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Background: Multi-residue methods for pesticide analysis in food are available for many compounds, but polar pesticides are not generally included due to their specific properties, which include high polarity and low molecular weight. Single residue methods are therefore needed for sample preparation, while chromatographic separation often requires derivatization, ion paring, or dedicated methods suitable for polar compounds, mostly ion chromatography and hydrophilic interaction liquid chromatography (HILIC). These challenges affect the important pesticide glyphosate and the related compounds aminomethylphosphonic acid (AMPA) and glufosinate. There are only a few methods including these compounds in large-scale analysis, mostly complex methods based on multidimensional chromatography., Results: A new method, for the global online extraction and analysis of pesticides in beer was developed and validated. The method exploited an online trapping device, with reversed-phase (RP) and anion exchange properties, that can trap small molecules from liquid samples. The ion exchange mechanism was used to retain the very polar pesticides glyphosate, AMPA, and glufosinate. The hydrophobic properties of the trapping column were also exploited to trap pesticides suitable for multi-residue investigations. The chromatographic separation was optimized by comparison of HILIC and RP C30, which could separate pesticides, including the polar ones, with modulation by the trapping column after proper selection of the mobile phase composition and basic modifier. The validation for beer provided recoveries in the range 71-112 %, with <15 % RSD, and LOD and LOQ values of 0.02-1 and 0.3-3 μg L -1 , respectively. The result was competitive with previous methods on polar pesticide analysis in beer., Significance: The method was validated for 15 pesticides, over the log K ow range from -4.4 to 4.5, using a methodology with single and fast chromatographic separation under conditions compatible with multi-residue analysis by RP-LC-MS/MS. In the case of beer, for which the method was validated, the sample preparation was also performed online, after simple degassing, and sample dilution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Biodegradability testing in soil helps to identify safe synthetic organic chemicals but is still obscured by the formation of soil-bound 'non-extractable' residues (NERs). Present-day methodologies using radiocarbon or stable ( 13 C, 15 N) isotope labeling cannot easily differentiate soil-bound parent chemicals or transformation products (xenoNERs) from harmless soil-bound biomolecules of microbial degraders (bioNERs). Hypothesizing a minimal retention of hydrogen in biomolecules, we here apply stable hydrogen isotope - deuterium (D) - labeling to unravel the origin of NERs. Soil biodegradation tests with D- and 13 C-labeled 2,4-D, glyphosate and sulfamethoxazole reveal consistently lower proportions of applied D than 13 C in total NERs and in amino acids, a quantitative biomarker for bioNERs. Soil-bound D thus mostly represents xenoNERs and not bioNERs, enabling an efficient quantification of xenoNERs by just measuring the total bound D. D or tritium (T) labeling could thus improve the value of biodegradability testing results for diverse organic chemicals forming soil-bound residues., (© 2024. The Author(s).)

Glyphosate (GLY) is widely applied in agriculture and horticulture as a herbicide. The development of genetically modified plants has caused abuse of GLY, with excessive residues potentially causing harm to human health. Consequently, a novel method needs to be built to detect GLY in soybeans and corn. Computer simulation was used to design an excellent hapten which was used to produce an anti-GLY monoclonal antibody (mAb) with outstanding sensitivity and affinity, and its 50%-inhibitory concentration (IC 50 ) was 128.59 ng mL -1 . Afterwards, an immunochromatographic assay strip was developed based on the mAb. In soybeans and corn, the visual detection limits were 1 mg kg -1 and 0.2 mg kg -1 , while the cut-off values were 50 mg kg -1 and 5 mg kg -1 , respectively. The reliability of the strips was proved by the existing methods. Thus, a rapid method to detect GLY residues on-site in soybeans and corn was established.

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 H 2 O 2 by Os-Rh nanozyme to produce HO∙. 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 H 2 O 2 . 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

