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A pilot annual monitoring survey (April 2018-March 2019) was conducted to investigate the presence of pesticides in superficial water and fish in Laguna del Cisne, one of the most critical drinking water sources in Uruguay. A total of 25 pesticide residues were detected in superficial water (89.3 % of the samples). Pesticide's temporal distribution was associated with crops and livestock practices, with higher occurrences in spring and summer than in autumn and winter. The most frequent compounds in superficial water were the insecticide chlorantraniliprole, and the herbicides glyphosate (including its metabolite AMPA) and metolachlor. The levels of Organochlorine pesticide, p,p'-DDT, was in some cases two order of magnitude above the international water quality guidelines for Ambient Water Criteria. In fishes, eight different pesticides were detected, at concentrations from 1000 to 453,000 ng·kg-1. The most frequent pesticides found were propiconazole, chlorpyrifos, and p,p'-DDE. The widespread occurrence of pesticides in fish suggests potential exposure effects on fish populations and the aquatic ecosystem. The sampling approach of this work allowed monitoring the continuous concentrations of several pesticides in surface waters and fishes to establish the influence from past and current agriculture practices in Laguna del Cisne basin. For safety measures, continuous monitoring programs must be performed in this system to prevent toxicity impacts on aquatic organisms and human health.

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The development of simple, reliable, and cost-effective methods is critically important to study the spatial and temporal variation of microcystins (MCs) in the food chain. Nanobodies (Nbs), antigen binding fragments from camelid antibodies, present valuable features for analytical applications. Their small antigen binding site offers a focused recognition of small analytes, reducing spurious cross-reactivity and matrix effects. A high affinity and broad cross-reactivity anti-MCs-Nb, from a llama antibody library, was validated in enzyme linked immunosorbent assay (ELISA), and bound to magnetic particles with an internal standard for pre-concentration in quantitative-matrix-assisted laser desorption ionization-time of flight mass spectrometry (Nb-QMALDI MS). Both methods are easy and fast; ELISA provides a global result, while Nb-QMALDI MS allows for the quantification of individual congeners and showed excellent performance in the fish muscle extracts. The ELISA assay range was 1.8-29 ng/g and for Nb-QMALDI, it was 0.29-29 ng/g fish ww. Fifty-five fish from a MC-containing dam were analyzed by both methods. The correlation ELISA/sum of the MC congeners by Nb-QMALDI-MS was very high (r Spearman = 0.9645, p < 0.0001). Using ROC curves, ELISA cut-off limits were defined to accurately predict the sum of MCs by Nb-QMALDI-MS (100% sensitivity; ≥89% specificity). Both methods were shown to be simple and efficient for screening MCs in fish muscle to prioritize samples for confirmatory methods.

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The herbicide glyphosate (GLY) and its metabolite aminophosphonic acid (AMPA) are troublesome compounds for analysis in the environment. Here we report a reliable technique for GLY and AMPA determination in freshwater and soils by means of derivatization with 9-fluorenylmethoxycarbonyl chloride (FMOC-Cl) and further liquid chromatography with fluorescence detection (FLD) and tandem mass spectrometry (MS/MS) analysis. Selected experiments were carried out to evaluate selectivity, sensitivity, repeatability, linearity and quantification performance in both matrices.

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Plastics pose a major threat to aquatic ecosystems especially in smaller size fractions. Salt marshes play a crucial role in maintaining the coastal zone and aquatic food web, yet their contamination, including by plastic materials, is still poorly investigated. This work investigated meso- (MEP, 5-25 mm) and microplastic (MIP, 1 µm-5 mm) contamination of a salt marsh, which reached average levels of 279.63 ± 410.12 items kg-1, 366.92 ± 975.18 items kg-1, and 8.89 ± 8.75 items L-1 in surface sediment, sediment cores and water, respectively. Photomicrographs revealed a complex fouling community on plastics surface for both different salt marsh zones and plastic formats. Abundance of plastics in sediment was higher in the dryer, vegetated zones compared to flooded, unvegetated zones. This is consistent with the role of vegetation as a trap for solid litter and final fate of plastic deposition, but also with local hydrodynamics influencing deposition pattern. Plastics were detected up to 66 cm-depth, presenting higher levels at surface sediments. It was also possible to identify the main groups of microorganisms (1638 bacterial cells, 318 microalgae cells, and 20049.93 µm2 of filamentous fungi) composing the Plastisphere communities on all plastic items recorded in the different zones. These results are a pioneer contribution, highlighting that regional salt marshes participate in sequestration and longstanding accumulation of plastic particles in estuarine environments, before exportation to the ocean.

