.4 61.6 7.6
219 Heptachlor OCPs GC 98.1 12.1 71.0 41.6 57.2 13.5 65.6 16.3 54.8 6.4
220 Hexachlorobenzene OCPs GC 140.9 8.2 112.9 27.0 103.0 9.7 110.9 12.3 97.1 5.2
221 Hexachlorocyclohexane (alpha) OCPs GC 127.2 11.4 103.5 39.5 80.9 15.2 79.0 10.2 67.3 5.2
222 Hexachlorocyclohexane (gamma, lindane) OCPs GC 103.9 11.8 72.1 36.8 57.5 7.6 57.7 18.5 62.6 1.9
223 Hexachlorocyclohexano (beta) OCPs GC 125.2 11.7 86.9 34.4 61.5 12.5 69.4 12.3 14.9 39.0
224 Hexaclorociclohexano (delta) OCPs GC 89.6 12.4 78.7 31.6 62.2 18.8 62.6 11.5 44.7 3.1
225 Mirex OCPs GC 91.7 15.7 69.0 31.9 56.8 8.9 60.7 5.5 59.6 9.4
226 PCB 28 PCBs GC 136.1 7.2 127.3 30.7 99.7 9.3 111.0 14.4 93.5 4.8
227 PCB 52 PCBs GC 130.1 13.0 108.4 27.4 100.1 19.0 109.9 17.3 94.7 6.7
228 PCB 77 PCBs GC 123.5 12.0 98.2 28.4 92.7 10.7 99.7 13.0 86.8 4.2
229 PCB 81 PCBs GC 117.1 8.3 95.8 30.0 85.1 5.4 94.5 12.4 79.3 10.5
230 PCB 101 PCBs GC 127.6 10.9 99.9 31.4 90.0 8.3 93.6 4.1 86.5 6.9
231 PCB 105 PCBs GC 132.6 9.3 109.0 29.4 104.8 8.0 110.1 13.2 95.2 8.8
232 PCB 114 PCBs GC 120.9 12.5 101.2 28.8 95.3 14.3 104.8 17.5 83.2 9.2
233 PCB 118 PCBs GC 106.4 16.3 88.2 25.1 90.6 13.9 89.8 4.4 77.2 5.2
234 PCB 123 PCBs GC 129.7 10.1 119.9 25.8 114.0 11.7 119.9 17.3 103.9 4.3
235 PCB 126 PCBs GC 104.7 17.3 77.9 14.8 75.7 5.2 85.7 11.8 73.9 6.6
236 PCB 138 PCBs GC 96.6 19.7 78.8 16.9 74.1 14.5 80.3 11.5 74.3 9.6
237 PCB 153 PCBs GC 117.7 16.2 95.3 25.0 96.2 9.1 100.2 18.1 81.1 6.5
238 PCB 156 PCBs GC 119.3 12.6 95.5 17.7 82.9 6.4 90.7 7.8 86.9 11.1
239 PCB 157 PCBs GC 127.0 12.4 92.5 20.4 89.2 9.9 95.2 9.2 85.1 10.2
240 PCB 167 PCBs GC 107.1 12.6 80.5 17.1 81.9 13.0 89.5 7.4 80.4 8.1
241 PCB 169 PCBs GC 109.1 15.4 90.2 20.0 84.7 12.1 89.8 7.5 75.4 8.3
242 PCB 180 PCBs GC 114.5 12.8 98.9 21.6 86.4 11.0 93.4 14.2 78.0 4.5
243 PCB 189 PCBs GC 110.7 14.5 88.6 15.3 89.5 11.1 88.2 8.8 83.1 9.9
244 PBDE 28 PBDEs GC 100.7 6.0 93.9 16.0 94.5 5.7 96.6 3.9 85.8 1.4
245 PBDE 47 PBDEs GC 96.7 10.0 89.6 13.2 84.2 3.6 86.8 6.5 75.5 3.7
246 PBDE 85 PBDEs GC 98.8 4.7 97.4 9.8 98.4 8.2 85.5 5.4 76.8 5.7
247 PBDE 99 PBDEs GC 102.5 5.9 89.3 19.9 91.1 8.9 95.9 5.3 85.2 7.8
248 PBDE 100 PBDEs GC 97.6 6.8 88.3 12.4 88.0 2.6 94.7 6.7 83.9 4.3
249 PBDE 153 PBDEs GC 90.4 6.4 91.9 11.2 89.4 3.5 88.2 6.2 75.5 2.7
250 PBDE 154 PBDEs GC 97.1 2.8 95.9 11.6 95.6 8.0 93.7 11.3 82.4 2.6
251 PBDE 183 PBDEs GC 91.8 6.4 76.1 10.8 81.8 4.9 71.7 7.5 64.3 6.5
252 Acenaphthene PAHs GC 123.3 20.1 116.6 37.1 79.7 6.1 78.8 10.2 76.1 5.5
253 Acenaphthylene PAHs GC 138.7 16.0 126.4 33.4 92.6 5.4 89.8 7.1 93.9 9.3
254 Anthracene PAHs GC 117.1 19.1 115.0 36.3 87.2 15.5 87.0 8.9 76.3 4.1
255 Benzo[a]anthracene PAHs GC 127.8 16.9 101.1 34.2 69.3 8.9 75.1 7.1 66.7 10.9
256 Benzo[b]fluoranthene PAHs GC 136.4 44.4 113.9 43.8 78.8 11.2 66.3 9.0 50.5 9.7
257 Chrysene PAHs GC 149.5 32.7 99.8 43.2 70.7 8.0 76.1 4.2 66.5 10.4
258 Fluoranthene PAHs GC 132.1 21.7 107.7 51.2 76.6 17.9 73.3 12.6 63.7 7.6
259 Fluorene PAHs GC 144.5 17.4 139.6 39.5 97.8 14.8 90.2 5.1 88.9 9.5
260 Naphthalene PAHs GC 125.7 16.1 132.0 33.1 93.4 10.9 89.1 9.1 88.6 6.5
261 Phenanthrene PAHs GC 128.5 11.6 147.1 37.3 95.7 16.2 94.6 5.4 81.7 14.1
262 Pyrene PAHs GC 132.9 17.5 106.8 48.5 74.0 12.4 76.5 5.7 67.4 7.8
263 Brodifacoum ARs LC 66.6 6.7 24.0 21.1 75.2 3.1 84.1 3.4 78.0 2.1
264 Bromadiolone ARs LC 69.5 2.4 43.1 4.5 68.5 2.7 73.1 3.2 63.5 3.7
265 Coumatetralyl ARs LC 69.4 1.9 57.5 4.6 69.2 3.7 75.0 3.5 69.4 2.5
266 Difenacoum ARs LC 79.6 3.3 31.6 5.8 87.8 2.0 91.5 1.2 94.9 0.8
267 Difetihalone ARs LC 68.6 9.1 27.7 8.4 70.2 4.6 85.8 2.1 76.9 3.5
268 Flocoumafen ARs LC 71.4 3.5 33.6 4.0 74.0 6.1 79.4 0.6 75.4 2.6
269 Warfarin ARs LC 80.4 5.1 81.6 5.7 74.9 3.8 77.2 3.9 75.1 3.7
270 Albendazole PhACs LC 56.6 6.5 46.9 1.0 67.6 1.6 71.6 1.2 65.4 1.6
271 Cefuroxima axetil PhACs LC 72.2 2.3 57.5 3.1 63.7 4.2 65.2 1.4 64.8 0.8
272 Chloramphenicol PhACs LC 88.0 7.3 82.2 9.3 76.9 11.6 84.2 14.1 77.6 8.4
273 Cloxacillin PhACs LC 58.3 17.6 87.8 9.8 36.9 5.0 33.6 12.0 62.3 2.8
274 Cortiscosterone 21 acetate PhACs LC 74.9 2.1 62.7 5.2 66.3 10.0 66.9 2.3 63.9 4.4
275 Dexamethasone PhACs LC 54.5 9.4 66.0 3.4 60.4 1.7 46.1 4.4 56.3 3.1
276 Diclofenac PhACs LC 60.0 19.2 69.9 2.8 61.0 7.2 66.3 3.1 64.2 6.1
277 Eprinomectin PhACs LC 71.1 8.1 46.0 28.2 69.4 4.8 60.5 2.6 57.6 5.0
278 Fenbendazole PhACs LC 65.6 9.2 46.7 3.3 62.8 2.8 65.3 1.4 59.4 0.8
279 Flunixin PhACs LC 47.0 2.6 30.4 3.1 53.1 2.9 44.9 2.7 65.6 1.6
280 Imipenem PhACs LC 102.4 6.4 76.7 16.0 73.7 17.7 83.6 11.7 83.7 10.3
281 Josamycin PhACs LC 52.7 3.7 63.7 3.6 37.2 3.8 20.9 4.5 58.4 2.0
282 Ketoprofen PhACs LC 69.4 3.8 80.3 4.2 66.6 1.8 66.4 1.2 65.0 3.4
283 Mebendazole PhACs LC 61.5 3.6 65.5 2.6 69.1 2.3 69.6 1.2 65.6 2.1
284 Mefenamic acid PhACs LC 48.3 20.9 66.3 5.0 41.5 13.0 57.5 8.1 45.1 8.3
285 Metronidazole PhACs LC 69.8 8.5 45.6 5.0 65.8 2.8 64.9 1.8 52.8 2.2
286 Moxidectin PhACs LC 67.5 8.5 26.1 15.1 54.3 9.1 74.4 4.6 71.3 2.5
287 Naproxen PhACs LC 68.1 5.0 73.5 4.3 68.7 4.9 69.2 5.8 63.5 5.2
288 Oxfendazole PhACs LC 46.9 3.8 54.3 2.7 64.3 2.3 57.2 0.4 63.1 2.7
289 Penicilina V PhACs LC 35.6 13.5 59.8 5.7 27.1 7.7 22.8 3.6 51.5 5.1
290 Sulfacetamide PhACs LC 60.3 7.8 51.4 4.0 63.9 0.7 67.0 3.1 47.0 2.0
291 Sulfacloropiridacine PhACs LC 64.2 4.7 56.4 5.5 69.5 3.6 77.3 1.8 54.4 3.2
292 Sulfadiacine PhACs LC 58.8 4.8 54.1 3.8 62.8 2.4 63.8 1.5 51.9 3.0
293 Sulfadimetoxine PhACs LC 69.6 3.0 73.8 4.8 66.5 1.5 69.7 1.1 62.5 1.6
294 Sulfadoxine PhACs LC 68.2 1.6 70.1 2.3 69.3 1.4 72.6 1.3 64.9 1.1
295 Sulfameracine PhACs LC 61.8 3.3 57.2 4.8 64.7 2.4 65.5 1.2 54.7 1.6
296 Sulfametacine PhACs LC 66.0 3.6 61.0 4.6 68.1 2.5 70.7 1.3 61.3 3.8
297 Sulfametizole PhACs LC 45.3 11.6 39.9 3.4 65.3 2.4 71.8 2.3 52.4 3.2
298 Sulfametoxazole PhACs LC 77.9 3.3 70.7 4.8 77.2 2.4 79.9 2.0 62.9 2.6
299 Sulfametoxipiridacine PhACs LC 57.7 4.4 53.4 5.8 67.7 1.7 69.6 1.8 57.9 3.1
300 Sulfamonomethoxine PhACs LC 60.5 2.8 55.5 3.8 63.9 2.4 70.6 2.1 58.0 1.5
301 Sulfanilamide PhACs LC 59.4 23.7 20.1 3.6 58.1 8.3 81.3 6.1 22.3 6.5
302 Sulfapiridine PhACs LC 57.2 4.6 50.4 3.7 68.0 2.2 70.0 3.2 57.9 3.9
303 Sulfaquinoxaline PhACs LC 61.8 3.0 63.1 4.7 66.4 1.5 68.4 2.4 60.9 0.5
304 Sulfisoxazole PhACs LC 40.4 38.1 66.4 3.3 54.7 3.8 70.3 1.4 38.8 8.1
305 Tolfenamic acid PhACs LC 79.4 4.9 60.6 2.8 77.9 9.0 90.1 6.6 85.5 6.2
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aPBDE – Polybrominated diphenyl ethers, OCP – Organochlorine pesticides, PAH – Polycyclic aromatic hydrocarbon, PCB – Polychlorinated biphenyl, PhACs – Pharmaceuticals Active Compounds, ARs – Anticoagulant Rodenticides, P-IS – Procedural Internal Standard.