By combining boric acid-modified carbon dots (p-CDs) and alizarin red (ARS), a double emission probe p-CDs@ARS with fluorescence at 410 nm and 600 nm is designed for the detection of glyphosate. When Cu 2+ is added, it binds with ARS to cause ARS release from p-CDs@ARS, which decreases the fluorescence at 600 nm. However, in the presence of glyphosate, glyphosate competes to the binding of Cu 2+ , releasing ARS to bind with p-CDs again. Therefore, the fluorescence of 600 nm recovers. Based on this, the fluorescence of 410 nm and 600 nm act as the reference and response signal, respectively, achieving the ratiometric fluorescence detection of glyphosate. The linear range of glyphosate detection is 0.5-50 µM with a limit of detection at 0.37 µM which is well below the maximum residue limit for glyphosate in food. When the probe is used to detect the glyphosate residue in Pearl River water and cucumber, the detection results are well consistent with those detected by HPLC. The established method based on p-CDs@ARS has the advantages that the assembly of ratiometric fluorescence probe is simple, and the detection speed is fast. Additionally, a typical INHIBIT logical system has been successfully constructed based on glyphosate, Cu 2+ , and the fluorescence signal of p-CDs@ARS., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The neurotoxin β-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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Glyphosate is the most widely used herbicide worldwide, with concerns over human exposure and potential health risks. Nevertheless, little is known about the sources of human exposure to glyphosate and its degradation product, aminomethylphosphonic acid (AMPA). In this study, we measured glyphosate and AMPA in 99 indoor dust samples collected from urban homes in sixteen states in the USA. Glyphosate and AMPA were detected in all samples at geometric mean (GM) concentrations of 193 and 30.8 ng/g, respectively. We found a strong and significant positive correlation between glyphosate and AMPA concentrations (r = 0.70, p < 0.01), indicating that the latter mainly originated from glyphosate. The concentrations of glyphosate (r = 0.40, p < 0.01) and AMPA (r = 0.33, p < 0.01) in indoor dust were significantly correlated with the county-wide agricultural usage of this herbicide. Human exposure to glyphosate and AMPA through dust ingestion were in the ranges of 0.05-0.85 and 0.01-0.14 ng/kg body weight (BW)/day, respectively, for various age groups, which were more than two orders of magnitude below the acceptable daily intake for glyphosate (500 μg/kg BW/day). Further studies are needed to identify the sources and health outcomes of human exposure to glyphosate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The long-term and excessive use of glyphosate (GLY) in diverse matrices has caused serious hazard to the human and environment. However, the ultrasensitive detection of GLY still remains challenging. In this study, the smartphone-assisted dual-signal mode ratiometric fluorescent and paper sensors based on the red-emissive gold nanoclusters (R-AuNCs) and blue-emissive carbon dots (B-CDs) were ingeniously designed accurate and sensitive detection of GLY. Upon the presence of GLY, it would quench the fluorescence of B-CDs through dynamic quenching effect, and strengthen the fluorescence response of R-AuNCs due to aggregation-induced enhancement effect. Through calculating the GLY-induced fluorescence intensity ratio of B-CDs to R-AuNCs by using a fluorescence spectrophotometer, low to 0.218 μg/mL of GLY could be detected in lab in a wide concentration range of 0.3-12 μg/mL with high recovery of 94.7-103.1% in the spiked malt samples. The smartphone-assisted ratiometric fluorescent sensor achieved in the 96-well plate could monitor 0-11 μg/mL of GLY with satisfactory recovery of 94.1-107.0% in real edible malt matrices for high-throughput analysis. In addition, a portable smartphone-assisted ratiometric paper sensor established through directly depositing the combined B-CDs/R-AuNCs probes on the test strip could realize on-site measurement of 2-8 μg/mL of GLY with good linear relationship. This study provides new insights into developing the dual-signal ratiometric sensing platforms for the in-lab sensitive detection, high-throughput analysis, and on-site portable measurement of more trace contaminants in foods, clinical and environmental samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

A novel dual-signal fluorometric and colorimetric probe FMDH (5-FAM-Met-Asp-His-NH 2 ), incorporating a tripeptide (Met-Asp-His-NH 2 ) 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 Cu 2+ . This was achieved through a distinctive naked-eye colorimetric and fluorescent quenching behaviour. A good linearity within the range of 0-3 μM (R 2  = 0.9914) was attained, and the limit of detection (LOD) for Cu 2+ was 47.4 nM. Furthermore, the FMDH-Cu 2+ ensemble responded to glyphosate with notable selectivity and sensitivity. A good linear correlation (R 2  = 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 Cu 2+ 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 Cu 2+ 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 Cu 2+ and glyphosate under 365 nm UV light. Increasing concentrations of Cu 2+ and glyphosate resulted in notable colour changes under 365 nm UV light, enabling visual semi-quantitative analysis via a smartphone colour-analysis App., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 MS 3 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., (© 2024 John Wiley & Sons Ltd.)

Heavy metal Cu 2+ 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 Cu 2+ and glyphosate was imminent. A novel dual-recognition fluorescence biosensor MPH was successfully synthesized based on triphenylamine, which demonstrated remarkable ratiometric fluorescence quenching toward Cu 2+ , while MPH-Cu 2+ (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 Cu 2+ and glyphosate, respectively. Surprisingly, the clearly binding mechanisms of MPH to Cu 2+ and MPH-Cu 2+ ensemble to glyphosate were determined, respectively, based on the Job's plot, FT-IR, ESI-HRMS, 1 H NMR titration and theoretical calculations of dynamics and thermodynamics. In addition, biosensor MPH demonstrated successful detection of Cu 2+ 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 Cu 2+ 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 Cu 2+ and glyphosate both in vitro and vivo., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A new peptide-based fluorescent probe named DMDH with easy-to-synthesize, excellent stability, good water solubility and large Stokes shift (225 nm) was synthesized for highly selective sequential detections of copper ions (Cu 2+ ) and glyphosate (Glyp). DMDH demonstrated great detection performance towards Cu 2+ via strong fluorescence quenching, and forming non-fluorescence DMDH-Cu 2+ ensemble. As a new promising cascade probe, the fluorescence of DMDH-Cu 2+ ensemble was significantly recovered based on displacement approach after glyphosate was added. Interestingly, the limit of detections (LODs) for Cu 2+ and glyphosate were 40.6 nM and 10.6 nM, respectively, which were far lower than those recommended by the WHO guidelines for drinking water. More importantly, DMDH was utilized to evaluate Cu 2+ and glyphosate content in three real water samples, demonstrating that its effectiveness in water quality monitoring. Additionally, it is worth noting that DMDH was also applied to analyze Cu 2+ and glyphosate in living cells in view of significant cells permeability and low cytotoxicity. Moreover, DMDH soaked in filter paper was used to create qualitative test strips and visually identify Cu 2+ and glyphosate through significant color changes. Furthermore, smartphone RGB color recognition provided a new method for semi-quantitative testing of Cu 2+ and glyphosate in the absence of expensive instruments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

