Analytical and Bioanalytical Chemistry Electronic ...10.1007/s00216-014-7819... · Analytical and...

44
Analytical and Bioanalytical Chemistry Electronic Supplementary Material Highly sensitive determination of 68 psychoactive pharmaceuticals, illicit drugs, and related human metabolites in wastewater by liquid chromatography – tandem mass spectrometry V. L. Borova, N. C. Maragou, P. Gago-Ferrero, C. Pistos, Ν .. S. Τhomaidis

Transcript of Analytical and Bioanalytical Chemistry Electronic ...10.1007/s00216-014-7819... · Analytical and...

Page 1: Analytical and Bioanalytical Chemistry Electronic ...10.1007/s00216-014-7819... · Analytical and Bioanalytical Chemistry Electronic Supplementary Material ... 59729-33-8 Citalopram

Analytical and Bioanalytical Chemistry

Electronic Supplementary Material

Highly sensitive determination of 68 psychoactive pharmaceuticals,

illicit drugs, and related human metabolites in wastewater by liquid

chromatography – tandem mass spectrometry

V. L. Borova, N. C. Maragou, P. Gago-Ferrero, C. Pistos, Ν.. S. Τhomaidis

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Table S1. Analyte names, CAS number, chemical structure, molecular formula, molecular weight, pKa and logKow of the analytes

n/n Compound

class

CAS

Number Compound Chemical structure

Empirical

formula

Molecular

Weight

(g/mol)

pKa logKow

1

Opiates, opioids

and metabolites

57-27-2 Morphine (MOR)

C17H19NO3 285.34

8.0, 9.9a/

(13.5, 9.5,

8.3)b

0.72c

2 2784-73-8 6-Monoacetylmorphine

(6-MAM)

C19H21NO4 327.37 - 1.72c

3 76-99-33 Methadone (METH)

C21H27NO 309.45 8.94a/(9.1)b 4.17c

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4 30223-73-5 EDDP

C20H23N 277.41 (8.4)b 4.94c

5 76-57-3 Codeine (COD)

C18H21NO3 299.36 8.2a/(13.4,

8.2)b 1.28c

6 76-42-6 Oxycodone (OC)

C18H21NO4 315.36 8.9a/(13.1,

7.6)b 0.66c

7 52485-79-7 Buprenorphine (BN)

C29H41NO4 467.64 8.5, 10.0a/

(9.5, 8.3)b

4.90c

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8

Stimulants

(cocaine

compounds)

50-36-2 Cocaine (COC)

C17H21NO4 303.15 8.6a/(8.9)b 2.17c

9 519-09-5 Benzoylecgonine

(BECG)

C16H19NO4 289.33 11.8a/(10.8,

3.3)b -1.32c

10 7143-09-1 Ecgonine methylester

(EME)

C10H17NO3 199.25 9.16a -0.29c

11

Stimulants

(amphetamines)

42542-10-9 MDMA

C11H15NO2 193.24 9.4a/(10.3)b 2.28c

12 82801-81-8 MDEA

C12H17NO2 207.27 (10.3)b 2.77c

13 4764-17-4 MDA

C10H13NO2 179.22 9.67a/(9.9)b 1.84c

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14 537-46-2 Methamphetamine (MA)

C10H15N 149.23 10.1a/(10.4)b 2.22c

15 300-62-9 Amphetamine

C9H13N 135.21 10.1a/(9.9)b 1.76c

16

Hallucinogenic

(cannabinoids)

