Sensitive and selective quantification of glyphosate and aminomethylphosphonic acid (AMPA) in urine of the general population by gas chromatography-tandem mass spectrometry

Connolly, Alison; Koslitz, Stephan; Bury, Daniel; Brüning, Thomas; Conrad, André; Kolossa-Gehring, Marike; Coggins, Marie; Koch, Holger M.

doi:10.1016/j.jchromb.2020.122348

Cited by 31 publications

(17 citation statements)

References 18 publications

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“…The fact that his urine was positive was in accordance with a systemic absorption of glyphosate in this subject. The urine concentration of glyphosate found in F1 was higher than that usually observed in the general population (Connolly, Koslitz, et al, 2020;Faniband et al, 2021) and half of the median found in exposed workers (Zhang et al, 2020).…”

Section: Discussioncontrasting

confidence: 60%

“…Glyphosate and AMPA can be measured in soils, water, plants, animals, and food (Koskinen et al, 2016). In humans, both compounds have been detected and measured in urine in many studies, reviewed by Gillezeau et al (2019) and more recently by Connolly, Koslitz, et al (2020). Urinary glyphosate concentration has therefore been proposed as a quantitative biomarker of oral exposure to glyphosate (Acquavella et al, 2004; Connolly, Coggins, & Koch, 2020; Dereumeaux et al, 2022; Faniband et al, 2021; Knudsen et al, 2017; Zoller et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

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Glyphosate and aminomethylphosphonic acid in human hair quantified by an LC‐MS/MS method

Alvarez

Etting

Larabi

2022

Biomedical Chromatography

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An LC-MS/MS method for hair testing of glyphosate and aminomethylphosphonic acid (AMPA), its main biodegradation product, has been developed. After decontamination, 50 mg of hair was ground and sonicated in water for 2 h. The method was fully validated in the 5-500 pg/mg range for glyphosate and 10-500 pg/mg for AMPA, and the limits of detection were 2 and 5 pg/mg, respectively. Matrix effect for glyphosate and AMPA was compensated by an isotope-labeled internal standard.Hair samples from four farmers who regularly used glyphosate and one farmer who used glyphosate but not his wife and 14 hair samples from nonoccupationally exposed subjects were tested. Glyphosate was found in head hair of three farmers, with concentration in the range 14-188 pg/mg. The fourth was found negative but with hair colored in red. Glyphosate was detected in 10 of 14 hair samples from nonoccupationally exposed subjects at concentrations of 11.5 pg/mg or lower and only in one segment (0-3 cm) of the farmer's spouse (6 pg/mg). AMPA was detected in five subjects, above the limit of quantification only in two of three occupationally exposed subjects with positive glyphosate.Further studies should be conducted to validate this potential new biomarker that could be useful for assessing long-term exposure to glyphosate.aminomethylphosphonic acid, biomonitoring, glyphosate, hair, long-term exposure | INTRODUCTIONGlyphosate (N-phosphonomethyl-glycine, M w = 169.1, Figure 1a) was registered in 1974 in the United States as a broad-spectrum contact herbicide. Its use has dramatically increased by more than 100-fold over the past four decades, and global estimates of its use suggest that sufficient glyphosate-based herbicide was applied in 2014 to spray nearly 0.5 kg of glyphosate on every hectare of cropland on the planet, making glyphosate the most widely used herbicide in the world (Vandenberg et al., 2017). Once applied, it diffuses into water where it persists for many weeks before being transformed by bacteria into aminomethylphosphonic acid (AMPA, Figure 1b) (La Cecilia & Maggi, 2018). Its environmental half-life is 47 days at 25 C with light exposure or 267 days in the dark at the same temperature (Mercurio et al., 2014). This persistence increases the risk, as with many pesticides, of accumulation and environmental exposure to this compound.In 2015, the European Food Safety Authority defined an acute reference dose (ARfD), corresponding to an estimate of a substance that can be ingested once without appreciable health risk to the consumer.Glyphosate ARfD has been estimated at 0.5 mg/kg of body weight, thus recognizing for the first time an acute toxicity of this chemical (European Food Safety Authority, 2015). Few epidemiological studies examining the impact of chronic glyphosate exposure on human diseases have been published. On March 20, 2015, the International Agency for Research on Cancer of the World Health Organization classified glyphosate in group 2A of active chemicals, namely a probable carcinogen to humans (Guyton et al., 2015). ...