As common pollutants, Cu 2+ 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 Cu 2+ 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-Cu 2+ complexes with glyphosate allows the amino and carboxyl groups in glyphosate molecules to coordinate with Cu 2+ strongly, competing for the Cu 2+ in the DDHC-Cu 2+ 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 Cu 2+ 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 Cu 2+ and glyphosate in the body, generating visible fluorescence quenching and recovery phenomena, achieving real-time visual monitoring of exogenous Cu 2+ 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., (© 2024 The Author(s). Journal of Environmental Quality © 2024 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

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 NH 2 , 50 × 2 mm, 3⎛ 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.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that there is no known conflict of interest, competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A novel zeolitic imidazolate framework-encapsulated zinc porphyrin (ZnTCPP@ZIF-90) photoresponsive nanozyme is proposed for the colorimetric/fluorescent dual-mode visual sensing of glyphosate (Gly). ZnTCPP@ZIF-90 exhibits photoresponsive oxidase-like activity and fluorescence quenching behavior. Meanwhile, the outer ZIF-90 layer can be selectively destroyed by Gly, causing the release of free ZnTCPP, resulting in the enhanced enzyme-like activity as well as fluorescence emission. The constructed ZnTCPP@ZIF-90 was successfully used for the colorimetric/fluorescent dual-mode detection of Gly. Additionally, the colorimetric and fluorescent images information captured by the smartphone were converted to color intensity (HSV/RGB values), with limits of detection of 0.27 μg/mL and 0.19 μg/mL, respectively. The proposed dual-mode sensor exhibits excellent selectivity and reliability for detecting Gly, and can be successfully applied to the analysis of real samples such as tap water, lake water, and fruit washing water. The current research efforts are expected to provide new perspectives for designing highly active photoresponsive nanozymes and their stimuli-responsive sensing systems, paving the way for their applications in portable dual-mode chemical sensing and environmental monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

N-myristoylation is one of the most widespread and important lipidation in eukaryotes and some prokaryotes, which is formed by covalently attaching various fatty acids (predominantly myristic acid C14:0) to the N-terminal glycine of proteins. Disorder of N-myristoylation is critically implicated in numerous physiological and pathological processes. Here, we presented a method for purification and comprehensive characterization of endogenous, intact N-glycine lipid-acylated peptides, which combined the negative selection method for N-terminome and the nanographite fluoride-based solid-phase extraction method (NeS-nGF SPE). After optimizing experimental conditions, we conducted the first global profiling of the endogenous and heterogeneous modification states for N-terminal glycine, pinpointing the precise sites and their associated lipid moieties. Totally, we obtained 76 N-glycine lipid-acylated peptides, including 51 peptides with myristate (C14:0), 10 with myristoleate (C14:1), 6 with tetradecadienoicate (C14:2), 5 with laurate (C12:0) and 4 with lauroleate (C12:1). Therefore, our proteomic methodology could significantly facilitate precise and in-depth analysis of the endogenous N-myristoylome and its heterogeneity., Competing Interests: Declaration of competing interest The authors declare that there are no conflicts of interest related to this article., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 ∼2.6-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.

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., Competing Interests: The authors declare no competing interests., (Copyright: © 2024 Popradit et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

The excessive emission of copper ions (Cu 2+ ) and the abuse of glyphosate (Glyp) have caused serious harm to the ecological environment and human health, so it is important to develop a fast and convenient method for the analysis of Cu 2+ and glyphosate to ensure environmental and food safety. Herein, a dual-signals peptide-based probe (FASRH) with fluorescent and colorimetric was prepared using 5-carboxyl fluorescein modified tetrapeptide (Ala-Ser-Arg-His-NH 2 ). FASRH was successfully used to recognize Cu 2+ as a fluorescence "on-off" probe, forming the FASRH-Cu 2+ complex with non-fluorescence. As a new promising cascade probe, FASRH-Cu 2+ complex probe has high selectivity (only Glyp), good sensitivity (50.2 nM), good anti-interference ability and wide pH range (7.0-11.0) for the detection of glyphosate by ligand replacement method. In addition, the recognizable color changed markedly under 365 nm UV light and natural light. Notably, FASRH not only achieved accurate monitoring of Cu 2+ and glyphosate in two real water samples, but also successfully applied to detect Cu 2+ and glyphosate in live Hacat cells based on low cytotoxicity. Moreover, it is worth noting that FASRH-impregnated test strips exhibited significant fluorescence and colorimetric color changes for Cu 2+ and glyphosate via naked eye. Furthermore, smartphone-assisted FASRH was used for the portable detection of Cu 2+ and glyphosate based on the advantages of simplicity, low cost and fast response., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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-(C 18 H 37 ) 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.

