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Optimization of QuEChERS method for the
determination of organic micropollutants in complex environmental matrices: applications for agricultural and urban contaminants in leaf litter and sediments
C. Guillemain, A. Daval, Cecile Miege, C. Margoum
To cite this version:
C. Guillemain, A. Daval, Cecile Miege, C. Margoum. Optimization of QuEChERS method for the
determination of organic micropollutants in complex environmental matrices: applications for agri-
cultural and urban contaminants in leaf litter and sediments. 16 th International Conference on
Chemistry and Environment, Jun 2017, Oslo, Norway. pp.1, 2017. �hal-02606445�
www.irstea.fr
Analysis of micropollutant traces in complex environmental solid matrices is a huge challenge, as it requires efficient analytical techniques to reach appropriate sensitivity and specificity. Extraction and purification are crucial steps that must be optimized. Comparing to other classical techniques, QuEChERS method [1],[2],[3] (Quick, Easy, Cheap, Effective, Rugged and Safe) presents the advantage to be rapid, simple, cheap, environment friendly and provides relatively clean extracts.
This study aims to optimize two methods for the extraction of 14 pesticides from leaves and 49 urban micropollutants from sediments by QuEChERS.
INTRODUCTION
The authors thank the Loire-Brittany Water Agency and the Rhone Sediment Observatory for financial support.
ACKNOWLEDGEMENT
[1] M. Anastassiades, K. Maštovská and S. J. Lehotay: J. Chromatogr. A (2003).
[2] N.F.15662 E.N, 01 Méthode polyvalente de détermination des résidus des pesticides par GC–MS et SL/SM/SM avec extraction/partition avec de l’acétonitrile et nettoyage par SPE disperses (Méthode QuEChERS) (2009).
[3] AOAC Official Method 2007.01 Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate (2007)
REFERENCES
CONCLUSIONS AND PERSPECTIVES
Two reliable, specific and sensitive methods were developed for the determination of 14 pesticides concentrations in leaves and of 49 urban contaminants concentrations in sediments. Good recoveries and low LOQ were obtained using the QuEChERS method. Such developments now offer new perspectives to better evaluate the effects of organic micropollutants on aquatic ecosystems in laboratory experiments and in situ studies.
Optimization of QuEChERS method for the determination of organic micropollutants in complex environmental matrices: applications for agricultural and urban contaminants in leaf litter and sediments
FRESHWATER SYSTEMS, ECOLOGY AND POLLUTIONS RESEARCH UNIT – Irstea, Lyon – Villeurbanne Center - France
C. Guillemain, A. Daval, C. Miège, C. Margoum
Contact : [email protected]
METHODS OPTIMIZATION AND VALIDATION
QuEChERS 10 mL ACN + salts
Vortex Ultrasonic bath
Centrifugation 5 min at 5000 rpm Supernatant collection Dispersive SPE (d-SPE) 10 mL ACN supernatant + salts
UHPLC-MS-MS analysis Purification Evaporation - Dilution
1
Centrifugation 5 min at 5000 rpm Supernatant collection
2
3
4
Dry and ground sample + H
2O:
- Pest.: 0.25 g leaves + 7 mL H
2O - Urb.: 1 g sediments + 10 mL H
2O
Molecule Abbreviation Use Log Kow Molecule Abbreviation Use Log KowAnalytical standards Abbreviation
Azithromycin AZI 4.0 Acebutolol ACE 1.7 Acebutolol d7 ACEd7
Ciprofloxacin CIPRO 0.3 Atenolol ATE 0.2 Amitriptyline d6 AMId6
Clarithromycin CLARI 3.2 Metoprolol METRO 1.9 Atenolol d7 ATEd7
Clindamycin CLINDA 2.2 Propranolol PROP 3.5 Atrazine d5 ATZd5
Erythromycin ERY 3.1 Sotalol SOT 0.2 Betaxolol d7 BETd7
Metronidazole METRO -0.0 Salbutamol SALBU 0.6 Carbamazepine d10 CARBAd10
Norfloxacin NORFLO 0.5 Theophylline THEO -0.0 Clarithromycin d3 CLARId3
Ofloxacin OFLO -0.4 Alprazolam APZ 2.1 Diclofenac d4 DICLOd4
Sulfamethoxazole SMX 0.9 Diazepam DIAZ 2.8 Diuron d6 DIUd6