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Section: Discussioncontrasting

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Glyphosate and aminomethylphosphonic acid in human hair quantified by an LC‐MS/MS method

Alvarez

Etting

Larabi

2022

Biomedical Chromatography

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“…After stopping the FMOC derivatization reaction, removing the excess of FMOC-Cl and its hydrolysis by-products is recommended. To this end, the HLB cartridge was rinsed with DCM [ 6 ]. The employed volume was 2 mL.…”

Section: Resultsmentioning

confidence: 99%

“…The quantification of trace concentrations of GLY and AMPA represents a challenging issue due to the high polar, zwitterion character, low molecular weight, and ligand properties of both species. Derivatization of polar moieties in the structure of both compounds (i.e., using a combination of trifluoroacetic acid and trifluoroethanol [ 6 ], or a silylation reagent [ 7 ]) allows their determination by gas chromatography-mass spectrometry (GC–MS) [ 6 , 8 ]. However, liquid chromatography-mass spectrometry (LC–MS) remains the most resorted technique for the quantification of GLY and AMPA in environmental and food samples.…”

Section: Introductionmentioning

confidence: 99%

Approaches to liquid chromatography tandem mass spectrometry assessment of glyphosate residues in wine

et al. 2021

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The performance of two different analytical methodologies to investigate the presence of glyphosate (GLY) and aminomethylphosphonic acid (AMPA) residues in wine samples was evaluated. Transformation of compounds in their fluorene-9-methyloxycarbonyl derivatives permitted their separation under reversed-phase liquid chromatography with tandem mass spectrometry (LC–MS/MS) determination. Although the wine matrix severely impaired the efficiency of GLY derivatization, this drawback was solved using a molecularly imprinted sorbent for the previous, selective extraction of GLY and AMPA from wine. Alternatively, the use of a strong anionic exchange, polyvinyl alcohol-based LC column, turned to be the most effective alternative for direct determination of both compounds in diluted wine samples. The chromatographic behavior of this column and the magnitude of matrix effects observed during analysis of diluted wine samples were significantly affected by the composition of the mobile phase. Under final working conditions, this column permitted the separation of AMPA and the fungicide fosetyl (which shows common transitions in tandem MS/MS methods), it improved significantly the sample throughput versus extraction-derivatization-purification method, and it allowed the use of solvent-based calibration standards. Both analytical procedures provided similar limits of quantification (LOQs) for GLY (0.5–1.0 ng mL−1), while the multistep method was 8 times more sensitive to AMPA than the direct procedure. GLY residues stayed above method LOQs in 70% of the processed wines; however, concentrations measured in 95% of positive samples remained 100 times below the maximum residue limit (MRL) set for GLY in vinification grapes. Graphical abstract

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“…Most noteworthy, it is challenging to determine GLY and GLU in plant samples at trace levels because of their physical and chemical properties, such as low molecular weight, high hydrophilicity, non-volatility, and lack of easily detectable chemical groups. Even so, several analytical methods were developed for the detection of GLY and GLU in agricultural products, using gas chromatography-tandem mass spectrometry (GC-MS), 7,8 high performance liquid chromatography (HPLC) with uorescence detection [9][10][11] and liquid chromatography-tandem mass spectrometry (LC-MS/MS) aer derivatization. [12][13][14] These methods were mostly employed for pre-column derivatization using 9-uorenylmethoxycarbonyl (FMOC) to facilitate chromatographic retention of analytes, and a general consensus exists on the use of FMOC for GLY determination.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous determination of glyphosate, glufosinate ammonium and their metabolites in maize and soybean by ultra-performance liquid chromatography with tandem mass spectrometry

et al. 2022

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Sensitive and selective quantification of glyphosate and aminomethylphosphonic acid (AMPA) in urine of the general population by gas chromatography-tandem mass spectrometry

Cited by 31 publications

References 18 publications

Glyphosate and aminomethylphosphonic acid in human hair quantified by an LC‐MS/MS method

Glyphosate and aminomethylphosphonic acid in human hair quantified by an LC‐MS/MS method

Approaches to liquid chromatography tandem mass spectrometry assessment of glyphosate residues in wine

Simultaneous determination of glyphosate, glufosinate ammonium and their metabolites in maize and soybean by ultra-performance liquid chromatography with tandem mass spectrometry

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