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Detection, identification, and quantification of microplastics have become increasingly relevant for determining their contribution and role in environmental pollution. Thermal analysis is positioned as one of the alternative techniques employed to quantify microplastics. However, a deeper investigation that explores its capabilities is required, since in techniques such as difference scanning calorimetry (DSC), the result of the melting curve is potentially affected by the size of the micro particles. Therefore, to use this technique in the field of quantitative analysis of microplastics, it is necessary to make an evaluation of how the micro particle size affects the signal obtained. We use spherical polyethylene (PE) particles of different sizes (75-710 µm) as a microplastic model to study the effect of particle size and the mixtures of different particle sizes on the melting curve. The effect of possible interferences on the DSC signal was studied and real microplastics isolated from wastewater were tested. It was found that the DSC signal (both melting temperature and peak shape) is affected by the size of the particles, even in the case of mixtures of particles of different sizes. However, through an appropriate sample preparation, it is possible to identify the signals corresponding to microplastics of different sizes and thus quantify their contribution to the mass of the sample. It was evidenced that factors such as the presence of inorganic materials tend to modify the melting temperature. Also, removal of interferences of organic origin is feasible. In addition, the presence of PP, HDPE and LDPE was evidenced in wastewater samples. Our results represent an important advance in the use of the DSC technique in the field of microplastics, since the existence of particles of different sizes can be evidenced in the same sample allowing for an estimation of the number of microplastic particles. Finally, we show the applicability of DSC study on microplastics in environmental matrices.

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Semiconductor nanoparticle-mediated photocatalysis is an attractive option for water decontamination, being the semiconductors as SnS2 with a bandgap in the visible region, the most promising materials. In the present work, we evaluated the influence of important parameters in the photocatalytic application of SnS2 nanoparticles. Our results show that the presence of citric acid (used as a capping agent) restricts the formation of hexagonal nanoparticles. We also demonstrated that using thioacetamide as a sulfur source results in smaller nanoparticles than thiourea, 24.0 nm and 616 nm respectively. Moreover, small hexagonal nanoparticles play a key role in the photocatalytic activity of SnS2 nanoparticles. Compared with TiO2 performance, SnS2 nanoparticles exhibited faster kinetics for methyl orange (MO) degradation, Kapp = 0.0102 min-1, and 0.029 min-1, respectively. We proved that SnS2 is capable of breaking the azo bond of methyl orange by direct reduction. Furthermore, our analyses indicate that SnS2 nanoparticles do not degrade atrazine and imazapic, but the photocatalytic route of metribuzin competed with photolysis, resulting in a particular transformation product that was not obtained with light irradiation only. We demonstrated that SnS2 nanoparticles have high bond selectivity for azo breaking. Furthermore, they represent an advance for the development of designed materials (such as heterostructures), where the properties of SnS2 can be tuned.

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Many reports state the potential hazards of microplastics (MPs) and their implications to wildlife and human health. The presence of MP in the aquatic environment is related to several origins but particularly associated to their occurrence in wastewater effluents. The determination of MP in these complex samples is a challenge. Current analytical procedures for MP monitoring are based on separation and counting by visual observation or mediated with some type of microscopy with further identification by techniques such as Raman or Fourier-transform infrared (FTIR) spectroscopy. In this work, a simple alternative for the separation, counting and identification of MP in wastewater samples is reported. The presented sample preparation technique with further polarized light optical microscopy (PLOM) observation positively identified the vast majority of MP particles occurring in wastewater samples of Montevideo, Uruguay, in the 70-600 µm range. MPs with different shapes and chemical composition were identified by PLOM and confirmed by confocal Raman microscopy. Rapid identification of polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were evidenced. A major limitation was found in the identification of MP from non-birefringent polymers such as PVC (polyvinylchloride). The proposed procedure for MP analysis in wastewater is easy to be implemented at any analytical laboratory. A pilot monitoring of Montevideo WWTP effluents was carried out over 3-month period identifying MP from different chemical identities in the range 5.3-8.2 × 103 MP items/m3.

