A multi-residue method for trace analysis of pesticides in soils with special emphasis on rigorous quality control
Andrea Rösch,
Felix E. Wettstein,
Daniel Wächter
et al.
Abstract:A multi-residue trace analytical method is presented to accurately quantify 146 currently used pesticides in (agricultural) soils with varying soil properties. Pesticides were extracted using an optimized quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach and chemical analysis was carried out by liquid chromatography coupled to tandem mass spectrometry (triple quadrupole). Quantification was based on matrix-matched internal standards calibration, using 95 isotopically labeled analyte analogues… Show more
“…So, also according to Horwitz, the RSD R of this study were good with only three compounds at the lowest fortification level (10 ng/g) exhibiting an RSD R >30%: endosulfane sulfate (35.1%), bifenthrin (36.6%) and pyraclostrobin (30.9%). Such precision ranges also compare well with those of earlier papers in this domain (Łozowicka et al 2017 , Rösch et al 2023 ).…”
Section: Resultssupporting
confidence: 90%
“…The ME ext of individual analytes in the different soils was compared with their respective properties (Table 1 ), in particular their OM content, but no correlation with any of them could be observed. This result is unlike the one for another method recently developed in our lab, also with different soils but measured with liquid chromatography MS/MS, where the ME increased with increasing OM and concomitantly shifted towards ion suppression (Rösch et al 2023 ). Fig 2 Matrix effect (ME) of skeletic regosol (SR), rhodic ferralic nitisol organically managed (RFNo), RFN conventionally managed (RFNc) xanthic ferralic nitisol (XFN), and dystric cambisol (DC).…”
Section: Resultscontrasting
confidence: 86%
“…The methods of Acosta-Dacal et al ( 2021 ) and Rösch et al ( 2023 ) were applied with modifications. Briefly, soil prepared as described in “ Soils, sampling, and sample preparation ” was mixed vigorously for 5 min in a Turbula shaker-mixer (Willy A. Bachofen AG, Muttenz, Switzerland) before taking a subsample of 5 g. It was put into a centrifuge tube (15 mL), and 10 ng/g IL-IS mixture was added (0.1 mL IL-IS solution).…”
We present an analytical method to detect and quantify residues of currently used pesticides (CUPs), which include 31 active ingredients (ai) and seven transformation products (TPs) in tropical and agricultural soils of Cuba. Ten isotopically labeled analogous compounds served as internal standards (IL-IS). The novelty of this research is the inclusion of different tropical soils type scarcely studied for CUPs and TPs, based on the QuEChERS (quick, easy, cheap, effective, rugged and safe) method, followed by chromatography tandem mass spectrometry. All figures of merit proved to be satisfactory according to SANTE guidelines 2020 and 2021. Matrix effects (ME) calculated by the external standard method were significant (|ME| > 20% for almost all compounds; grand mean ± standard deviation (STD) 104 ± 108%) in all soils. The internal standard method compensated ME to non-significant levels (8 ± 50%), even for analytes with a non-structure identical IL-IS (STD, 13 ± 57%). Repeatability (relative standard deviation, RSDr) and reproducibility (RSDR) for skeletic regosol (SR) were 7.5 ± 2.8% and 11.7 ± 4.7%, respectively. Absolute (quantified for 11 analytes with structure identical IL-IS) and relative recovery from SR was 92 ± 13% (mean ± STD) and 90 ± 12%, respectively. Limits of quantification for SR ranged from 0.1 to 10 ng/g, except metalaxyl and oxyfluorfen (25 ng/g each). Linearity of matrix-matched (MM) calibration curves (5 to 100 ng/g) had an R2 of ≥ 0.99 for all soils and almost all analytes. The method was successfully applied to 30 real soil samples.