bGas chromatography (GC) or liquid chromatography (LC), both coupled with tandem triple quadrupole mass spectrometry.

This method was optimized and validated for a representative agricultural soil of the Canary Islands that can be classified as clay loam. However, soil is a heterogeneous and highly complex matrix whose components may influence the degree of adsorption of the organic compounds. Therefore, not only the chemical properties of the compound may affect the mobility and availability of these compounds in the soil but also the soil characteristics, such as pH, moisture, texture and organic matter content [16]. Generally, they are mostly absorbed in soils rich in organic matter or clay [17]. Consequently, it is necessary to consider soil physicochemical properties to achieve more reliable quantifications with the analytical methods.

This study aims to extend the use of the QuEChERS-based method for the extraction and analysis of the above mentioned 305 organic compounds of different nature and origin to other types of soil frequently used in agriculture.

Chemicals and reagents

Certified standards stock mix solutions of the pesticides included in the coordinated multi-annual plan of the EU for the investigation of residues in food of vegetable or animal origin during the years 2020, 2021 and 2022 [7] were purchased from CPA Chem (Stara Zagora, Bulgaria) in 10 mixes of compatible pesticides at 10 μg mL−1, each in acetonitrile (ACN). Standard stock solutions of the selected POPs were also supplied by CPA Chem in 5 mixes, each of them at 100 μg mL−1: one for the OCPs (in acetone), one for the PAHs (in dichloromethane), one for the PBDEs (in iso-octane) and two for PCBs (in iso-octane). Individual certified standards of ARs, PhACs and additional pesticides (purity 95.19% to 99.9%) were acquired from Dr. Ehrenstorfer (Augsburg, Germany), Sigma-Aldrich (Augsburg, Germany) and European Pharmacopoeia Reference Standards (Strasbourg, France). Atrazine-d5, Carbendazim-d3, Chlorpyrifos-d10, Coumachlor, Cyromazine-d4, Diazinon-d10, Linuron-d3, Pirimicarb-d6 and PCB 200 (Dr. Ehrenstorfer and Sigma-Aldrich, 99.3-99.9% purity) were used as procedural internal standards (P-IS). These internal standards were added to the samples at the beginning of the procedure to account for various sources of errors throughout all stages in the method [18].

LC-MS grade methanol (MeOH), acetonitrile (ACN), acetone (Ac) and formic acid (FA, HCOOH) were obtained from Honeywell (Morristown, NJ). Ammonium acetate (NH4CH3CO2) was purchased from Fisher Scientific (Loughborough, UK). AOAC method QuEChERS salts [19] (6 g of MgSO4 and 1.5 g of CH3COONa) were acquired in commercial premixes from Agilent Technologies (Palo Alto, USA). The ultrapure water was produced in the laboratory using a Gradient A10 Milli-Q System (Millipore, Bedfore, MA, USA).

Standard solutions and calibration curves

Individual stock standard solutions at a concentration of 1000 µg mL−1 were prepared for PhACs, ARs, P-IS and additional pesticides in MeOH for the first group and ACN for the last three. From these, mixed stock solutions were prepared in ACN or MeOH at 10 μg mL−1 for each group. Then, working solutions of PhACs, ARs and P-IS were prepared at 1 µg mL−1 in those solvents. A working solution containing all the pesticides at a final concentration of 0.833 µg mL−1 was prepared by mixing the ten parts of the European Commission commercial mix and the additional in-house solution containing the rest of the pesticides (10 μg mL−1/each). For the POPs, an intermediate solution containing all the analytes at a final concentration of 20 μg mL−1/each was prepared by mixing the five parts of the commercial mix. Then, a working mix solution was prepared at 1 µg mL−1 in Ac.

Matrix-matched calibration curves ranging from 0.195 to 100 ng g−1 were prepared with the standard working mix solutions of each compound group in either soil extract for GC-MS/MS or in in a mixture of this extract with ultrapure water (1:1, v/v) for LC-MS/MS.

All standards, working mix solutions and matrix-matched calibrators were stored in glass amber vials at -20 °C and checked periodically for stability.

