Solid-phase extraction method for stable isotope analysis of pesticides from large volume environmental water samples

Torrentó, Clara; Bakkour, Rani; Glauser, Gaëtan; Melsbach, Aileen; Ponsin, Violaine; Hofstetter, Thomas B.; Elsner, Martin; Hunkeler, Daniel

doi:10.1039/c9an00160c

Cited by 47 publications

(65 citation statements)

References 66 publications

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“…For one sample, accurate δ 37 C-ATR value was obtained even at a concentration below the instrumental LPIA of 0.05 nmol Cl on-column. The combination of this Cl-isotope method with large-volume SPE 28 will enable determination of chlorine isotope ratios of target herbicides in environmental water samples. Hydrolysis experiment.…”

Section: Resultsmentioning

confidence: 99%

“…These isotope ratios need to cover the measurement range to minimize distortion relative to the SMOC scale and to account for potentially variable calibration slopes for the same instrument over time. 11,26,27 Finally, it needs to be demonstrated that, in combination with large-volume solid-phase extraction (SPE) 28 , environmentally relevant concentrations can indeed be reached, which would open a route for analyzing the compounds at environmentally relevant levels with potentially large benefits for understanding the longterm fate of these compounds. As such model herbicides that bear one chlorine but numerous carbon atoms, challenging Cl-CSIA at environmental concentrations, we selected three of the most frequently detected contaminants in groundwater: atrazine (ATR), acetochlor (ACETO) and metolachlor (METO) ( Table S1, Supporting Information, SI).…”

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confidence: 99%

“…21 The method was tested on samples from a degradation experiment. Furthermore, the optimized method was coupled with the SPE method we recently developed 28 and the whole SPE-Cl-CSIA method was validated using large volume environmental water samples spiked with the target herbicides. This study therefore presents a benchmark for routine application of Cl-CSIA of micropollutants bearing numerous carbon atoms and only one Cl, which opens new possibilities for its application to newer classes of contaminants.…”

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confidence: 99%

“…Spiked large-volume water samples. 10 L samples of drainage water were spiked with standards of ATR, ACETO and METO with known isotope signatures at 0.5 to 5 μg/L and SPE was performed, as explained by Torrentó et al 28 For Cl-CSIA, standards were interspersed within the sequences and the twopoint calibration approach was used for normalizing δ 37 Cl raw values to the SMOC scale, except for ACETO, for which the one-point calibration approach was used since only one external standard was available at that time. Hydrolysis experiment.…”

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confidence: 99%

“…Carbon isotope ratios in the extracts were measured by GC-IRMS, as explained elsewhere. 28 Chlorine isotope ratios were measured with the optimized method, using the two-point calibration approach and applying corrections to take into account fragments with two 13 C atoms. The chlorine and carbon isotope fractionations (ε Cl and ε C ) were determined according to the Rayleigh equation 38 :…”

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Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor

et al. 2019

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A gas chromatography-single quadrupole mass spectrometry method was developed and validated for compoundspecific chlorine isotope analysis (Cl-CSIA) of three chlorinated herbicides, atrazine, acetochlor and metolachlor, which are widespread contaminants in the environment. For each compound, the two most abundant ions containing chlorine (202/200 for atrazine, 225/223 for acetochlor and 240/238 for metolachlor) and a dwell time of 30 ms were determined as optimized MS parameters. A Limit of Precise Isotope Analysis for ethyl acetate solutions of 10 mg/L atrazine, 10 mg/L acetochlor and 5 mg/L metolachlor could be reached with an associated uncertainty between 0.5 and 1‰. To this end, samples were measured tenfold and bracketed with two calibration standards which covered a wide range of δ 37 Cl values and whose amplitudes matched those of the samples within 20% tolerance. The method was applied to investigate chlorine isotope fractionation during alkaline hydrolysis of metolachlor, which showed a shift in δ 37 Cl of +46‰ after 98% degradation, demonstrating that chlorine isotope fractionation could be a sensitive indicator of transformation processes even when limited degradation occurs. This method, combined with large-volume solid-phase extraction (SPE), allowed application of Cl-CSIA to environmentally relevant concentrations of widespread herbicides (i.e. 0.5 to 5 µg/L in water before extraction). Therefore, the combination of large-volume SPE and Cl-CSIA is a promising tool for assessing the transformation processes of these pollutants in the environment. fractionation associated with reaction mechanisms relevant for field studies. Hence, future studies are warranted to better understand how variable dual isotope slopes are for specific processes in order to identify them unequivocally in the field. ASSOCIATED CONTENT Supporting Information Further details on target analytes, analytical and extraction methods, GC-qMS method performance and results of the validation tests are available in Supporting Information. The Supporting Information is available free of charge on the ACS Publications Website.

