supplementary material to the paper entitled ......list of omcs included in the target analysis and...

1

Supplementary material to the paper entitled:

Determination of organic microcontaminants in agricultural soils

irrigated with reclaimed wastewater: target and suspect approaches

A.B. Martínez-Piernas a, P. Plaza-Bolaños

a, E. García-Gómez

a, P. Fernández-Ibáñez

b, A.

Agüera a,*

a CIESOL (Solar Energy Research Center), Joint Centre University of Almeria-CIEMAT,

Carretera de Sacramento s/n, E-04120, Almeria, Spain

b Nanotechnology and Integrated BioEngineering Centre, School of Engineering, University of

Ulster, Newtownabbey, Northern Ireland, United Kingdom

*Corresponding author

Email: aaguera@ual.es, Tel: +0034 950 015 531, Fax: +0034 950 015 008

This document provides more detailed information to the main paper mentioned above.

The following information is included:

Content Page

Description of EN-based QuEChERS extraction method 2

Table S1 Summary of the reported methods for the determination of

OMCs in agricultural soils irrigated with wastewater

conducted under field conditions.

3

Table S2 List of OMCs included in the target analysis and confirmed

analytes after the suspect analysis

6

Table S3 Characterization of the main physical-chemical properties of

the agricultural soils included in the study

9

Table S4 Optimal LC-QqLIT-MS/MS conditions for target analyses 10

Table S5 Recoveries for selected compounds at the different spiking

times tested (20 ng g-1

, n=3)

14

Table S6 Validation data obtained for the proposed method in

agricultural soil

15

Fig. S1. Different QuEChERS variations and clean-up tested in the

present study

17

Fig. S2. Scheme of the different sample spiking conditions tested and

the applied procedure

18

Fig. S3. Recoveries of compounds affected by the presence of PSA 19

2

Description of EN-based QuEChERS extraction method

The EN-based method (European Standard Method EN Code 15662 published by CEN,

European Committee for Standardization) was also evaluated and it was applied as follows: 1 g

of sample was weighed in a 50-ml polypropylene tube. After that, 4 mL of Milli-Q H2O were

added, then shaken in a vortex for 30 s and left for 15 min. 10 mL of ACN and 20 µL of the

extraction surrogate standard solution at 1000 µg L-1

were added to the sample and the tube was

shaken for 5 min. The same volume of extraction quality control solution as in the AOAC

method was added. After shaking the mixture for 5 min, 5 g of anhydrous MgSO4, 1 g of NaCl,

1 g of sodium citrate tribasic dihydrate and 0.5 g of disodium hydrogen citrate sesquihydrate

were added. The tube was then shaken for 5 min and centrifuged at 3500 rpm (5 min).

3

Table S1

Summary of the reported methods for the determination of OMCs in agricultural soils irrigated with wastewater conducted under field conditions.

Country Sampling

site Type of soil

Irrigation

water

Irrigation

practice

Reuse

period Crop Targets

Extraction

and analysis Compounds found

Concentration

Range (ng.g-1

) Reference (DOI)

Spain Garden Type of soil not

provided

WW effluent Pulse

irrigation

- Grass 46 PLE + SPE+

LC-MS/MS

Acetaminophen, Diclofenac,

Ibuprofen, Mefenamic acid,

Phenazone, Bezafibrate,

Gemfibrozil, Nadolol,

Carbamazepine, Caffeine,

Flumequine, Sulfamethoxazole,

Ornidazole, Trimethoprim,

Glyburide, Hydrochlorothiazide

<LOQ - 5.95 10.1016/j.envpol.2017.12.085

China - Sandy clay silty Domestic

and fishpond

WW

- > 20

years

- 2 SLE + SPE +

LC-MS/MS

Tetracycline, Sulfamethazine 5.0 - 21. 10.1016/j.scitotenv.2017.12.008

Cyprus Open-field Sandy clay loam RWW - 3 years Tomato 3 SLE + SPE +

LC-MS/MS

Sulfamethoxazole, Trimethoprim,

Diclofenac

0.06 - 0.98 10.1016/j.watres.2016.11.033

Mexico Open-field Clay agricultural

soil

Municipal

WW

- 100

years

- 9 PLE +

LC-MS/MS

Ciprofloxacin, Enrofloxacin,

Sulfamethoxazole, Trimethoprim,

Clarithromycin, Carbamazepine,

Naproxen, Diclofenac,

Bezafibrate

0.01 - 6.76 10.1371/journal.pone.0045397

Israel Open-field Loamy sand,

Sandy loam,

Sandy clay

RWW Drip

irrigation

3 years Carrot 12 PLE +

LC-MS/MS

Caffeine, Carbamazepine,

Lamotrigine, Metoprolol,

Sildenafil, Sulfamethoxazole,

Sulfadiazine

0.11 - 19.91 10.1016/j.envpol.2013.10.038

4

Spain Farmland

soils

Type of soil not

provided. Only

physicochemical

properties

indicated

Natural

water +

municipal

WW

- - Rice, citrus

orchards,

potato,

cabbage,

wheat, barley

15 USE +

GC-MS/MS

Clofibric acid, Ibuprofen,

Salicylic acid, Allopurinol,

Paracetamol, Gemfibrozil,

Fenoprofen, Amitriptyline,

Metoprolol, Naproxen,

Mefenamic acid, Ketoprofen,

Carbamazepine, Diclofenac,

Fenofibrate

0.7 - 47 10.1007/s11356-013-2438-7

Spain Open-field Silty loam soil RWW +

Amendation

biosolids

- 10

years

amenda

tion

biosoli

ds

Lettuce,

melon,

tomato,

fruit trees

7 - Triclosan, Carbamazepine,

Diazepam

0.03 - 0.95

10.1016/j.chemosphere.2017.05.

049

Israel

(Abstract)

Vadose zone 50% clay Treated

sewage

effluents

- - - 20 - Carbamazepine, 10-hydroxy-

10,11-dihydrocarbamazepine,

Acridone, Acridine,

Oxcarbazepine, Venlafaxine, O-

desmethylvenlafaxine, Caffeine,

Sulfamethoxazole

0.05 – 3.6 10.2136/vzj2014.09.0115

Spain Vadose zone Loamy sand,

Sandy loam and

Silt loam

Recycled

water / /

River water

+ aquifer //

Sludge

amendation

- - Cotton,

beetroot

64 PLE + SPE +

LC-MS/MS

Ketoprofen, Diclofenac,

Acetaminophen, Atenolol,

Metoprolol, Clofibric acid,

Fenofibrate, Carbamazepine,

Clarithromycin, Sulfamethazine,

Famotidine, Hydrochlorothiazide

< LOQ - 1.3

10.1016/j.chemosphere.2014.04.

098

Spain - Type of soil not

provided

RWW - - - 32 PLE + SPE +

LC-MS/MS

Omeprazole, Diazepam, Losartan,

Spironolactone

< LOQ - 24.3

10.1007/s00216-010-3862-x

China - Type of soil not

provided. Only

physicochemical

properties

indicated

Industrial

and

municipal

WW or

ground water

- 50

years

- 43 USE +

LC-MS/MS

Bisphenol-A, Triclocarban,

Triclosan, 4-nonylphenol,

Salicylic acid, Oxytetracycline,

Tetracycline, Trimethoprim,

Primidone

< LOQ – 212

10.1016/j.envpol.2011.03.016

5

Mexico - Type of soil not

provided. Only

physicochemical

properties

indicated

Municipal

WW

Complete

flooding

- Alfalfa and

maize

19 PLE + SPE +

GC-MS

Clofibric acid, Ibuprofen, 2,4-D,

Gemfibrozil, Naproxen,

Ketoprofen, Diclofenac,

Carbamazepine, 4-Nonylphenols,

Triclosan, Bisphenol-A, Di-n-

BuP, BuBeP, DEHP, Estrone,

17β-Estradiol, EE2

< LOD – 2079

10.1016/j.talanta.2009.01.035

USA Gardens and

Golf course

Type of soil not

provided

RWW - Grass 19 PLE +

LC-MS

1, 7-Dimethylxanthine,

Acetaminophen, Caffeine,

Carbamazepine, Cimetidine,

Codeine, Cotinine,

Dehydronifedipine, Diltiazem,

Diphenhydramine, Erythromycin,

Fluoxetine, Gemfibrozil,

Miconazole, Salbutamol,

Sulfamethoxazole,

Thiabendazole, Trimethoprim,

Warfarin

0.02–15 10.1897/05-187R.1

Israel Open field Type of soil not

provided. Only

physicochemical

properties

indicated

RWW and/or

biosolid

amendation

Drip

irrigation

< 4

months

Lettuce,

tomato,

wheat

3 PLE +

LC-MS/MS

Carbamazepine, 10,11-epoxide-

carbamazepine, trans-10,11-

dihydro-10,11-dihydroxy-

carbamazepine

0.49 – 5.85 10.1016/j.envpol.2017.09.029

6

Table S2

List of OMCs included in the target analysis and confirmed analytes after the suspect

analysis.

CAS number Compound Group

Target analytes

83-15-8 4-Acetamidoantipyrine (4AAA) Metabolite

1672-58-8 N-Formyl-4-aminoantipyrine (4FAA) Metabolite

103-90-2 Acetaminophen Analgesic

103-84-4 Acetanilide Analgesic

549-18-8 Amitriptyline Antidepressant

60-80-0 Antipyrine Analgesic

29122-68-7 Atenolol Beta blocker

1912-24-9 Atrazine Herbicide

83905-01-5 Azithromycin Antibiotic

378-44-9 Betamethasone Corticosteroid

41859-67-0 Bezafibrate Antihyperlipoproteinemic agent

58-08-2 Caffeine Stimulant

298-46-4 Carbamazepine Anticonvulsant

36507-30-9 Carbamazepine 10-11 epoxide Metabolite

470-90-6 Chlorfenvinphos Insecticide

120-32-1 Chlorophene Bactericide

59729-33-8 Citalopram Antidepressant

81103-11-9 Clarithromycin Antibiotic

882-09-7 Clofibric acid Lipid modifying Agent

303-49-1 Clomipramine Antidepressant

23593-75-1 Clotrimazole Disinfectant

50-18-0 Cyclophosphamide Chemotherapeutic

439-14-5 Diazepam Benzodiazepine

76824-35-6 Famotidine Antihistaminic

49562-28-9 Fenofibrate Lipid modifying agent

42017-89-0 Fenofibric acid Metabolite

31879-05-7 Fenoprofen Analgesic

42835-25-6 Flumequine Antibiotic

54910-89-3 Fluoxetine Antidepressant

54-31-9 Furosemide Diuretic

25812-30-0 Gemfibrozil Lipid modifying Agent

58-93-5 Hydrochlorothiazide Diuretic

3778-73-2 Ifosfamide Chemotherapeutic

53-86-1 Indomethacin Analgesic

22071-15-4 Ketoprofen Analgesic

74103-06-3 Ketorolac Analgesic

137-58-6 Lidocaine Anesthetic

154-21-2 Lincomycin Antibiotic

79794-75-5 Loratadine Antihistaminic

7

61-68-7 Mefenamic acid Analgesic

96-88-8 Mepivacaine Anesthetic

59263-76-2 Meptazinol Analgesic

83-43-2 Methylprednisolone Corticosteroid

364-62-5 Metoclopramide Nausea inhibitor

37350-58-6 Metoprolol Beta blocker

443-48-1 Metronidazole Antibiotic

42200-33-9 Nadolol Beta-adrenergic antagonist

22204-53-1 Naproxen Analgesic

39562-70-4 Nitrendipine Dihydropyridine calcium channel blocker

93413-62-8 O-Desmethylvenlafaxine Metabolite

611-59-6 Paraxanthine Metabolite

61869-08-7 Paroxetine Antidepressant

6493-05-6 Pentoxifylline Analgesic

81093-37-0 Pravastatin Lipid modifying agent

125-33-7 Primidone Anticonvulsant

525-66-6 Propranolol Adrenergic agent

479-92-5 Propyphenazone Analgesic

66357-35-5 Ranitidine Stomach protector

80214-83-1 Roxythromycin Antibiotic

18559-94-9 Salbutamol Bronchodilator

122-34-9 Simazine Herbicide

3930-20-9 Sotalol Adrenergic agent

68-35-9 Sulfadiazine Antibiotic

57-68-1 Sulfamethazine Antibiotic

144-82-1 Sulfamethizole Antibiotic

723-46-6 Sulfamethoxazole Antibiotic

144-83-2 Sulfapyridine Antibiotic

72-14-0 Sulfathiazole Antibiotic

23031-25-6 Terbutaline Adrenergic agent

58-55-9 Theophylline Bronchodilator/Stimulant

36282-47-0 Tramadol Analgesic

738-70-5 Trimethoprim Antibiotic

93413-69-5 Venlafaxine Antidepressant

Suspect analytes

31161-17-8 2-Ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) Metabolite

260-94-6 Acridine Metabolite

578-95-0 Acridone Metabolite

81403-68-1 Alfuzosin Alpha blocker

71675-85-9 Amisulpride Antipsychotic

169590-42-5 Celecoxib Antiinflammatory

83881-52-1 Cetirizine Antihistaminic

185453-02-5 Desmethyltramadol Metabolite

144025-14-9 Desmethylcitalopram Metabolite

6700-34-1 Dextromethorphan Antitussive

8

147-24-0 Diphenhydramine Antihistaminic

57808-66-9 Domperidone Nausea inhibitor

884740-09-4 Donepezil Alzheimer's disease

144143-96-4 Eprosartan Antihypertensive agent

54143-55-4 Flecainide Anti-arrhythmia agent

138402-11-6 Irbesartan Antihypertensive agent

32780-64-6 Labetalol Antihypertensive agent

84057-84-1 Lamotrigine Anticonvulsant

41100-52-1 Memantine Alzheimer's disease

76-99-3 Methadone Opioid analgesic

98-92-0 Nicotinamide Vitamin B3

34183-22-7 Propafenone Anti-arrhythmia agent

79559-97-0 Sertraline Antidepressant

15676-16-1 Sulpiride Antipsychotic

144701-48-4 Telmisartan Antihypertensive

25332-39-2 Trazodone Antidepressant

396-01-0 Triamterene Diuretic

152-11-4 Verapamil Anti-arrhythmia agent

9

Table S3

Characterization of the main physical-chemical properties of the agricultural soils

included in the study.

Parameter GH1a

GH2 GH3

pH 8.34 7.96 8.53

CE (25ºC) (mmhos/cm) 7.32 16.89 2.38

P. Saturation (%) 22.58 48.84 48.41

SAR 5.93 8.65 2.89

Chlorides (mg/L) 1065 3195 319.50

Sulphates (mg/L) 2520 2915 315

Nitrates (mg/L) 142 2178 355

Magnesium (mg/L) 310 731 50

Calcium (mg/L) 519 1210 168

Sodium (mg/L) 692 1545 166

Potasium (mg/L) 291 375 173

Organic matter (%) 0.74 2.01 1.51

Total Carbonates (%) 2.35 8.62 6.27

Olsen Phosophorum (ppm) 252.00 177.00 115.00

Texture (%) Sandy clay loam Silt loam Loam

Clay (%) 18.00 13.60 15.60

Sand (%) 56.40 24.40 48.40

Silt (%) 25.60 62.00 36.00 aGH: Greenhouse soil sample.

10

Table S4

Optimal LC-QqLIT-MS/MS conditions for the target analytes.

Compound RT

a

(min) ESI

Precursor ion

(m/z)

Product ion

(m/z)

DPb

(V)

EPc

(V)

CEd

(eV)

CXPe

(V)

4-Acetylaminoantipyrine 4.6 + 246.2 228.1 46 5 18 2

83.1 46 5 40 2

4-Formylaminoantipyrine 4.6 + 232.2 214.2 60 5 18 2

77.1 60 5 50 2

Acetaminophen 3.2 + 152.1 110.1 40 5 20 2

64.8 40 5 45 2

Acetanilide 5.6 + 136 94.1 70 10 24 15

77.1 70 11 40 10

Amitriptyline 6.6 + 278.4 233.1 30 5 22 2

91.2 30 5 35 2

Antipyrine 5.3 + 189.2 77.1 48 5 51 2

104.1 48 5 32 2

Atenolol 2.1 + 267.3 190.2 70 5 27 2

145.2 70 5 35 2

Atrazine 7.6 + 216.1 174.1 45 5 24 2

104.1 45 5 40 2

Azithromycin 6.4 + 749.5 591.4 50 12 40 13

83.1 65 5 84 2

Betamethasone 6.6 + 393.3 373.1 70 10 13 20

355.1 70 11 18 20

Bezafibrate 6.7 - 360 274.2 -55 -8 -22 -10

154.1 -55 -8 -35 -10

Caffeine 4.5 + 195.1 138.2 40 5 25 2

110.2 40 5 30 2

Carbamazepine 6.7 + 237.2 194.3 80 5 25 2

192.1 80 5 35 2

Carbamazepine d10 6.6 + 247.2 204.3 80 5 25 2

202.1 80 5 30 5

Carbamazepine-10.11-

Epoxide

6.0 + 253.2 210.2 75 5 20 2

180.2 75 5 40 2

Chlorfenvinphos 9.7 + 359.1 127.1 55 5 21 2

155.2 55 5 15 2

Chlorophene 7.6 - 217 181.2 -75 -8 -25 -10

153.1 -75 -8 -30 -10

Citalopram 6.0 + 325.3 109.1 100 5 30 2

262.1 100 5 25 2

Clarithromycin 6.4 + 748.4 158.4 45 5 35 2

590.4 45 5 26 2

Clomipramine 6.9 + 315.2 86.1 40 5 27 2

11

58.1 40 5 60 2

Clofibric acid 6.7 - 213 127.1 -45 -8 -20 -10

85.1 -45 -8 -12 -10

Clotrimazole 6.9 + 344.9 277.3 30 5 15 2

165.1 30 5 43 2

Cyclophosphamide 6.0 + 261.1 233.2 40 8 30 8

140.1 40 12 23 12

Cyclophosphamide d4 6.0 + 265.2 140.1 80 8 30 15

106.1 80 5 30 5

Diazepam 8.2 + 285.2 154.2 100 12 36 10

193.2 100 12 42 10

Famotidine 2.1 + 338 189.3 25 5 24 2

259.4 25 5 15 2

Fenofibrate 11.5 + 361.2 139.1 60 5 35 2

233.1 60 5 25 2

Fenofibric acid 9.0 + 319.1 139.1 65 5 42 2

233.1 65 5 22 2

Fenoprofen 7.0 - 241.1 197.1 -50 -8 -10 -10

93.1 -50 -8 -50 -8

Flumequine 7.1 + 262.3 244.1 50 5 21 14

202.3 50 5 41 12

Fluoxetine 6.5 + 310.3 44.2 30 5 25 2

148.2 30 5 10 2

Furosemide 6.0 - 329.1 205.1 -60 -10 -30 -10

285.2 -60 -10 -21 -15

Gemfibrozil 7.8 - 249 121.1 -50 -10 -30 -15

127.1 -50 -8 -15 -15

Hydrochlorothiazide 4.7 - 296 269.1 -80 -10 -27 -16

205.1 -80 -10 -40 -14

Ifosfamide 5.9 + 261.1 154.3 60 5 29 2

91.9 60 5 33 2

Indomethacin 8.9 + 358.2 139.1 50 5 25 2

174.3 50 5 15 2

Ketoprofen 7.7 + 255.2 105.1 47 5 33 2

209.2 47 5 16 2

Ketorolac 7.1 + 256.2 105.1 70 5 25 2

178.1 70 5 34 2

Lidocaine 4.9 + 235.0 86.1 70 7 20 5

58.1 70 8 50 4

Lincomycin 4.2 + 407.1 126.3 50 5 45 2

359.3 50 5 23 2

Loratadine 7.2 + 383.1 337.3 50 5 29 2

267.2 50 5 40 2

Mefenamic acid 9.7 + 242.2 224.2 36 5 34 2

180.2 36 5 53 2

Mepivacaine 4.9 + 247.4 98.1 28 5 23 2

12

70.1 28 5 53 2

Meptazinol 5.0 + 233.9 107 202 6 36 18

133 202 6 34 21

Methylprednisolone 7.0 + 475.3 321.1 76 6 29 13

339.3 76 6 29 13

Metoclopramide 5.0 + 300.0 184.1 80 6 42 11

141.1 80 11 66 10

Metoprolol 5.1 + 268.2 159.2 30 5 28 2

116.2 30 5 25 2

Metronidazole 3.3 + 172.1 128.1 35 5 20 2

82.1 35 5 30 2

229.3 55 5 20 2

