Method For Glyphosate Research Articles

Method Validation for the Determination of Glyphosate and Aminomethylphosphonic Acid in Water by LC-MS/MS

The massive use of glyphosate as a herbicide compound has led to the ubiquity of AMPA in the environment, especially in water. So, the present work aimed to establish the validation parameters of the LC-MS/MS method for glyphosate and its metabolite AMPA, determination in water. During the extraction process the derivatization of glyphosate as an extreme polar pesticide, was done using FMOC. The validation results show that the method met the criteria given in SANTE/11312/2021 for all the investigated validation parameters as well as estimated measurement uncertainty.

Effective and rugged analysis of glyphosate, glufosinate, and metabolites in Tenebrio molitor larva (mealworms) using liquid chromatography tandem mass spectrometry

Tenebrio molitor larva (mealworms) has recently attracted attention as a protein source for food and feed. The larva is generally fed with wheat bran, which can be possibly contaminated with glyphosate. To establish food safe standards, a rugged and effective analytical method for glyphosate, aminomethylphosphonic acid, glufosinate, and their metabolites including 3-methylphosphinico-propionic acid, and N-acetyl glufosinate, in mealworms was optimized using liquid chromatography tandem mass spectrometry. An anionic polar pesticide column was used due to its high suitability for glyphosate. Acidified water and acetonitrile were used to extract the target compounds without contribution from various fatty and pigment interferences derived from brownish insects. Seven different clean-up procedures ((1) 50 mg C18 (2) 20 mg C18/Z-sep (3) PRiME hydrophilic-lipophilic balance (HLB) cartridge (4) 75 mg Z-sep, (5) 75 mg Z-sep+, (6) EMR-lipid cartridge, and (7) 50 mg ENVI-Carb) were compared. Due to its simplicity and cost-effectiveness, PRiME HLB was selected for clean-up. The recoveries of the target compounds were ranged from 86 to 96% with < 20% relative standard deviations. Therefore, this simple and effective method can be applied for the two pesticides and their metabolites in other edible insects or high-fat matrices.

Validation of a simple method for the determination of glyphosate and aminomethylphosphonic acid in human urine by UPLC-MS/MS

Environmental pollutants such as pesticides can be detrimental to human health and/or to the environment. Their excessive use may produce toxicity through various mechanisms. Glyphosate is a broad-spectrum herbicide with a high worldwide distribution. Due to this, this chemical is classified as a ‘Group 2A – probably carcinogenic to humans’ by the International Agency for Research on Cancer. Human biomonitoring is considered the golden standard for exposure assessment and provides a very useful tool in public health. Therefore, it is important to develop methods to determine traces of this herbicide and its metabolite, aminomethyl phosphonic acid, in human biological samples. A new method for glyphosate and aminomethyl phosphonic acid determination in human urine is herein described and discussed. It is based on the derivatization procedure with Fluorenylmethoxycarbonyl chloride and quantification by ultra-performance liquid chromatography-tandem mass spectrometry. The method was optimized and suitably validated, with a linear range from 1 to 20 µg L−1 in the case of glyphosate and 0.5–20 µg L−1 for aminomethyl phosphonic acid. Limits of detection and quantification were 0.5 and 1 µg L−1 for glyphosate and 0.1 and 0.5 µg L−1 for aminomethyl phosphonic acid, respectively. Mean relative recoveries ranged 108–109% for glyphosate and 104–119% for aminomethyl phosphonic acid and intermediate precision values varied from 11.90 to 12.70% for glyphosate and 4.8–9% for aminomethyl phosphonic acid. The validated method has been applied in human urine from female farmers indirectly exposed to pesticides. This procedure can be used to monitor potential exposure of humans to glyphosate and aminomethyl phosphonic acid in epidemiological studies and for routine controls in public health.

An ion chromatography tandem mass spectrometry (IC-MS/MS) method for glyphosate and amino methyl phosphoric acid in serum of occupational workers

A non-suppressed ion chromatography tandem mass spectrometry (IC-MS/MS) has been established to measure glyphosate (GLY) and amino methyl phosphoric acid (AMPA) in serum of the occupational workers. After the inhibition of metal-chelating with EDTA aqueous solution and protein precipitation with acetonitrile, the samples were purified with a modified liquid–liquid extraction method and separated on an ion chromatographic column (250 mm × 2.1 mm) by using a gradient program of 0.4 mol/L methylamine aqueous solution and acetonitrile as mobile phase. Multiple reactions monitoring (MRM) model was used to obtain the sensitivity of the method, and the isotopically labelled internal standards were applied in the calibration process. Good linearities and recoveries were obtained in the validation process. The recovery experiment provided satisfied results with a range of 91%~101% for GLY and 92%~99% for AMPA in human serum and RSD values for both two analytes were <4%. The limits of detection for GLY and AMPA were 0.6 ng/mL and 1.2 ng/mL, respectively. The association between the posts in workplace and the concentration of two contaminants in serum samples was investigated throughout the analysis of the 307 worker serum samples. The data analysis results indicated the distribution of compounds in human serum was significantly related to the exposure probability and duration during the manufacture process of GLY.

