Geochemical characterization and the assessment of trace element retention in sediments of the Reconquista River, Argentina.

The mineralogical and geochemical characterization of sediments of the Reconquista River allows analyzing the geochemical partition of trace elements in one of the most polluted water courses of Argentina. The low dissolved oxygen and high ammonia contents, together with the high chemical oxygen demand, attest to the poor water quality. Ammonia, Cd and Cu content in surficial water exceeds the maximum guidelines for freshwater in Argentina. The recent sediments of the uppermost bed are enriched in organic matter (OM), sulfur, Zn, Cu and Pb. The enrichment factor is moderate, and the geoaccumulation index (Igeo) for Cu and Pb indicates uncontaminated to moderately contaminated sediments. The positive and significant correlation between As, Cr, Pb and Zn with the iron content suggests that their retention is controlled by the amount of iron oxy (hydr)oxides in the sediments, probably combined with the silt + clay abundance. In comparison with its tributary, the Las Catonas Stream, the Reconquista River, has less OM and trace elements in the sediments and more dissolved trace elements in the interstitial water. We interpret that OM is the main sorbent of the trace element. In the absence of OM, the iron oxy (hydr)oxides and the silt + clay fraction are a less efficient substitute. Consequently, the interstitial waters of the Reconquista River are enriched in these elements. Therefore, minor changes in the environmental conditions may generate significant release of hazardous trace elements from the sediments to the interstitial water and, in turn, to the surficial water of the river. As most of the big cities and the agricultural activities of Argentina are developed on the loessic substrate, the understanding of its interaction with polluted waters is crucial.

Effects on Ultrastructure, Composition and Specific Surface Area of the Gills of Odontesthes bonariensis Under Subchronic Glyphosate-Based Herbicide Exposure.

Gills represent one of the major sites of gas exchange of fish, consequently they are in continuous close contact with the aquatic environment and its pollutants. In the present study the effects on gills of pejerrey fish, Odontesthes bonariensis, under glyphosate-based herbicide subchronic exposure were analyzed. Adult animals were exposed to sublethal concentrations of a glyphosate-based commercial formulation (1 and 10 PMG mg L-1, PMG: glyphosate active ingredient) for 15 days, while control group was maintained in rearing water. Ultrastructural changes in gills were observed by scanning electron microscopy (SEM). The composition of the surface epithelium and specific surface area were determined by energy dispersive spectroscopy (EDS) and N2 (g) adsorption-desorption isotherms, respectively. The herbicide exposure induced severe alterations in gill ultrastructure, as shown in the SEM micrographs. Accordingly, an increase in surface area of the gills of exposed animals was determined. These results support that gills parameters of freshwater fish are sensitive morphological biomarkers for glyphosate exposure.

Seasonal variations in the dose-response relationship of acetylcholinesterase activity in freshwater fish exposed to chlorpyrifos and glyphosate.

The herbicide glyphosate [N- (phosphonomethyl) glycine; PMG] and the insecticide chlorpyrifos [O, O-diethyl O- (3,5,6-trichloro-2-pyridinyl) -phosphorothioate, CPF] are widely used in agricultural practices around the world and can reach aquatic environments. Therefore, it is necessary to characterize the toxicity of these pesticides on non-target species. The use of biomarkers as a tool to assess responses of organisms exposed to pollutants requires the understanding of their natural fluctuation and the dose-response relationship. In the present work, the effect of the exposure to PMG and CPF on the acetylcholinesterase activity (AChE, biomarker of neurotoxicity) in Cnesterodon decemmaculatus, a native teleost, was evaluated in different environmental conditions. Semi-static bioassays of acute toxicity were carried out under controlled conditions during the four weather seasons of the year using animals of homogeneous size. Circannual rhythms in the basal levels of AChE activity in homogenates of the anterior section were confirmed. Statistically significant average inhibition of AChE activity (47.1 ±â€¯0.7% for 1 µg CPF × L-1; 69.7 ±â€¯2.5% for 5 µg CPF × L-1; 23.1 ±â€¯1.1% for 1 mg PMG × L-1 and 32.9 ±â€¯3.3% for 10 mg PMG × L-1) was determined during summer, winter and spring weather seasons. Interestingly, animals exhibit an increased susceptibility to exposure during the autumn season (inhibition of 55.4 ±â€¯0.6% for 1 µg CPF × L-1; 81.9 ±â€¯3.3% for 5 µg CPF × L-1; 41.4 ±â€¯1.7% for 1 mg PMG × L-1 and 61.1 ±â€¯0.3% for 10 mg PMG × L-1). A different sensitivity of the enzyme between seasons was evaluated by in vitro tests. The inhibition pattern for chlorpyrifos-oxon (CPF-oxon, the active metabolite of CPF) was not affected when test was performed using homogenates of unexposed specimens of summer or autumn. Otherwise, PMG in vitro inhibitory effect was not observed in a wide range of concentrations. The results confirm that AChE activity is a sensitive biomarker for exposure to CPF and PMG, even at environmentally relevant concentrations. Finally, this work highlights the existence of seasonal variations in the dose-response relationship, which could be due to variations in the metabolism of the pollutants.