Trimethoprim TRIM 0.9 Nordiazepam NDZ 2.9 Imidacloprid d4 IMId4
Acetylsulfamethoxazole ACSMX Metab-Ab 1.2 Oxazepam OXA 2.2 Ketoprofen d3 KETOd3
Cyclophosphamide CYCLO Ac 0.6 Furosemide FURO D 2.0 Metoprolol d7 METd7
Amitriptyline AMI 4.9 Atrazine ATZ 2.6 Naproxen d3 NAPROXd3
Fluoxetine FLUOX 4.5 Dimethoate DIM 0.8 Norfloxacin d5 NORFLOd5
Norfluoxetine NORFLUO Metab-Ad 3.8 Diuron DIU 2.7 Ofloxacin d3 OFLOd3
Metformin METFOR Adi -0.5 Imidacloprid IMI 0.6 Paracetamol d3 PARAd3
Carbamazepine CARBA Ae 2.5 Isoproturon IPU 2.9 Propanolol d7 PROPd7
Carbamazepine-10,11-
epoxide CARBA-EP Metab-Ae 1.3 Mecoprop MCPP 3.1 Salbutamol d3 SALBUd3
Diclofenac DICLO 4.5 Pirimicarb PIRI 1.7 Sotalol d7 SOTd7
Ketoprofen KETO 3.1 Simazine SMZ 2.2 Sulfamethoxazole d4 SMXd4
Naproxen NAPROX 3.2 3,4-Dichloroaniline DCA Metab-P 2.7
Paracetamol PARA An 0.5 Desethylatrazine DEA Metab-P 1.5
Bezafibrate BEZA 4.3 Desisopropylatrazine DIA Metab-P 1.5
Fenofibrate FENO 5.2
Fenofibric acid AC FENO 4.0
Gemfibrozil GEM 4.8
Bz BB
Br
P Ad
Ap AI Ab
2 MULTI-RESIDUE ANALYSIS FOR AGRICULTURAL AND URBAN CONTAMINANTS
F: Fungicide, H: Herbicide, I: Insecticide Metab : metabolite
Log Kow: Octanol-water partition coefficient
Pesticides UHPLC-MS-MS analysis
UHPLC-ESI(+)-QqQ-MS-MS Shimadzu Nexera 2 - API4000 ABSciex,
Columns HSS T3 (Pest. analysis) / BEH C18 (Urb. analysis) Waters® 100 mm*2.1 mm, 1.8 µm
Mobile phase : gradient with acidified water and acidified acetonitrile
14 pesticides (pest.) indicator of agricultural release and 49 urban micropollutants (urb.) indicator of domestic wastewater release were selected
Urban contaminants
Ab: Antibiotic, Ac: Anticancer agent, Ad: Antidepressant, Adi: Antidiabetic, Ae: Antiepileptic, AI : Anti-inflammatories, An: Analgesic, Ap: Antilipemic drug, BB: Beta-blocker, Br : Bronchodilator, Bz: Benzodiazepine, D: Diuretic, P: Pesticide, Metab : Metabolite Molecule Abbreviation Use Log Kow Analytical standards Abbreviation
Azoxystrobine AZS F 2.5 Diuron d6 DIUd6
Carbendazime CBZ F 1,5 Tebuconazole d6 TBZd6
Dimethomorph DMM F 2.7 Simazine d5 SMZd5
Procymidone PCM F 3.3 Diflufenican d3 DFFd3
Spiroxamine SPX F 2.9 Linuron d6 LINUd6
Tebuconazole TBZ F 3.7 Carbendazime d4 CBZd4
Diflufenican DFF H 4.2 Metolachlor d6 MTCd6
S-Metolachlor S-MTC H 3.1 Chlorfenvinphos d10 CFVd10
Metolachlor oxanilic
acid MTC-OXA metab-H 2.3 Chlorpyrifos Ethyl d10 CPEd10 Metolachlor ethane
sulfonic acid MTC-ESA metab-H 0.7 Chlorpyrifos Methyl d6 CPMd6
Chlorfenvinphos CFV I 3.8
Chlorpyrifos Ethyl CPE I 4.7
Chlorpyrifos Methyl CPM I 4.0
Flufenoxuron FFX I 5.1
Study of matrix effects
Three types of leaves (alder, poplar and oak leaves – decomposed or not) were spiked at three concentration levels.
To limit strong matrix effects, several steps of SPE purification and extract dilution were tested:
- 2 Oasis Prime HLB: 6 cc 200 mg and 3cc 60mg - 3 dilution factors: 1/2, 1/5, 1/10.
Signal inhibition decreased to less than 16 % after “Pass through” SPE purification (Oasis HLB 6cc 200 mg) and extract dilution (1/10).
Pass through SPE Purification step
We observed a 2 - 4 fold increase of the extraction recoveries with the addition of the step of ultrasonic bath during 1 min.
To enhance recoveries, the use of ultrasonic bath during one minute was tested.
Use of ultrasonic bath Choice of extraction method
Mass and type of extraction salts, mass and type of purification salts and centrifugation durations were optimized using an experimental design.
Final pest. method:
Extraction: 4 g MgSO
4+ 1 g NaCitr. + 0.5 g NaCitr. Sesquihydrate
d-SPE: 0.9 g MgSO
4+ 0.15 g C18 + 0.15 g PSA
Final urb. method:
Extraction: 6 g MgSO
4+ 1.5 g NaCH₃ ₃₃ ₃COO d-SPE: 0.9 g MgSO
4+ 0.15 g PSA + 0.045 g GCB
QuEChERS and d-SPE optimization
1 2
3 4
4
17 7
10 2
