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1.
Water Res ; 263: 122140, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-39096811

ABSTRACT

The most widely used herbicide glyphosate contaminates surface waters around the globe. Both agriculture and urban applications are discussed as sources for glyphosate. To better delineate these sources, we investigated long-term time series of concentrations of glyphosate and its main transformation product aminomethylphosphonic acid (AMPA) in a large meta-analysis of about 100 sites in the USA and Europe. The U.S. data reveal pulses of glyphosate and AMPA when the discharge of the river is high, likely indicating mobilization by rain after herbicide application. In contrast, European concentration patterns of glyphosate and AMPA show a typical cyclic-seasonal component in their concentration patterns, correlating with patterns of wastewater markers such as pharmaceuticals, which is consistent with the frequent detection of these compounds in wastewater treatment plants. Our large meta-analysis clearly shows that for more than a decade, municipal wastewater was a very important source of glyphosate. In addition, European river water data show rather high and constant base mass fluxes of glyphosate all over the year, not expected from herbicide application. From our meta-analysis, we define criteria for a source of glyphosate, which was hidden so far. AMPA is known to be a transformation product not only of glyphosate but also of aminopolyphosphonates used as antiscalants in many applications. As they are used in laundry detergents in Europe but not in the USA, we hypothesize that glyphosate may also be a transformation product of aminopolyphosphonates.


Subject(s)
Environmental Monitoring , Glycine , Glyphosate , Herbicides , Rivers , Water Pollutants, Chemical , Glycine/analogs & derivatives , Glycine/analysis , Rivers/chemistry , Herbicides/analysis , Water Pollutants, Chemical/analysis , Europe , Organophosphonates/analysis , Wastewater/chemistry , United States
2.
Water Res ; 261: 121986, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-38924948

ABSTRACT

Glyphosate is widely used in agriculture for weed control; however, it may pollute water systems with its by-product, aminomethylphosphonic acid (AMPA). Therefore, a better understanding of the flows of glyphosate and AMPA from soils into rivers is required. We developed the spatially explicit MARINA-Pesticides model to estimate the annual inputs of glyphosate and AMPA into rivers, considering 10 crops in 10,226 sub-basins globally for 2020. Our model results show that, globally, 880 tonnes of glyphosate and 4,090 tonnes of AMPA entered rivers. This implies that 82 % of the river inputs were from AMPA, with glyphosate accounting for the remainder. Over half of AMPA and glyphosate in rivers globally originated from corn and soybean production; however, there were differences among sub-basins. Asian sub-basins accounted for over half of glyphosate in rivers globally, with the contribution from corn production being dominant. South American sub-basins accounted for approximately two-thirds of AMPA in rivers globally, originating largely from soybean production. Our findings constitute a reference for implementing and supporting effective control strategies to achieve Sustainable Development Goals 2 and 6 (food production and clean water, respectively) simultaneously in the future.


Subject(s)
Glycine max , Glycine , Glyphosate , Rivers , Water Pollutants, Chemical , Zea mays , Glycine/analogs & derivatives , Glycine/analysis , Rivers/chemistry , Water Pollutants, Chemical/analysis , Herbicides/analysis , Organophosphonates/analysis , Environmental Monitoring , Agriculture
3.
Mar Pollut Bull ; 202: 116376, 2024 May.
Article in English | MEDLINE | ID: mdl-38636342

ABSTRACT

In the present study, we determined glyphosate (GPS) and aminomethylphosphonic acid (AMPA) in the water and sediments of the Ofanto River (Italy), evaluating their transport from the mouth to the sea. Sediments were collected twice in 2021 during low and high tide; waters were sampled on a seasonal basis. The results showed the prevalence of GPS and AMPA in the water with concentrations equal to 190 and 3053 ng/l, respectively. We also found GPS and AMPA in the sediments with values of 0.95 and 11.34 ng/g. In water, pesticides were detected in all seasons with peaks in concentrations during summer and spring. A significant positive correlation between the pesticides in the sediments and the water pH and a negative correlation with salinity was observed. An estimation of the average loads revealed a discharge of 64.11 kg/yr. of GPS and 958.37 kg/yr. of AMPA from the river to the marine environment.