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confidence: 99%

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Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor

et al. 2019

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Application of solid‐phase extraction: High‐resolution mass spectrometry analysis strategy in the characterization and quantification of amide herbicides in aquatic products

et al. 2022

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In this study, we developed a new method combining thin-layer ultrasonic extraction, efficient SPE purification, ultra-performance liquid chromatography separation, and high-resolution mass spectrometry characterization for seven amide herbicides in fishery products. In sample preparation, to rapidly increase the contact area between the fish meat and the extractant, the fish meat was smeared on a glass slide. This process resulted in quickly reaching the extraction equilibrium and relatively high extraction efficiency. In data analysis, a strategy for characterization and qualitative analysis was constructed by analyzing the fragmentation of amide herbicides using product ion scans. Isomeric pretilachlor and butachlor were separated chromatographically, while the coeluting isomers, alachlor and acetochlor, could be separated by differences in the fragmentation of their selected precursor ions. This method overcame the challenge of poor dispersion in the extractant caused by the high viscosity of fish meat, and the challenge of separation and characterization for isomers. Compared with other methods, the extraction efficiency was improved and the amide herbicides in aquatic products was characterized and quantified rapidly and accurately. Moreover, the qualitative information was much greater and provided an additional strategy for analytes identification. This rapid and accurate method will benefit workers involved in monitoring fishery.

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The carbon stable isotope compositions of glyphosate and aminomethylphosphonic acid (AMPA): Improved analytical sensitivity and first application to environmental water matrices

Limon

Moingt

Wîdory

2021

Rapid Comm Mass Spectrometry

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Rationale The presence of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) in the environment has adverse effects on environmental quality, raising the need to better constrain their fates, in particular the processes that control their production and degradation. Our aim was to improve the sensitivity of their δ13C analysis and demonstrate the feasibility of measuring them in natural surface water. Methods The δ13C values of dissolved glyphosate and AMPA were determined using isotope ratio mass spectrometry (IRMS) (Delta V Plus instrument) coupled to a high‐performance liquid chromatography (HPLC) unit, where glyphosate and AMPA were separated on a Hypercarb column. Results We demonstrated an improved sensitivity of the δ13C analysis for glyphosate and AMPA by LC/IRMS compared with previous studies. For waters from the carbonate and silicate hydrofacies, while no pretreatment was required for the isotope analysis of glyphosate, removal by H3PO4 acidification of dissolved inorganic carbon, that co‐elutes with AMPA, was required prior to its analysis. We successfully tested a freeze‐drying pre‐concentration method showing no associated isotope fractionation up to concentration factors of 500 and 50 for glyphosate and AMPA, respectively. Conclusions We demonstrated, for the first time, the feasibility of measuring the δ13C values of glyphosate and AMPA in natural surface waters with contrasted hydrofacies (calcium carbonate and silicate types). This opens new fields in pesticide research, especially on the characterization of processes that control their degradation and the production of their secondary byproducts.

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Solid-phase extraction method for stable isotope analysis of pesticides from large volume environmental water samples

Abstract: We validated a SPE-CSIA method that allows analysis of isotope ratios of mixtures of pesticides that commonly occur together in environmental water samples.

Cited by 47 publications

References 66 publications

Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor

Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor

Application of solid‐phase extraction: High‐resolution mass spectrometry analysis strategy in the characterization and quantification of amide herbicides in aquatic products

The carbon stable isotope compositions of glyphosate and aminomethylphosphonic acid (AMPA): Improved analytical sensitivity and first application to environmental water matrices

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