Nadolol 4.5 + 310.2 254.4 45 5 30 2

201.2 45 5 30 2

Naproxen 7.8 + 231.2 185.1 86 5 17 10

170.1 86 5 35 10

Nitrendipine 8.9 + 361 315 80 10 18 17

329.1 80 10 15 15

O-Desmethylvenlafaxine 4.8 + 264.1 57.9 190 9 50 6

107.1 190 13 25 6

Paraxanthinef 3.3 + 181.2 124.2 50 5 25 2

69.2 50 5 43 2

Paroxetine 6.2 + 330.3 192.2 70 5 25 2

151.2 70 5 30 2

Pentoxifylline 5.4 + 279 181.1 60 10 23 10

138.1 60 10 35 10

Pravastatin 5.5 - 423.3 321.1 -90 -8 -20 -10

100.9 -90 -8 -40 -8

Primidone 5.3 + 219.2 91.1 35 5 35 2

162.3 35 5 16 2

Propranolol 5.7 + 260 116.2 35 5 23 2

183.2 35 5 23 2

Propyphenazone 7.2 + 231.3 201.2 55 5 30 2

189.2 55 5 22 2

Ranitidine 2.4 + 315.3 176.2 38 5 21 2

130.1 38 5 30 2

Roxithromycin 6.4 + 837.5 158.1 140 8 43 15

679.4 140 8 31 10

Salbutamol 2.0 + 240.3 148.2 44 5 26 2

222.2 44 5 14 2

Simazine 6.8 + 202.2 132.1 45 5 26 2

104.1 45 5 34 2

199.1 45 5 15 2

Sotalol 2.4 + 273.3 255.1 140 10 18 11

213.1 140 10 26 11

Sulfadiazine 4.5 + 251.2 92.1 40 5 35 2

13

108.1 40 5 30 2

Sulfamethazine 5.3 + 279.1 156.1 42 5 26 2

124.1 42 5 30 2

Sulfamethizole 5.3 + 271.1 156.1 80 6 20 8

92.1 80 6 37 10

Sulfamethoxazole 6.0 + 254.2 156.1 47 5 21 2

108.1 47 5 30 2

Sulfapyridine 4.8 + 250.1 156.1 47 5 21 2

108.3 47 5 34 2

Sulfathiazole 4.7 + 256.2 156.1 45 5 18 2

92.2 45 5 34 2

Terbutaline 2.0 + 226.3 152.2 47 5 20 2

107.1 47 5 40 2

Theophyllinef 3.3 + 181.1 69.1 50 8 35 12

124.2 50 8 24 19

Tramadol 4.9 + 264 246.1 15 8 15 3

58.1 15 8 7 3

Trimethopim 4.6 + 291.3 230.2 45 5 28 2

123.2 45 5 30 2

Venlafaxine 5.5 + 278.4 58.1 50 5 45 2

260.4 150 10 47 11

aRetention time; bDeclustering potential; cEntrance potential; dCollision energy; eCollision cell exit potential; fConfimation of coeluting compounds; analytical column: Pursuit 3 PFP (150 x 2.0 mm, 3 µm particle size, Agilent

Technologies); flow rate: 0.3 mL min-1; mobile phases: 0.1% formic acid in water (eluent A) and MeOH (eluent B);

chromatographic gradient: 10% B (1 min), increased to 99% within 9 min, kept constant for 4 min and reduced to 10% in

0.1 min. Paraxanthine (Rt: 6.9); Theophylline (Rt: 7.1).

14

Table S5

Recoveries for selected compounds at the different spiking times tested (20 ng g-1

, n=3)

Recovery, % (RSD, %)

Compound 1 h 24 h 48 h 6 days

Acetaminophen 102 (6) 97 (2) 82 (20) 34 (8)

Betamethasone 76 (13) 16 (11) 26 (63) 23 (2)

Furosemide 82 (7) 80 (3) 74 (10) 58 (4)

Methylprednisolone 94 (0) 82 (1) 82 (12) 65 (3)

Ranitidine 101 (6) 58 (2) 47 (9) 23 (3)

Salbutamol 96 (9) 91 (3) 101 (5) 66 (10)

Sulfadiazine 82 (2) 53 (38) 46 (9) 42 (8)

Sulfamethazine 82 (5) 45 (5) 58 (8) 38 (6)

Sulfamethizole 72 (14) 41 (7) 41 (7) 35 (6)

Sulfamethoxazole 86 (3) 48 (4) 63 (12) 37 (9)

Sulfapyridine 90 (4) 63 (14) 60 (15) 48 (3)

Sulfathiazole 75 (4) 47 (7) 48 (16) 42 (9)

Terbutaline 87 (7) 38 (4) 48 (9) 33 (7)

15

Table S6

Validation data obtained for the proposed method in agricultural soil.