Subject(s)
Environmental Monitoring , Geologic Sediments , Glycine , Glyphosate , Rivers , Water Pollutants, Chemical , Glycine/analogs & derivatives , Glycine/analysis , Rivers/chemistry , Water Pollutants, Chemical/analysis , Geologic Sediments/chemistry , Pesticides/analysis , Italy , Organophosphonates/analysis , Seasons
4.
J Environ Sci (China) ; 135: 669-680, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37778837

ABSTRACT

The co-occurrence of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment and plants is a cause for concern due to potential threats to the ecosystem and human health. A major route of exposure is through contact with contaminated soil and consumption of crops containing GLP and AMPA residues. However, clay-based sorption strategies for mixtures of GLP and AMPA in soil, plants and garden produce have been very limited. In this study, in vitro soil and in vivo genetically modified corn models were used to establish the proof of concept that the inclusion of clay sorbents in contaminated soils will reduce the bioavailability of GLP and AMPA in soils and their adverse effects on plant growth. Effects of chemical concentration (1-10 mg/kg), sorbent dose (0.5%-3% in soil and 0.5%-1% in plants) and duration (up to 28 days) on sorption kinetics were studied. The time course results showed a continuous GLP degradation to AMPA. The inclusion of calcium montmorillonite (CM) and acid processed montmorillonite (APM) clays at all doses significantly and consistently reduced the bioavailability of both chemicals from soils to plant roots and leaves in a dose- and time-dependent manner without detectable dissociation. Plants treated with 0.5% and 1% APM inclusion showed the highest growth rate (p ≤ 0.05) and lowest chemical bioavailability with up to 76% reduction in roots and 57% reduction in leaves. Results indicated that montmorillonite clays could be added as soil supplements to reduce hazardous mixtures of GLP and AMPA in soils and plants.


Subject(s)
Bentonite , Bioaccumulation , Herbicides , Organophosphonates , Soil Pollutants , Zea mays , Humans , Bentonite/chemistry , Clay/chemistry , Ecosystem , Herbicides/analysis , Herbicides/chemistry , Herbicides/pharmacokinetics , Soil/chemistry , Soil Pollutants/analysis , Soil Pollutants/pharmacokinetics , Zea mays/chemistry , Zea mays/physiology , Organophosphonates/analysis , Organophosphonates/chemistry , Organophosphonates/pharmacokinetics , Plants, Genetically Modified/chemistry , Plants, Genetically Modified/physiology , Bioaccumulation/physiology , Glyphosate
5.
Anal Bioanal Chem ; 414(3): 1445-1455, 2022 Jan.
Article in English | MEDLINE | ID: mdl-34820706

ABSTRACT

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.


Subject(s)
Glycine/analogs & derivatives , Organophosphonates/analysis , Wine/analysis , Chromatography, Liquid/methods , Fungicides, Industrial/analysis , Glycine/analysis , Limit of Detection , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Glyphosate
6.
Int J Mol Sci ; 22(21)2021 Oct 25.
Article in English | MEDLINE | ID: mdl-34768931

ABSTRACT

Phosphorus is one of the most important elements essential for all living beings. Plants accumulate and store phosphorous in various forms that have diverse physiological and biochemical functions. In this study, we determine and then examine the phosphorus profiles of seeds of plants belonging to different taxa based on extractable inorganic phosphates and organic forms of phosphorus. We paid particular attention to the presence of natural phosphonates in the tested materials. The inorganic phosphates were determined colorimetrically, whereas phosphorus profiles were created by using 31P NMR spectroscopy. Our study on phosphorus profiles revealed that the obtainedsets of data vary significantly among the representatives of different taxa and were somehow specific for families of plants. It should be emphasised that the measurements obtained using 31P NMR spectroscopy undoubtedly confirmed-for the first time-the presence of phosphonates among the natural components of plant seeds. Hence, the classification of plants considering the phosphorus profiles, including the presence of phosphonates, may be a new additional chemotaxonomic feature.