1972-08-3 Δ9-THC

C21H30O2 314.46 10.6a 7.60c

17 56354-06-4 11-nor-Δ9-THC acid

C21H28O4 344.44 4.7a 6.36c

18 Hallucinogenic

(LSD) 50-37-3 LSD

C20H25N3O 323.43 7.5a/(7.4)b 2.26c

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19 - 2-oxo-3-hydroxy-LSD

C20H25N3O3 355.43 (11.7, 6.8)b -

20

Benzodiazepines

tranquilizers

92623-85-3 Alprazolam

C17H13ClN4 308.76 8.2a 3.87c

21 1812-30-2 Bromazepam

C14H10BrN3O 316.15 2.5, 5.2, 11.8a 1.93c

22 58-25-3 Chlordiazepoxide

C16H14ClN3O 299.75 4.8a/ (8.6, 6.5)b -1.57c

23 22316-47-8 Clobazam

C16H13ClN2O2 300.74 1.6a 1.94c

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24 439-14-5 Diazepam

C16H13ClN2O 284.74 3.3a 2.70c

25 1088-11-5 Nordiazepam

C15H11ClN2O 270.71

12.0,

3.5a/(11.7,

3.2)b

3.89c

26 1622-62-4 Flunitrazepam

C16H12FN3O3 313.28 1.71a 1.91

27 34084-50-9 7-amine-flunitrazepam

C16H14FN3O 283.30 - 0.78

28 846-49-1 Lorazepam

C15H10Cl2N2O2 321.16 1.3, 11.5a 3.98

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29 146-22-5

Nitrazepam

C15H11N3O3 281.30

3.2,

10.8a/(11.4,

2.6)b

2.45c

30 59467-70-8 Midazolam

C18H13ClFN3 325.77 6.15, 1.7a 4.33c

31 604-75-1 Oxazepam

C15H11ClN2O2 286.71

11.6,

1.7a/(12.8,

10.9, 1.2)b

3.34c

32 846-50-4

Temazepam

C16H13ClN2O2 300.74 1.6a/(11.7,1.6)b 2.15c

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33

Barbiturates

50-06-6 Phenobarbital

C12H12N2O3 232.24 7.48a

1.33c

34 76-74-4 Pentobarbital

C11H18N2O3 226.27 7.94a

2.00c

35

Antipsychotics

50-53-3 Chlorpromazine

C17H19ClN2S 318.86 9.32a 4.32c

36 5786-21-0 Clozapine

C18H19ClN4 326.82 3.58, 7.94a 3.35c

37 6104-71-8 Norclozapine

C17H17ClN4 312.80 - 3.01c

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38 132539-06-1 Olanzapine

C17H20N4S 312.43 5.0, 7.4a 2.56c

39 106266-06-2 Risperidone

C23H27FN4O2 410.48 8.3a 3.49c

40 147687-18-1

9-OH-Risperidone

C23H27FN4O3 426.48 - 1.95c

41

Anesthetics

137-58-6 Lidocaine

C14H22N2O 234.34 7.96a

1.66c

42 437-38-7 Fentanyl

C22H28N2O 336.47 8.99a/(8.9,

0.3)b

3.89c

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43 1609-66-1 Norfentanyl

C14H20N2O 232.32 (9.8, 0.3)b 1.70c

44 76-75-5 Thiopental

C11H18N2O2S 242.34 7.4a/(10.72)b 2.87c

45 1867-66-9 Ketamine

C13H16ClNO 237.73 7.5a/(6.5)b

3.12c

46 35211-10-0

Norketamine

C12H14ClNO 223.7 6.7a 2.66c

47 Antiepileptic 298-46-4 Carbamazepine

C15H12N2O 236.27 4.17,12.49a 2.25c

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48 84057-84-1 Lamotrigine

C9H7Cl2N5 256.09 5.7a/(19.22)b 0.99c

49 97240-79-4 Topiramate

C12H21NO8S 339.37 8.66a -0.33c

50 102767-28-2 Levetiracetam

C8H14N2O2 170.21 <-2a -0.49c

51 57-41-0 Phenytoin

C15H12N2O2 252.27 8.33a 2.16c

52 125-33-7 Primidone

C12H14N2O2 218.26 11.6a 0.73c

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53 99-66-1 Valproic acid

C8H16O2 144.21 4.6a 2.96c

54

Tricyclic

antidepressants

(TCAs)

50-48-6 Amitriptylline

C20H23N 277.40 9.4a 4.95c

55 894-71-3 Nortriptyline

C19H21N 263.4 10.1a 4.74c

56 303-49-1 Clomipramine

C19H23ClN2 314.85 9.38a 5.25c

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57 50-49-7 Imipramine

C19H24N2 280.41 9.62a 5.01c

58 1668-19-5

Doxepine

C19H21NO 279.38 8.0a 3.86d

59

Tetracyclic

antidepressants

(TeCAs)

61337-67-5 Mirtazapine

C17H19N3 265.35 7.1a 3.03c

60 - 8-OH mirtazapine

C17H19N3O 281.36 - -

61

SSRIs

(serotonin

replacing

inhibitors)

59729-33-8

Citalopram

C20H21FN2O 324.39 9.38a 3.74c

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62 54910-89-3 Fluoxetine

C17H18F3NO 309.33 (10.1)b 4.65c

63 61869-08-7 Paroxetine

C19H20FNO3 329.37 9.51a 2.57c

64 79617-96-2 Sertraline

C17H17Cl2N 306.23 9.48a 5.29c

65 87857-41-8 Norsertraline

(Desmethylsertraline)

C16H15Cl2N 292.20 - 4.82c

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66

SNRIs

(Serotonin–

norepinephrine

reuptake

inhibitors)

93413-69-5 Venlafaxine

C17H27NO2 277.40 (9.3)b 3.28c

67

Sympathomimetic

299-42-3 Ephedrine

C10H15NO 165.23 9.6a/(9.5)b 0.68c

68 492-41-1 Norephedrine

C9H13NO 151.21 (12.1, 8.5)b 0.22c

aexperimental pka; btheoretically pka; cKOWWIN v1.67 estimate, (EPI: Estimation Program Interface (EPI) Suite) (from EPA US environmental protection 

agency) http://www.epa.gov/opptintr/exposure/pubs/episuite.htm 

(‐): Data not available

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Table S2. Total Ion Chromatographs and optimum MS source conditions

Column:

reversed-phase, fused-core PentaFluoroPhenyl (PFP)

Positive mode, ESI (+) Spray Voltage: 3500 V

Sheath Gas: 30 a.u

Aux. Gas: 10 a.u

Capillary Temperature: 270°C

Negative mode, ESI (-) Spray Voltage: 2500 V

Sheath Gas: 10 a.u

Aux. Gas: 7 a.u

Capillary Temperature: 300°C

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50 

100 

150 

200 

250 

300 

350 

400 

450 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Opiates, Opioids and Metabolites