A ratiometric fluorescence sensing strategy has been developed for the determination of Cu 2+ 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 Cu 2+ , 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 Cu 2+ 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 Cu 2+ 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 Cu 2+ 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 Cu 2+ and glyphosate in environmental water samples. The study provides a reliable detection strategy in the environment safety fields., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Objectives: In the context of a supply disruption of mebrofenin (Cholediam)-based kits for radiolabelling with technetium-99m [ 99m Tc], the medicine agencies allowed the importation of a back-up radiopharmaceutical diagnostic agent, etifenin (Techida), to ensure continuous management of patients with hepatobiliary disorders in nuclear medicine departments. There are still issues regarding the measurement of radiochemical purity (RCP) with these kits based on the European Pharmacopoeia and the Summary of Product Characteristics (SPC). This study aims to identify and to optimise, in a clinical context, the most suitable thin layer chromatography (TLC) method for the determination of the RCP in terms of speed of response and reliability for [ 99m Tc]Tc-mebrofenin and [ 99m Tc]Tc-etifenin., Methods: [ 99m Tc]Tc-etifenin (n=4) and [ 99m Tc]Tc-mebrofenin (n=5) were individually controlled using six different TLC methods and one high-performance liquid chromatography (HPLC) method for impurity identification ([ 99m Tc](TcO 2 ) n and Na[ 99m Tc]TcO 4 ), RCP (%) and duration of analysis (min). Two TLC methods were selected according to the recommendations of the Pharmacopoeia and SPC, two others were exactly the same but with a heating step, and the other two corresponded to a mix between the methods of the SPC and the Pharmacopoeia that were chosen to optimise RCP determination parameters., Results: Radio-HPLC analysis allowed effective separation of [ 99m Tc]Tc-etifenin and [ 99m Tc]Tc-mebrofenin with a retention time of 8.05±0.02 min and 8.94±0.07 min, respectively, from Na[ 99m Tc]TcO 4 (retention time 2.76±0.03 min). HPLC showed an absence of Na[ 99m Tc]TcO 4 for [ 99m Tc]Tc-mebrofenin and 0.2% for [ 99m Tc]Tc-etifenin. Among the TLC methods, we identified the most suitable method which ensures the most compliant RCP (98.3±0.9%) in a time of 31.5±1.1 min. Also, it allowed a time saving of 15 min compared with the methods proposed by the Pharmacopoeia and the SPCs., Conclusion: We propose a TLC method that accelerates quality control by an average of 15 min while guaranteeing a reliable RCP., Competing Interests: Competing interests: None declared., (© European Association of Hospital Pharmacists 2024. No commercial re-use. See rights and permissions. Published by BMJ.)

Background: Presently, glyphosate (Gly) is the most extensively used herbicide globally, Nevertheless, its excessive usage has increased its accumulation in off-target locations, and aroused concerns for food and environmental safety. Commonly used detection methods, such as high-performance liquid chromatography and gas chromatography, have limitations due to expensive instruments, complex pre-processing steps, and inadequate sensitivity. Therefore, a facile, sensitive, and reliable Gly detection method should be developed., Results: A photoelectrochemical (PEC) sensor consisting of a three-dimensional polymer phenylethnylcopper/nitrogen-doped graphene aerogel (PPhECu/3DNGA) electrode coupled with Fe 3 O 4 NPs nanozyme was constructed for sensitive detection of Gly. The microscopic 3D network of electrodes offered fast transfer routes for photo-generated electrons and a large surface area for nanozyme loading, allowing high signal output and analytical sensitivity. Furthermore, the use of peroxidase-mimicking Fe 3 O 4 NPs instead of natural enzyme improved the stability of the sensor against ambient temperature changes. Based on the inhibitory effect of Gly on the catalytic activity Fe 3 O 4 NPs, the protocol achieved Gly detection in the range of 5 × 10 -10 to 1 × 10 -4  mol L -1 . Additionally, feasibility of the detection was confirmed in real agricultural matrix including tea, maize seedlings, maize seeds and soil., Significance: This work achieved facile, sensitive and reliable analysis towards Gly, and it was expected to inspire the design and utilization of 3D architectures in monitoring agricultural chemicals in food and environmental matrix., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Polar pesticides such as anionic or ionisable compounds have always provided a challenge for analytical chemists. Methods of analysis have been developed using a range of techniques including normal phase chromatography, ion-pairing, derivatisation and HILIC or multi-mode chromatography. These work well with some of these compounds but, except for HILIC, all of them have their limitations and none of them cover the range required by legislation. Some of these compounds, glyphosate, chlorate and phosphonic acid, are found regularly in a range of food matrices, and therefore reliable methods of analysis are essential. This study describes an ion chromatography method with tandem mass spectrometry detection which not only covers the full range of compounds required by legislation but also can be expanded to include other anionic or ionisable pesticides and metabolites. These include glyphosate and its metabolites, glufosinate and its metabolites, ethephon and its metabolites as well as fosetyl aluminium, chlorate and perchlorate. The method is fully validated according to the performance criteria from the SANTE guidelines for the analysis of pesticides in food and feed over a wide range of matrices, including milk, infant formula, cereals and fruits and vegetables. Over 300 food samples have analysed as part of our routine monitoring program.