Sample selection and pretreatment

The method was originally developed, optimized and validated in an agricultural soil which did not present any of the analytes of interest. This sample, located in the midlands of the Canary Islands, can be considered representative of the most fertile soil of the archipelago and is classified as clay loam according to its characteristics (see soil A in Table 1). To test whether this method could be transferred to other types of cropland on the islands, samples were taken from farms located in different areas of the archipelago that may represent other areas typically used for cultivation. In each sampling plot, a composite sample was prepared from subsamples collected in depths between 20 and 30 cm. Then, the soil was homogenized, air-dried at room temperature and sieved (2 mm mesh). Once analyzed, it was observed that these soils could be classified into 5 types according to their characteristics, which have been designated with a letter from A to E.

Table 1.

Physicochemical properties of the soil samples.

ID Classification pH CE (μS cm−1) OOC (%) Coarse sand (%) Fine Sand (%) Thick slit (%) Fine slit (%) Clay (%) Moisture (%)
Soil A Clay loam 4.88 209 2.19 11.48 19.39 11.27 28.33 29.53 6%
Soil B Sandy loam 7.16 246 6.51 52.83 10.88 7.71 19.39 9.20 6%
Soil C Sandy clay 8.41 1072 0.49 21.96 26.52 2.70 6.82 42.99 6%
Soil D Clay 9.00 228 0.46 18.42 11.11 0.12 0.29 70.06 8%
Soil E Loamy sand 9.53 328 0.29 54.92 27.41 2.49 6.27 8.91 4%
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CE: Conductivity; OOC: Oxidizable Organic Carbon.

Soil characterization

The physicochemical properties of each soil type (texture, oxidizable organic carbon, moisture, conductivity and pH) are shown in Table 1 together with their edaphology classification. The electrical conductivity and pH were measured with suitable electrodes in soil-water suspensions (1:5, w/v). Moisture was calculated as the difference between the air-dried soil weight and the weight after 24 h in an oven at 105°C. Particle distribution was obtained using the hydrometer method [20]. The oxidizable organic carbon to calculate the organic matter content was determined according to the spectrophotometric method in which the absorbance reading is compared with a curve of sucrose solutions with increasing carbon concentration. Once these properties were determined, the soils were classified using the texture diagram of the United States Department of Agriculture (USDA) [21].

Modified QuEChERS method

First, 10 ± 0.05 g of dried and sieved soil were weighed into a 50 mL centrifuge tube. Before starting the extraction process, the appropriated volume of the standard mix solutions to achieve the desired concentration (50 ng g−1) were added to the recovery samples. Likewise, all samples and blanks were spiked with 50 µL of the P-IS solution, thoroughly shaken, and left to stand for an hour. Then, 10 mL of ACN-2.5%FA were added to each tube and vigorously shaken for 1 min. After that, 6 g of MgSO4 and 1.5 g of CH3COONa were incorporated to the tubes, energetically shaken for another minute, and sonicated in an ultrasonic bath (50/60 Hz, 120 V VWR, Radnor, Pennsylvania, USA) for 15 min to ensure aggregate breakdown. After that, samples were placed in a rotatory shaker (Ovan, Barcelona, Spain) for 25 min and then centrifuged for 10 min at 4200 rpm (3175.16 × g) (5804 R, Eppendorf, Hamburg, Germany). Finally, the supernatant was filtered through 0.20 µm Chromafil® PET filters (Macherey-Nagel, Düren, Germany) and either directly analyzed in GC-MS/MS or dissolved in ultrapure water (1:1, v/v) and analyzed in LC-MS/MS.

Instrumentation

The LC-MSMS analysis was performed using a 1290 Infinity II LC System coupled to a Triple Quad 6460 mass spectrometer (Agilent Technologies, Palo Alto, CA, USA). A Poroshell 120 EC-C18 column (2.1 × 100 mm, 2.7 µm; Agilent Technologies) equipped with a guard pre-filter with a 0.3 µm SS frit and a pre-column (2.1 × 5 mm, 1.8 µm; Agilent Technologies) at 50 °C was used for the chromatographic separation. The mobile phases were 2 mM ammonium acetate 0.1% FA in ultrapure water (A) and 2 mM ammonium acetate in MeOH (B). A binary gradient using mobile phases A and B was programmed as follows: 5% B - 0.5 min; 5% B - 1 min; 40% B - 2.5 min; 85% B - 8 min; 100% B - 10 to 14 min; 5% B - 14.01 min. The flow rate was set at 0.4 mL min−1, the volume injected was 5 μL and the total run time was 18 min. MS/MS analyses were performed using the Agilent Jet Stream Electrospray Ionization Source (AJS-ESI), in both positive and negative ionization mode, with dynamic multiple reaction monitoring (dMRM). The nitrogen supplied by Zefiro 40 nitrogen generator (F-DGSi, Evry, France) was used as desolvation and drying gas. Nitrogen 6.0 (99.9999% purity, Linde, Dublin, Ireland) was used as collision gas. The sheath gas was set at 12 L min−1 at 330 °C. The desolvation and nebulizing gas temperature was 190 °C and the flow rate was 11 L min−1 with a pressure of 26 psi. The capillary voltages were set at 3900 and 2600 V in positive and negative ionization mode, respectively. The cycle time was 700 ms and dwell time 3-83 ms.