Luminescent Lanthanide Metal Organic Frameworks as Chemosensing Platforms towards Agrochemicals and Cations.

Since the first studies of luminescent sensors based on metal organic frameworks (MOFs) about ten years ago, there has been an increased interest in the development of specific sensors towards cations, anions, explosives, small molecules, solvents, etc. However, the detection of toxic compounds related to agro-industry and nuclear activity is noticeably scarce or even non-existent. In this work, we report the synthesis and characterization of luminescent lanthanide-based MOFs (Ln-MOFs) with diverse crystalline architectures obtained by solvothermal methods. The luminescent properties of the lanthanides, and the hypersensitive transitions of Eu3+ (5D0→7F2) and Tb3+ (5D4→7F5) intrinsically found in the obtained MOFs in particular, were evaluated and employed as chemical sensors for agrochemical and cationic species. The limit of detection (LOD) of Tb-PSA MOFs (PSA = 2-phenylsuccinate) was 2.9 ppm for [UO22+] and 5.6 ppm for [Cu2+]. The variations of the 4f⁻4f spectral lines and the quenching/enhancement effects of the Ln-MOFs in the presence of the analytes were fully analyzed and discussed in terms of a combinatorial "host⁻guest" vibrational and "in-silico" interaction studies.

Effect of glyphosate on the growth, morphology, ultrastructure and metabolism of Scenedesmus vacuolatus.

The effects of a commercial glyphosate formulation on the oxidative stress parameters and morphology (including the ultrastructure) of the phytoplanktonic green microalga Scenedesmus vacuolatus were evaluated. After 96 h of exposure to increasing herbicide concentrations (0, 4, 6, 8 mg L-1 active ingredient) with the addition of alkyl aryl polyglycol ether surfactant, the growth of the cultures decreased (96 h-IC50- 4.90 mg L-1) and metabolic and morphology alterations were observed. Significant increases in cellular volume (103-353%) and dry weight (105%) and a significant decrease in pigment content (41-48%) were detected. Oxidative stress parameters were significantly affected, showing an increase in the reactive oxygen species (ROS) and reduced glutathione (GSH) contents, oxidative damage to lipids and proteins and a decrease in the activities of the antioxidant enzymes superoxide dismutase (SOD) and catalase (CAT) and the detoxifying enzyme glutathione-S-transferase (GST). Cells exposed to glyphosate formulation were larger and showed an increase in vacuole size, bleaching, cell wall thickening and alteration of the stacking pattern of thylakoids. The results of this study showed the participation of oxidative stress in the mechanism of toxic action of the commercial glyphosate formulation on S. vacuolatus and the relation between the biochemical, morphological and ultrastructure alterations.

Adsorption of picloram on clays nontronite, illite and kaolinite: equilibrium and herbicide-clays surface complexes.

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite < illite < nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.

Some aspects of the adsorption of glyphosate and its degradation products on montmorillonite.

The most worldwide used herbicide is glyphosate, phosphonomethylglycine (PMG). Consequently, a significant amount of PMG, its metabolites (sarcosine, SAR, and aminomethylphosphonic acid, AMPA) and the degradation product, methylphosphonic acid (MPA), reaches the soil, which acts as final sink. Because clays are one of the most reactive components of soils, expansive clays such as montmorillonite (Mt) are used to retain agriculture contaminants with some success. In this work, as a preliminary step for the evaluation of the risk that PMG, SAR, AMPA, and MPA occurrence could have on the environment, their adsorption on Mt surface was performed. The adsorption process was analyzed at constant adsorbate concentrations and two pH values to take into account the different protonation states of the amino group. DTA, XRD, zeta potential measurements, and XPS were used to identify the interactions or association mechanisms with the clay surface, the entry of adsorbates into the Mt interlayer, and electric charge changes on the Mt surface, and evaluate the acid-base surface complex constants, respectively. The interlayer thickness in acid media indicated that adsorbates are able to enter the interlayer in planar form. Besides, for the Mt-PMG sample, some PMG molecules could be also inserted as a bilayer or with a tilt angle of 52.4° in the interlayer. However, in alkaline media, the interlayer thickness indicated that the adsorbate arrangement differed from that of acidic media where PMG and MPA could have more than one orientation. The surface complex deprotonation constants were determined for the =NH+2 â‡† =NH+H+ process, being 3.0, 5.0, and 7.3 for PMG, AMPA, and SAR, respectively.