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g -1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H 2 O 2 -directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The increasing concern over pesticide pollution in water bodies underscores the need for effective mitigation strategies to support the transition towards sustainable agriculture. This study assesses the effectiveness of landscape mitigation strategies, specifically vegetative buffer strips, in reducing glyphosate loads at the catchment scale under realistic conditions. Conducted over six years (2014-2019) in a small agricultural region in Belgium, our research involved the analysis of 732 water samples from two monitoring stations, differentiated by baseflow and event-driven sampling, and before (baseline) and after the implementation of mitigation measures. The results indicated a decline in both the number and intensity of point source losses over the years. Additionally, there was a general decrease in load intensity; however, the confluence of varying weather conditions (notably dry years during the mitigation period) and management practices (the introduction of buffer strips) posed challenges for a statistically robust evaluation of each contributing factor. A reduction of loads was measured when comparing mitigation with baseline, although this reduction is not statistically significant. Glyphosate loads during rainfall events correlated with a rainfall index and runoff ratio. Overall, focusing the mitigation strategy on runoff and erosion was a valid approach. Nevertheless, challenges remain, as evidenced by the continuous presence of glyphosate in baseflow conditions, highlighting the complex dynamics of pesticide transport. The study concludes that while progress has been made towards reducing pesticide pollution, the complexity of interacting factors necessitates further research. Future directions should focus on enhancing farmer engagement in mitigation programs and developing experiments with more intense data collection that help to assess underlying dynamics of pesticide pollution and the impact of mitigation strategies in more detail, contributing towards the goal of reducing pesticide pollution in water bodies., Competing Interests: Declaration of competing interest The authors declare the following financial support which may be considered as potential competing interests: Ingeborg Joris, Nele Desmet, and Piet Seuntjens report financial support provided by Glyphosate Environmental Stewardship Steering Group (GESSG). If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A method was developed to determine glyphosate and their metabolites in water. The widespread use of this herbicide in agricultural activities worldwide, despite the reported adverse effects on both the environment and health, is a cause for concern and makes it necessary to monitor its presence through a method that guarantees the determination at trace levels. A direct extraction of the analytes with phosphate buffer was performed with subsequent derivatization with 9-fluorenylmethyl chloroformate. The quantification was determined by Ultra Performance Liquid Chromatography-tandem mass spectrometer. The method was validated through the following parameters: selectivity, detection and quantification limits, linearity, accuracy, precision and uncertainty. The average recoveries ranged between 94.08 and 103.31%. Additionally, detection limits from 0.396 to 0.433 μg/L, and the quantification limit was 5.0 μg/L for all the analytes evaluated. In terms of linearity and precision, the results obtained were in the ranges considered adequate (R2 ≥ 0.99 and CV ≤ 20%), the estimated expanded uncertainty was 12.95, 11.15 and 13.83% for glyphosate, aminomethylphosphonic acid and glufosinate, respectively. This method was successfully applied for the determination of the target analytes in irrigation water samples, detecting concentrations of aminomethylphosphonic acid over limit detection for some sampling sites., (© The Author(s) 2023. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Interest has increased in the role of N-acyl amino acids in a variety of disease states and as potential pharmacotherapies. Recently, N-oleoyl glycine and N-oleoyl alanine have shown promise in reducing the rewarding effects of drugs of abuse and alleviating withdrawal signs in rodent models. Previously published methods for the quantitation of these analytes by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in tissue were part of extensive lipidomic panels which may result in limited sensitivity and selectivity and also reported low recovery. Presented is a method for the extraction and HPLC-MS/MS analysis of N-oleoyl glycine and N-oleoyl alanine. The bias and precision of the assay were determined to be within ± 20%. The method was shown to be reliable and robust, with over 90% recovery for the low-level analytes. Increasing concentrations of N-oleoyl glycine and N-oleoyl alanine were quantitated in mouse brain and plasma following exogenous administration. This method was developed to serve to support studies investigating the pharmacokinetics and involvement of N-oleoyl glycine and N-oleoyl alanine in drug dependence and other diseases., (© 2023 The Authors. Journal of Separation Science published by Wiley-VCH GmbH.)

Identifying the metabolome of human seminal plasma (HSP) is a new research area to screen putative biomarkers of infertility. This case-control study was performed on HSP specimens of 15 infertile patients with teratozoospermia (defined as normal sperm morphology < 4%) and 12 confirmed fertile normozoospermic men as the control group to investigate the seminal metabolic signature and whether there are differences in the metabolome between two groups. HSPs were subjected to LC-MS-MS analysis. MetaboAnalyst5.0 software was utilized for statistical analysis. Different univariate and multivariate analyses were used, including T-tests, fold change analysis, random forest (RF), and metabolite set enrichment analysis (MSEA). Teratozoospermic samples contained seventeen significantly different amino acids. Upregulated metabolites include glutamine, asparagine, and glycylproline, whereas downregulated metabolites include cysteine, γ-aminobutyric acid, histidine, hydroxylysine, hydroxyproline, glycine, proline, methionine, ornithine, tryptophan, aspartic acid, argininosuccinic acid, α-aminoadipic acid, and β-aminoisobutyric acid. RF algorithm defined a set of 15 metabolites that constitute the significant features of teratozoospermia. In particular, increased glutamine, asparagine, and decreased cysteine, tryptophan, glycine, and valine were strong predictors of teratozoospemia. The most affected metabolic pathways in teratozoospermic men are the aminoacyl-tRNA, arginine, valine-leucine, and isoleucine biosynthesis. Altered metabolites detected in teratozoospermia were responsible for various roles in sperm functions that classified into four subgroups as follows: related metabolites to antioxidant function, energy production, sperm function, and spermatogenesis. The altered amino acid metabolome identified in this study may be related to the etiology of teratozoospermia, and may provide novel insight into potential biomarkers of male infertility for therapeutic targets., (© 2023. The Author(s), under exclusive licence to Society for Reproductive Investigation.)