“…So, also according to Horwitz, the RSD R of this study were good with only three compounds at the lowest fortification level (10 ng/g) exhibiting an RSD R >30%: endosulfane sulfate (35.1%), bifenthrin (36.6%) and pyraclostrobin (30.9%). Such precision ranges also compare well with those of earlier papers in this domain (Łozowicka et al 2017 , Rösch et al 2023 ).…”
Section: Resultssupporting
confidence: 90%
“…The ME ext of individual analytes in the different soils was compared with their respective properties (Table 1 ), in particular their OM content, but no correlation with any of them could be observed. This result is unlike the one for another method recently developed in our lab, also with different soils but measured with liquid chromatography MS/MS, where the ME increased with increasing OM and concomitantly shifted towards ion suppression (Rösch et al 2023 ). Fig 2 Matrix effect (ME) of skeletic regosol (SR), rhodic ferralic nitisol organically managed (RFNo), RFN conventionally managed (RFNc) xanthic ferralic nitisol (XFN), and dystric cambisol (DC).…”
Section: Resultscontrasting
confidence: 86%
“…The methods of Acosta-Dacal et al ( 2021 ) and Rösch et al ( 2023 ) were applied with modifications. Briefly, soil prepared as described in “ Soils, sampling, and sample preparation ” was mixed vigorously for 5 min in a Turbula shaker-mixer (Willy A. Bachofen AG, Muttenz, Switzerland) before taking a subsample of 5 g. It was put into a centrifuge tube (15 mL), and 10 ng/g IL-IS mixture was added (0.1 mL IL-IS solution).…”
We present an analytical method to detect and quantify residues of currently used pesticides (CUPs), which include 31 active ingredients (ai) and seven transformation products (TPs) in tropical and agricultural soils of Cuba. Ten isotopically labeled analogous compounds served as internal standards (IL-IS). The novelty of this research is the inclusion of different tropical soils type scarcely studied for CUPs and TPs, based on the QuEChERS (quick, easy, cheap, effective, rugged and safe) method, followed by chromatography tandem mass spectrometry. All figures of merit proved to be satisfactory according to SANTE guidelines 2020 and 2021. Matrix effects (ME) calculated by the external standard method were significant (|ME| > 20% for almost all compounds; grand mean ± standard deviation (STD) 104 ± 108%) in all soils. The internal standard method compensated ME to non-significant levels (8 ± 50%), even for analytes with a non-structure identical IL-IS (STD, 13 ± 57%). Repeatability (relative standard deviation, RSDr) and reproducibility (RSDR) for skeletic regosol (SR) were 7.5 ± 2.8% and 11.7 ± 4.7%, respectively. Absolute (quantified for 11 analytes with structure identical IL-IS) and relative recovery from SR was 92 ± 13% (mean ± STD) and 90 ± 12%, respectively. Limits of quantification for SR ranged from 0.1 to 10 ng/g, except metalaxyl and oxyfluorfen (25 ng/g each). Linearity of matrix-matched (MM) calibration curves (5 to 100 ng/g) had an R2 of ≥ 0.99 for all soils and almost all analytes. The method was successfully applied to 30 real soil samples.
“…Since the focus is on PPP residues, and monitoring must not target the effect of PPP during the application periods, sampling will take place at the end of the winter period (February-March) when no PPP application is expected, before the first application of the year and where only the residues will be assessed. Samples will be collected in this period for the chemical monitoring and analysed using a multiresidue method (Rösch et al, 2023). The same sampling period will be used for bioindicator methods for sites identified as potentially at risk.…”
Plant Protection Products (PPPs) are widely used to maintain high productivity and protect crops, but can have unintended toxic effects on beneficial non‐target soil organisms. To avoid unacceptable adverse effects of PPPs on soil organisms, a prospective risk assessment is carried out, which focuses on individual substances and their effects on a few individual species or groups. However, the reality of agricultural soils consists of complex networks of organisms exposed to mixtures of several PPP active substances. It is therefore essential to monitor PPP residues in soils. This paper describes the ConSoil project and its proposed framework for monitoring PPP residues in Swiss Agricultural soils which includes and integrates (1) risk‐based reference values for PPP residues in soil and (2) indicators of their effects on long‐term soil fertility. For risk‐based reference values, a proposal has been developed to derive Soil Guideline Values (SGVs) for PPP residues and a mixture risk assessment concept is being developed. Regarding indicators, a toolbox of ecological and ecotoxicological indicators will be proposed to reflect the protection goal of long‐term soil fertility in agricultural soils. For this objective, standardised and/or well‐established bioindicator methods will be selected for the key soil organisms that support soil fertility. To integrate SGVs and the biomonitoring toolbox, an adapted TRIAD approach is proposed, where generic SGVs are used as a screening tool to identify monitoring sites potentially at risk and to trigger more detailed monitoring. Detailed monitoring will refine the SGVs based on site‐specific characteristics and implement the bioindicator toolbox to measure the effects of PPP residues and their risk to long‐term soil fertility. As a novel integrated framework, it is essential to use the data generated in detailed assessments to calibrate and refine the SGVs and bioindicator tools and improve the monitoring over time.
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