Effect of glyphosate acid on biochemical markers of periphyton exposed in outdoor mesocosms in the presence and absence of the mussel Limnoperna fortunei.

Glyphosate is currently the most widely used herbicide in agricultural production. It generally enters aquatic ecosystems through surface water runoff and aerial drift. We evaluated the effect of glyphosate acid on biochemical parameters of periphyton exposed to concentrations of 1, 3, and 6 mg/L in outdoor mesocosms in the presence and absence of the mussel Limnoperna fortunei. Periphyton ash-free dry weight, chlorophyll a content, carotene/chlorophyll a ratio, lipid peroxidation levels, and superoxide dismutase and catalase activities were determined at days 0, 1, 7, 14, and 26 of the experimental period. Ash-free dry weight was similar between control and glyphosate-treated periphyton in the absence of L. fortunei. The latter had significantly lower carotene to chlorophyll a ratios and enzyme activities, and higher lipid peroxidation levels and chlorophyll a content than the former. These results show an adverse effect of glyphosate on the metabolism of periphyton community organisms, possibly inducing oxidative stress. On the contrary, no differences were observed in any of these variables between control and glyphosate-treated periphyton in the presence of L. fortunei. Mussels probably attenuated the herbicide effects by contributing to glyphosate dissipation. The results also demonstrate that biochemical markers provide useful information that may warn of herbicide impact on periphyton communities. Environ Toxicol Chem 2017;36:1775-1784. © 2016 SETAC.

Slow-release formulations of the herbicide picloram by using Fe-Al pillared montmorillonite.

Slow-release formulations of the herbicide picloram (PCM, 4-amino-3,5,6-trichloropyridine-2-carboxylic acid) were designed based on its adsorption on pillared clays (pillared clays (PILCs)) for reducing the water-polluting risk derived from its use in conventional formulations. Fe-Al PILCs were synthesized by the reaction of Na+-montmorillonite (SWy-2) with base-hydrolyzed solutions of Fe and Al. The Fe/(Fe + Al) ratios used were 0.15 and 0.50. The PCM adsorption isotherms on Fe-Al PILCs were well fitted to Langmuir and Freundlich models. The PCM adsorption capacity depended on the Fe content in the PILCs. Slow-release formulations were prepared by enhanced adsorption of the herbicide from PCM-cyclodextrin (CD) complexes in solution. CDs were able to enhance up to 2.5-fold the solubility of PCM by the formation of inclusion complexes where the ring moiety of the herbicide was partially trapped within the CD cavity. Competitive adsorption of anions such as sulfate, phosphate, and chloride as well as the FTIR analysis of PCM-PILC complexes provided evidence of formation of inner sphere complexes of PCM-CD on Fe-Al PILCs. Release of the herbicide in a sandy soil was lower from Fe-Al PILC formulations relative to a PCM commercial formulation.

Subcellular energy balance of Odontesthes bonariensis exposed to a glyphosate-based herbicide.

Water pollution by agrochemicals is currently one of the most critical problems for the conservation of aquatic ecosystems. Glyphosate [N-(phosphonomethyl) glycine); PMG] is the main broad-spectrum post emergence herbicide used for the control of a wide range of pests in soybean crops. Adenylate energy charge (AEC) reflects the energy balance of the cells, a measure of the energy available from the adenylate pool: adenosine triphosphate (ATP), adenosine diphosphate (ADP) and adenosine monophosphate (AMP). Background adenylates, phosphagens and the AEC index of two year old Odontesthes bonariensis were determined in some tissues by HPLC, and the impact on subcellular energy balance of sublethal glyphosate-based herbicide exposure was analyzed. The doses used were 0 (control tank), 1 or 10mg PMGL(-1), trials were carried out during 15 days. AEC values in brain, liver and muscle from control fish were 0.37 ± 0.02, 0.49 ± 0.05 and 0.56 ± 0.03, respectively (means ± SEM). While brain ATP concentrations were undetectable (hence low values of AEC), the muscle tissue showed the highest concentrations of the more energetic molecules: 0.18 µmole ATP g(-1) and 8 µmole phosphocreatine g(-1) (PCrg(-1)). In the brain, no significant changes were detected in exposed fish compared to controls. Instead, in both the liver and muscle of animals exposed to the highest concentration of the herbicide, significant changes in the AEC (reduction of 26% and 15%, p<0.05) with respect to the control group were determined. