Challenges in direct determination of Glyphosate and aminomethylphosphonic acid in water by liquid chromatography-tandem mass spectrometry at modified reverse phase columns: Effect of matrix interferences in fresh and hard water systems.

This study validated two underivatized methods (M1 and M2) according to the Eurachem guidelines to analyze the herbicide Glyphosate and its major metabolite aminomethylphosphonic acid simultaneously by liquid chromatography-tandem mass spectrometry in both fresh and hard waters. Samples were analyzed directly after filtration through 0.22 µm syringe filters in M1, while samples were acidified with acetic acid before filtration in M2. Spike recoveries were greater than 80% for Glyphosate and aminomethylphosphonic acid in both methods. The limit of quantitation was 0.5 µg/L for M1, and 0.1 µg/L for M2 by using matrix-matched calibrations. The linear regression coefficient of both methods was greater than 0.995. The expanded uncertainty was found to be less than 25% for both. Moreover, M1 has an additional mass spectral confirmation ability, and the column and the mobile phase used in M2 can be used to analyze the inert surfactant used in Glyphosate formulations, Polyethoxylated tallow amine. The accuracy of the developed methods was assured by participating in a proficiency testing program against M2 and conducting the t-test for results generated by both M1 and M2. Both methods, therefore, can be used to determine Glyphosate and aminomethylphosphonic acid content concurrently in fresh and hard waters.

Development and validation of an integrated microfluidic device with an in-line Surface Enhanced Raman Spectroscopy (SERS) detection of glyphosate in drinking water.

Glyphosate, also known as N-(phosphonomethyl)glycine, is one of the most widely used herbicides in the world. However, the controversy surrounding the toxicity of glyphosate and its main breakdown product, aminomethylphosphonic acid (AMPA), remains a serious public concern. Therefore, there is a clear need to develop a rapid, sensitive and automated alternative method for the quantification of glyphosate and AMPA. In this context, surface enhanced Raman spectroscopy (SERS) coupled with a microfluidic system for the determination of glyphosate in tap water was developed, optimized and validated. The design of the microfluidic configuration for this application was built constructed to integrate the synthesis of the SERS substrate through to the detection of the analyte. To optimize the microfluidic setup, a design of experiments approach was used to maximize the SERS signal of glyphosate. Subsequently, an approach based on the European guideline document SANTE/11312/2021 was used to validate the method in the range of 78-480 µg/L using the normalized band intensities. The limit of detection and quantification obtained for glyphosate were 40 and 78 µg/L, respectively. Recoveries were in the range 76-117%, while repeatability and intra-day reproducibility were ≤17%. Finally, the method was also tested for the determination of AMPA in tap water matrix and for the simultaneous detection of AMPA and glyphosate.

Different Approaches in Manipulating Ratio Spectra for Analyzing Amlodipine Besylate and Irbesartan Combination.

BACKGROUND: Hypertension is a key risk factor for ischemic heart disease and atherosclerosis. Most patients require a combination of antihypertensive medications to accomplish their therapeutic goals. Antihypertensive medicines such as calcium channel blockers and angiotensin receptor blockers are indicated for patients whose high blood pressure cannot be controlled with monotherapy. The combination of amlodipine besylate (AML) with irbesartan (IRB) is an example of this synergistic activity in lowering blood pressure. OBJECTIVE: In this regard, the goal of the research is to develop sensitive spectrophotometric methods for the simultaneous determination of amlodipine besylate and irbesartan. METHODS: Three simple ratio spectra-manipulating spectrophotometric methods namely, ratio difference, mean centering of ratio spectra, and derivative ratio, were developed for the simultaneous assay of the cited mixture. RESULTS: Linear correlations were attained over the concentration range of 1-35 µg/mL and 2-35 µg/mL for amlodipine besylate and irbesartan, respectively. The methods were validated according to the International Conference on Harmonization guidelines with good results. CONCLUSION: The methods developed were successfully applied for the assay of the cited drugs in their marketed formulation. They could be efficiently used for routine analysis of the mentioned drugs in QC laboratories. HIGHLIGHTS: The proposed approaches do not require expensive solvents or complex instruments. They could be used in routine laboratory tests where time and cost are crucial.