Subject(s)
Organophosphonates/analysis , Phosphorus/analysis , Plants/classification , Seeds/chemistry , Magnetic Resonance Spectroscopy/methods , Plants/chemistry
7.
J Chromatogr A ; 1651: 462339, 2021 Aug 16.
Article in English | MEDLINE | ID: mdl-34161838

ABSTRACT

A new sensitive and selective analytical methodology to quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), and glufosinate (GLU) in both soil and earthworms (Allolobophora chlorotica) was developed. The extraction and purification methods were optimized. The samples were extracted with various aqueous solutions (HNO3, H2O, KOH and borate buffer) and derivatized with 9-Fluorenylmethyl chloroformate (FMOCCl). To optimize the extraction step, a method to remove the excess FMOCCl was applied based on liquid-liquid extraction with diethyl ether. The purification of derivatized extracts was carried out using XLB solid phase extraction (SPE) cartridges before internal standard quantification by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The elution step was optimized to obtain the best recoveries possible, which was with acidic methanol (1% formic acid) (67% for GLY, 70% for GLU and 65% for AMPA). The extraction and purification method followed by analysis of the two herbicides and AMPA in soils using LC/MS/MS determined limit of quantification (LOQ) values of 0.030 µg g - 1 for GLY, 0.025 µg g - 1 for AMPA and 0.020 µg g - 1 for GLU . For earthworms, LOQ were 0.23 µg g - 1 for GLY, 0.20 µg g - 1 for AMPA and 0.12 µg g - 1 for GLU. . The developed method was applied to determine these compounds in natural soils and earthworms.


Subject(s)
Aminobutyrates/analysis , Chemistry Techniques, Analytical/methods , Glycine/analogs & derivatives , Oligochaeta/chemistry , Organophosphonates/analysis , Soil/chemistry , Aminobutyrates/isolation & purification , Animals , Chemistry Techniques, Analytical/instrumentation , Chromatography, Liquid , Glycine/analysis , Glycine/isolation & purification , Herbicides/analysis , Herbicides/isolation & purification , Organophosphonates/isolation & purification , Solid Phase Extraction , Tandem Mass Spectrometry , Glyphosate
8.
Article in English | MEDLINE | ID: mdl-34098182

ABSTRACT

Glyphosate and other polar and acidic pesticides have been particularly studied due to the concerns over widespread and intensive use. The chemical properties of these compounds necessitate use of customised methods, such as derivatisation or ion exchange chromatography. These approaches present a compatibility problem with ESI-MS due to presence of salts and non-volatile compounds. For that reason, a simple procedure has been developed for the extraction, pre-column derivatisation with dansyl chloride (5-(dimethylamino)naphthalene-1-sulfonyl chloride), and mass spectrometric detection of glyphosate, AMPA, and glufosinate after the separation on a C18stationary phase. The dansyl derivatives were characterised with ESI-MS and their separation from derivatisation reagent byproducts was demonstrated with UV absorption detection. Reagent byproducts eluted before the analytes and were separated from the analytes completely, thus the proposed procedure did not contaminate the mass spectrometers. The proposed procedure was evaluated with respect to the matrix effects and extraction efficiency, and was validated with different mass spectrometers for milk, cucumber, honey, porridge formula, bovine kidney and liver matrix. The LOQ was 10 µg kg-1 for AMPA and glufosinate, and 10-25 µg kg-1for glyphosate, depending on matrix. Measurement uncertainties ranged from 4 to 44%. Method performance was compared to the QuPPe (Quick Polar Pesticides) procedure in combination with a diethylamino-based column from Waters™. In the case of Orbitrap™ detection, the proposed procedure had a comparable performance to the QuPPe procedure. Although, improved peak shape, higher absolute peak intensity, and lower standard deviation of the calibration curve slope was observed with the proposed procedure. This could be explained by the superior electrospray stability and lower extent of ion suppression.


Subject(s)
Aminobutyrates/analysis , Chromatography, Liquid/methods , Dansyl Compounds/analysis , Organophosphonates/analysis , Pesticide Residues/analysis , Animals , Cattle , Cucumis sativus/chemistry , Food Analysis , Honey/analysis , Meat/analysis , Tandem Mass Spectrometry/methods
9.
J Chromatogr A ; 1649: 462188, 2021 Jul 19.
Article in English | MEDLINE | ID: mdl-34034108

ABSTRACT

A new green method for trace level quantification of four herbicides, glyphosate (GLYP), glufosinate (GLUF), and their main metabolites, aminomethylphosphonic acid (AMPA) and 3-(methyl-phosphinico)-propionic acid (MPPA), was developed. The purification step without any derivatization was conducted by solid-phase extraction using Chelex-100 resin in the Fe (III) form, followed by elution with 5% NH4OH. The four analytes were quantified by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The developed extraction method was validated on five fresh and sea water matrices with mean recoveries ranging from 80.1% to 109.4% (relative standard deviation < 20%). The extraction conditions were evaluated and certified for the high applicability of the extraction method too. The limits of detection (ng/L) in the five water matrices were in ranges 0.70 - 4.0, 2.4 - 3.9, 1.8 - 4.7, and 1.6 - 4.0 for GLYP, AMPA, GLUF, and MPPA, respectively. The method was successfully applied to detect the four compounds in surface waters sampled along the Red River Delta region in July 2019. The highest concentrations were detected at 565, 1,330, 234, and 871 ng/L for GLYP, AMPA, GLUF, and MPPA, respectively. These results showed the potential capacity of this new method for convenient monitoring of herbicides and their metabolites in the diverse natural water system.


Subject(s)
Aminobutyrates/isolation & purification , Glycine/analogs & derivatives , Organophosphonates/isolation & purification , Solid Phase Extraction/methods , Water Pollutants, Chemical/isolation & purification , Aminobutyrates/analysis , Chromatography, High Pressure Liquid , Fresh Water/chemistry , Glycine/analysis , Glycine/isolation & purification , Herbicides/analysis , Herbicides/isolation & purification , Organophosphonates/analysis , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis , Glyphosate
10.
J Environ Sci Health B ; 56(4): 313-332, 2021.
Article in English | MEDLINE | ID: mdl-33560904

ABSTRACT

The aim of this study is to understand the spatial and seasonal variations of persistent herbicides metabolites and to determine their origins in the Vilaine River watershed, Britany-France. Improving knowledge on herbicides metabolites sources and seasonality is important for drinking water resource management. Data were collected at 13 sampling stations during five sampling campaigns in 2016 and 2017. Relations between water quality parameters, herbicides and metabolites were analyzed using statistical methods. The influence of land use and wastewater treatment plants (WWTP) on streams water quality has been identified. Cluster Analysis revealed that two groups of sampling stations can be described as "urban" with stations downstream the urban area and as "agricultural" with stations located downstream of the watershed. Chloroacetamids metabolites have been associated together with nitrates and agricultural areas as could be expected. Thus, the drinking water treatment plant located in the estuary of the Vilaine River is exposed to high metolachlor ESA and nitrate loads all year long. Aminomethylphosphonic acid (AMPA) is associated to anthropogenic urban contamination and nutrient loads. AMPA has its major sources in both glyphosate and phosphonate detergents issued from WWTP. This can help to adapt surface water treatment process and water management policies concerning herbicides metabolites.


Subject(s)
Herbicides/analysis , Herbicides/metabolism , Water Pollutants, Chemical/analysis , Agriculture , Detergents/chemistry , Environmental Monitoring/methods , Estuaries , Glycine/analogs & derivatives , Glycine/chemistry , Organophosphonates/analysis , Pesticide Residues/analysis , Rivers , Seasons , Spatio-Temporal Analysis , Waste Disposal Facilities , Waste Disposal, Fluid , Water Quality , Glyphosate
11.
Biomed Chromatogr ; 35(5): e5061, 2021 May.
Article in English | MEDLINE | ID: mdl-33398885

ABSTRACT

Brincidofovir (BCV) is an investigational lipid conjugate of the nucleotide analog cidofovir (CDV), which is being developed as a medical countermeasure for the treatment of smallpox. BCV is active against double-stranded DNA viruses including BK and JC viruses. Here, we validated procedures for quantifying BCV and its pharmacologically active moiety cidofovir diphosphate (CDV-PP) in mouse kidney, brain and spleen tissue homogenates. Following homogenization, BCV and CDV-PP were extracted from the tissues by protein precipitation with their stable, isotopically labeled internal standards, BCV-d6 and 13 C3 15 N2 -CDV-PP. Then, samples were analyzed for BCV by reverse-phase chromatography on a Waters Xterra MS C18 (50 × 2.1 mm, 3.5 µm particle size) column while CDV-PP was analyzed on a Thermo BioBasic AX (50 × 2.1 mm, 5 µm particle size) column using anion exchange chromatography. Detection was achieved by electrospray ionization in positive ion mode on an AB Sciex API-5000 triple quadrupole mass spectrometer. The calibration curves were linear over a range of 1.00-1,000 ng/ml homogenate and 0.050-50.0 ng/ml homogenate for BCV and CDV-PP, respectively. These methods were validated according to US Food and Drug Administration guidance for industry and may be used to characterize the tissue pharmacology of both analytes to advance its preclinical development.


Subject(s)
Antiviral Agents , Brain Chemistry , Cidofovir , Cytosine/analogs & derivatives , Kidney/chemistry , Organophosphonates , Spleen/chemistry , Animals , Antiviral Agents/analysis , Antiviral Agents/pharmacokinetics , Chromatography, High Pressure Liquid/methods , Cidofovir/analysis , Cidofovir/pharmacokinetics , Cytosine/analysis , Cytosine/pharmacokinetics , Mice , Mice, Inbred C57BL , Organophosphonates/analysis , Organophosphonates/pharmacokinetics , Polyomavirus Infections/drug therapy , Tandem Mass Spectrometry/methods
12.
Food Chem ; 342: 128213, 2021 Apr 16.
Article in English | MEDLINE | ID: mdl-33129618

ABSTRACT

The use of reference materials (RMs) is critical for validating and testing the accuracy of analytical protocols. The National Institute of Standards and Technology (NIST) is in initial stages of developing a glyphosate in oats RM. The first aim of this study was to optimize and validate a robust method for the extraction and analysis of glyphosate and aminomethylphosphonic acid (AMPA). The optimized method was used to screen thirteen commercially available oat products to identify candidate RMs. Glyphosate was detected in all samples, with the highest glyphosate mass fraction of 1100 ng/g; lower levels were measured in grains from organic agriculture. AMPA was quantified in nine samples up to 40 ng/g. The findings of this study led to the identification of candidate RMs, with "high" and "low" glyphosate levels. A preliminary stability study determined that glyphosate is stable in oat material at room temperature for six months.


Subject(s)
Avena/chemistry , Food Analysis/standards , Glycine/analogs & derivatives , Organophosphonates/analysis , Glycine/analysis , Glycine/isolation & purification , Organophosphonates/isolation & purification , Reference Standards , Glyphosate
13.
Chemosphere ; 262: 128327, 2021 Jan.
Article in English | MEDLINE | ID: mdl-33182089

ABSTRACT

The globally used herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) have not yet been reported to occur in the marine environment, presumably due to a lack of suitable analytical methods. In this study, we developed two new methods for the analysis of glyphosate and AMPA in seawater: a small-scale method, which includes an SPE cleanup step that minimizes salt-matrix effects during LC-MS/MS analysis, and a large-scale method that employs an additional SPE preconcentration step. Different SPE materials were evaluated for their suitability to enrich glyphosate and AMPA from saltwater and a molecularly imprinted polymer was selected. Both methods were validated in ultrapure water and environmental seawater. Achieved limits of detection with the small-scale method were 6 and 8 ng/L for glyphosate and AMPA, while the large-scale method achieved 0.12 and 0.22 ng/L, respectively. The small-scale method was used to analyze environmental samples from the Warnow Estuary in Germany. Glyphosate and AMPA could be successfully detected in the samples, but could not be measured beyond the saline estuary due to dilution and degradation effects. A set of samples from the western Baltic Sea was analyzed with the large-scale method. Glyphosate and AMPA could be detected in all Baltic Sea samples, especially at stations close to estuaries. To the best of our knowledge, this is the first report on the occurrence of glyphosate and AMPA in seawater.


Subject(s)
Environmental Monitoring/methods , Glycine/analogs & derivatives , Herbicides/analysis , Organophosphonates/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Chromatography, Liquid/methods , Estuaries , Germany , Glycine/analysis , Limit of Detection , Oceans and Seas , Tandem Mass Spectrometry/methods , Glyphosate
14.
Ecotoxicol Environ Saf ; 206: 111209, 2020 Dec 15.
Article in English | MEDLINE | ID: mdl-32891912

ABSTRACT

In this paper, several experiments were carried out to study the environmental behavior and influencing factors of glyphosate (PMG) in peach orchard ecosystem. The results of field experiments showed that PMG and its metabolite aminomethylphosphonic acid (AMPA) were detected in peach tree leaves and peach tree fruits, although PMG was only sprayed on the soil. The residues of PMG and AMPA in peach tree leaves were ~0.1 mg/kg and ~0.5 mg/kg and in peach tree fruits were ~0.01 mg/kg and 0.07-0.11 mg/kg, respectively. By conducting a series of laboratory simulation experiments, the environmental factors affecting the degradation of PMG were screened and evaluated. The results showed that PMG metabolized much faster in loess soil than red soil and black soil (with the DT50 of 11.6 days, 62.4 days, and 34.1 days, respectively). By analyzing the basic properties of the soil, we investigated the effects of pH, moisture content, organic matter (exogenous biochar) and ambient temperature using orthogonal experiments, and the results were further confirmed by microbial experiment. The results showed that alkaline conditions (pH = 7.8/9), high water content (25%) and microorganisms could promote the degradation of PMG. Sterile soil environment had a negative impact on the metabolic behavior of PMG to AMPA.


Subject(s)
Environmental Monitoring/methods , Glycine/analogs & derivatives , Herbicides/metabolism , Organophosphonates/metabolism , Prunus persica/growth & development , Soil Pollutants/metabolism , Biodegradation, Environmental , China , Ecosystem , Glycine/analysis , Glycine/metabolism , Herbicides/analysis , Models, Theoretical , Organophosphonates/analysis , Prunus persica/metabolism , Soil/chemistry , Soil Pollutants/analysis , Glyphosate
15.
Int J Hyg Environ Health ; 228: 113526, 2020 07.
Article in English | MEDLINE | ID: mdl-32305862

ABSTRACT

BACKGROUND: Since the classification of glyphosate as a Group 2A substance "probably carcinogenic to humans" by the IARC in 2015, human health concerns have been raised regarding the exposure of operators, bystanders, and consumers. Urine measurement studies have been conducted, but since toxicokinetic data on glyphosate in humans is lacking, a meaningful interpretation of this data regarding exposure is not possible. OBJECTIVE: This study aims to determine the fraction of glyphosate and AMPA excretion in urine after consuming ordinary food with glyphosate residue, to estimate dietary glyphosate intake. METHODS: Twelve participants consumed a test meal with a known amount of glyphosate residue and a small amount of AMPA. Urinary excretion was examined for the next 48 h. RESULTS: Only 1% of the glyphosate dose was excreted in urine. The urinary data indicated the elimination half-life was 9 h. For AMPA, 23% of the dose was excreted in urine, assuming that no metabolism of glyphosate to AMPA occurred. If all of the excreted AMPA was a glyphosate metabolite, this corresponds to 0.3% of the glyphosate dose on a molar basis. CONCLUSION: This study provides a basis for estimating oral glyphosate intake using urinary biomonitoring data.


Subject(s)
Biological Monitoring/methods , Dietary Exposure/analysis , Glycine/analogs & derivatives , Herbicides/urine , Organophosphonates/urine , Pesticide Residues/urine , Adult , Biomarkers/urine , Cicer , Female , Flour/analysis , Food Contamination/analysis , Glycine/analysis , Glycine/pharmacokinetics , Glycine/urine , Herbicides/analysis , Herbicides/pharmacokinetics , Humans , Male , Organophosphonates/analysis , Organophosphonates/pharmacokinetics , Pesticide Residues/analysis , Pesticide Residues/pharmacokinetics , Glyphosate
16.
Mikrochim Acta ; 186(7): 427, 2019 06 11.
Article in English | MEDLINE | ID: mdl-31187299

