RESUMEN
This study presents the contents of α-methylenecyclopropylglycine, a potentially toxic amino acid, in the peel, pulp and seed fractions of two well-known litchi varieties, namely Shahi and China, over a span of three harvest-seasons. For analysing α-methylenecyclopropylglycine, an LC-MS/MS-based method was validated. The method-accuracies fell within 75-110 % (RSD, <15 %) at 0.1 mg/kg (LOQ) and higher levels. A comparative evaluation of the results in peel, pulp and seed at 30 days before harvest (DBH), 15-DBH, and edible-ripe stage revealed that α-methylenecyclopropylglycine content increased as the litchi seeds grew towards maturity, regardless of the cultivar. In arils, at maturity, the concentration of α-methylenecyclopropylglycine ranged from not-detected to 11.7 µg/g dry weight. The Shahi cultivar showed slightly higher α-methylenecyclopropylglycine content in comparison to China litchi. This paper presents the first known analysis of combined seasonal data on different fruit components at various growth stages for the two chosen litchi cultivars grown in India.
Asunto(s)
Frutas , Litchi , Semillas , Espectrometría de Masas en Tándem , Litchi/química , Litchi/crecimiento & desarrollo , Litchi/metabolismo , Frutas/química , Frutas/crecimiento & desarrollo , China , Semillas/química , Semillas/crecimiento & desarrollo , Glicina/análogos & derivados , Glicina/análisis , Cromatografía Líquida de Alta Presión , Ciclopropanos/análisisRESUMEN
BACKGROUND: To minimize the impact of pesticide residues in food on human health, it is necessary to enhance their detection. Recently, many nanozyme-based colorimetric methods for pesticides detection have been developed, however, they often required the assistance of natural enzymes, which made the process and result of methods susceptible to the stability and activity of natural enzymes. To overcome these drawbacks, methods for direct detection of pesticides using nanozymes have been developed, and there are few studies in this field currently. Thus, it is of great research and practical significance to develop more nanozymes-based colorimetric methods for direct detection of pesticides. RESULTS: Dual colorimetric platforms based on Os-Rh nanozyme with excellent peroxidase-like activity were constructed for directly detection of glyphosate in this work. Results showed that glyphosate was able to sensitively and selectively inhibit the peroxidase-like activity of Os-Rh nanozyme through hindering the decomposition of H2O2 by Os-Rh nanozyme to produce HOâ. Based on this, the dual colorimetric platforms achieved highly sensitive detection for glyphosate over a wide linear concentration range (50-1000 µg L-1 in solution platform and 200-1000 µg L-1 in paper platform), with the detection limits of 28.37 µg L-1 in solution platform and 400 µg L-1 (naked-eye detection limit)/123.25 µg L-1 (gray scale detection limit) in paper platform, respectively. Moreover, the dual colorimetric platforms possessed satisfactory reliability and accuracy for practical applications, and has been successfully applied to the detection of real samples with the spiked recoveries of 92.78-102.75 % and RSD of 1.17-3.88 %. SIGNIFICANCE: The dual colorimetric platforms for glyphosate direct detection based on Os-Rh nanozyme developed in this work not only owned considerable practical application potential, but also could provide more inspirations and ideas for the rational design and development of colorimetric sensing methods for the rapid detection of pesticides based on nanozymes.
Asunto(s)
Colorimetría , Glicina , Glifosato , Colorimetría/métodos , Glicina/análogos & derivados , Glicina/análisis , Glicina/química , Peroxidasa/metabolismo , Peroxidasa/química , Límite de Detección , Peróxido de Hidrógeno/químicaRESUMEN
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.
Asunto(s)
Monitoreo del Ambiente , Glicina , Glifosato , Herbicidas , Ríos , Contaminantes Químicos del Agua , Europa (Continente) , Glicina/análogos & derivados , Glicina/análisis , Glifosato/análisis , Herbicidas/análisis , Organofosfonatos/análisis , Ríos/química , Estados Unidos , Aguas Residuales/química , Contaminantes Químicos del Agua/análisisRESUMEN
In a national park in Northeast Thailand, agricultural land has been converted from natural forest by small-scale farmers for cassava agriculture. We hypothesise that long-termed cassava monoculture leads to the degradation of soil properties. To test the hypothesis, we conducted a five-year (2016-2020) study on the physical and chemical properties of soil in cassava farmland, and also examined the soil properties of its adjacent natural forests, as a control. The examined cassava farmland was converted from the natural forest during the five years from 2011 to 2015. The significant decrease in organic carbon and the increases in exchangeable potassium and bulk density were found in 2016, indicating that these soil properties varied quickly following the farmland conversion. On the other hand, the significant increase in soil nitrogen and the decrease in pH were found later in 2020, indicating that these soil properties were gradually altered by repeated agricultural activities, such as fertilizer application and trampling. In contrast, there were no significant differences in available phosphate, electrical conductivity, cation exchange capacity, and the soil texture (the fractions of sand, silt, and clay) among the forest and farmland soils. The cation exchange capacity was positively correlated to the fraction of clay, the organic carbon, and pH. The use of glyphosate and paraquat herbicides is prohibited within national parks in Thailand. However, in 2020, glyphosate was detected in farmland soil (up to 5.0 mg kg-1) during both the rainy and dry seasons, and glyphosate (up to 2.5 mg l-1) was detected in stream water from the farmland during the dry season at least in 2020. Soil degradation and herbicide pollution may carry a high risk of causing irreversible changes in terrestrial ecosystems. We discuss the root causes of this issue from perspectives of agricultural production, economy, and the environmental impact, and propose effective policy measures.
Asunto(s)
Agricultura , Herbicidas , Manihot , Suelo , Tailandia , Manihot/química , Manihot/crecimiento & desarrollo , Suelo/química , Herbicidas/análisis , Contaminantes del Suelo/análisis , Glicina/análogos & derivados , Glicina/análisis , Granjas , Conservación de los Recursos Naturales , Bosques , Concentración de Iones de HidrógenoRESUMEN
The neurotoxin ß-N-methylamino-L-alanine (BMAA), produced by cyanobacteria and diatoms, has been implicated as an environmental risk factor for neurodegenerative diseases. This study first investigated the occurrence and monthly distributions of BMAA and its isomers, 2,4-diaminobutyric acid (DAB) and N-2-aminoethylglycine (AEG), in phytoplankton and mussels from 11 sites along the South Sea Coast of Korea throughout 2021. These toxins were quantified using LC-MS/MS, revealing elevated BMAA concentrations from late autumn to spring, with phase lags observed between phytoplankton and mussels. The highest concentration of BMAA in phytoplankton was detected in November (mean: 1490 ng g-1 dry weight (dw)), while in mussels, it peaked in December (mean: 1240 ng g-1 dw). DAB was detected in phytoplankton but was absent in mussels, indicating limited bioaccumulation potential. In February, the peak mean DAB concentration in phytoplankton was 89 ng g-1 dw. AEG was not detected in any samples. Chlorophyll-a concentrations consistently showed an inverse correlation with BMAA concentrations in mussels throughout the year. Through correlation analysis, four diatom genera, Bacillaria, Hemiaulus, Odontella, and Pleurosigma, were identified as potential causative microalgae of BMAA. This study offers insights into identifying the causative microalgae for BMAA and informs future regulatory efforts regarding unmanaged biotoxins.
Asunto(s)
Aminoácidos Diaminos , Bivalvos , Toxinas de Cianobacterias , Microalgas , Neurotoxinas , Fitoplancton , Aminoácidos Diaminos/análisis , República de Corea , Animales , Fitoplancton/metabolismo , Microalgas/metabolismo , Microalgas/química , Bivalvos/metabolismo , Bivalvos/química , Neurotoxinas/análisis , Monitoreo del Ambiente , Aminobutiratos/análisis , Glicina/análogos & derivados , Glicina/análisis , Diatomeas/metabolismo , Estaciones del Año , Espectrometría de Masas en Tándem , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/metabolismoRESUMEN
Soil structural degradation and water erosion processes were observed even in no-tillage schemes in the Pampas region. Within these conservation systems, agrochemical application per hectare is one of the highest globally. Thus, this entails a serious risk of water contamination. The objectives of this study were to (1) test the hypothesis that the hydrological dynamics and sediment concentration related to surface runoff were conditioned by soil structure regardless of the presence of maize (Zea mays L.) crop residue and (2) assess the incidence of maize crop residue on glyphosate and aminomethylphosphonic acid (AMPA) concentration in runoff. The soil under study corresponded to Arroyo Dulce Series (Typic Argiudoll silty loam soil). Rain simulations were performed in the laboratory on undisturbed soil samples. Total runoff and infiltration rate were similar between treatments with C(+) and without C(-) maize crop residues (C(+) 1381.40 mL and 14.27 mm h-1, C(-): 1529.70 mL and 21.67 mm h-1). The C(-) treatments showed a higher sediment concentration than C(+) (1.58 and 0.42 g 100 mL-1, respectively). Glyphosate and AMPA average values in runoff were 15.9 and 33.9 µg L-1. High variability of the hydro-physical properties and occurrence of soil structure, particularly platy ones, were detected. The hydrological variables were conditioned mainly by the occurrence of platy structures regardless of crop residue presence. Glyphosate concentration was increased in the first runoff event by the presence of corn residues, while AMPA concentrations were higher in the second runoff event in both residue treatments. In this study, maize residue on the soil surface protected the soil from sediment detachment but did not change runoff or infiltration. Thus, the implementation of agricultural management practices that promote vegetative residue cover has shown positive results to erosion.