Objectives: To identify the metabolomic differences in the saliva of healthy children versus children with active carious lesions and to estimate the predictive capacity of a model based on the salivary metabolomic profile., Methods: A study of cases (n = 31) and controls (n = 37) was designed for children aged between 6 and 12 (mean age of the cases: 8.9; controls: 8.7). The said children attended public health centers in Valencia, Spain. Intraoral examinations were performed by a single examiner using ICDAS II diagnostic criteria. Unstimulated total saliva samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy., Results: The dft index for cases was 2.84 while it was 0.19 for the control group, the DMFT index was 1.13 and 0.11, respectively. The predictive model generated by the multivariate PLS-DA analysis projects a separation between the cases and the controls on the score chart with a predictive capacity and generating an area under the curve of 0.71. The metabolites: 3-methyl-2-oxovalerate, 3-hydroxybutyrate, lactate, acetone, citrate, ornithine, ethanolamine, taurine, proline, glycine, mannose, glucose, 1-6-Anhydro-β-d-glucose and citraconate, are those that show greater significance in the model. In the controls, glycine (Cohen's d = 0.430) and glucose (Cohen's d = 0.560) present higher means compared to the cases. On the contrary, taurine (Cohen's d= -0.474) and mannose (Cohen's d= -0.456) show higher means in cases compared to controls., Conclusions: Our findings show a difference in the salivary metabolomic profiles, specifically in the groups of saccharides and amino acids, suggesting an association of these with the level of caries risk., Clinical Significance: The results reported in the present study reinforce the use of salivary metabolomics as a research method for the search for salivary biomarkers that allow the evaluation of caries risk in patients. Furthermore, it brings us closer to a personalized medicine that will help in dental caries prevention strategies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Hypoglycin A (HGA), methylenecyclopropylglycine (MCPrG), hypoglycin B (HGB), and γ-glutamyl-α-(methylenecyclopropyl) glycine (γ-glutamyl-MCPrG) are secondary plant metabolites occurring in sycamore maple ( Acer pseudoplatanus ) as well as several other Sapindaceae (e.g., Blighia sapida ). By interfering with energy metabolism, they may cause severe intoxication in humans and other species. However, to date, there is not enough data available concerning the intake, metabolism, or excretion of sycamore maple toxins in dairy cows. In May 2022, five cows were observed over four days, when they had first access to a pasture with two sycamore maples. Grazing of their seedlings that grew numerously in between the pasture plants was monitored by direct observation. Milk samples were drawn both from individual cows and from the bulk tank. Spontaneous urine samples were collected from all cows on day 3 after access to the pasture. Seedlings (100 g) were sampled on the pasture and analyzed, together with milk and urine samples, for sycamore toxins and their metabolites using liquid chromatography-tandem mass spectrometry and liquid chromatography-high-resolution mass spectrometry. Cows ingested sycamore seedlings while grazing. Values of HGA in milk were below the limit of quantification. However, metabolites of HGA and MCPrG were detected in individual milk samples already at the end of the first day of grazing. Urine samples of all five cows showed higher concentrations of conjugated HGA and MCPrG metabolites than in milk. Observations suggest that dairy cows may have a low susceptibility toward sycamore maple toxins. However, whether this could be attributed to foregut fermenting species in general requires further elucidation.

Among all known compounds with herbicide activity glyphosate, has been the most commercially successful one. Currently, it is under evaluation because of its possible cancerogenic properties. However, the question is-if it is possible to completely withdraw it from use. Before it can happen, it is important to be sure of all its benefits and limitations, and this requires further detailed research. Due to the extent and prevalence of its use, glyphosate ends up in the environment and then in food and our bodies. There are several methods used for their determination. One of them is ion chromatography. Taking into account its advantages and disadvantages, as well as its rapid development, their importance in this field can be expected to increase in the near future. This paper summarizes the literature data from the past 22 years. The applications of ion chromatography in the determination of glyphosate in various types of environmental, food, and other samples are described. Moreover, the methods used so far are compared with the possibilities offered by ion chromatography, which main advantages and benefits are easy availability, low operating costs, green chemistry aspects, and suitable validation parameters., (© 2023 Wiley-VCH GmbH.)

Hypoglycin A (HGA) and its homologue methylenecyclopropylglycine (MCPrG) are present in ackee and lychee as well as seeds, leaves, and seedlings of some maple (Acer) species. They are toxic to some animal species and humans. The determination of HGA, MCPrG, and their glycine and carnitine metabolites in blood and urine is a useful tool for screening for potential exposure to these toxins. In addition, HGA, MCPrG, and/or their metabolites have been detected in milk. In this work, simple and sensitive ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) methods without derivatization were developed and validated for the quantification of HGA, MCPrG, and their metabolites in cow's milk and urine. An extraction procedure from milk samples has been developed, whereas a dilute-and-shoot approach was implemented for urine samples. For quantification, the MS/MS analysis was performed in multiple reaction monitoring mode. The methods were validated according to the European Union guidelines using blank raw milk and urine as matrices. The limit of quantification presented here for HGA in milk (1.12 µg/L) is noticeably lower than the lowest published limit of detection (9 µg/L). Acceptable values for recovery (89-106% and 85-104% in milk and urine, respectively) and precision (≤ 20%) were obtained for all the quality control levels. The stability of HGA and MCPrG in frozen milk over a period of 40 weeks has been demonstrated. The method was applied to 68 milk samples from 35 commercial dairy farms and showed the absence of any quantifiable amounts of HGA, MCPrG, and their metabolites., (© 2023. The Author(s).)