ABSTRACT

An electrochemical sensor for adefovir dipivoxil (ADV) detection was prepared by electropolymerization of o-phenylenediamine in the presence of ADV on a glassy carbon electrode modified with multi-walled carbon nanotubes and carbon nitride. The electrode was characterized by field emission scanning electron microscopy and differential pulse voltammetry. The performance was optimized by response surface methodology. The changes in differential pulse voltammetric peak currents of the redox probe, ferricyanide, were linear to ADV concentrations in the range from 0.1 to 9.9 µmol L-1, with the detection limit of 0.05 µmol L-1 (S/N = 3). The sensor was applied to the determination of ADV in drug formulations, human serum and urine samples. It is selective due to the use of an imprinted material, well reproducible, long-term stable, and regenerable. Graphical abstract By merging the unique properties of carbon nitride with intrinsic properties of MWCNTs, and molecularly imprinted polymers, a novel electrochemical sensor with selective binding sites was prepared for determination of adefovir dipivoxil in pharmaceutical and biological samples.


Subject(s)
Adenine/analogs & derivatives , Electrochemical Techniques/methods , Nanocomposites/chemistry , Nanotubes, Carbon/chemistry , Nitriles/chemistry , Organophosphonates/analysis , Phenylenediamines/chemistry , Adenine/analysis , Adenine/blood , Adenine/urine , Electrochemical Techniques/instrumentation , Electrodes , Humans , Limit of Detection , Molecular Imprinting , Organophosphonates/blood , Organophosphonates/urine , Reproducibility of Results
17.
J Chromatogr A ; 1601: 189-204, 2019 Sep 13.
Article in English | MEDLINE | ID: mdl-31130225

ABSTRACT

In drinking water production, phosphonates are frequently applied as antiscalants in order to prevent the precipitation of salts on reverse osmosis membranes. Whereas the nominal constituents are defined, phosphonate-based antiscalants were found to contain significant amounts of undeclared phosphorous contaminants, particularly noticeable technical diethylenetriamine penta(methylene phosphonic acid) (DTPMP). Following a literature review on impurities of phosphonic acids, separation by anion exchange chromatography coupled with ICP-MS- and ESI-TOF-detection allowed the comprehensive characterization of technical phosphonates. After the identification of synthesis by-products, intermediates and degradation products, the quantification of the phosphorus compounds was accomplished by complementary phosphorus-sensitive ICP-MS detection. The contents of the nominal constituents as well as the organophosphorous impurities of 24 technical antiscalants were determined and compared with the manufacturer's declaration. Of all compounds detected within the technical formulations, 86% were confirmed with reference compounds. Phosphorous impurities were found to contribute to the total phosphorus content with close to 20% (in ATMP- and PBTC-based products) and 38%-65% (in DTPMP-based products). Correspondingly, the nominal compounds were found to contribute with 78%-80% (based on 6 ATMP products) and with 81.5%-83% (based on 2 PBTC products), whereas in 10 out of 12 DTPMP products the nominal compound was found to contribute with 34%-44% to the total phosphorus. Only in two products, elevated DTPMP proportions of 55% and 62% with regard to total phosphorus were determined. The screening for aminomethylphosphonic acid (AMPA) revealed contents between 1.9 mg/L and 157 mg/L. This study represents the first in-depth characterization of phosphonate-based antiscalant products and stock solutions used for drinking water production.


Subject(s)
Chromatography, Liquid , Organophosphonates/chemistry , Spectrometry, Mass, Electrospray Ionization , Water Purification , Filtration , Organophosphonates/analysis , Spectrum Analysis
18.
Arch Environ Contam Toxicol ; 77(2): 279-290, 2019 Aug.
Article in English | MEDLINE | ID: mdl-30963189

ABSTRACT

The occurrence and spatial distribution of 13 organophosphorus flame retardants (OPFRs), 11 polybrominated diphenyl ethers (PBDEs), and eight novel brominated flame retardants (NBFRs) were investigated in Jinjiang river water, sediment, crucian carp, and groundwater in Chengdu, China. OPFRs were predominant and ubiquitous contaminants in the Jinjiang river water, sediment, groundwater, fish muscle, fish gills, and viscera with concentrations ranging from 19.1 to 533 ng L-1, 12.5 to 253 ng g-1, 11.7 to 149 ng L-1, 114 to 2108 ng g-1 lipid weight (lw), 220 to 638 ng g-1 lw, and 116 to 1356 ng g-1 lw, respectively. The halogenated OPFRs were the primary pollutant in the Jinjiang river water samples, whereas nonhalogenated OPFRs were the dominant OPFRs in the sediments. Brominated flame retardants were not detected in the groundwater, whereas the NBFRs detected in aquatic environment at low frequency. The ΣPBDEs ranged from n.d. to 23.4 ng L-1 and n.d. to 48.7 ng g-1 in the Jinjiang river water and sediment, respectively. BDE-209 was dominant in the sediment samples with concentrations ranging from n.d. to 47.2 ng g-1. The PBDEs levels in the muscle, gills, and viscera of the crucian carp ranged from 10.6 to 90.6 ng g-1 lw, n.d. to 75.6 ng g-1 lw, and n.d. to 219 ng g-1 lw, respectively. BDE-47, chlorinated, and alkyl OPFRs were the main contaminants in the fish samples.


Subject(s)
Flame Retardants/analysis , Groundwater/analysis , Halogenated Diphenyl Ethers/analysis , Organophosphonates/analysis , Water Pollutants, Chemical/analysis , Animals , Carps , China , Environmental Monitoring/methods , Geologic Sediments/analysis , Gills/chemistry , Muscles/chemistry , Rivers/chemistry
19.
J Chromatogr A ; 1577: 31-37, 2018 Nov 23.
Article in English | MEDLINE | ID: mdl-30274693

ABSTRACT

In the work reported here, a screening procedure was developed for the detection and identification of RMPAs (nerve agent degradation products) after pentafluorobenzylation using liquid chromatography-tandem mass spectrometry (LC-MS/MS). With this method, all RMPAs, including highly hydrophilic types such as methylphosphonic acid (MPA) and ethyl methylphosphonic acid (EMPA), were sufficiently retained in commonly used reversed-phase columns (retention times: 15.7 and 11.0 min.), and the presence of RMPAs was determined more efficiently than with the conventional direct LC-MS/MS method. The detection limits of RMPAs using this approach (<33 ng) were mostly superior to those observed with direct LC-MS/MS (<74 ng) and gas chromatography-mass spectrometry (GC-MS) after pentafluorobenzylation (<1.1 µg). The applicability of newly developed method toward real samples was evaluated via recovery tests involving urine/serum and wipe tests on various surfaces.


Subject(s)
Blood Chemical Analysis/methods , Chromatography, Liquid , Nerve Agents/analysis , Tandem Mass Spectrometry , Urinalysis/methods , Benzoates/chemistry , Chemical Warfare Agents/analysis , Chemical Warfare Agents/chemistry , Gas Chromatography-Mass Spectrometry/methods , Humans , Hydrophobic and Hydrophilic Interactions , Limit of Detection , Nerve Agents/chemistry , Organophosphonates/analysis , Organophosphonates/isolation & purification , Organophosphorus Compounds/analysis , Organophosphorus Compounds/isolation & purification
20.
Water Sci Technol ; 2017(2): 450-456, 2018 May.
Article in English | MEDLINE | ID: mdl-29851397

ABSTRACT

This study compares and contrasts the glyphosate removal efficiency of alum sludge (waterworks residue) and Irish peat in aqueous solution. Organic phosphonate of glyphosate aqueous solution was removed in pot tests separately filled with peat and alum sludge, while effluent samples were taken from each pot to analyse the concentration of phosphorus (P) and COD (chemical oxygen demand); physical and chemical analysis for both media before and after use was carried out subsequently. The results show that the P removal capacity of alum sludge was significant (>99%), while the removal capacity of peat was considerably less than 10% after 10 weeks. Both materials significantly reduced the levels of COD, but it was noted that peat had a marginally greater initial P removal capacity (68 ± 22%) and did perform better than alum sludge (57 ± 12%). Moreover, pre-treatment is a crucial step to harness the full potential of peat. Overall, this study provides a scientific clue for sorbents selection when considering alum sludge and peat to maximize their value in practice.


Subject(s)
Alum Compounds/analysis , Glycine/analogs & derivatives , Soil , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/chemistry , Biological Oxygen Demand Analysis , Glycine/chemistry , Herbicides/chemistry , Organophosphonates/analysis , Phosphorus/analysis , Glyphosate
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