MOR

6MAM

EDDP

COD

OC

50 

100 

150 

200 

250 

300 

350 

400 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Cocaine and Metabolites

COC

BECG

EME

100 

200 

300 

400 

500 

600 

Nor

mal

ized

pea

k ar

ea

Mobile phase

THC/THCA, LSD/8-OH-LSD

THC

LSD

THCA

OH-LSD

50 

100 

150 

200 

250 

300 

350 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Amphetamines

AMP MDMA MDEA MDA MA

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50 

100 

150 

200 

250 

300 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Benzodiazepines

Alprazolam Nordiazepam Flunitrazepam 7-Amino-Flunitrazepam Bromazepam Diazepam

100 

200 

300 

400 

500 

600 

700 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Antipsychotics

Clorpromazine Olanzapine Clozapine Venlafaxine Risperidone 9-OH-Risperidone

50 

100 

150 

200 

250 

300 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Anesthetic

Lidocaine

Fentanyl

Norfentanyl

Ketamine

50 

100 

150 

200 

250 

300 

350 

400 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Antidepressants

Mirtazapine 8-OH-Mirtazapine Clomipramine Amitriptyline Imipramine

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50 

100 

150 

200 

250 

300 

350 

400 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Antiepileptics

Levetiracetam

Carbamazepine

20 

40 

60 

80 

100 

120 

140 

Nor

mal

ized

pea

k ar

ea

Mobile phase

SSRIs'

Fluoexetine

Paroxetine

50 

100 

150 

200 

250 

300 

350 

400 

450 

Nor

mal

ized

pea

k ar

ea

Mobile phase

Ephedrine/Norephedrine

Ephedrine

Norephedrine

Fig. S1. Influence of different mobile phases on the peak areas of target compounds

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Table S3. ESI-MS/MS fragmentation patterns of target compounds

n/n  Compound class Compound Chemical structure

1

Opiates, opioids and

metabolites

Morphine (MOR)

2 6-Monoacetylmorphine

(6-MAM)

3 Methadone (METH)

4 EDDP

5 Codeine (COD)

6 Oxycodone (OC)

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7 Buprenorphine (BN)

8

Stimulants

(cocaine

compounds)

Cocaine (COC)

9 Benzoylecgonine

(BECG)

10 Ecgonine methylester

(EME)

11

Stimulants

(amphetamines)

MDMA

12 MDEA

13 MDA

14 Methamphetamine

(MA)

15 Amphetamine

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16

Hallucinogenic

(cannabinoids)

Δ9-THC

17 11-nor-Δ9-THC acid

18

Hallucinogenic

(LSD)

LSD

19 2-oxo-3-hydroxy-LSD

20

Benzodiazepines

tranquilizers

Alprazolam

21 Bromazepam

22 Chlordiazepoxide

23 Clobazam

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24 Diazepam

25 Nordiazepam

26 Flunitrazepam

27 7-amine-flunitrazepam

28 Lorazepam

29 Nitrazepam

30 Midazolam

31 Oxazepam

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32 Temazepam

33

Barbiturates

Phenobarbital

34 Pentobarbital

35

Antipsychotics

Chlorpromazine

36 Clozapine

37 Norclozapine

(Desmethylclozapine)

38 Olanzapine

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39 Risperidone

40 9-OH-Risperidone

41

Anesthetics

Lidocaine

42 Fentanyl

43 Norfentanyl

44 Thiopental

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45 Ketamine

46 Norketamine

47

Antiepileptic

Carbamazepine

48 Lamotrigine

49 Topiramate

50 Levetiracetam

51 Phenytoin

52 Primidone

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53 Valproic acid

54

Tricyclic

antidepressants

(TCAs)

Amitryptilline

55 Nortriptyline

56 Clomipramine

57 Imipramine

58 Doxepine

59 Tetracyclic

antidepressants

(TeCAs)

Mirtazapine

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60 8-OH mirtazapine

61

SSRIs

(serotonin replacing

inhibitors)

Citalopram

62 Fluoxetine

63 Paroxetine

64 Sertraline

65 Norsertraline

(Desmethylsertraline)

66

SNRIs

(Serotonin–

norepinephrine

reuptake inhibitors)

Venlafaxine

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67

Sympathomimetic

Ephedrine

68 Norephedrine

 

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Table S4. Concentrations of psychiatric and illicit drugs in influents and effluent wastewaters of Santorini

n Compound

class Compound Kamari Fira Karterados Emporio Ia

Influent

(ng/L)

Effluent

(ng/L)

Influent

(ng/L)

Effluent

(ng/L)

Influent

(ng/L)

Effluent

(ng/L)

Influent

(ng/L)

Effluent

(ng/L)

Influent

(ng/L)

Effluent

(ng/L)