Asunto(s)
Monitoreo del Ambiente , Glicina , Glifosato , Herbicidas , Lluvia , Suelo , Zea mays , Glicina/análogos & derivados , Glicina/análisis , Suelo/química , Herbicidas/análisis , Agricultura , Contaminantes del Suelo/análisis , Isoxazoles/análisis , Contaminantes Químicos del Agua/análisis , Productos Agrícolas , Movimientos del Agua , Tetrazoles/análisisRESUMEN
Plant protection products (PPPs) play a fundamental role in the maintenance of agricultural fields and private/public green areas, however they can contaminate zones nearby the application point due to wind drift, resuspension, and evaporation. Several studied have deepened the relationship between PPPs and living beings' health, suggesting that these products might have a negative influence. Some PPPs belong to the class of Emergent Contaminants, which are compounds whose knowledge on the environmental distribution and influence is limited. These issues are even more stressed in urban aerosol, due to the high residential density that characterizes this area. Therefore, this study assessed the contamination caused by polar PPPs, such as herbicides (i.e., Glyphosate), fungicides (i.e., Fosetyl Aluminium), and growth regulators (i.e. Maleic Hydrazide), in size-segregated urban aerosol and evaluated their concentration variability with respect to atmospheric parameters (humidity, temperature, rain). Moreover, hypotheses on possible sources were formulated, exploiting also back-trajectories of air masses. A total of six PPPs were found in the samples: glyphosate was more present in the coarse fraction (2.5-10 µm), Fosetyl Aluminium, chlorate and perchlorate were more present in the coarse/fine fractions (10-1 µm), while cyanuric acid and phosphonic acid were mostly concentrated in the fine/ultrafine fractions (<1 µm). While for the first four we suspect of local sources, such as private gardening, the two latter might derive from the entire Po Valley, a highly polluted area in the North of Italy, and from degradation of other substances.
Asunto(s)
Aerosoles , Contaminantes Atmosféricos , Monitoreo del Ambiente , Glicina , Glifosato , Herbicidas , Glicina/análogos & derivados , Glicina/análisis , Aerosoles/análisis , Herbicidas/análisis , Contaminantes Atmosféricos/análisis , Ciudades , Fungicidas Industriales/análisisRESUMEN
Glyphosate, a commonly used organophosphorus herbicide in rice-crayfish cropping regions, may alter regional phosphorus cycle processes while affecting the structure of microbial communities. However, the effects of glyphosate residues on rice-crayfish systems remain unclear. In this study, we assessed the spatial and temporal distribution characteristics of glyphosate and its primary degradation products, as well as the impact mechanisms of glyphosate on microbial communities and the phosphorus cycle in rice-crayfish systems such as paddy fields, breeding ditches and recharge rivers. The detection rates of glyphosate and aminomethylphosphonic acid (AMPA) were 100% in rice-crayfish systems. Concentrations of glyphosate in the water phase and soil/sediment were as high as 0.012 µg/L and 7.480 µg/kg, respectively, and concentrations of AMPA were as high as 17.435 µg/L and 13.200 µg/kg, respectively. Glyphosate concentrations were not affected by rainfall or sampling site, but concentrations of AMPA in the water phase of recharge rivers were affected by rainfall. The glyphosate concentration was significantly and positively correlated with RBG-16-58-14 abundance, and the AMPA concentration was significantly and positively correlated with Actinobacteria and Lysobacter abundance, and negatively correlated with Cyanobacteria abundance (P < 0.05). The highest abundances of phoD, phnK, and ppx genes were found in all soils/sediments. Glyphosate concentration in soil/sediment was significantly and positively correlated with the abundance of phoD gene encoding an organophosphorus-degrading enzyme and ppx gene encoding poly inorganic phosphate (Pi) hydrolase (P < 0.05). In addition, the glyphosate concentration was significantly and positively correlated with the Ca-bonded Pi content (P < 0.05). This implies that glyphosate may promote the production of stable Pi in rice-crayfish systems by increasing the abundance of phoD and ppx genes. The results of this study reveal the impact mechanism of glyphosate on the phosphorus cycle in rice-crayfish systems and provide a basis for the risk assessment of glyphosate.
Asunto(s)
Glicina , Glifosato , Herbicidas , Organofosfonatos , Fósforo , Glicina/análogos & derivados , Glicina/toxicidad , Glicina/análisis , Animales , Fósforo/análisis , Herbicidas/análisis , Organofosfonatos/análisis , Oryza/microbiología , Microbiota/efectos de los fármacos , Contaminantes Químicos del Agua/análisis , Microbiología del SueloRESUMEN
In this work, we demonstrate the electrochemical (EC) sensing of glycine (GLY) on a gold-copper nanocluster on nitrogen-doped graphene quantum dot-modified (indigenously fabricated) screen-printed electrode (AuCuNC@N-GQD/SPE). SPE was fabricated by step-by-step printing of reference, working, and counter electrodes to develop an all-printed SPE. A comparison strategy between SPE and the glassy carbon electrode (GCE) towards the EC sensing of GLY was carried out. The sensing performance was enhanced while replacing GCE with SPE. The limit of detection (LOD) for GLY obtained by EC sensing with AuCuNC@N-GQD/GCE was 10 nM and that with AuCuNC@N-GQD/SPE was 10 times lower, 1 nM, and is the lowest LOD value reported hitherto. Compared with AuCuNC@N-GQD/GCE, the current response of AuCuNC@N-GQD/SPE exhibited a â¼2.6-times enhancement with a sensitivity of 0.206 µA µM-1 cm-2. Thus, the successful shift from GCE to SPE not only miniaturizes the sensor device but also enhances the electrochemical detection performance.
Asunto(s)
Carbono , Técnicas Electroquímicas , Electrodos , Glicina , Glicina/química , Glicina/análisis , Carbono/química , Grafito/química , Límite de Detección , Oro/química , Vidrio/química , Puntos Cuánticos/química , Cobre/químicaRESUMEN
Heavy metal Cu2+ emitted in industry and residues of glyphosate pesticides are pervasive in ecosystems, accumulated in water bodies and organisms' overtime, constituting hazard to human and ecological balance. The development of rapid, highly selective, reversibility and sensitive biosensor in vivo detection for Cu2+ and glyphosate was imminent. A novel dual-recognition fluorescence biosensor MPH was successfully synthesized based on triphenylamine, which demonstrated remarkable ratiometric fluorescence quenching toward Cu2+, while MPH-Cu2+ (1:1) ensemble exhibited ratiometric fluorescence restoration for glyphosate, both with observable color changes in daylight and UV lamp. The biosensor exhibited rapid, outstanding selectivity, anti-interference, and multiple cycles reversibility through "turn-off-on" fluorescence towards Cu2+ and glyphosate, respectively. Surprisingly, the clearly binding mechanisms of MPH to Cu2+ and MPH-Cu2+ ensemble to glyphosate were determined, respectively, based on the Job's plot, FT-IR, ESI-HRMS, 1H NMR titration and theoretical calculations of dynamics and thermodynamics. In addition, biosensor MPH demonstrated successful detection of Cu2+ and glyphosate across diverse environmental samples including tap water, extraction solutions of traditional Chinese medicine honeysuckle and soil samples. In the meantime, fluorescence imaging of Cu2+ and glyphosate at both micro and macro scales in various living organisms, such as rice roots, MCF-7 cells, zebrafish, and mice, were successfully achieved. Overall, this work was expected to become a promising and versatile fluorescence biosensor for rapid and reversible detection of Cu2+ and glyphosate both in vitro and vivo.
Asunto(s)
Técnicas Biosensibles , Cobre , Glicina , Glifosato , Herbicidas , Pez Cebra , Cobre/análisis , Cobre/química , Glicina/análogos & derivados , Glicina/análisis , Glicina/química , Técnicas Biosensibles/métodos , Animales , Herbicidas/análisis , Herbicidas/química , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Humanos , Fluorescencia , Ratones , Colorantes Fluorescentes/químicaRESUMEN
Large volumes of pesticides are applied every year to support agricultural production. The intensive use of pesticides affects soil quality and health, but soil surveys on pesticide residues are scarce, especially for northern Europe. We investigated the occurrence of 198 pesticide residues, including both banned and currently used substances in 148 field sites in Finland. Results highlight that pesticide residues are common in the agricultural soils of Finland. A least one residue was found in 82% of the soils, and of those 32% contained five or more residues. Maximum total residue concentration among the conventionally farmed soils was 3043 µg/kg, of which AMPA and glyphosate contributed the most. Pesticide residues were also found from organically farmed soils, although at 75-90% lower concentrations than in the conventionally farmed fields. Thus, despite the application rates of pesticides in Finland being generally much lower than in most parts of central and southern Europe, the total residue concentrations in the soils occurred at similar or at higher levels. We also established that AMPA and glyphosate residues in soil are significantly higher in fields with cereal dominated rotations than in grass dominated or cereal-grass rotations. However, risk analyses for individual substances indicated low ecological risk for most of the fields. Furthermore, the total ecological risk associated with the mixtures of residues was mostly low except for 21% of cereal dominated fields with medium risk. The results showed that the presence of mixtures of pesticide residues in soils is a rule rather than an exception also in boreal soils. In highly chemicalized modern agriculture, the follow-up of the residues of currently used pesticides in national and international soil monitoring programs is imperative to maintain soil quality and support sustainable environment policies.
Asunto(s)
Agricultura , Monitoreo del Ambiente , Residuos de Plaguicidas , Contaminantes del Suelo , Suelo , Contaminantes del Suelo/análisis , Residuos de Plaguicidas/análisis , Finlandia , Suelo/química , Medición de Riesgo , Taiga , Glicina/análogos & derivados , Glicina/análisis , GlifosatoRESUMEN
Purpose: The World Health Organization's International Agency on Research for Cancer has determined that glyphosate is "probably carcinogenic to humans." There is a great public interest to investigate whether glyphosate are detected in breast milk. Thus, the goal of this study was to assess the concentration of glyphosate and its main metabolite in breast milk. Materials and Methods: Liquid chromatography was performed at 25°C using a Luna NH2, 50 × 2 mm, 3â m (Phenomenex) analytical column. Electrospray ionization mass spectrometry was collected using negative ionization mode. The calibration curve for glyphosate ranged from 10 to 250 ng/mL. The detection limit was 1 ng/mL. Results: Breast milk samples were collected from 74 women, which included vegans (n = 26), vegetarians (n = 22), and nonvegetarians (n = 26). One of the 74 milk samples contained a detectable concentration of glyphosate and an additional 7 were found to contain aminomethylphosphonic acid. Conclusions: In breast milk samples collected mainly from women residing in urban regions of the United States, glyphosate detection was rare. Consistently, breastfed infants have a low or minimal risk of being exposed to glyphosate through ingestion of mother's milk. It is possible that the presence/absence and/or level of concentration of milk glyphosate depend on a place of residency and time of breastfeeding vis-à-vis time of its agricultural application.
Asunto(s)
Glicina , Glifosato , Leche Humana , Humanos , Femenino , Leche Humana/química , Glicina/análogos & derivados , Glicina/análisis , Adulto , Cromatografía Liquida , Herbicidas/análisis , Organofosfonatos/análisis , Lactancia Materna , Espectrometría de Masa por Ionización de Electrospray , Cromatografía Líquida con Espectrometría de Masas , Isoxazoles , TetrazolesRESUMEN
The growing reliance on pesticides for pest management in agriculture highlights the need for new analytical methods to detect these substances in food and water. Our research introduces a SPRWG-(C18H37) lipopeptide (LP) as a functional analog of acetylcholinesterase (AChE) for glyphosate detection in environmental samples using phosphatidylcholine (PC) monolayers. This LP, containing hydrophilic amino acids linked to an 18-carbon aliphatic chain, alters lipid assembly properties, leading to a more flexible system. Changes included reduced molecular area and peak pressure in Langmuir adsorption isotherms. Small angle X-ray scattering (SAXS) and atomic force microscopy (AFM) analyses provided insights into the LP's structural organization within the membrane and its interaction with glyphosate (PNG). Structural and geometric parameters, as derived from in silico molecular dynamics simulations (MD), substantiated the impact of LP on the monolayer structure and the interaction with PNG. Notably, the presence of the LP and glyphosate increased charge transfer resistance, indicating strong adherence of the monolayer to the indium tin oxide (ITO) surface and effective pesticide interaction. A calibration curve for glyphosate concentration adjustment revealed a detection limit (LOD) of 24 nmol L-1, showcasing the high sensitivity of this electrochemical biosensor. This LOD is significantly lower than that of a similar colorimetric biosensor in aqueous media with a detection limit of approximately 0.3 µmol L-1. Such an improvement in sensitivity likely stems from adding a polar residue to the amino acid chain of the LP.
Asunto(s)
1,2-Dipalmitoilfosfatidilcolina , Glicina , Glifosato , Lipopéptidos , Simulación de Dinámica Molecular , Glicina/química , Glicina/análogos & derivados , Glicina/análisis , 1,2-Dipalmitoilfosfatidilcolina/química , Lipopéptidos/química , Lipopéptidos/análisis , Agua/química , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Propiedades de SuperficieRESUMEN
A novel dual-signal fluorometric and colorimetric probe FMDH (5-FAM-Met-Asp-His-NH2), incorporating a tripeptide (Met-Asp-His-NH2) linked to 5-carboxyfluorescein (5-FAM), was firstly synthesised. FMDH demonstrated exceptional selectivity and sensitivity, rapid response, wide pH response range and robust anti-interference capabilities for monitoring Cu2+. This was achieved through a distinctive naked-eye colorimetric and fluorescent quenching behaviour. A good linearity within the range of 0-3 µM (R2 = 0.9914) was attained, and the limit of detection (LOD) for Cu2+ was 47.4 nM. Furthermore, the FMDH-Cu2+ ensemble responded to glyphosate with notable selectivity and sensitivity. A good linear correlation (R2 = 0.9926) was observed at the lower concentration range (2.4-7.8 µM) and achieving a detection limit as low as 29.9 nM. The response time of FMDH with Cu2+ and glyphosate were less than 20 s, and the pH range of 7-11 that was suitable for practical application under physiological pH conditions. MTT assays confirmed that FMDH offers good permeability and low toxicity, facilitating successful application in imaging analysis of Cu2+ and glyphosate in living cells and zebrafish. In addition, FMDH was employed in the detection of these analytes in real water samples. Cost-effective, highly sensitive and easily prepared FMDH-impregnated test strips were developed for the efficient visual detection of Cu2+ and glyphosate under 365 nm UV light. Increasing concentrations of Cu2+ and glyphosate resulted in notable colour changes under 365 nm UV light, enabling visual semi-quantitative analysis via a smartphone colour-analysis App.
Asunto(s)
Colorimetría , Cobre , Fluorometría , Glicina , Glifosato , Contaminantes Químicos del Agua , Cobre/análisis , Glicina/análogos & derivados , Glicina/análisis , Colorimetría/métodos , Contaminantes Químicos del Agua/análisis , Fluorometría/métodos , Colorantes Fluorescentes/química , Herbicidas/análisis , Límite de Detección , Péptidos , Monitoreo del Ambiente/métodos , AnimalesRESUMEN
A ratiometric fluorescence sensing strategy has been developed for the determination of Cu2+ and glyphosate with high sensitivity and specificity based on OPD (o-phenylenediamine) and glutathione-stabilized gold nanoclusters (GSH-AuNCs). Water-soluble 1.75-nm size GSH-AuNCs with strong red fluorescence and maximum emission wavelength at 682 nm were synthesized using GSH as the template. OPD was oxidized by Cu2+, which produced the bright yellow fluorescence oxidation product 2,3-diaminophenazine (DAP) with a maximum fluorescence emission peak at 570 nm. When glyphosate existed in the system, the chelation between glyphosate and Cu2+ hindered the formation of DAP and reduced the fluorescence intensity of the system at the wavelength of 570 nm. Meanwhile, the fluorescence intensity at the wavelength of 682 nm remained basically stable. It exhibited a good linear relationship towards Cu2+ and glyphosate in water in the range 1.0-10 µM and 0.050-3.0 µg/mL with a detection limit of 0.547 µM and 0.0028 µg/mL, respectively. The method was also used for the semi-quantitative determination of Cu2+ and glyphosate in water by fluorescence color changes visually detected by the naked eyes in the range 1.0-10 µM and 0.30-3.0 µg/mL, respectively. The sensing strategy showed higher sensitivity, more obvious color changes, and better disturbance performance, satisfying with the detection demands of Cu2+ and glyphosate in environmental water samples. The study provides a reliable detection strategy in the environment safety fields.
Asunto(s)
Colorimetría , Cobre , Glicina , Glifosato , Oro , Límite de Detección , Nanopartículas del Metal , Fenilendiaminas , Espectrometría de Fluorescencia , Contaminantes Químicos del Agua , Glicina/análogos & derivados , Glicina/análisis , Glicina/química , Cobre/química , Nanopartículas del Metal/química , Fenilendiaminas/química , Oro/química , Espectrometría de Fluorescencia/métodos , Contaminantes Químicos del Agua/análisis , Colorimetría/métodos , Glutatión/química , Glutatión/análisis , Herbicidas/análisis , Colorantes Fluorescentes/químicaRESUMEN
Communities neighboring monoculture plantations are vulnerable to different forms of pollution associated with agro-industrial operations. Herein, we examine the case of El Tiple, a rural Afro descendant community embedded within one of the largest sugarcane plantations in the Americas. We implemented a participatory approach to assess water pollution, exposure via water ingestion, and non-carcinogenic health risks associated with the use of local water sources available to the community. We conducted household surveys to unveil demographic characteristics and family dynamics linked to water consumption. Additionally, we measured water quality parameters and assessed the concentration glyphosate, its major metabolite (aminomethylphosphonic acid) and metals and metalloids. Drinking water El Tiple households is sourced from three primary sources: the local aqueduct system, water delivery trucks, and private deep wells. Tests on water samples from both the local aqueduct and delivery trucks showed no traces of pesticides, metals, or metalloids surpassing regulatory limits set by Colombian or EPA standards. However, we found concentration of contaminants of primary concern, including mercury (up to 0.0052 ppm) and lead (up to 0.0375 ppm) that exceed the permissible regulatory thresholds in water from groundwater wells. Residents of the peripheric subdivisions of El Tiple are four times more reliant on well water extraction than residents of the central area of the town due to lack of access to public drinking water and sanitation infrastructure. Finally, adult women and school-age children have a higher health risk associated with exposure to local pollutants than adult men due to their constant presence in the town. We conclude that expanding the coverage of clean water and sanitation infrastructure to include all households of the community would be the most recommended measure to minimize exposure and risk via ingestion of water pollutants.
Asunto(s)
Saccharum , Contaminantes Químicos del Agua , Colombia , Contaminantes Químicos del Agua/análisis , Humanos , Medición de Riesgo , Agricultura , Agua Potable/química , Monitoreo del Ambiente , Contaminación del Agua/estadística & datos numéricos , Contaminación del Agua/análisis , Glicina/análogos & derivados , Glicina/análisis , Exposición a Riesgos Ambientales/estadística & datos numéricos , Exposición a Riesgos Ambientales/análisis , Abastecimiento de Agua , GlifosatoRESUMEN
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.
Asunto(s)
Glycine max , Glicina , Glifosato , Ríos , Contaminantes Químicos del Agua , Zea mays , Glicina/análogos & derivados , Glicina/análisis , Ríos/química , Contaminantes Químicos del Agua/análisis , Herbicidas/análisis , Organofosfonatos/análisis , Monitoreo del Ambiente , AgriculturaRESUMEN
To satisfy the public's urgent demand for food safety and protect the ecological environment, sensitive detection of glyphosate holds paramount importance. Here, we discovered that glyphosate can engage in specific interactions with iron organic frameworks (Fe-MOFs) nanozymes, enabling a selective detection of glyphosate. Based on this principle, an innovative colorimetric and fluorescent dual-mode detection approach was devised. Specifically, Fe-MOFs were synthesized at room temperature, exhibiting remarkable peroxidase-mimic activity. These nanozymes catalyze the conversion of colorless and fluorescent 3,3',5,5'-Tetramethylbenzidine (TMB) into blue oxidized and nonfluorescent TMB (oxTMB) in the presence of H2O2. However, the introduction of glyphosate disrupts this process by interacting with Fe-MOFs, significantly inhibiting the catalytic activity of Fe-MOFs through both physical (electrostatic and hydrogen bonding) and chemical interactions. This suppression further hindered the conversion of TMB to oxTMB, resulting in a reduction in absorbance and a corresponding enhancement in fluorescence. The method offers a colorimetric and fluorescence dual-mode detection capability with enhanced applicability. Notably, our approach avoids complex material modifications and is more stable and cost-effective than the traditional enzyme inhibition methods. This innovative detection technique holds immense potential for practical applications and provides a fresh perspective for the detection of pesticide residues.