Determination of glyphosate, aminomethylphosphonic acid, and glufosinate in river water and sediments using microwave-assisted rapid derivatization and LC-MS/MS.

Glyphosate (N-phosphonomethyl glycine) and glufosinate (ammonium dl-homoalanin- 4-methyl phosphinate) are nonselective, broad-spectrum, and highly polar herbicides that are wildly used for weed control in aquatic systems and vegetation control in non-crop areas. Aminomethylphosphonic acid (AMPA) is the major degradation product of glyphosate. To address the concerns to its environmental residue and the possible adverse effects, the analytical methods by using microwave-assisted derivatization were developed for determining glyphosate, AMPA, and glufosinate in river water and sediments. The methods applied the 9-fluorenylmethyloxycarbonyl chloride (FMOC-Cl) derivatization for the analytes. The microwave heating is first-time applied to reduce the FMOC-reaction time of glyphosate, AMPA, and glyphosate in the environmental samples to less than 2.5 min. The microwave-assisted methods were successfully validated for river water and sediment. The linear ranges of 7.8-2000.0 ng/L and 0.78-100.0 ng/g were achieved by using 10 mL of water and 2 g of sediments. Glyphosate was found in 30/32% and 25/32% of 32 water and 32 sediments at 27.1-1353.9 ng/L and 2.4-189.6 ng/g levels. AMPA was found in 30/32% and 30/32% of 32 water and 32 sediments at 60.2-1509.0 ng/L and 1.8-233.6 ng/g levels. Glyphosate was found in 10/32% of 32 water at 14.8-503.1 ng/L levels. No glufosinate residue was observed for 32 sediments. The residues of glyphosate and AMPA were wildly detected in the river waters and sediments near the agricultural regions, and glufosinate was less detected. This is the first study that reported herbicide levels in water and sediment from Taiwan rural areas using microwave-assisted rapid derivatization, useful information for environmental management.

Secondary Effects of Hypochlorite Treatment on the Emerging Pollutant Candesartan: The Formation of Degradation Byproducts and Their Toxicological Profiles.

In recent years, many studies have reported the frequent detection of antihypertensive agents such as sartans (olmesartan, valsartan, irbesartan and candesartan) in the influents and effluents of wastewater treatment plants (WWTPs) and in the superficial waters of rivers and lakes in both Europe and North America. In this paper, the degradation pathway for candesartan (CAN) was investigated by simulating the chlorination process that is normally used to reduce microbial contamination in a WWTP. Twelve isolated degradation byproducts (DPs), four of which were isolated for the first time, were separated on a C-18 column by employing a gradient HPLC method, and their structures were identified by combining nuclear magnetic resonance and mass spectrometry and comparing the results with commercial standards. On the basis of these results, a mechanism of formation starting from the parent drug is proposed. The ecotoxicity of CAN and its DPs was studied by conducting a battery of ecotoxicity tests; bioassays were performed using Aliivibrio fischeri (bacterium), Daphnia magna (planktonic crustacean) and Raphidocelis subcapitata (alga). The ecotoxicity results shed new light on the increased toxicity of DPs compared with the parent compound.

LC and NMR Studies for Identification and Characterization of Degradation Byproducts of Olmesartan Acid, Elucidation of Their Degradation Pathway and Ecotoxicity Assessment.

The discovery of various sartans, which are among the most used antihypertensive drugs in the world, is increasingly frequent not only in wastewater but also in surface water and, in some cases, even in drinking or groundwater. In this paper, the degradation pathway of olmesartan acid, one of the most used sartans, was investigated by simulating the chlorination process normally used in a wastewater treatment plant to reduce similar emerging pollutants. The structures of nine isolated degradation byproducts (DPs), eight of which were isolated for the first time, were separated via chromatography column and HPLC methods, identified by combining nuclear magnetic resonance and mass spectrometry, and justified by a proposed mechanism of formation beginning from the parent drug. Ecotoxicity tests on olmesartan acid and its nine DPs showed that 50% of the investigated byproducts inhibited the target species Aliivibrio fischeri and Raphidocelis subcapitata, causing functional decreases of 18% and 53%, respectively.

UPLC-MS/MS assay of Tedizolid in rabbit aqueous humor: Application to ocular pharmacokinetic study.

Tedizolid phosphate (TZP) a prodrug of Tedizolid (TDZ) is a novel oxazolidinone antibiotic, used for the treatment of acute bacterial skin, skin structure infections and other serious gram positive and MRSA infections. In the present study, a sensitive UPLC-MS/MS analytical method was developed and validated for the quantification of TDZ in rabbit's aqueous humor (AqH) by using linezolid as internal standard (IS). Both TDZ and IS were separated on an Acquity™ HILIC column using an isocratic mobile phase comprising of acetonitrile: 20 mM ammonium acetate (85:15, v/v), eluted at 0.3mLmin-1 flow rate with total run time of 3 min. The AqH samples were processed by protein precipitation method by using acetonitrile as precipitating agent. TDZ and IS were detected in positive mode using electrospray ionization source. The precursor to product ion transitions at m/z 371.15 to 343.17 for TDZ and m/z 338.18 to 296.22 for IS were used for the quantification in multiple reaction monitoring mode. The calibration curve was linear in the concentration range of 4.98-1000ngmL-1 and the lower limit of detection was 1.97ngmL-1 only. The method was validated following US-FDA-guidelines and the results of validation parameter were found within the set limits. The developed UPLC-MS/MS method was fast, sensitive and reliable for the quantification of TDZ in the rabbit AqH and was successfully employed for ocular pharmacokinetic study of TDZ in AqH after topical ocular application of TZP-containing formulations in rabbit eyes.

Toxicity, residue and risk assessment of tetraniliprole in soil-earthworm microcosms.

Maize seed treatment with chemicals to control underground pests is a common agricultural practice, but inappropriate use of insecticides poses a considerable threat to plant development and soil nontarget organisms. In this study, the availability of tetraniliprole seed dressing to control the black cutworm Agrotis ipsilon (Lepidoptera: Noctuidae) in the maize seeding stage and its safety to earthworms (Eisenia fetida) were investigated. The selective toxicity (ST) of tetraniliprole between E. fetida and A. ipsilon was greater than 4000. No significant adverse effect of tetraniliprole seed treatment on the germination of maize seeds was observed at concentrations of 2.4-9.6 g a.i. /kg seed. Compared with the untreated control, seed treatment with tetraniliprole at 9.6 g a.i. /kg seed greatly reduced the percentage of damaged plants from 88.73% to 26.67%, and achieved the highest control effect of 69.91%. Tetraniliprole of 2.4 g a.i. /kg seed can effectively inhibit A. ipsilon until 14 days after seed germination, with the lowest mortality rate of 44.44%. During the entire exposure period, the maximum residual concentration of tetraniliprole detected in the soil (5.86 mg/kg) was considerably lower than the LC50 value of tetraniliprole to E. fetida (>4000 mg/kg). According to the low-tier risk assessment, the highest risk quotient (RQ) of tetraniliprole seed treatment to earthworms at test concentrations was 2.8 × 10-3, which was evaluated as acceptable. This study provided data support for tetraniliprole seed treatment to control underground pests in maize fields.

Simultaneous quantification of candesartan and irbesartan in rabbit eye tissues by liquid chromatography-tandem mass spectrometry.

Diabetic retinopathy is a major cause of vision loss in adults. Novel eye-drop formulations of candesartan and irbesartan are being developed for its cure or treatment. To support a preclinical trial in rabbits, it was critical to develop and validate a new LC-MS/MS method for simultaneous quantification of candesartan and irbesartan in rabbit eye tissues (cornea, aqueous humor, vitreous body and retina/choroid). Eye tissue samples were first homogenized in H2 O-diluted rabbit plasma. The candesartan and irbesartan in the supernatants together with their respective internal standards (candesartan-d4 and irbesartan-d4 ) were extracted by solid-phase extraction. The extracted samples were injected onto a C18 column for gradient separation. The MS detection was in the positive electrospray ionization mode using the multiple reaction monitoring transitions of m/z 441 → 263, 445 → 267, 429 → 207, and 433 → 211 for candesartan, candesartan-d4 , irbesartan and irbesartan-d4 , respectively. For the validated concentration ranges (2-2000 and 5-5000 ng/g for candesartan and irbesartan, respectively), the within-run and between-run accuracies (% bias) were within the range of -8.0-10.0. The percentage CV ranged from 0.6 to 7.3. There was no significant matrix interference nor matrix effect from different eye tissues and different rabbits. The validated method was successfully used in the Good Laboratory Practice (GLP) study of rabbits.

HPLC method transfer study for simultaneous determination of seven angiotensin II receptor blockers.

In this study, a sensitive high-performance liquid chromatography method was developed and validated for the simultaneous determination of seven angiotensin II receptor blockers, namely, hydrochlorothiazide, chlorthalidone, eprosartan mesylate, valsartan, losartan potassium, irbesartan, and candesartan cilexetil. Different chromatographic parameters were tested and fully optimized. Best chromatographic separation was accomplished on a reversed-phase octadecylsilyl column (250 × 4.6 mm id; 5 µm) under gradient elution using methanol/sodium phosphate monobasic buffer (0.01 M, pH 6.5) as mobile phase. The detection of target analytes was obtained at 254 nm. The pH of the buffer has been selected according to Marvin® sketch software. The proposed method was validated according to ICH guidelines and showed good precision (relative standard deviation < 1), good linearity (square of correlation coefficient ≥ 0.999), and high accuracy (between 98 and 102%) with detection limit and quantitation limit (40 and 160 ng/mL, respectively) for all the detected analytes.

Transfer of Candesartan Into Human Breast Milk.

BACKGROUND: There are currently no data regarding the transfer of candesartan into human milk. This report provides data on this transfer, an estimation of the amount breastfed infants receive, and plasma concentrations from two breastfed infants. CASES: Three breastfeeding mothers, all stabilized on candesartan (8-32 mg/d), provided milk and plasma samples over one dosing interval (24 hours). Two infant plasma samples were obtained. The amount the infants ingested was estimated to be 0.09% (95% CI 0.07-0.11) of the maternal dose (weight-adjusted). Candesartan was undetectable (less than 0.2 micrograms/L) in infant plasma samples. CONCLUSION: A relative infant dose of 0.09% suggests that maternal benefit from candesartan at standard therapeutic doses may outweigh risk in breastfeeding healthy, term infants.

Adsorption-Desorption and Leaching Behaviors of Tetraniliprole in Three Typical Soils of China.

Tetraniliprole (TTP) is a new bisimide-based insecticide. Three typical surface soil samples were collected in farmland across China, including Jiangxi red soil (RS), Shandong yellow brown soil (YBS), and Heilongjiang black soil (BS). Adsorption, desorption and leaching experiments were conducted by using equilibrium oscillation and soil column leaching methods at 25°C ± 1°C. The isothermal adsorption and desorption curves of TTP in the above three soils were in accordance with the Freundlich model. The adsorption/desorption constants (Kads-f/Kdes-f) were 41.96-64.48 and 3.62-43.65, respectively. There is a certain hysteresis in the desorption curve, and the hysteresis coefficient (H) was between 0.14 and 0.89. Besides, the leaching properties of TTP in three soils were different. The leaching of TTP in RS and YBS was easy, while difficult for BS. It is concluded that the different adsorption-desorption ability and leaching ability of TTP in the above three soils was attributed to the distinct contents of organic matter (OM) and cation exchange capacity (CEC) in soil.