Development of Analytical Method for Glyphosate and Glufosinate in Animal Feeds using LC-MS/MS

Development of Analytical Method for Glyphosate and Glufosinate in Animal Feeds using LC-MS/MS

A rapid screening color test for glyphosate using dabsyl derivatization

Glyphosate is the most common herbicide in the world, and involved in many poisoning cases. However, the analysis of glyphosate has been difficult because of its high polarity and zwitterionic structure, and no simple screening tests for glyphosate have been known. The purpose of this study was to develop a rapid screening test for glyphosate. Glyphosate was visualized through a color change induced by dabsyl derivatization, and the derivatized glyphosate was trapped on the surface of zirconia-coated silica particles by specific chemical interaction between a phosphonate group of glyphosate and the zirconia surface. The presence of glyphosate was indicated by the color change of zirconia surface, which was easily noticed by the naked eye. The developed method was applied to biological samples (urine and serum), beverage samples (green tea and cola drink), and soil samples. No false positive was observed and the detection limit was 100 μg/mL for the biological samples and 800 μg/mL for the beverage samples. A simple screening method for glyphosate based on a color test was established. The method is rapid and requires less than 30 μL of samples. The sensitivity was sufficient for most cases of moderate to severe poisoning.

A simple and rapid direct injection method for the determination of glyphosate and AMPA in environmental water samples.

Glyphosate is currently the most widely used herbicide in the world, yet screening of environmental waters for this chemical is limited by the need for specialized derivatization and measurement methods that can be tedious and time-consuming. In this work, we present a novel method for the detection and quantification at trace levels of glyphosate and aminomethylphosphonic acid (AMPA) in environmental water samples. The detection and quantification of the analytes was performed by liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS). Chromatographic separation was achieved with an ion-exchange column and a pH-gradient elution of a solution of ammonium hydroxide and ammonium acetate. The limit of detection for glyphosate and AMPA was 0.25 μg L-1 and the limit of quantification was 0.5 μg L-1with a 20-μL injection. The method was used to investigate the levels of glyphosate and AMPA in surface water samples from the Yarra River catchment area and urban constructed stormwater wetlands. The results indicate that at the time of sampling, no glyphosate or AMPA was present in the samples from the Yarra River catchment area (n = 10). However, glyphosate was detected above the limit of quantification in 33% of the wetland samples (n = 12), with concentrations ranging from 1.95 to 2.96 μg L-1. Similarly, AMPA was quantified in 83% of the wetland samples, with concentrations ranging from 0.55 to 2.42 μg L-1. To our knowledge, this is the first report of a pH-gradient LC-MS/MS method for glyphosate and AMPA analysis at ultratrace levels, with minimal sample processing, avoiding costly, time-consuming derivatization and preconcentration steps. Graphical abstract ᅟ.

Simultaneous determination of phosphorous by-products and inorganic anions in glyphosate mother liquor by ion chromatography with suppressed-conductivity detection

The by-product anion content was an important index for the evaluation of pesticide glyphosate's productivity technology. A method was developed for the simultaneous determination of glyphosate, phosphorous by-products and other trace impurity anions in the mother liquor of glyphosate procedure by ion chromatography (IC). The sample was diluted with deionized water and filtrated by 0.22 microm nylon filter membrane, and then analyzed by IC directly without anymore pretreatment. The analytical column was Dionex IonPac AS11-HC (250 mm x 4 mm) with a guard column IonPac AG11-HC (50 mm x 4 mm). Gradient KOH eluent generated by an eluent generation cartridge was used at a flow rate of 1.0 mL/min. The detection was performed by a Dionex suppressed conductivity detector. The quantitative analysis of external standard calibration curves was used. The linear ranges of the method for glyphosate, methyl glyphosate, hexamethylphosphoramide (HMPA), glyphosine, phosphite, phosphate, chloride and sulfate were 0.1 - 20 mg/L (r = 0.9995), 0.1 - 20 mg/L (r = 0.9993), 0.1 - 50 mg/L (r = 0.9999), 0.25 - 50 mg/L ( r = 0.9998), 0.05 - 20 mg/L (r = 0.9999), 0.2 - 50 mg/L ( r = 0.9985), 0.02 - 20 mg/L (r = 0.9999) and 0.05 - 50 mg/L (r = 0.9980), respectively. The average recoveries were 93.7% - 104.0% with the relative standard deviations less than 2.5% (n = 7), and the detection limits (S/N = 3) were 0.002 - 0.025 mg/L. The method has been applied to determine the contents of glyphosate, phosphorous by-products and inorganic anions in the mother liquor of glyphosate with satisfactory results.

Determination of glyphosate and its metabolite aminomethylphosphonic acid in fruit juices using supported-liquid membrane preconcentration method with high-performance liquid chromatography and UV detection after derivatization with p-toluenesulphonyl chloride

The application of supported-liquid membrane (SLM) technique for effective extraction of N-(phosphonomethyl)glycine (glyphosate) and its primary metabolite aminomethylphosphonic acid (AMPA) from juices (orange, grapefruit, apple and blackcurrant) in combination with HPLC-UV detection after derivatization with p-toluenesulphonyl chloride (TsCl) is presented. The influence of various parameters such as the composition of acceptor phase, flow-rate, concentration of analytes, on the performance of extraction procedure, was studied. It was shown that by appropriate manipulation of SLM parameters the level of detection could be significantly improved. The influence of SLM conditions on extraction efficiency of studied compounds was also discussed. Selection of the optimal conditions enable detection of glyphosate and AMPA in juices at concentrations as low as 0.025 mg/l. The calculated recoveries for glyphosate were—71.1, 72.1, 93.6, and 102.7% and for AMPA—64.1, 64.6, 81.7, and 89.2%, for orange, grapefruit, apple and blackcurrant juices, respectively. The results suggest that the application of SLM extraction as a method for glyphosate and AMPA enrichment from complicated liquid matrices may be useful mean of routine analysis.