1

Opiates, Opioids

and metabolites

MOR 19.8 2.6 9.6 <LOD 4.6 <LOD 1.8 <LOD 7.8 <LOD

2 6-MAM <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

3 METH 0.9 4.4 5.6 2.9 <LOD <LOD <LOD 0.6 3.4 <LOD

4 EDDP 2.3 6.3 4.4 6.5 1.2 1.6 1.6 <LOD <LOD <LOD

5 COD 1632 71.9 222.9 111.9 154.5 55.9 97.5 <LOD 85.3 6.7

6 OC 46.8 10.5 43.7 <LOD 15.8 <LOD 27.2 7.9 34.0 <LOD

7 BN 43.7 <LOD 45.2 <LOD 174.5 <LOD <LOD <LOD 36.0 23.6

8 Cocaine and

metabolites

COC 10.2 3.2 9.8 11.4 4.4 <LOD 21.6 <LOD 49.3 <LOD

9 BECG 57.9 3.3 86.9 77.2 9.0 <LOD 81.3 9.4 104.6 <LOD

10 EME 226.9 125.0 212.5 198.4 234.5 117.2 284.2 132.6 114.7 24.2

11

Amphetamines

MDMA <LOD 1.4 <LOD 2.0 2.2 7.8 1.4 0.9 1.0 <LOD

12 MDEA 1.0 0.7 1.2 0.4 0.3 0.3 0.5 <LOD <LOD 1.0

13 MDA <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

14 MA <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

15 Amph 8.9 <LOD 10.0 <LOD 7.5 <LOD 5.0 <LOD <LOD <LOD

16 Cannabinoids

Δ9-THC 31.7 7.8 25.5 17.1 9.4 3.9 31.1 22.0 2.8 1.2

17 Δ9-THCA 11.7 30.2 74.4 28.0 237.8 40.9 587.3 40.6 14.2 33.3

18 LSD

LSD 0.7 0.5 1.5 <LOD <LOD <LOD <LOD <LOD <LOD 0.3

19 OH-LSD 42.7 42.7 4.8 22.6 <LOD 27.5 26.8 34.6 9.7 52.1

20

Benzodiazepines

Alprazolam 17.3 10.3 42.0 2.9 11.6 6.4 10.5 7.1 6.6 2.6

21 Bromazepam 315.9 76.4 100.7 87.0 165.5 51.9 73.5 47.5 52.4 33.8

22 Chlordiazepoxide <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

23 Clobazam 2.4 <LOD <LOD <LOD <LOD <LOD 6.4 <LOD <LOD <LOD

24 Diazepam 1.4 <LOD <LOD 1.8 <LOD <LOD <LOD <LOD <LOD <LOD

25 Nordiazepam 1.4 2.9 1.5 2.6 1.6 3.9 3.1 3.9 0.6 4.7

26 Flunitrazepam <LOD 8.5 <LOD 10.3 <LOD <LOD <LOD <LOD <LOD <LOD

27 7-amine-

flunitrazepam 15.6 <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

28 Lorazepam 30.0 16.0 24.2 8.3 18.3 11.3 17.9 22.5 13.1 26.6

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29 Nitrazepam <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

