Influence of QuEChERS modifications on recovery and matrix effect during the multi-residue pesticide analysis in soil by GC/MS/MS and GC/ECD/NPD

Environmental Science and Pollution Research, Jan 2017

A QuEChERS extraction followed by GC/MS/MS and GC-μECD/NPD for 216 pesticide and metabolites determination in soil simultaneously were developed and compared. Volume of water, volume and polarity of solvent, and cleanup sorbents (C18, GCB, PSA) were optimized. The QuEChERS with and without purification step were applied to estimate effectiveness of the method. The recovery and matrix effect (ME) were critical parameters within each tested procedure. The optimal method without cleanup was validated. Accuracy (expressed as recovery), precision (expressed as RSD), linearity, LOQ, and uncertainty were determined. The recoveries at the three spiking levels using matrix-matched standards ranged between 65 and 116% with RSD ≤17 and 60–112% with RSD ≤18% for MS/MS and μEC/NP, respectively. The LOQ ranged from 0.005–0.01 mg/kg for MS/MS to 0.05 mg/kg for μEC/NP. The ME for most of pesticides resulted in enhancement of the signal and depended on the analyte and detection system: MS/MS showed ME from −25 to 74%, while μEC/NP from −45 to 96%. A principal component analysis was performed to explain the relationships between physicochemical parameters and ME of 216 pesticides. The QuEChERS protocol without the cleanup step is a promising option to make the method less expensive and faster. This methodology was applied in routine analysis of 263 soil samples in which p,p’ DDT was the most frequently detected (23.5% of samples) and pendimethalin with the highest concentration (1.63 mg/kg).

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Influence of QuEChERS modifications on recovery and matrix effect during the multi-residue pesticide analysis in soil by GC/MS/MS and GC/ECD/NPD

Environ Sci Pollut Res Influence of QuEChERS modifications on recovery and matrix effect during the multi-residue pesticide analysis in soil by GC/MS/MS and GC/ECD/NPD Bożena Łozowicka 0 1 Ewa Rutkowska 0 1 Magdalena Jankowska 0 1 0 Plant Protection Institute - National Research Institute, Laboratory of Pesticide Residues , Chelmonskiego 22, Postal code: 15-195 Bialystok , Poland 1 Responsible editor: Roland Kallenborn 2 Ewa Rutkowska A QuEChERS extraction followed by GC/MS/MS and GC-μECD/NPD for 216 pesticide and metabolites determination in soil simultaneously were developed and compared. Volume of water, volume and polarity of solvent, and cleanup sorbents (C18, GCB, PSA) were optimized. The QuEChERS with and without purification step were applied to estimate effectiveness of the method. The recovery and matrix effect (ME) were critical parameters within each tested procedure. The optimal method without cleanup was validated. Accuracy (expressed as recovery), precision (expressed as RSD), linearity, LOQ, and uncertainty were determined. The recoveries at the three spiking levels using matrix-matched standards ranged between 65 and 116% with RSD ≤17 and 60-112% with RSD ≤18% for MS/MS and μEC/NP, respectively. The LOQ ranged from 0.005-0.01 mg/kg for MS/MS to 0.05 mg/kg for μEC/NP. The ME for most of pesticides resulted in enhancement of the signal and depended on the analyte and detection system: MS/MS showed ME from −25 to 74%, while μEC/NP from −45 to 96%. A principal component analysis was performed to explain the relationships between physicochemical parameters and ME of 216 pesticides. The QuEChERS protocol without the cleanup step is a promising option to make the method less expensive and Pesticide; Soil; Optimization; Multi-residue method; QuEChERS; Gas chromatography - faster. This methodology was applied in routine analysis of 263 soil samples in which p,p’ DDT was the most frequently detected (23.5% of samples) and pendimethalin with the highest concentration (1.63 mg/kg). Introduction Soil is an important resource of agriculture which has an ability to retain agro-chemicals. Soil contamination causes the presence of xenobiotic chemicals and very varied from industrial activity, improper disposal of waste to agricultural chemicals. The presence of pesticide compounds in soils may have different sources: direct application, accidental spillage, runoff from the surface of plants, or from incorporation of pesticide contaminated plant materials (Rashid et al. 2010) . Agricultural soil is a high value component, so its irreversible degradation should be avoided to guarantee its fertility and current and future value. Soil is a complex and heterogeneous matrix with a porous structure that contains both inorganic (variable percentage of sand, silt, and clay) and natural organic components mainly composed by humic substances (10–15%), lipids, carbohydrates, lignin, flavonoids, pigments, resins and fulvic acids (Pinto et al. 2011) . These compounds are characterized by the diverse chemical structure and physicochemical properties, which cause many analytical problems. Therefore, pesticide analysis at low concentration levels in these samples is a very difficult and challenging task. In the literature, the analytical procedures for the determination of pesticide residues in soil commonly are based on traditional sample preparation methods, such as: liquid solid (LSE) ( Durović et al. 2012 ), solid phase extraction (SPE) (Dąbrowska et al. 2003) , ultrasonication in acetone (Harrison et al. 2013) , and in soxhlet apparatus extraction (Sanghi and Kannamkumarath 2004) . Other methods, such as accelerated solvent (ASE) ( Rouvière et al. 2012 ), dispersive liquid-liquid microextraction (DLLME) (Pastor-Belda et al. 2015) , matrix solid phase dispersion (MSPD) (Łozowicka et al. 2012), ultrasonic solvent (USE) (Tor et al. 2006) , microwave assisted (MAE) (Guo and Lee 2013; Fuentes et al. 2007) , pressurized liquid (PLE) (Martinez Vidal et al. 2010; Masiá et al. 2015), solid phase microextraction (SPME) (Moreno et al. 2006) , supercritical fluid extraction (SFE) (Naeeni et al. 2011) have been developed to reduce the amount of reagents and time provided on sample preparation. Nowadays, in pesticide residue analysis, QuEChERS method (ang. Ouick, Easy, Cheap, Effective, Rugged and Safe), developed by Anastassiades et al. (2003) , become a very popular technique for different matrix sample preparations such as: cereals (He et al. 2015) , fruit and vegetables (Lehotay et al. 2010) , honey ( Bargańska et al. 2013 ), tea (Lozano et al. 2012) and tobacco (Łozowicka et al. 2015), because of its simplicity, low cost, amenability to high throughput, and high efficiency with a minimal number of steps. It involves two steps, extraction based on partitioning between an aqueous and an organic layer via salting-out and dispersive SPE for further cleanup using combinations of MgSO4 and (...truncated)


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Bożena Łozowicka, Ewa Rutkowska, Magdalena Jankowska. Influence of QuEChERS modifications on recovery and matrix effect during the multi-residue pesticide analysis in soil by GC/MS/MS and GC/ECD/NPD, Environmental Science and Pollution Research, 2017, pp. 7124-7138, Volume 24, Issue 8, DOI: 10.1007/s11356-016-8334-1