Modeling the mobility of glyphosate from two contrasting agricultural soils in laboratory column experiments.

Glyphosate (GLP) currently is one of the most widely used herbicides worldwide. The persistence of GLP and its major metabolite, aminomethylphosphonic acid (AMPA) in the environment has been described by other authors. This study was aimed at comparing the GLP and AMPA behavior in sandy and loamy sand soils after spiking with enhanced (445 µg g-1) concentrations of GLP in herbicide KLINIK® (Nufarm, Austria) and bioaugmentation followed by 40 days weathering and a consistent three-stage leaching in a laboratory column experiment. Soil samples were obtained from mineral topsoil (0-10 cm) within former agricultural lands where soil parent material was formed by glacigenic deposits. The total amount of GLP and AMPA collected during three leaching stages was significantly (p<.05) higher from columns with sandy soil, compared to loamy sand soil. Bioaugmentation resulted in considerably lower concentrations of AMPA in leachates, especially in the sets with sandy soil (p=.01). Leachates were tested using FTIR spectroscopy and Daphnia magna. Statistical analysis of the changes in Ntot, Ctot, K+, Mg2+, Al3+, Ca2+, Mn2+ and Fe3+ concentrations in soils after the leaching experiment revealed that the loamy sand soil was likely to be more sensitive to the addition of GLP and bioaugmentation than sandy soil.

Fast analysis of glufosinate, glyphosate and its main metabolite, aminomethylphosphonic acid, in edible oils, by liquid chromatographycoupled with electrospray tandem mass spectrometry.

A method has been developed for the rapid, specific, accurate, precise and sensitive determination of glufosinate, glyphosate and its major metabolite, aminomethylphosphonic acid, in edible oils, by liquid chromatography coupled to tandem mass spectrometry. Oils were extracted with acidified water (1% formic acid), and the extracts were directly injected into an LC using a Hypercarb column as the stationary phase. The analytes were eluted by a mobile phase of methanol and water containing 1% acetic acid, and they were ionised by electrospray ionisation in negative ion mode. The method was validated and limits of quantification ranged from 5 µg kg-1 (aminomethylphosphonic acid) to 10 µg kg-1 (glyphosate and glufosinate). Three concentrations (10, 50 and 100 µg kg-1) were selected to perform recovery studies. Mean recoveries ranged from 81.4% to 119.4%. Intra and inter-day precision were lower than 19%. Different edible oils were analysed, and no residues of the studied herbicides were detected above limits of quantification.

Selective determination of sartan drugs in environmental water samples by mixed-mode solid-phase extraction and liquid chromatography tandem mass spectrometry.

Herein, a method for the simultaneous determination of the currently prescribed sartan drugs (eprosartan, EPR; olmesartan, OLM; losartan, LOS; candesartan, CAN; telmisartan, TEL; irbesartan, IRB; and valsartan, VAL), and the biodegradation product valsartan acid (VALA), in water samples (raw and treated wastewater, river and tap water) was developed. Solid-phase extraction (SPE) and ultra-performance liquid chromatography (UPLC) tandem mass spectrometry (MS/MS) were employed as concentration and determination techniques, respectively. Different sorbents and elution solvents were tested for sample preparation. Under optimized conditions, samples at neutral pH (6-8 units) were concentrated using mixed-mode (reversed-phase and anionic exchange) cartridges. Thereafter, the sorbent was washed with 5 mL of a methanol: water (1:1) solution, dried under a nitrogen stream and compounds were eluted with 2 mL of methanol: NH3 (98:2). The accuracy of the method (accounting for SPE efficiency and matrix effects during electrospray ionization) was investigated using solvent-based calibration standards. Global recoveries, obtained for different water matrices (tap, river, treated and raw wastewater), ranged from 82% to 134%, with standard deviations between 2 and 18%. LOQs varied from 2 to 50 ng L-1. Analysis of un-spiked samples confirmed: (1) the incomplete removal of sartans at sewage treatment plants (STPs), (2) the formation of VALA during municipal water treatment, and (3) the presence of VALA in the processed tap water samples. Additional findings of the current study are the detection of hydroxylated derivatives of the sartan drugs IRB and LOS in wastewater, and the E-Z isomerization of EPR in environmental water samples.

Determination of glyphosate, AMPA, and glufosinate in honey by online solid-phase extraction-liquid chromatography-tandem mass spectrometry.

A simple method was developed for the simultaneous determination of glyphosate, its main degradation product (aminomethylphosphonic acid), and glufosinate in honey. Aqueous honey solutions were derivatised offline prior to direct analysis of the target analytes using online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry. Using the developed procedure, accuracies ranging from 95.2% to 105.3% were observed for all analytes at fortification levels of 5, 50, and 150 µg kg-1 with intra-day precisions ranging from 1.6% to 7.2%. The limit of quantitation (LOQ) was 1 µg kg-1 for each analyte. Two hundred honey samples were analysed for the three analytes with AMPA and glyphosate being most frequently detected (99.0% and 98.5% of samples tested, respectively). The concentrations of glyphosate were found to range from <1 to 49.8 µg kg-1 while those of its degradation product ranged from <1 to 50.1 µg kg-1. The ratio of glyphosate to AMPA was found to vary significantly amongst the samples where both analytes were present above the LOQ. Glufosinate was detected in 125 of 200 samples up to a maximum concentration of 33.0 µg kg-1.

Direct Determination of Glyphosate and its Metabolite AMPA in Soil Using Mixed-Mode Solid-Phase Purification and LC-MS/MS Determination on a Hypercarb Column.

Background: Although glyphosate is widely used in agriculture, information on its residue level in soils remains scarce partly because of the difficulty in its analysis. Objective: Develop and validate a method to directly analyze glyphosate and its metabolite aminomethylphosphonic acid (AMPA) in soil. Method: Soils were extracted with 0.6 M KOH solution, and coextracted interferences were removed using a mixed-mode Bond Elut Plexa PAX®. The extracts were analyzed by LC-tandem MS fitted with a Hypercarb column and isotope-labeled (13C,15N) glyphosate and AMPA were used as internal standards. Results: LOQs were 0.05 mg/kg for both glyphosate and AMPA in soils. Correlation coefficients were ≥0.99, residuals were below 20%, and calibrations were linear in the range 0.02-1.0 µg/mL. The method was validated on five contrasting soils (Vertosol, Calcarosol, Chromosol, Sodosol, and Tenosol) commonly used for grain production in Australia. The recoveries for glyphosate and AMPA in the soils were 96-121 and 91-118%, respectively, with RSD in the range of 3-16%. Conclusions: This paper presents using the validated method in analysis glyphosate and AMPA in soils collected from crop production paddocks in Australia. The survey data showed that glyphosate and AMPA were detected in all collected soils, with concentrations ranging between 0.05 and 1.2 mg/kg. Highlights: The study demonstrates that the mixed-mode solid-phase extraction is effective in removing interferences and validates the use of Hypercarb as an alternative stationary phase for glyphosate and AMPA analysis from soils.

Biogenic transport of glyphosate in the presence of LDPE microplastics: A mesocosm experiment.

The accumulation of plastic debris and herbicide residues has become a huge challenge and poses many potential risks to environmental health and soil quality. In the present study, we investigated the transport of glyphosate and its main metabolite, aminomethylphosphonic acid (AMPA) via earthworms in the presence of different concentrations of light density polyethylene microplastics in the litter layer during a 14-day mesocosm experiment. The results showed earthworm gallery weight was negatively affected by the combination of glyphosate and microplastics. Glyphosate and AMPA concentrated in the first centimetre of the top soil layer and the downward transport of glyphosate and AMPA was only detected in the earthworm burrows, ranging from 0.04 to 4.25 µg g-1 for glyphosate and from 0.01 (less than limit of detection) to 0.76 µg g-1 for AMPA. The transport rate of glyphosate (including AMPA) from the litter layer into earthworm burrows ranged from 6.6 ±â€¯4.6% to 18.3 ±â€¯2.4%, depending on synergetic effects of microplastics and glyphosate application. The findings imply that earthworm activities strongly influence pollutant movement into the soil, which potentially affects soil ecosystems. Further studies focused on the fate of pollutants in the microenvironment of earthworm burrows are needed.

[Determination of glyphosate, glufosinate, and main metabolite aminomethylphosphonic acid residues in dry tea using ultra-high performance liquid chromatography-tandem mass spectrometry].

A method has been developed for the determination of glyphosate (GLY), glufosinate (GLUF), and the main metabolite aminomethylphosphonic acid (AMPA) residues in dry tea based on ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) coupled with pre-column derivatization. A systematic study of the effects of pretreatment methods including extraction and purification procedures was designed and carried out for the determination of GLY, GLUF, and AMPA. The results indicated that the optimal pretreatment method was as follows:the tea sample was first extracted by water in vortex, and then purified by a cation exchange solid-phase extraction column with the elution of 0.5% (v/v) formic acid aqueous solution. Finally, the eluant was derivatized by 9-fluorenylmethyl chloroformate, and the target compounds were separated on a C18 chromatographic column and analysed by UPLC-MS/MS (ESI+). GLY, GLUF, and AMPA showed good linearity in the range of 1-100 µ g/L, with correlation coefficients above 0.991. The limits of detection and limits of quantification were found to be 0.0160-0.0300 mg/kg and 0.0530-0.100 mg/kg, respectively. The average spiked recoveries of GLY, GLUF, and AMPA varied from 78.3% to 108% at three spiked levels (0.0500, 0.400, and 1.20 mg/kg), while the relative standard deviations ranged from 5.46% to 9.63%. The proposed method was utilized to detect 837 batches of tea samples. The detection ratios of GLY, GLUF, and AMPA were 3.46%, 0.24%, and 4.42%, respectively, while 0.24% of the investigated tea samples had values above maximum residue limits. The developed method is simple, rapid, sensitive, and accurate for the determination of GLY, GLUF, and AMPA in dry tea and may be used for routine analysis.

Determination of glyphosate, AMPA and glufosinate in dairy farm water from Argentina using a simplified UHPLC-MS/MS method.

Argentina, together with the USA and Brazil, produces approximately 80% of the total worldwide glyphosate loadings. The development of a simplified ultra-high performance liquid chromatographic tandem mass spectrometric method (UHPLC-MS/MS) for the determination of glyphosate, aminomethylphosphonic acid (AMPA) and glufosinate in water is described, including studies of several alternatives of 9-fluorenylmethylchloroformate (FMOC-Cl) derivatization and pretreatment steps. The proposed method includes acidification and neutralization of a low sample volume (3 mL), 2 hours derivatization step, cleanup with dichloromethane, followed by reverse phase UHPLC-MS/MS determination of the analytes. Figures of merit were satisfactory in terms of linearity, selectivity, accuracy and intermediate precision (%REC 70-105% with RSD < 15%). Limits of quantification (LOQ) were suitable for monitoring purposes (0.6, 0.2, 0.1 µg/L for glyphosate, AMPA and glufosinate respectively). The validated methodology was applied for the analysis of livestock wells waters from 40 dairy farms located in the central region of Argentina. Glyphosate and AMPA were quantified in 15% and 53% of the analyzed samples with concentrations ranging from 0.6-11.3 µg/L and 0.2-6.5 µg/L respectively. Greater concentrations of glyphosate were also verified in waters from open-reservoir tanks, which are directly exposed to the farm environment. In these cases glyphosate and AMPA occurrence increased, being quantified in the 33% and 61% of the samples with values ranging 0.6-21.2 µg/L and 0.2-4.2 µg/L respectively. Also in this case glufosinate was found in 52% samples at