30 Midazolam 0.9 0.6 <LOD 0.4 0.5 <LOD <LOD 0.3 0.7 <LOD

31 Oxazepam 62.7 61.3 35.5 26.8 24.5 18.4 38.4 74.1 19.7 5.8

32 Temazepam 2.8 15.9 151.7 22.9 19.3 12.3 20.6 13.0 15.8 3.4

33 Barbiturates

Phenobarbital <LOD <LOD <LOD <LOD <LOD 127.3 <LOD 70.3 <LOD <LOD

34 Pentobarbital 9.9 <LOD <LOD <LOD <LOD <LOD 9.0 <LOD 35.2 <LOD

35

Antipsychotics

Chlorpromazine <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

36 Clozapine <LOD <LOD <LOD <LOD 19.8 47.7 <LOD <LOD <LOD <LOD

37 Norclozapine 3.0 <LOD 2.8 0.4 2.6 9.7 <LOD 0.5 <LOD 1.5

38 Olanzapine <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

39 Risperidone 0.5 1.0 <LOD 0.6 0.5 0.6 3.2 0.4 0.4 0.4

40 9-OH-

Risperidone 2.0 6.1 2.3 3.8 11.8 6.6 1.6 6.2 0.7 0.4

41

Anesthetics

Lidocaine 37.5 102.3 355.7 174.4 13.5 142.0 180.1 145.7 15.3 <LOD

42 Fentanyl <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

43 Norfentanyl 2.5 0.5 1.9 0.4 1.1 2.6 0.9 1.2 1.7 <LOD

44 Thiopental <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

45 Ketamine <LOD <LOD 6.1 <LOD <LOD <LOD <LOD <LOD <LOD <LOD

46 Norketamine 6.7 11.9 7.0 <LOD 9.9 8.8 7.8 <LOD <LOD <LOD

47

Antiepileptic

Carbamazepine 6822 94.0 1586 2200 9.7 21.3 772.4 528.9 273.9 171.7

48 Lamotrigine 316.7 469.0 334.0 155.1 388.1 391.4 19.1 107.5 55.0 12.2

49 Topiramate 260.8 155.8 26.9 98.2 815.2 98.8 206.2 322.2 35.0 9.4

50 Levetiracetam 5554 12.3 282.4 93.4 343.1 24.3 5819 35.4 1161 49.2

51 Phenytoin <LOD <LOD <LOD <LOD <LOD 53.0 <LOD 124.6 <LOD <LOD

52 Primidone <LOD 55.5 191.5 168.8 <LOD <LOD 102.3 293.6 <LOD <LOD

53 Valproic acid 1006 232.8 3008 264.3 1571 321.6 366.4 202.8 916.1 790.3

54

TCAs

Amitriptylline 98.2 59.5 95.1 43.8 35.6 11.3 35.3 16.9 30.7 <LOD

55 Nortriptyline 7.0 23.2 6.5 3.6 8.4 1.9 3.9 3.9 4.6 <LOD

56 Clomipramine 2.3 4.3 1.5 2.1 5.3 3.2 6.9 1.9 <LOD <LOD

57 Imipramine <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

58 Doxepin 564.8 316.0 303.2 93.8 669.9 227.1 574.3 270.4 262.2 50.4

59

TeCAs

Mirtazapine 178.2 57.1 39.6 35.7 50.1 32.4 55.0 43.8 39.2 <LOD

60 8-OH

mirtazapine 91.8 1.9 21.9 1.8 16.5 9.5 4.9 4.2 38.4 1.3

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61

SSRIs

Citalopram 540.6 766.2 298.3 407.0 176.3 285.1 323.3 356.6 109.7 19.9

62 Fluoxetine 19.5 16.6 17.4 23.6 0.7 9.3 10.2 14.4 6.9 0.7

63 Paroxetine 9.1 <LOD 17.3 <LOD 3.7 4.4 30.2 <LOD <LOD <LOD

64 Sertraline 19.0 11.9 40.8 12.4 12.7 8.5 31.3 9.7 44.5 0.5

65 Norsertraline 21.6 10.4 12.5 <LOD 24.4 15.2 <LOD 12.2 87.2 14.7

66 SNRIs Venlafaxine 733.0 392.5 330.5 350.0 209.7 327.8 236.0 353.7 231.5 340.1

67 Sympathomimetic

Ephedrine 3249 165.8 6784 319.5 961.8 113.5 1241 41.1 1525 135.5

68 Norephedrine 10.4 <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD

<LOD: Below limit of detection

 

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Table S5. SRM chromatograms of the compounds in spiked wastewater samples

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RT: 15.85AA: 15277445SN: 18717

RT: 2.88AA: 1173026SN: 1044 RT: 11.59

AA: 363726SN: 450

RT: 18.47AA: 78569SN: 129

NL: 5.14E5m/z= 90.70-91.70 F: + c ESI SRM ms2 [email protected] [91.000-91.400, 118.800-119.200] MS ICIS XC_SPIK_01_06

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RT: 18.47AA: 18216794SN: 93427

RT: 21.94AA: 46691SN: 536

RT: 8.78AA: 87947SN: 473

NL: 9.38E5m/z= 162.50-163.50 F: + c ESI SRM ms2 [email protected] [134.800-135.200, 162.800-163.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 20.63AA: 18941812SN: 32062

RT: 22.86AA: 123553SN: 228

RT: 15.92AA: 61812SN: 126

RT: 11.33AA: 71226SN: 96

NL: 8.57E5m/z= 162.50-163.50 F: + c ESI SRM ms2 [email protected] [134.800-135.200, 162.800-163.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 16.96AA: 12210202SN: 2214

RT: 15.39AA: 845273SN: 270

NL: 5.48E5m/z= 162.50-163.50 F: + c ESI SRM ms2 [email protected] [134.800-135.200, 162.800-163.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 18.07AA: 16439906SN: 42809

RT: 21.15AA: 172544SN: 517

NL: 6.98E5m/z= 90.70-91.70 F: + c ESI SRM ms2 [email protected] [91.000-91.400, 118.900-119.300] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 19.94AA: 24952451SN: 38929

NL: 9.74E5m/z= 85.80-86.80 F: + c ESI SRM ms2 [email protected] [58.200-58.600, 86.100-86.500] MS ICIS XC_SPIK_01_06

Amphetamine  MDMA  MDEA 

MDA  Methamphetamine  Lidocaine 

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 27.74AA: 95254458SN: 70551

NL: 2.94E6m/z= 187.50-188.50 F: + c ESI SRM ms2 [email protected] [104.900-105.300, 187.800-188.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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5

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RT: 19.42AA: 6026032SN: 109546

NL: 3.56E5m/z= 83.70-84.70 F: + c ESI SRM ms2 [email protected] [84.000-84.400, 176.800-177.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 21.19AA: 20132428SN: 10622

NL: 6.33E5m/z= 124.50-125.50 F: + c ESI SRM ms2 [email protected] [124.800-125.200, 206.700-207.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 19.25AA: 52160302SN: 6518

NL: 2.48E6m/z= 206.40-207.40 F: + c ESI SRM ms2 [email protected] [124.800-125.200, 206.700-207.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 35.01

0 5 10 15 20 25 30 35Time (min)

0

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RT: 12.07AA: 10633SN: 2741

12.722.33 33.9524.713.39 13.968.59 25.5520.2216.24 29.46 31.658.08 10.55 23.72

NL: 1.27E3m/z= 57.80-58.80 F: - c ESI SRM ms2 [email protected] [58.100-58.500, 100.600-101.000] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 32.99AA: 14087881SN: 77222

RT: 35.22AA: 113259SN: 1872

NL: 4.07E5m/z= 85.70-86.70 F: + c ESI SRM ms2 [email protected] [58.200-58.600, 86.000-86.400] MS ICIS XC_SPIK_01_06

Fentanyl  Norfentanyl  Ketamine 

Norketamine  Thiopental  Clomipramine 

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RT: 29.84AA: 19647913SN: 20716

NL: 6.74E5m/z= 232.50-233.50 F: + c ESI SRM ms2 [email protected] [190.800-191.200, 232.800-233.200] MS ICIS XC_SPIK_01_06

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 29.78AA: 10808198SN: 66698

RT: 25.79AA: 409286SN: 3624 RT: 31.55

AA: 186033SN: 1058

NL: 4.05E5m/z= 85.70-86.70 F: + c ESI SRM ms2 [email protected] [58.200-58.600, 86.000-86.400, 233.800-234.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 21.46AA: 23743292SN: 44510

NL: 8.74E5m/z= 194.50-195.50 F: + c ESI SRM ms2 [email protected] [194.800-195.200, 208.800-209.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 17.80AA: 12422844SN: 221624

NL: 8.62E5m/z= 210.40-211.40 F: + c ESI SRM ms2 [email protected] [210.700-211.100, 224.700-225.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 29.12AA: 29634416SN: 233839