Recovery, % (RSD

c, %)

Compound MQL

a

(ng g-1

)

R2 range

MQL-100

(ng g-1

)

MEb

(%) 0.1 ng g

-1 0.5 ng g

-1 1 ng g

-1 5 ng g

-1 20 ng g

-1

4-Acetylaminoantipyrine 0.50 0.993 -16 ND 102 (7) 85 (7) 95 (5) 95 (2)

4-Formylaminoantipyrine 1.00 0.999 -7 ND ND 99 (5) 94 (1) 98 (10)

Acetaminophen 5.00d 0.999 3 ND ND ND 42 (3) 82 (20)

Acetanilide 5.00 0.999 -3 ND ND ND 97 (2) 106 (11)

Amitriptyline 0.50 0.998 -12 ND 79 (8) 69 (1) 76 (7) 63 (11)

Antipyrine 1.00 0.999 1 ND ND 97 (11) 95 (6) 108 (1)

Atenolol 1.00 0.999e -18 ND ND 64 (8) 70 (2) 74 (6)

Atrazine 0.10 0.999 -10 108 (1) 102 (2) 87 (2) 94 (1) 87 (0)

Azithromycin 0.50 0.998 -16 ND 95 (6) 96 (2) 85 (2) 90 (7)

Betamethasone 0.50d 0.999 -7 ND 37 (4) 32 (9) 32 (3) 26 (13)

Bezafibrate 0.10 0.999 6 97 (9) 99 (3) 102 (3) 96 (4) 95 (4)

Caffeine 0.10 0.998 -13 110 (6) 116 (12) 84 (3) 90 (2) 102 (2)

Carbamazepine 0.10 0.999e 15 99 (6) 100 (1) 99 (4) 96 (2) 95 (4)

Carbamaz-Epoxide 0.10 0.996e 10 109 (9) 107 (2) 111 (10) 94 (8) 102 (1)

Chlorfenvinphos 0.10 0.999 -2 93 (5) 97 (1) 96 (7) 96 (5) 82 (10)

Chlorophene 0.50 0.999 -10 ND 75 (8) 76 (11) 84 (6) 66 (1)

Citalopram 0.10 0.999 -4 99 (2) 93 (5) 92 (4) 96 (5) 102 (8)

Clarithromycin 0.10 0.999 -18 86 (3) 88 (3) 100 (7) 84 (10) 89 (5)

Clofibric acid 0.50 0.999 -2 ND 88 (4) 89 (4) 89 (5) 89 (4)

Clomipramine 0.50d 0.998 -18 ND 60 (16) 71 (5) 71 (14) 73 (15)

Clotrimazole 1.00d 0.998 -52 ND ND 47 (81) 167 (29) 37 (25)

Cyclophosphamide 0.50 0.996f 6 ND 102 (7) 99 (7) 103 (1) 100 (3)

Diazepam 0.10 1.000 6 110 (4) 106 (0) 102 (11) 92 (4) 92 (2)

Famotidine 0.50 0.999 -8 ND 71 (3) 62 (17) 79 (12) 81 (7)

Fenofibrate 5.00 0.997 -45 ND ND ND 90 (14) 49 (8)

Fenofibric acid 0.50d 0.999 4 ND 43 (29) 41 (7) 52 (2) 41 (29)

Fenoprofen 5.00 0.999 2 ND ND ND 120 (20) 91 (6)

Flumequine 1.00 0.999 2 ND ND 95 (3) 29 (39) 34 (17)

Fluoxetine 0.10d 0.999 -17 62 (13) 67 (20) 74 (8) 82 (17) 64 (16)

Furosemide 0.50 0.998 3 ND 71 (11) 67 (1) 69 (3) 74 (10)

Gemfibrozil 0.50 0.999 -10 ND 84 (17) 99 (22) 107 (8) 95 (14)

Hydrochlorothiazide 0.10 0.999 4 101 (6) 93 (3) 91 (4) 95 (4) 93 (2)

Ifosfamide 0.10 0.999 -7 101 (2) 99 (5) 107 (4) 96 (2) 102 (1)

Indomethacin 0.50 0.999 8 ND 98 (12) 82 (6) 89 (1) 69 (6)

Ketoprofen 1.00 0.999 0 ND ND 83 (4) 91 (1) 79 (7)

Ketorolac 1.00d 0.999 3 ND ND 66 (4) 70 (2) 63 (12)

Lidocaine 0.50 0.996f 3 ND 96 (6) 94 (4) 95 (2) 104 (3)

Lincomycin 0.10 1.000 0 86 (4) 77 (5) 83 (4) 73 (1) 95 (2)

Loratadine 0.50 0.998 -20 ND 82 (5) 90 (15) 105 (12) 82 (8)

16

Mefenamic acid 0.50 0.999 -10 ND 98 (1) 73 (17) 108 (5) 63 (12)

Mepivacaine 0.10 0.999f 6 86 (4) 88 (9) 88 (6) 85 (5) 99 (1)

Meptazinol 0.50 0.995f -1 ND 91 (6) 77 (2) 84 (4) 94 (1)

Methylprednisolone 5.00 0.999 11 ND ND ND 85 (7) 82 (12)

Metoclopramide 0.10 1.000 0 90 (3) 83 (11) 79 (2) 83 (2) 82 (1)

Metoprolol 0.50 0.998 -9 ND 91 (6) 92 (7) 85 (3) 104 (7)

Metronidazole 0.50 0.999 0 ND 81 (4) 84 (2) 90 (3) 141 (7)

Nadolol 0.50 0.998 -3 ND 79 (5) 75 (7) 79 (3) 88 (3)

Naproxen 5.00 0.999 -16 ND ND ND 93 (2) 79 (3)

Nitrendipine 0.50 0.999 -6 ND 95 (6) 89 (7) 93 (2) 81 (2)

O-Desmethylvenlafaxine 1.00 0.999 -27 ND ND 88 (11) 80 (10) 93 (0)

Paraxanthine 0.50 0.999 1 ND 101 (2) 76 (6) 78 (1) 78 (7)

Paroxetine 1.00 0.999 -23 ND ND 70 (10) 82 (11) 77 (13)

Pentoxifylline 0.10 0.997f 9 98 (3) 93 (1) 102 (3) 98 (3) 110 (3)

Pravastatin 0.50d 0.999 1 ND 125 (1) 142 (32) 84 (17) 78 (5)

Primidone 5.00 0.999 13 ND ND ND 99 (6) 84 (5)

Propranolol 0.50 1.000 -6 ND 88 (3) 89 (1) 87 (5) 98 (3)

Propyphenazone 0.50 0.999 -7 ND 112 (2) 96 (3) 102 (2) 100 (2)

Ranitidine 1.00d 0.999 9 ND ND 23 (3) 26 (9) 47 (9)

Roxithromycin 0.10 0.999 -20 118 (9) 97 (9) 109 (14) 80 (4) 89 (4)

Salbutamol 0.50 0.997e -26 ND 72 (5) 69 (12) 66 (2) 101 (5)

Simazine 0.50 0.999 0 ND 101 (4) 78 (3) 94 (1) 91 (2)

Sotalol 0.50 0.999 -11 ND 115 (5) 89 (6) 90 (2) 112 (2)

Sulfadiazine 0.50d 0.999 -25 ND 46 (10) 27 (28) 44 (5) 46 (9)

Sulfamathazine 1.00d 0.999 -18 ND ND 54 (2) 59 (2) 58 (8)

Sulfamethizole 1.00d 1.000 0 ND ND 40 (21) 47 (4) 41 (7)

Sulfametoxazole 0.50d 0.999 3 ND 86 (24) 64 (9) 57 (15) 63 (12)

Sulfapyridine 0.50d 1.000 -16 ND 53 (17) 60 (14) 71 (7) 60 (15)

Sulfathiazole 1.00d 0.999 -15 ND ND 51 (7) 51 (9) 48 (16)

Terbutaline 0.50d 0.999 -41 ND 52 (6) 44 (14) 45 (4) 48 (9)

Theophylline 5.00 0.999 1 ND ND ND 77 (1) 77 (5)

Tramadol 0.50 0.999 -13 ND 85 (6) 77 (4) 80 (2) 89 (3)

Trimethopim 0.50 0.999 -21 ND 86 (9) 91 (8) 93 (2) 114 (18)

Venlafaxine 1.00 0.999 -6 ND ND 83 (4) 73 (3) 83 (3) aMQL: Method quantification limit; bME: Matrix effect calculated: cRSD: Relative standard deviation; dThis value corresponds

to the LOQ; eLinear range MQL-10 ng g-1; fLinear range MQL-50 ng g-1.

17

Fig. S1. Different QuEChERS variations and clean-up tested in the present study.

18

Fig. S2. Scheme of the different sample spiking conditions tested and the applied

procedure.

19

Fig. S3. Recoveries of compounds affected by the presence of PSA