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Emerging contaminants (ECs) such as pharmaceuticals, personal care products, drugs of abuse and polar pesticides are under particular attention due to their high consumption, frequent detection in the environment and reported ecotoxicological risk. This study investigates the occurrence and distribution of multiclass of ECs in surface waters at basin scale of two Atlantic coastal lagoons of Uruguay, South America. For this purpose, a target screening approach covering up to 362 compounds was employed using nanoflow liquid chromatography - high resolution mass spectrometry (nanoLC/HRMS). 56 compounds were identified including five banned pesticides in the European Union: atrazine, carbendazim, chlorpyrifos ethyl, diazinon, and ethion. Pharmaceuticals, hormones and drugs of abuse showed maximum detection frequencies and concentrations downstream cities. The highest occurrence of pesticides was found in lagoons and streams with neighboring agricultural activity. ECs were also found in coastal sea. Environmental risk assessment revealed that the hormones 17α-ethinylestradiol and 17-ß-estradiol showed the highest risk to aquatic organisms in these basins. This study represents the first basin- scale monitoring of ECs in superficial waters encompassing streams, lagoons, and coastal seas in Uruguay, South America.

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Abstract Workflows based on gas and liquid chromatography coupled to mass spectrometry for the identification of toxic pyrrolizidine alkaloids present in plants were developed and applied to Echium plantagineum L., Boraginaceae, extracts. GC-MS based determinations need reduction and derivatization steps prior to MS analysis, which is performed using a Full Scan and Single Ion Monitoring sequence for screening, identification and quantification purposes. The LC-(ESI)-MS/MS determination was performed directly from the extract without derivatization. Acetyl lycopsamine, echimidine, echimidine N-oxide, echiumine, echiumine N-oxide, lycopsamine, lycopsamine N-oxide, 7,9-ditigloylretronecine N-oxide and a not reported PA of m/z 466, were identified and quantified in E. plantagineum extracts, through three operating modes of LC-QTRAP: precursor ion scan, enhanced product ion scan and multiple reaction monitoring. Precursor ion scan detects all the ions that give rise to a daughter ion at m/z 120, the presence of the parent pyrrolizidine alkaloid is confirmed through its MS2 spectrum (enhanced product ion) and quantified by multiple reaction monitoring. These workflows are general approaches to study chemical families using GC/LC-MS. For extracts suspicious of containing pyrrolizidine alkaloids, they are suitable tools for the quality and safety control of food, feed as well as phytotherapeutics.

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With the aim of monitoring multiclass semi-polar pesticide residues in freshwater fatty fish, two QuEChERS approaches (so-called acetate buffered and unbuffered versions) were evaluated for the determination of 77 pesticide residues. Compounds were selected according to the dominant rainfed agriculture activities in South America. Unbuffered QuEChERS was finally chosen for validation purposes owing that it provided the best results in terms of recovery yields. Method performance was evaluated in two instrumental systems, liquid chromatography - tandem mass spectrometry (LC-MS/MS) in Scheduled MRM™ algorithm available on hybrid quadrupole - linear ion trap (QLIT) instrument, and gas chromatography - mass spectrometry (GC-MS) under selected ion monitoring (SIM) mode. Spiking experiments were carried out to determine the trueness, precision, linearity, limit of quantification of the method as well as matrix effect. The Unbuffered QuECHERS method described here: •Was validated for the analysis of 67 pesticide residues in fish muscle tissue.•Presented quantification limits in the range 1-15 µg kg-1 for the vast majority of the studied compounds.•Enable environmental monitoring of pesticide residues in fish due to their low LOQs.