Background: In 2017, the European Commission renewed the approval of glyphosate (GLY) but only for five years. GLY remains one of the most controversial and studied molecules. Method: A simplified method was tested for the determination of GLY in white rice (WR) and brown rice (BR), after extraction only with a methanol solution, by liquid chromatography coupled with inductively coupled mass triple quadrupole (HPLC-ICP-MS/MS) with a PRP-X100 anionic column. After performing a test on groundwater, the quantification of GLY in WR and BR was validated in terms of the LOD, LOQ, accuracy, precision, linearity, and the matrix effect. Results: The LOD was 0.0027 mg kg−1 for WR and 0.0136 mg kg−1 for BR. The LOQ was 0.0092 mg kg−1 for WR and 0.0456 mg kg−1 for BR. The mean recoveries were within 76−105% at three fortification levels. The relative standard deviation for the analysis (five replicates for three spike levels) was < 11% for both matrices. A linear response was confirmed in all cases in the entire concentration range (R2WR = 1.000 and R2BR = 0.9818). Conclusion: The proposed method could be considered useful for the determination of GLY in different types of rice and designed and adapted for other cereals. The matrix effect, quantified in BR matrix extraction, could be avoided by using a matrix-matched calibration line.

Maintaining the health of seafarers is a difficult task during long-term voyages. Little is known about the corresponding changes in the gut microbiome-host interaction. This study recruited 30 seafarers undertaking a 6-month voyage and analyzed their gut microbiota using 16S rRNA gene sequencing. Fecal untargeted metabolomics analysis was performed using liquid chromatography-mass spectrometry. Significant changes in the composition of the gut microbiota and an increased ratio of Firmicutes / Bacteroidetes at the end (day 180) of the 6-month voyage, relative to the start (day 0), were observed. At the genus level, the abundances of Holdemanella and Plesiomonas were significantly increased, while the abundance of Bacteroides was decreased. Predicted microbial functional analysis revealed significant decreases in folate biosynthesis and biotin metabolism. Furthermore, 20 differential metabolites within six differentially enriched human metabolic pathways (including arginine biosynthesis, lysine degradation, phenylalanine metabolism, sphingolipid metabolism, pentose and glucuronate interconversions, and glycine, serine, and threonine metabolism) were identified by comparing the fecal metabolites at day 0 and day 180. Spearman correlation analysis revealed close relationships between the 14 differential microbiota members and the six differential fecal metabolites that might affect specific human metabolic pathways. This study adopted a multi-omics approach and provides potential targets for maintaining the health of seafarers during long-term voyages. These findings are worthy of more in-depth exploration in future studies. IMPORTANCE Maintaining the health of seafarers undertaking long-term voyages is a difficult task. Apart from the alterations in the gut microbiome and fecal metabolites after a long-term voyage, our study also revealed that 20 differential metabolites within six differentially enriched human metabolic pathways are worthy of attention. Moreover, we found close relationships between the 14 differential microbiota members and the six differential fecal metabolites that might impact specific human metabolic pathways. Accordingly, preventative measures, such as adjusting the gut microbiota by decreasing potential pathobionts or increasing potential probiotics as well as offsetting the decrease in B vitamins and beneficial metabolites (e.g., d-glucuronic acid and citrulline) via dietary adjustment or nutritional supplements, might improve the health of seafarers during long-term sea voyages. These findings provide valuable clues about gut microbiome-host interactions and propose potential targets for maintaining the health of seafarers engaged in long-term sea voyages.

Background/aims: Congenital cataracts, which are genetically heterogeneous eye disorders, result in visual loss in childhood around the world. CRYBA1/BA3 serves as an abundant structural protein in the lens, and forms homomers and heteromers to maintain lens transparency. In previous study, we identified a common cataract-causing mutation, βA3-glycine at codon 91 (G91del) (c.271-273delGAG), which deleted a highly conserved G91del and led to perinuclear zonular cataract. In this study, we aimed to explore the underlying pathogenic mechanism of G91del mutation., Methods: Protein purification, size-exclusion chromatography, spectroscopy and molecular dynamics simulation assays were used to investigate the effects on the heteromers formation and the protein structural properties of βA3-crystallin caused by G91del mutation. Intracellular βA3-G91del overexpression, MTT (3-(4,5)-dimethylthiahiazo (-z-y1)-3,5-di-phenytetrazoliumromide) and cell apoptosis were used to investigate the cellular functions of βA3-G91del., Results: βA3-crystallin and βB2-crystallin could form heteromers, which have much more stable structures than βA3 homomers. Interestingly, βA3/βB2 heteromers improved their resistance against the thermal stress and the guanidine hydrochloride treatment. However, the pathogenic mutation βA3-G91del destroyed the interaction with βB2, and thereby decreased its structural stability as well as the resistance of thermal or chemical stress. What's more, the βA3-G91del mutation induced cell apoptosis and escaped from the protection of βB2-crystallin., Conclusions: βA3/βB2 heteromers play an indispensable role in maintaining lens transparency, while the βA3-G91del mutation destabilises heteromers formation with βB2-crystallin, impairs cellular viability and induces cellular apoptosis. These all might contribute to cataract development., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2022. No commercial re-use. See rights and permissions. Published by BMJ.)

