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Analytical Standards for Environmental Analysis

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LC-MS grade methanol and water were obtained from VWR, Darmstadt, Germany. Quercetin dehydrate (≥95%, high performance liquid chromatography (HPLC)) was purchased from Enzo Life Sciences GmbH, Lörrach, Germany. Diclofenac (>99%) was obtained from Cayman Chemical Company, Ann Arbor, Michigan, MI, USA. Glyphosate (100 quality level, HPLC), gabapentin (200 quality level, HPLC), monuron (100 quality level, HPLC), chloridazon (100 quality level, HPLC), carbetamide (100 quality level, HPLC), metobromuron (100 quality level, HPLC), sotalol (≥98%), quinoxyfen (100 quality level, HPLC), metconazol (100 quality level, HPLC) and fenofibrate (≥99%) were obtained from Sigma, Darmstadt, Germany. Metformin (300 quality level, HPLC) was obtained from Fluka, Buchs, Switzerland. Furthermore, chlorbromuron (99.24%) and diazinon (99.53%) were obtained from Dr. Ehrenstorfer, Augsburg, Germany. Carbamazepine, 2,3-dihydro-2,3-dihydroxycarbamazepine, 10,11-dihydro-10,11-dihydroxy-carbamazepine, 10,11-dihydro-10-hydroxy-carbamazepine, 9-acridine carboxaldehyde and carbamazepine-10,11-epoxide were kindly provided by the German Research Center for Environmental Health, Comparative Microbiome Analysis (COMI), Helmholtz Centrum of Munich, Munich, Germany.
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2

HPLC-MS/MS Multianalyte Quantification

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Methanol HPLC Ultragradient Gold, formic acid 99% and ammonia solution 25% were purchased from Carlo Erba Reagents, SAS (Marseille, France). H2O - Pierce™. Water, acetonitrile and formic acid LC-MS grade Optima® were from Fisher Chemical (Hampton, NH, USA), state abbrev if USA, country). Caffeine-13C3 (99%, 1 mg/mL in methanol) was obtained from Sigma-Aldrich (Schnelldorf, Germany). Standards (purity ≥97%) of all the chemicals listed (tert-butylazine; desethyl-tert-butylazine; dimethoate; atrazine; desethylatrazine; tebuconazole; alachlor; omethoate; bentazone; diuron; linuron; chlorotoluron; cymoxanil; thiamethoxam; clothianidin; imidacloprid; acetamiprid; thiacloprid; simazine; isoproturon; cybutryne; methiocarb; quinoxyfen; chlorpyrifos; 2,4D; MCPP; aclonifen; bifenox; MCPA; dichlorvos; bezafibrate; ibuprofen; amoxicillin·3H2O; azithromycin; diclofenac; α-ethinylestradiol; β-estradiol; erythromycin; clarithromycin; trimethoprim; ciprofloxacin; enrofloxacin; sulfamethoxazole; bisoprolol; carbamazepine) were purchased from Sigma-Aldrich.
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3

Analytical Standards for Environmental and Forensic Analysis

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Materials. HPLC-grade acetonitrile, water, hexafluorobenzene (99%) and chlorobenzene (99.9%), iodobenzene (>99%) and fluorobenzene (>99.5%) were obtained from Sigma-Aldrich (Buchs, Switzerland), and toluene (99.85%) and acetone (99.9%) from Acros Organics (Geel, Belgium). Analytical-grade pesticide and drug standards were purchased from Sigma-Aldrich, and were: ametryn, atrazine, prometon, prometryn, propazine, simazine, terbutryn, disulfoton, famphur, parathion, parathion-methyl, phorate, sulfotep, thionazin, triethyl thiophosphate, dimethoate, metolachlor, pyrimethanil, malathion, cyprodinil, flusilazole, cyproconazole, trifloxystrobin, quinoxyfen, tebuconazole, pyriproxyfen, pyridaben, difenoconazole, azoxystrobin, diazepam, cocaine, methadone, desipramine, imipramine, MDMA, ketamine, lidocaine and fentanyl. Phenanthrene-d10, pyrene-d10, and a polycyclic aromatic hydrocarbon mix (CRM 47930) were purchased from Sigma-Aldrich.
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4

Pesticide Residue Analysis in Grape Juice

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Materials. HPLC-grade water and acetonitrile and dimethyldichlorosilane (DMDCS, 5% in toluene) were obtained from Sigma-Aldrich (Buchs, Switzerland). PESTANAL© analyticalgrade standards were purchased from Sigma-Aldrich: famphur, parathion, parathion-met, sulfotep, thionazin, ametryn, atrazine, atrazine-D 5 , metolachlor, prometon, prometryn, terbutryn, propazine, simazine, pyrimethanil, cyproconazole, quinoxyfen, flusilazole, trifloxystrobin, azoxystrobin, pyridaben, pyraclostrobin, pyriproxyfen, tebuconazole, cyprodinil, difenoconazole and malathion. Organic grape juice was purchased at local grocery stores in Zurich (Switzerland) and in Waterloo (ON, Canada). PDMS/DVB/PDMS coatings were prepared in-house following the procedure described by Souza-Silva et al. 16 Sample preparation. Individual pesticide standard stock solutions were prepared at a concentration of 5 mg/mL in acetonitrile, and stored at -20 °C. A mix of the pesticides at 100 µg/mL in acetonitrile was prepared from the stock solutions. Diluted solutions used for SPME analysis were prepared in ACN from the mix and were stored at a temperature of 4 °C.
The grape juice samples were spiked with an aliquot of the pesticides standards mixtures, always keeping the total amount of solvent spiked in the matrix below 1% (v:v).
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