The GC-MS/MS analysis was conducted with a GC System 7890B equipped with a 7693 Autosampler and Triple Quad 7010 mass spectrometer (Agilent Technologies, Palo Alto, USA). The chromatographic separations were performed using two fused silica ultra-inert capillary columns Agilent J&WHP-5MS (Crosslinked 5% phenyl-methyl-polysiloxane, Agilent Technologies) 15 m length, 0.25 mm i.d., and 0.25 µm film thickness of 0.25 µm each connected in series by a Purged Ultimate Union (PUU; Agilent Technologies). This configuration allowed the use of the back-flushing technique. Helium (99.999% purity, Linde, Dublin, Ireland) was used as the carrier gas and the flow was adjusted by the retention time lock feature using chlorpyrifos methyl as a reference (retention time = 9.143 min). The column temperature was maintained at 80 °C for 1.8 min, increased to 170 °C at a rate of 40 °C min−1, then increased to 310 °C at a rate of 10 °C min−1 and held for 3 min. The injection volume was 1.5 µL in splitless mode using a 4 mm Ultra Inert Liner with glass wool (Agilent Technologies) and it was set at 250 °C. Each chromatographic analysis lasted 20.75 min. Post-run backflush was set at -5.8 mL min−1 and 315 °C for 5 min. MS/MS analyses were performed using electron impact (EI) ionization source in multiple reaction monitoring (MRM) mode, using 24-time segments. The EI source temperature was set at 280 °C. Nitrogen 6.0 (99,9999% purity, Linde, Dublin, Ireland) was used as the collision gas at a flow of 1.5 mL min−1. The transfer line temperature was 280 °C. A solvent delay of 3.7 min was left. The cycle time was in the range of 52-334 ms and the dwell time was between 15-40 ms.

Data analysis was performed using Agilent software MassHunter Quantitative Analysis (for QQQ) version B.07.01 and MassHunter Qualitative Analysis version B.07.00 for both GC-MS/MS and LC-MS/MS.

Method performance study

Recovery studies

The performance of the method in soils B, C, D, and E in comparison with soil A, the claim loam soil used in the previous validation of the method, was assessed through recovery experiments in quintuplicate at a single concentration of 50 ng g−1. This concentration was selected as it is typically fixed as the limit of quantification (LOQ) for residues in soils [18]. Moreover, all the compounds are efficiently extracted at this concentration in clay loam soil, and actually it is the LOQ of two of the analytes: naphthalene and imipenem. In addition, extractions without the addition of analytes (blanks) were performed for each soil type in duplicates.

The mean and the standard deviation of the recoveries in each type of soil (A-E) are summarized in Table 2 (this information is also represented in Figure 1, Panels A-L, in the supplementary material). The range where recoveries are considered acceptable is 70-120% and a Relative Standard Deviation (%RSD) below 20% according to the guidelines followed in the validation [18,22].

Correction factors

From the data obtained in the recovery experiments, the difference in the performance of the compounds in each type of soil was calculated. It was calculated by taking soil A as a reference. Thus, it is the quotient of the recoveries in soils B, C, D, and E by the recoveries in soil A. In those cases where this factor was within the range of 0.8 and 1.2, it has been considered that there is no marked difference between the two types of soil for a given compound, and, therefore, it would not be necessary to apply any correction to the results obtained in the respective soil. The correction factors are intended to correct the concentrations obtained with the proposed method for each analyte in soils of types B to E and can be consulted in Table 3.

Table 3.

Multiplying factors for the correction of the concentration found after the application of the analytical method to sandy loam soil (B), sandy clay soil (C), clay soil (D), and loamy sand soil (E).