Bile acids are a group of steroid compounds essential for lipid digestion. However, when bile acids are refluxed into the stomach and the esophagus, during the so called duodenogastroesophageal reflux, they can have a detrimental effect on the esophageal epithelium and cause pathological changes of esophageal tissue, e.g., Barrett's esophagus (BE). The levels of bile acids in saliva could therefore serve as possible biomarkers for the diagnostics of BE. In this work, we focused on optimization of sample collection and preparation by solid-phase extraction and subsequent quantification of 11 bile acids (unconjugated, glycine-conjugated) in saliva from healthy volunteers and BE patients by ultra-high-performance liquid chromatography coupled to triple-quadrupole tandem mass spectrometry. Moreover, high resolution MS (Orbitrap-MS) was utilized for identification of new bile acids in saliva. Methods for saliva collection including simple spitting and the Salivette® saliva collection system were compared; the latter was found to be unsuitable due to excessive retention of bile acids in the cotton swab. Methanol with 0.1% formic acid were selected for protein precipitation and bile acid extraction prior to SPE. Separation was performed in gradient elution of methanol and 0.1% formic acid in less than 10 min. Saliva from BE patients contained higher levels of almost all bile acids, and the tested groups could be distinguished by principal component analysis. In untargeted analysis by high resolution MS, taurine-conjugated bile acids and glycine-conjugated dihydroxy-bile acid sulfate were identified in saliva from healthy volunteers. We propose that analysis of salivary bile acids including taurine conjugates could be applicable in diagnostics of BE, following a larger clinical study., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Glyphosate is the most used herbicide worldwide. It is a small and highly polar pesticide whose physicochemical properties makes its analytical determination difficult. Here, a procedure based on liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS) was developed for glyphosate determination in samples of gastric content from wildlife. Iberian hare (Lepus granatensis), a herbivorous mammal species, strongly associated to agrosystems was selected as model species. The procedure involves direct analysis of sample without derivatization or instead of neither further cleaning steps. The procedure was validated by inter-day accuracy and precision studies with gastric content of hare spiked with glyphosate at ecologically relevant concentrations for the species (0.1-6 μg/g), and with 1 μg/g of isotopically labelled internal standard (glyphosate-2- 13 C, 15 N). Finally, glyphosate residues in hunted animals from pesticide-treated and pesticide-free areas (n = 75 and 28, respectively), as well as from hares found dead in the field (n = 11) were analysed. The linearity of both standards in extraction solutions and procedural calibration curves with spiked samples was similar, both with determination coefficients (r 2 ) higher than 0.99. Satisfactory recoveries in spiked samples were achieved within the range of 95% to 118% (CV ≤ 20%). The limit of detection of glyphosate in hare gastric content was 0.03 μg/g. Prevalence of glyphosate in hunted animals from pesticide-treated areas ranged between 9 and 22%, increasing to 45% in animals found dead. The glyphosate concentrations detected in the gastric content of hares ranged from 0.11 to 16 μg/g. No residues were detected in animals from pesticide-free areas. In practice, the developed methodology may be particularly useful in the context of research and other work on the exposure in wildlife of one of the most used pesticides nowadays., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Glyphosate is the most used herbicide in the world. Unfortunately, contamination of water bodies by this herbicide has been reported. A severe concern has been triggered given its detrimental impact on the environment and wildlife. The American horseshoe crab (Limulus polyphemus) is a benthic arthropod that inhabits the Yucatan Peninsula in Southeast Mexico. This study evaluates the glyphosate concentration in 34 recently dead specimens of L. polyphemus from four localities of the Ria Lagartos Biosphere Reserve in Yucatan, Mexico. The analysis was carried out using High-Performance Liquid Chromatography coupled with a Triple Quadrupole Mass Spectrometer. All the samples showed residues of glyphosate in the range from 0.08 to 2.38 ng g -1 . These records constitute the first evidence of glyphosate bioaccumulation in this species. Although the scope might be limited, the results demonstrate a potentially prejudicial exposition of the marine biota to glyphosate-based herbicides, given its use in the region., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Mycosporine-like amino acids (MAAs) are widespread in various microbes and protect them against harsh environments. Here, four different Aphanizomenon species were isolated from severely eutrophic waterbodies, Lake Dianchi and the Guanqiao fishpond. Morphological characters and molecular phylogenetic analysis verified that the CHAB5919, 5921, and 5926 strains belonged to the Aphanizomenon flos-aquae clade while Guanqiao01 belonged to the Aphanizomenon gracile clade. Full wavelength scanning proved that there was obvious maximal absorption at 334 nm through purified methanol extraction, and these substances were further analyzed by HPLC and UPLC-MS-MS. The results showed that two kinds of MAAs were discovered in the cultured Aphanizomenon strains. One molecular weight was 333.28 and the other was 347.25, and the daughter fragment patterns were in accordance with the previously articles reported shinorine and porphyra-334 ion characters. The concentration of the MAAs was calibrated from semi-prepared MAAs standards from dry cells of Microcystis aeruginosa PCC7806 algal powder, and the purity of shinorine and porphyra-334 were 90.2% and 85.4%, respectively. The average concentrations of shinorine and porphyra-334 were 0.307−0.385 µg/mg and 0.111−0.136 µg/mg in Aphanizomenon flos-aquae species, respectively. And there was only one kind of MAAs (shinorine) in Aphanizomenon gracile species.,with a content of 0.003−0.049 µg/mg dry weight among all Aphanizomenon gracile strains. The shinorine concentration in Aphanizomenon flos-aquae was higher than that in Aphanizomenon gracile strains. The total MAAs production can be ranked as Aphanizomenon flos-aquae > Aphanizomenon gracile.