RT: 30.89AA: 209894SN: 1645

NL: 1.45E6m/z= 232.50-233.50 F: + c ESI SRM ms2 [email protected] [91.000-91.400, 232.800-233.200] MS ICIS XC_SPIK_01_06

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 26.98AA: 5006586SN: 4701

25.80

23.44

28.6818.20 35.09 38.83 44.26 49.04 51.4613.759.43 62.662.88 53.497.33

NL: 3.90E5m/z= 106.60-107.60 F: + c ESI SRM ms2 [email protected] [106.900-107.300, 234.800-235.200] MS ICIS XC_SPIK_01_06

Amitriptyline  Imipramine  Mirtazapine 

Nortryptiline  Doxepine 8‐OH‐Mirtazapine 

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RT: 9.79AA: 9312270SN: 2614

NL: 1.87E5m/z= 125.60-126.60 F: + c ESI SRM ms2 [email protected] [125.900-126.300, 153.800-154.200] MS ICIS X_SPIK_01_06

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0

50000

100000

150000

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250000

300000

350000

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450000

500000

550000

600000

650000

700000

750000

800000

850000

900000

950000

1000000

1050000

1100000

1150000

1200000

1250000

1300000

1350000

1400000

1450000

Intensi

ty

RT: 15.75AA: 15380646SN: 14999

NL: 1.49E6m/z= 193.50-194.50 F: + c ESI SRM ms2 [email protected] [191.800-192.200, 193.800-194.200] MS ICIS X_SPIK_01_06

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0

10000

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90000

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110000

120000

130000

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150000

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ty

RT: 14.27AA: 2537984SN: 30400

NL: 1.82E5m/z= 161.50-162.50 F: + c ESI SRM ms2 [email protected] [91.000-91.400, 161.800-162.200] MS ICIS X_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 18.93AA: 5207280SN: 51085

NL: 3.67E5m/z= 158.50-159.50 F: + c ESI SRM ms2 [email protected] [158.800-159.200, 165.800-166.200] MS ICIS SPIKE_C

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RT: 16.63AA: 11203326SN: 396305

RT: 19.54AA: 65587SN: 2462

RT: 17.91AA: 139593SN: 2385

RT: 8.99AA: 47625SN: 1874

RT: 15.82AA: 51554SN: 1809

NL: 1.05E6m/z= 264.50-265.50 F: + c ESI SRM ms2 [email protected] [206.700-207.100, 264.800-265.200] MS ICIS SPIKE_C

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0 5 10 15 20 25 30 35Time (min)

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RT: 10.81AA: 166090SN: 1853

RT: 1.89AA: 470SN: 24

RT: 9.77AA: 411SN: 19

11.248.986.144.39 30.8015.03 19.04 23.88 25.5422.02 32.3228.14

NL: 1.41E4m/z= 207.40-208.40 F: - c ESI SRM ms2 [email protected] [102.000-102.400, 207.700-208.100] MS ICIS XC_SPIK_01_06

Levetiracetam 

8‐OH‐Mirtazapine 

Carbamazepine  Primidone 

Lamotrigine  Topiramate  Phenytoin 

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RT: 12.98AA: 717691SN: 280

13.64

4.00

3.87 4.22

3.549.94

12.593.2712.17 14.08

4.9614.999.615.13

9.136.45 15.5228.34 31.8226.7916.52 32.3725.5723.6517.73

22.86

NL: 5.44E4m/z= 142.70-143.70 F: - c ESI SRM ms2 [email protected] [143.000-143.400] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 36.97AA: 22436790SN: 7164

NL: 1.33E5m/z= 255.40-256.40 F: + c ESI SRM ms2 [email protected] [212.700-213.100, 255.700-256.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 31.60AA: 5707211SN: 62252

NL: 2.01E5m/z= 85.70-86.70 F: + c ESI SRM ms2 [email protected] [86.000-86.400, 245.600-246.000] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 26.82AA: 29354128SN: 130522

RT: 29.64AA: 263591SN: 1161

NL: 1.17E6m/z= 269.40-270.40 F: + c ESI SRM ms2 [email protected] [191.700-192.100, 269.700-270.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 27.08AA: 11698106SN: 68312

RT: 29.64AA: 69011SN: 780

NL: 4.05E5m/z= 191.40-192.40 F: + c ESI SRM ms2 [email protected] [191.700-192.100, 269.700-270.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 28.99AA: 59122582SN: 43823

NL: 1.62E6m/z= 190.50-191.50 F: + c ESI SRM ms2 [email protected] [109.900-110.300, 190.800-191.200] MS ICIS XC_SPIK_01_06

Chlorpromazine Olanzapine 

Clozapine  Norclozapine  Risperidone 

Valproic Acid 

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RT: 23.82AA: 33608111SN: 169275

RT: 17.20AA: 203491SN: 2431

RT: 26.37AA: 202625SN: 1135

NL: 1.51E6m/z= 206.40-207.40 F: + c ESI SRM ms2 [email protected] [109.800-110.200, 206.700-207.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 32.32AA: 10165358SN: 53310

NL: 3.69E5m/z= 274.30-275.30 F: + c ESI SRM ms2 [email protected] [158.700-159.100, 274.600-275.000] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 31.34AA: 2519879SN: 4693

NL: 1.26E5m/z= 274.30-275.30 F: + c ESI SRM ms2 [email protected] [158.700-159.100, 274.600-275.000] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

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20

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65

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RT: 23.22AA: 14028932SN: 3871

NL: 7.56E5m/z= 259.50-260.50 F: + c ESI SRM ms2 [email protected] [120.900-121.300, 259.800-260.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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10

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RT: 29.26AA: 4394475SN: 43404

RT: 30.31AA: 136094SN: 1313

NL: 2.35E5m/z= 191.50-192.50 F: + c ESI SRM ms2 [email protected] [134.800-135.200, 191.800-192.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 30.50AA: 190562SN: 22053

NL: 9.91E3m/z= 44.00-45.00 F: + c ESI SRM ms2 [email protected] [44.300-44.700, 91.100-91.500] MS ICIS XC_SPIK_01_06

Sertraline  Norsertraline 9‐OH‐Risperidone 

Venlafaxine  Fluoxetine Paroxetine 

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 29.05AA: 15195183SN: 24036

NL: 5.62E5m/z= 108.60-109.60 F: + c ESI SRM ms2 [email protected] [108.900-109.300, 261.700-262.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 19.80AA: 6143045SN: 96386

RT: 22.09AA: 163214SN: 1344

NL: 4.29E5m/z= 280.40-281.40 F: + c ESI SRM ms2 [email protected] [204.800-205.200, 280.700-281.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

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85

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100

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RT: 17.57AA: 2493280SN: 51567

NL: 1.86E5m/z= 181.47-182.47 F: + c ESI SRM ms2 [email protected] [181.770-182.170, 208.720-209.120] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

15

20

25

30

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45

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RT: 20.91AA: 4957423SN: 46460

NL: 4.06E5m/z= 192.50-193.50 F: + c ESI SRM ms2 [email protected] [153.800-154.200, 192.800-193.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 19.99AA: 945152SN: 23923

RT: 14.95AA: 306184SN: 3017

NL: 7.92E4m/z= 139.50-140.50 F: + c ESI SRM ms2 [email protected] [139.800-140.200, 164.800-165.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 20.00AA: 9276938SN: 71239

RT: 21.70AA: 555719SN: 1699

NL: 9.02E5m/z= 267.40-268.40 F: + c ESI SRM ms2 [email protected] [210.700-211.100, 267.700-268.100] MS ICIS XC_SPIK_01_06

Citalopram  Alprazolam  Bromazepam 

Diazepam  Nordiazepam  Flunitrazepam 

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RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 16.26AA: 4161805SN: 10901

NL: 3.33E5m/z= 134.60-135.60 F: + c ESI SRM ms2 [email protected] [134.900-135.300, 147.800-148.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

20000

40000

60000

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100000

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380000

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420000

440000

460000

480000

500000

520000

Intensi

ty

RT: 19.01AA: 6488844SN: 17521

NL: 5.28E5m/z= 240.40-241.40 F: + c ESI SRM ms2 [email protected] [240.700-241.100, 268.700-269.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

50000

100000

150000

200000

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350000

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600000

650000

700000

750000

800000

850000

900000

950000

1000000

Intensi

ty

RT: 19.21AA: 12461181SN: 67437

NL: 1.03E6m/z= 258.40-259.40 F: + c ESI SRM ms2 [email protected] [223.700-224.100, 254.700-255.100, 258.700-259.100, 282.600-283.000] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

20000

40000

60000

80000

100000

120000

140000

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240000

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280000

300000

320000

340000

360000

380000

400000

420000

440000

460000

Intensi

ty

RT: 18.82AA: 5523799SN: 88889

RT: 19.47AA: 93024SN: 1297

NL: 4.62E5m/z= 274.30-275.30 F: + c ESI SRM ms2 [email protected] [274.600-275.000, 302.600-303.000] MS ICIS XC_SPIK_01_06

RT: 14.79 - 36.50

16 18 20 22 24 26 28 30 32 34 36Time (min)

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

1100000

1200000

1300000

1400000

1500000

1600000

1700000

Intensi

ty

RT: 19.53AA: 18853567SN: 56873

NL: 1.72E6m/z= 235.50-236.50 F: + c ESI SRM ms2 [email protected] [235.800-236.200, 249.800-250.200] MS ICIS XC_SPIK_01_06

RT: 14.79 - 36.50

16 18 20 22 24 26 28 30 32 34 36Time (min)

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

1100000

1200000

1300000

1400000

1500000

1600000

1700000

1800000

1900000

2000000

Intensi

ty

RT: 19.67AA: 24873754SN: 84433

RT: 20.71AA: 611511SN: 752

NL: 2.09E6m/z= 254.40-255.40 F: + c ESI SRM ms2 [email protected] [223.700-224.100, 254.700-255.100, 258.700-259.100, 282.600-283.000] MS ICIS XC_SPIK_01_06

7‐amine flunitrazepam  Oxazepam  Clobazam 

Lorazepam  Nitrazepam  Temazepam 

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 25.50AA: 27168114SN: 34735

RT: 28.38AA: 258063SN: 648

NL: 7.75E5m/z= 290.40-291.40 F: + c ESI SRM ms2 [email protected] [208.700-209.100, 290.700-291.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 20.97AA: 8874048SN: 129228

RT: 20.52AA: 58445SN: 1251

NL: 5.12E5m/z= 226.40-227.40 F: + c ESI SRM ms2 [email protected] [226.700-227.100, 240.700-241.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