N° Compound Group Technique Factor B Factor C Factor D Factor E
1 4,4′-Dichlorobenzophenone Pesticides, OCPs GC 1.9 1.7 1.3
2 4,4′-Dicofol Pesticides, OCPs GC 1.4 1.6 1.6 3.5
3 Abamectine Pesticides LC 2.1
4 Acephate Pesticides LC 1.5
5 Acetamiprid Pesticides LC
6 Acrinathrin Pesticides LC 2.1
7 Aldicarb Pesticides LC
8 Aldicarb sulfone Pesticides LC
9 Atrazine Pesticides LC 1.4
10 Azinphos methyl Pesticides LC
11 Azoxystrobin Pesticides LC 1.3
12 Benalaxyl Pesticides LC 1.3
13 Bendiocarb Pesticides LC
14 Bifenthrin Pesticides GC 1.6 1.5 1.7
15 Bitertanol Pesticides LC 1.3
16 Boscalid Pesticides GC 0.6 1.4 1.5 1.7
17 Bromopropylate Pesticides GC 1.4 1.4 1.5
18 Bromuconazole Pesticides LC 1.3
19 Bupirimate Pesticides LC 1.3
20 Cadusafos Pesticides LC 1.7
21 Carbaryl Pesticides LC
22 Carbofuran Pesticides LC 1.3 1.3
23 Carbofuran-3-hydroxy Pesticides LC
24 Chlorantraniliprole Pesticides LC 1.3
25 Chlorfenapyr Pesticides GC 1.4 1.5 1.9
26 Chlorobenzilate Pesticides GC 1.3 1.3 1.6
27 Chlorpropham Pesticides GC 1.4 1.5 1.6
28 Chlorpyrifos Pesticides GC 1.3 1.4 1.5 1.8
29 Chlorpyrifos methyl Pesticides GC 1.5 1.5 2.1
30 Chlorthal dimethyl Pesticides GC 1.4 1.3 1.5
31 Clofentezine Pesticides LC 1.7
32 Clothianidin Pesticides LC 1.3
33 Coumachlor Pesticides LC
34 Coumaphos Pesticides LC
35 Cyazofamid Pesticides LC 1.3 1.4
36 Cyflufenamid Pesticides LC 1.5
37 Cyfluthrin Pesticides GC 1.3 1.6 1.7 2.1
38 Cyhalothrin (lambda isomer) Pesticides LC 2.8 1.3
39 Cymoxanil Pesticides LC
40 Cypermethrin Pesticides GC 1.7 1.9 2.3
41 Cyproconazole Pesticides LC
42 Cyprodinil Pesticides GC 1.4 1.4 1.6
43 Deltamethrin Pesticides GC 1.6 1.9 2.5
44 Demeton-S-methyl Pesticides LC 1.3
45 Demeton-S-methyl-sulfone (Dioxydemeton) Pesticides LC
46 Diazinon Pesticides GC 1.3 1.3 1.6
47 Dichlofluanid Pesticides GC 1.3 1.5 1.5 2.1
48 Dichloran Pesticides GC 1.3 1.6 1.9 2.0
49 Diethathyl ethyl Pesticides LC 1.3
50 Diethofencarb Pesticides LC
51 Difenoconazole Pesticides LC 1.3
52 Diflubenzuron Pesticides LC
53 Diflufenican Pesticides LC 1.6
54 Dimethenamide Pesticides LC
55 Dimethoate Pesticides LC
56 Dimethomorph Pesticides LC 1.3 1.3 1.3
57 Diniconazole-M Pesticides LC 1.3 1.3 1.4
58 Dinocap Pesticides LC 2.2 1.7 1.6 1.5
59 Diphenylamine Pesticides LC 1.3
60 Endosulfan alfa Pesticides, OCPs GC 1.3 1.5 1.4 1.7
61 Endosulfan beta Pesticides, OCPs GC 1.3 1.5 1.6 1.8
62 EPN Pesticides LC 1.7
63 Epoxiconazole Pesticides LC 1.4
64 Esfenvalerate Pesticides GC 1.7 1.8 2.4
65 Ethion Pesticides LC 2.3
66 Ethofumesate Pesticides GC 1.3 1.5 1.3 1.6
67 Ethoprophos Pesticides LC 1.3
68 Etofenprox Pesticides LC 2.0 1.4 2.9 1.5
69 Etoxazole Pesticides LC 2.5
70 Fenamidone Pesticides LC 1.3
71 Fenamiphos Pesticides LC 1.3
72 Fenamiphos sulfone Pesticides LC 1.3 1.3
73 Fenamiphos sulfoxide Pesticides LC 1.4
74 Fenarimol Pesticides GC 1.5 1.6 1.6
75 Fenazaquin Pesticides LC 3.5
76 Fenbuconazole Pesticides LC
77 Fenbutatin oxide Pesticides LC 1.9 1.8 1.3
78 Fenitrothion Pesticides GC 1.4 1.5 2.1
79 Fenoxycarb Pesticides LC 1.3
80 Fenpropathrin Pesticides LC 3.0 1.3
81 Fenpropimorph Pesticides LC 1.7
82 Fenpyroximate Pesticides LC 3.2
83 Fenthion Pesticides LC 1.4 1.3
84 Fenthion oxon Pesticides LC
85 Fenthion oxon sulfone Pesticides LC
86 Fenthion oxon sulfoxide Pesticides LC 1.3
87 Fenthion sulfone Pesticides LC
88 Fenthion sulfoxide Pesticides LC
89 Fenvalerate Pesticides GC 1.6 1.9 2.2
90 Fipronil Pesticides LC
91 Fipronil sulfide Pesticides GC 1.3
92 Fluazinam Pesticides LC
93 Flubendiamide Pesticides LC
94 Flucythrinate Pesticides GC 1.5 1.7 2.0
95 Fludioxonil Pesticides LC
96 Flufenoxuron Pesticides LC 1.8
97 Fluopyram Pesticides LC 1.3
98 Fluquinconazole Pesticides LC 1.3
99 Flusilazole Pesticides LC 1.3 1.3
100 Flutolanil Pesticides LC 1.3
101 Flutriafol Pesticides LC
102 Fluvalinate tau Pesticides LC 1.9 1.3 1.4
103 Fonofos Pesticides GC 1.4 1.3 1.6
104 Fosthiazate Pesticides LC
105 Hexaconazole Pesticides LC 1.3
106 Hexaflumuron Pesticides LC 1.3 1.4
107 Hexythiazox Pesticides LC 2.7
108 Imidacloprid Pesticides LC
109 Indoxacarb Pesticides LC 1.3 1.3
110 Iprodione Pesticides GC 1.4 1.8 1.9 2.3
111 Iprovalicarb Pesticides LC
