supplementary material to the paper entitled ......list of omcs included in the target analysis and...
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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: [email protected], 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
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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).
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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
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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
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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
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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
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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
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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
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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.
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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
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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
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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
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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).
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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)
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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)
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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.
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Fig. S1. Different QuEChERS variations and clean-up tested in the present study.
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Fig. S2. Scheme of the different sample spiking conditions tested and the applied
procedure.
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Fig. S3. Recoveries of compounds affected by the presence of PSA