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Robust and highly sensitive micro Liquid Chromatography-tandem Mass Spectrometry method for analyses of polar pesticides (glyphosate, aminomethylphosfonic acid, N-acetyl glyphosate and N-acetyl aminomethylphosfonic acid) in multiple biological matrices

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@article{4fb048a9e85946108057b2a2aa01c192,
title = "Robust and highly sensitive micro Liquid Chromatography-tandem Mass Spectrometry method for analyses of polar pesticides (glyphosate, aminomethylphosfonic acid, N-acetyl glyphosate and N-acetyl aminomethylphosfonic acid) in multiple biological matrices",
abstract = "Glyphosate is the most used herbicide in agriculture. To monitor glyphosate exposure, analytical methods have to fulfill requirements with regard to sensitivity, reproducibility, ease of handling/high-throughput and applicability to multiple biological matrices. Furthermore, the methods have to include the degradation product of glyphosate, aminomethylphosfonic acid (AMPA) and preferably metabolites of glyphosate and AMPA, N-acetyl AMPA and N-acetyl glyphosate. Majority of the published methods for glyphosate and AMPA require derivatization to be able to achieve high sensitivity. In this work, we present highly sensitive microLC–MS/MS method for simultaneous quantification of glyphosate, AMPA, N-acetyl AMPA and N-acetyl glyphosate in multiple biological matrices without derivatization. The combination of simple sample clean-up procedures for simultaneous handling of 96 sample and short chromatographic run of only 3.4 min, meets the requirements for high-throughput methods. Simple mobile phase of water containing formic and medronic acids and isocratic run provided robust chromatographic separation on hypercarb column. The use of micro-flow system decreased the background noise, increasing the sensitivity. Achieved Low Limits of Quantification (LOQs) for liquid samples (plasma/serum/urine) were 0.00005 mg L−1 and 0.0001 mg kg−1 for solid samples (grain and soybean based feed/stomach/gizzard/intestinal content), which is more than 100 time more sensitive compared to QuPPe-Method. The method was validated in representative matrices with minimum of five fortification levels, six measurements per spiked concentration and three batches. All the samples were spiked with corresponding internal standards for all four analytes before sample clean-up procedures, ensuring high accuracy and precision. Recoveries for plasma/serum ranged between 86–108%, urine 93–120%, feed 91–115% and stomach/gizzard/intestinal content 92–110% with precision below 20%. The method{\textquoteright}s applicability was tested on 2000 samples measured during one year period.",
keywords = "glyphosate, microLC-MS/MS, aminomethylphosphonic acid, metabolites, solid-phase extraction",
author = "Natalja N{\o}rskov and Jensen, {S{\o}ren Krogh} and S{\o}rensen, {Martin Tang}",
note = "Copyright {\textcopyright} 2019 Elsevier B.V. All rights reserved.",
year = "2019",
month = nov,
doi = "10.1016/j.chroma.2019.06.064",
language = "English",
volume = "1605",
journal = "Journal of Chromatography A",
issn = "0021-9673",
publisher = "Elsevier BV",

}

RIS

TY - JOUR

T1 - Robust and highly sensitive micro Liquid Chromatography-tandem Mass Spectrometry method for analyses of polar pesticides (glyphosate, aminomethylphosfonic acid, N-acetyl glyphosate and N-acetyl aminomethylphosfonic acid) in multiple biological matrices

AU - Nørskov, Natalja

AU - Jensen, Søren Krogh

AU - Sørensen, Martin Tang

N1 - Copyright © 2019 Elsevier B.V. All rights reserved.

PY - 2019/11

Y1 - 2019/11

N2 - Glyphosate is the most used herbicide in agriculture. To monitor glyphosate exposure, analytical methods have to fulfill requirements with regard to sensitivity, reproducibility, ease of handling/high-throughput and applicability to multiple biological matrices. Furthermore, the methods have to include the degradation product of glyphosate, aminomethylphosfonic acid (AMPA) and preferably metabolites of glyphosate and AMPA, N-acetyl AMPA and N-acetyl glyphosate. Majority of the published methods for glyphosate and AMPA require derivatization to be able to achieve high sensitivity. In this work, we present highly sensitive microLC–MS/MS method for simultaneous quantification of glyphosate, AMPA, N-acetyl AMPA and N-acetyl glyphosate in multiple biological matrices without derivatization. The combination of simple sample clean-up procedures for simultaneous handling of 96 sample and short chromatographic run of only 3.4 min, meets the requirements for high-throughput methods. Simple mobile phase of water containing formic and medronic acids and isocratic run provided robust chromatographic separation on hypercarb column. The use of micro-flow system decreased the background noise, increasing the sensitivity. Achieved Low Limits of Quantification (LOQs) for liquid samples (plasma/serum/urine) were 0.00005 mg L−1 and 0.0001 mg kg−1 for solid samples (grain and soybean based feed/stomach/gizzard/intestinal content), which is more than 100 time more sensitive compared to QuPPe-Method. The method was validated in representative matrices with minimum of five fortification levels, six measurements per spiked concentration and three batches. All the samples were spiked with corresponding internal standards for all four analytes before sample clean-up procedures, ensuring high accuracy and precision. Recoveries for plasma/serum ranged between 86–108%, urine 93–120%, feed 91–115% and stomach/gizzard/intestinal content 92–110% with precision below 20%. The method’s applicability was tested on 2000 samples measured during one year period.

AB - Glyphosate is the most used herbicide in agriculture. To monitor glyphosate exposure, analytical methods have to fulfill requirements with regard to sensitivity, reproducibility, ease of handling/high-throughput and applicability to multiple biological matrices. Furthermore, the methods have to include the degradation product of glyphosate, aminomethylphosfonic acid (AMPA) and preferably metabolites of glyphosate and AMPA, N-acetyl AMPA and N-acetyl glyphosate. Majority of the published methods for glyphosate and AMPA require derivatization to be able to achieve high sensitivity. In this work, we present highly sensitive microLC–MS/MS method for simultaneous quantification of glyphosate, AMPA, N-acetyl AMPA and N-acetyl glyphosate in multiple biological matrices without derivatization. The combination of simple sample clean-up procedures for simultaneous handling of 96 sample and short chromatographic run of only 3.4 min, meets the requirements for high-throughput methods. Simple mobile phase of water containing formic and medronic acids and isocratic run provided robust chromatographic separation on hypercarb column. The use of micro-flow system decreased the background noise, increasing the sensitivity. Achieved Low Limits of Quantification (LOQs) for liquid samples (plasma/serum/urine) were 0.00005 mg L−1 and 0.0001 mg kg−1 for solid samples (grain and soybean based feed/stomach/gizzard/intestinal content), which is more than 100 time more sensitive compared to QuPPe-Method. The method was validated in representative matrices with minimum of five fortification levels, six measurements per spiked concentration and three batches. All the samples were spiked with corresponding internal standards for all four analytes before sample clean-up procedures, ensuring high accuracy and precision. Recoveries for plasma/serum ranged between 86–108%, urine 93–120%, feed 91–115% and stomach/gizzard/intestinal content 92–110% with precision below 20%. The method’s applicability was tested on 2000 samples measured during one year period.

KW - glyphosate

KW - microLC-MS/MS

KW - aminomethylphosphonic acid

KW - metabolites

KW - solid-phase extraction

U2 - 10.1016/j.chroma.2019.06.064

DO - 10.1016/j.chroma.2019.06.064

M3 - Journal article

C2 - 31307794

VL - 1605

JO - Journal of Chromatography A

JF - Journal of Chromatography A

SN - 0021-9673

M1 - 360343

ER -