112 Isocarbophos Pesticides GC 1.5 1.5 1.8
113 Isofenphos methyl Pesticides LC 1.4
114 Isoprothiolane Pesticides LC 1.3
115 Kresoxim methyl Pesticides LC 1.5
116 Linuron Pesticides LC 1.3
117 Lufenuron Pesticides LC 1.7
118 Malaoxon Pesticides LC
119 Malathion Pesticides LC 1.3
120 Mandipropamid Pesticides LC 1.3
121 Mefenoxam (metalaxyl-M) Pesticides LC
122 Mepanipyrim Pesticides LC 1.5
123 Metaflumizone Pesticides LC 1.3
124 Metalaxyl Pesticides GC 1.5 1.4 1.6
125 Metaldehyde Pesticides LC
126 Metconazole Pesticides LC 1.3
127 Methamidophos Pesticides LC
128 Methidathion Pesticides LC 1.3
129 Methiocarb Pesticides LC 1.3
130 Methiocarb sulfone Pesticides LC
131 Methiocarb sulfoxide Pesticides LC
132 Methomyl Pesticides LC
133 Methomyl oxime Pesticides LC
134 Methoxyfenozide Pesticides LC
135 Metrafenone Pesticides LC 1.3
136 Mevinphos (phosdrin) Pesticides LC
137 Monocrotophos Pesticides LC
138 Myclobutanil Pesticides LC 1.3 1.3 1.3
139 N,N-Dimethyl-N'-p-tolylsulphamide (DMST) Pesticides LC 1.3
140 N,N-dimethylformamidine (DMF) Pesticides LC 1.3 1.3
141 Nuarimol Pesticides LC
142 Ofurace Pesticides LC 1.3
143 Omethoate Pesticides LC 1.4
144 Oxadixyl Pesticides LC
145 Oxamyl Pesticides LC
146 Oxamyl oxime Pesticides LC 1.3
147 Oxyfluorfen Pesticides GC 1.3 1.5 1.6
148 Paclobutrazol Pesticides LC
149 Paraoxon methyl Pesticides GC 1.4 1.5 1.8
150 Parathion ethyl Pesticides GC 1.3 1.6 1.8
151 Parathion methyl Pesticides GC 1.4 1.6 2.2
152 Penconazole Pesticides LC 1.3
153 Pencycuron Pesticides LC 1.6 1.4
154 Pendimethalin Pesticides LC 2.3
155 Permethrin Pesticides GC 1.4 1.4 1.8
156 Phosalone Pesticides LC 1.4
157 Phosmet Pesticides LC
158 Phosmet oxon Pesticides LC
159 Phthalimide (Folpet deg) Pesticides GC 1.3
160 Pirimicarb Pesticides LC 0.7
161 Pirimiphos ethyl Pesticides LC 2.2
162 Pirimiphos methyl Pesticides LC 1.7
163 Prochloraz Pesticides LC 1.4
164 Procymidone Pesticides GC 1.3 1.4 1.3 1.6
165 Profenofos Pesticides LC 2.0
166 Propargite Pesticides LC 2.7
167 Propoxur Pesticides LC
168 Propyzamide (pronamide) Pesticides LC 1.3
169 Proquinazid Pesticides LC 3.7
170 Prothioconazole-desthio Pesticides LC 1.4 1.3
171 Prothiophos Pesticides GC 1.3 1.5 1.5 1.9
172 Pyraclostrobin Pesticides LC 1.4
173 Pyrazophos Pesticides LC 1.3
174 Pyridaben Pesticides LC 3.0
175 Pyridaphenthion Pesticides LC 1.3 1.3 1.4
176 Pyrimethanil Pesticides GC 1.4 1.4 1.6
177 Pyriproxifen Pesticides LC 2.5
178 Quinalphos Pesticides LC 1.3
179 Quinoxyfen Pesticides LC 3.5
180 Rotenone Pesticides LC 1.3
181 Simazine Pesticides LC 1.4
182 Spirodiclofen Pesticides LC 3.2
183 Spiromesifen Pesticides LC 2.6 1.3
184 Spirotetramat Pesticides LC 0.7 1.3
185 Spirotetramat-enol Pesticides LC 0.7 1.3
186 Spiroxamine Pesticides GC 0.6 1.7 3.6 0.7
187 Tebuconazole Pesticides LC 1.3
188 Tebufenocide Pesticides LC 1.3
189 Tebufenpyrad Pesticides LC 2.1
190 Teflubenzuron (artifact 3) Pesticides GC 1.5 1.6 1.6
191 Tefluthrin Pesticides GC 1.3 1.4 1.6
192 Telodrin Pesticides GC 1.3 1.6 1.5 1.7
193 Terbufos Pesticides GC 1.4 1.4 1.7
194 Terbuthylazine Pesticides LC 1.5
195 Tetrachlorvinphos Pesticides LC 1.3
196 Tetraconazole Pesticides LC 1.3
197 Tetradifon Pesticides GC 1.6 1.6 2.0
198 Tetramethrin Pesticides GC 2.0 1.9 2.3
199 Thiacloprid Pesticides LC
200 Thiamethoxam Pesticides LC 1.3 1.3 1.3
201 Thiodicarb Pesticides LC 1.3
202 Tolclofos methyl Pesticides GC 1.4 1.3 1.9
203 Tolylfluanid Pesticides GC 1.3 1.6 1.7 2.2
204 Triadimefon Pesticides LC
205 Triadimenol Pesticides LC
206 Triazophos (hostathion) Pesticides LC
207 Trichlorfon Pesticides LC 1.3
208 Trifloxystrobin Pesticides LC 1.7
209 Triflumizole Pesticides LC 1.7
210 Triflumuron Pesticides LC 1.5
211 Trifluralin Pesticides GC 1.4 1.5
212 Triticonazole Pesticides LC
213 Vinclozolin Pesticides GC 1.5 1.4 1.7
214 Aldrin OCPs GC 1.4 1.3 1.5
215 Dichlorodiphenyldichloroethane (p,p’ DDD) OCPs GC 1.3 1.4 1.5
216 Dichlorodiphenyldichloroethylene (p,p’ DDE) OCPs GC 1.3 1.3
217 Dieldrin OCPs GC 1.3 1.4 1.9
218 Endrin OCPs GC 1.3 1.4 1.4 1.5
219 Heptachlor OCPs GC 1.4 1.7 1.5 1.8
220 Hexachlorobenzene OCPs GC 1.3 1.4 1.3 1.5
221 Hexachlorocyclohexane (alpha) OCPs GC 1.3 1.6 1.6 1.9
222 Hexachlorocyclohexane (gamma, lindane) OCPs GC 1.4 1.8 1.8 1.7
223 Hexachlorocyclohexano (beta) OCPs GC 1.4 2.0 1.8 8.4
224 Hexaclorociclohexano (delta) OCPs GC 1.4 1.4 2.0
225 Mirex OCPs GC 1.3 1.6 1.5 1.5
226 PCB 28 PCBs GC 1.4 1.3 1.5
227 PCB 52 PCBs GC 1.3 1.4
228 PCB 77 PCBs GC 1.3 1.3 1.3 1.4
229 PCB 81 PCBs GC 1.3 1.4 1.3 1.5
230 PCB 101 PCBs GC 1.3 1.4 1.4 1.5
231 PCB 105 PCBs GC 1.3 1.3 1.3 1.4
232 PCB 114 PCBs GC 1.3 1.5
233 PCB 118 PCBs GC 1.3 1.4
234 PCB 123 PCBs GC 1.3
235 PCB 126 PCBs GC 1.3 1.4 1.3 1.4
236 PCB 138 PCBs GC 1.3 1.3 1.3 1.3
237 PCB 153 PCBs GC 1.3 1.3 1.5
238 PCB 156 PCBs GC 1.3 1.4 1.3 1.4
239 PCB 157 PCBs GC 1.4 1.4 1.3 1.5
240 PCB 167 PCBs GC 1.3 1.3 1.3
241 PCB 169 PCBs GC 1.3 1.3 1.3 1.4
242 PCB 180 PCBs GC 1.3 1.3 1.5
243 PCB 189 PCBs GC 1.3 1.3 1.3 1.3
244 PBDE 28 PBDEs GC
245 PBDE 47 PBDEs GC 1.3
246 PBDE 85 PBDEs GC 1.3
247 PBDE 99 PBDEs GC 1.3
248 PBDE 100 PBDEs GC
249 PBDE 153 PBDEs GC
250 PBDE 154 PBDEs GC
251 PBDE 183 PBDEs GC 1.3 1.3 1.4
252 Acenaphthene PAHs GC 1.5 1.6 1.6
253 Acenaphthylene PAHs GC 1.5 1.5 1.5
254 Anthracene PAHs GC 1.3 1.3 1.5
255 Benzo[a]anthracene PAHs GC 1.3 1.8 1.7 1.9
256 Benzo[b]fluoranthene PAHs GC 1.7 2.1 2.7
257 Chrysene PAHs GC 1.5 2.1 2.0 2.2
258 Fluoranthene PAHs GC 1.3 1.7 1.8 2.1
259 Fluorene PAHs GC 1.5 1.6 1.6
260 Naphthalene PAHs GC 1.3 1.4 1.4
261 Phenanthrene PAHs GC 1.3 1.4 1.6
262 Pyrene PAHs GC 1.3 1.8 1.7 2.0
263 Brodifacoum ARs LC 2.8 0.7
264 Bromadiolone ARs LC 1.6
265 Coumatetralyl ARs LC 1.3
266 Difenacoum ARs LC 2.5
267 Difetihalone ARs LC 2.5 0.7
268 Flocoumafen ARs LC 2.1
269 Warfarin ARs LC
270 Albendazole PhACs LC 1.3 0.7
271 Cefuroxima axetil PhACs LC 1.3
272 Chloramphenicol PhACs LC
273 Cloxacillin PhACs LC 0.7 1.6 1.7
274 Cortiscosterone 21 acetate PhACs LC
275 Dexamethasone PhACs LC
276 Diclofenac PhACs LC
277 Eprinomectin PhACs LC 1.5 1.3
278 Fenbendazole PhACs LC 1.4
279 Flunixin PhACs LC 1.5 0.7
280 Imipenem PhACs LC 1.3 1.4 1.3 1.3
281 Josamycin PhACs LC 1.4 2.5
282 Ketoprofen PhACs LC
283 Mebendazole PhACs LC
284 Mefenamic acid PhACs LC 0.7
285 Metronidazole PhACs LC 1.5 1.3
286 Moxidectin PhACs LC 2.6 1.3
287 Naproxen PhACs LC
288 Oxfendazole PhACs LC 0.7 0.7
289 Penicilina V PhACs LC 0.6 1.3 1.6 0.7
290 Sulfacetamide PhACs LC 1.3
291 Sulfacloropiridacine PhACs LC
292 Sulfadiacine PhACs LC
293 Sulfadimetoxine PhACs LC
294 Sulfadoxine PhACs LC
295 Sulfameracine PhACs LC
296 Sulfametacine PhACs LC
297 Sulfametizole PhACs LC 0.7 0.6
298 Sulfametoxazole PhACs LC 1.3
299 Sulfametoxipiridacine PhACs LC
300 Sulfamonomethoxine PhACs LC
301 Sulfanilamide PhACs LC 3.0 0.7 2.7
302 Sulfapiridine PhACs LC
303 Sulfaquinoxaline PhACs LC
304 Sulfisoxazole PhACs LC 0.6 0.7 0.6
305 Tolfenamic acid PhACs LC 1.3
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Empty cell: when the calculated factor is between 0.8 and 1.2, it is considered that there is not enough difference, and no correction should be applied.

Acknowledgements

The authors would like to thank Dr. Jesús Notario from the Department of Animal Biology, Edaphology and Geology of the University of La Laguna for his help in the identification and characterization of the soil samples. This research was supported by the Spanish  Ministry of Education, Culture and Sports, grant number FPU16-01888, to A. Acosta-Dacal, and by the University of Las Palmas de Gran Canaria, grant number ULPGC-012-2016, to C. Rial-Berriel.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Footnotes

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.mex.2021.101476.

Contributor Information

Andrea Acosta-Dacal, Email: andrea.acosta@ulpgc.es.

Cristian Rial-Berriel, Email: cristian.rial@ulpgc.es.

Ricardo Díaz-Díaz, Email: rdiaz@itccanarias.org.

María del Mar Bernal-Suárez, Email: mbernal@itccanarias.org.

Manuel Zumbado, Email: manuel.zumbado@ulpgc.es.

Luis Alberto Henríquez-Hernández, Email: luis.henriquez@ulpgc.es.

Ana Macías-Montes, Email: ana.macias@ulpgc.es.

Octavio P. Luzardo, Email: octavio.perez@ulpgc.es.

Appendix. Supplementary materials

mmc1.docx (8.3MB, docx)

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