50000

100000

150000

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250000

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350000

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550000

600000

650000

700000

750000

800000

850000

900000

950000

1000000

1050000

1100000

Intensi

ty

RT: 22.14AA: 31616845SN: 49550

NL: 1.12E6m/z= 181.50-182.50 F: + c ESI SRM ms2 [email protected] [149.800-150.200, 181.800-182.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

50000

100000

150000

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350000

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550000

600000

650000

700000

750000

800000

850000

900000

950000

1000000

1050000

1100000

Intensi

ty

RT: 16.18AA: 15060563SN: 118171

NL: 1.12E6m/z= 167.50-168.50 F: + c ESI SRM ms2 [email protected] [104.900-105.300, 167.800-168.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

20000

40000

60000

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100000

120000

140000

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420000

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520000

540000

560000

580000

600000

620000

640000

660000

680000

Intensi

ty

RT: 2.10AA: 9158083SN: 9768

NL: 6.82E5m/z= 181.50-182.50 F: + c ESI SRM ms2 [email protected] [82.100-82.500, 181.800-182.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 13.80AA: 2662777SN: 1370

NL: 9.37E4m/z= 147.60-148.60 F: + c ESI SRM ms2 [email protected] [114.900-115.300, 147.900-148.300] MS ICIS XC_SPIK_01_06

Midazolam  Chlordiazepoxide  Cocaine 

Benzoylecgonine Ethyl methyl ecgonine  Ephedrine 

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0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 7.84AA: 19668678SN: 8605

NL: 4.91E5m/z= 133.60-134.60 F: + c ESI SRM ms2 [email protected] [116.900-117.300, 133.900-134.300] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 8.26AA: 2200263SN: 11558

NL: 5.76E4m/z= 200.50-201.50 F: + c ESI SRM ms2 [email protected] [164.800-165.200, 200.800-201.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 15.01AA: 2865222SN: 35575

RT: 25.42AA: 86668SN: 1093

RT: 15.79AA: 120557SN: 899

NL: 2.16E5m/z= 164.50-165.50 F: + c ESI SRM ms2 [email protected] [164.800-165.200, 210.700-211.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

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20

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RT: 33.14AA: 84447485SN: 9509

NL: 1.49E6m/z= 264.50-265.50 F: + c ESI SRM ms2 [email protected] [104.900-105.300, 264.800-265.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

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RT: 31.50AA: 54145905SN: 13665

NL: 8.08E5m/z= 233.50-234.50 F: + c ESI SRM ms2 [email protected] [233.800-234.200, 248.800-249.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

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RT: 14.35AA: 2915089SN: 70288

RT: 20.05AA: 50237SN: 2454

NL: 1.82E5m/z= 214.50-215.50 F: + c ESI SRM ms2 [email protected] [164.800-165.200, 214.800-215.200] MS ICIS XC_SPIK_01_06

Norephedrine  Morphine  6‐MAM 

Methadone  EDDP  Codeine 

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RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

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RT: 15.60AA: 11156408SN: 15707

NL: 5.46E5m/z= 297.40-298.40 F: + c ESI SRM ms2 [email protected] [240.700-241.100, 297.700-298.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.02

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 26.06AA: 229840SN: 8741

NL: 1.23E4m/z= 186.40-187.40 F: + c ESI SRM ms2 [email protected] [186.700-187.100, 210.800-211.200] MS ICIS XC_SPIK_01_06

RT: 0.00 - 65.01

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

5

10

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RT: 24.19MA: 1116051SN: 64

16.14

17.7115.88 18.43

20.46

15.16

14.37

13.6512.34

11.7511.23

10.77

6.19

33.7525.635.9227.332.91

30.02 53.7842.59 55.0339.18 60.0747.43

NL: 7.47E4m/z= 326.50-327.50 F: + c ESI SRM ms2 [email protected] [192.800-193.200, 326.800-327.200] MS X_SPIK_01_06

RT: 0.00 - 65.01

0 5 10 15 20 25 30 35 40 45 50 55 60 65Time (min)

0

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RT: 26.09MA: 424675SN: 9847

24.19

11.35 13.1226.67

15.6818.03

10.8353.525.92 8.74 27.20 46.7132.11 42.91 63.1449.3934.602.78 53.71 60.91

NL: 2.35E4m/z= 122.60-123.60 F: + c ESI SRM ms2 [email protected] [122.900-123.300, 192.800-193.200, 258.700-259.100] MS X_SPIK_01_06

RT: 0.00 - 35.01

0 5 10 15 20 25 30 35Time (min)

0

5

10

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RT: 8.59AA: 16115SN: 658

8.852.05

2.46 13.648.96

12.86

12.762.92

1.78 9.093.30 26.81 28.04 30.146.46 14.01 21.70 24.76 32.1017.72

NL: 1.31E3m/z= 187.40-188.40 F: - c ESI SRM ms2 [email protected] [42.300-42.700, 187.700-188.100] MS ICIS XC_SPIK_01_06

RT: 0.00 - 35.01

0 5 10 15 20 25 30 35Time (min)

0

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RT: 11.27AA: 5777SN: 467

2.01

2.98

3.13

10.886.814.69 17.3511.7610.369.58 12.91 24.60 26.16 30.2319.34 32.2721.27

NL: 7.70E2m/z= 181.60-182.60 F: - c ESI SRM ms2 [email protected] [42.400-42.800, 181.900-182.300] MS ICIS XC_SPIK_01_06

Oxycodone  Buprenorphine  THCA 

THC  Pentobarbital  Phenobarbital