Asunto(s)
Colorimetría , Glicina , Glifosato , Hierro , Estructuras Metalorgánicas , Espectrometría de Fluorescencia , Glicina/análogos & derivados , Glicina/análisis , Glicina/química , Hierro/química , Hierro/análisis , Estructuras Metalorgánicas/química , Colorimetría/métodos , Espectrometría de Fluorescencia/métodos , Bencidinas/química , Peróxido de Hidrógeno/análisis , Peróxido de Hidrógeno/química , Catálisis , Herbicidas/análisis , Nanoestructuras/químicaRESUMEN
RATIONALE: 1,2-Diacyl-sn-glycero-3-phospho-O-[N-(2-hydroxyethyl)glycines] (PHEGs) are a class of rare aminophospholipids found specifically in brown algae, including kombu seaweed. Despite their potential importance in algal physiology, a comprehensive mass spectrometry (MS) characterization, useful to understand their biological behaviour, is still lacking. METHODS: To establish the structural regiochemical features of PHEGs, we employed hydrophilic interaction liquid chromatography (HILIC). Following separation, the isolated band of PHEGs was analyzed using MS techniques. This included multistage tandem MS experiments, performed in both positive and negative electrospray ionization modes at low and high resolution. RESULTS: By comparing MS/MS and MS3 spectra acquired in negative ion mode, the regiochemical rules for PHEG identification were established. The most abundant PHEG species in kombu seaweed, from both Laminaria ochroleuca (European Atlantic) and Laminaria longissima (Japan), was identified as PHEG 20:4/20:4. Less abundant species included PHEG 20:4/20:5 and hydroxylated forms of both PHEG 20:4/20:4 (i.e. 40:8;O) and 20:4/20:5 (40:9;O). The presence of a lyso PHEG 20:4 was consistently detected but at very low levels. CONCLUSIONS: This study employed MS analysis to elucidate the regiochemical patterns of PHEGs in kombu seaweed. We identified PHEG 20:4/20:4 as the dominant species, along with several less abundant variants, including hydroxylated forms. These findings provide valuable insights into the potential roles and metabolism of PHEGs in brown algae, paving the way for further investigation into their biological functions.
Asunto(s)
Espectrometría de Masas en Tándem , Espectrometría de Masas en Tándem/métodos , Algas Marinas/química , Fosfolípidos/química , Fosfolípidos/análisis , Glicina/análogos & derivados , Glicina/química , Glicina/análisis , Phaeophyceae/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Laminaria/química , Cromatografía Liquida/métodos , Algas ComestiblesRESUMEN
As common pollutants, Cu2+ and glyphosate pose a serious threat to human health and the ecosystem. Herein, a fluorescent probe (E)-7-(diethylamino)-N'(4-(diethylamino)-2-hydroxybenzyl)-2-oxo-2H chromophore-3-carbazide (DDHC) was designed and synthesised for the sequential recognition of Cu2+ and glyphosate. DDHC has the advantages of a short synthesis path, easy-to-obtain raw materials, good anti-interference ability, and strong stability. The interaction of the DDHC-Cu2+ complexes with glyphosate allows the amino and carboxyl groups in glyphosate molecules to coordinate with Cu2+ strongly, competing for the Cu2+ in the DDHC-Cu2+ complexes and releasing the DDHC, leading to the recovery of fluorescence. The recognition was further validated through Job's plot, HRMS, and DFT calculations. In addition, the successful recovery of Cu2+ and glyphosate in different environmental water samples fully demonstrates the practical application potential of DDHC. Especially, DDHC has low cytotoxicity and can enter zebrafish and HeLa cells, rapidly reacting with Cu2+ and glyphosate in the body, generating visible fluorescence quenching and recovery phenomena, achieving real-time visual monitoring of exogenous Cu2+ and glyphosate in zebrafish and HeLa cells. The targeting and dual selectivity of DDHC greatly enhance its potential application value in the field of detection, providing important theoretical support for studying the fate of multiple pollutants in the environment.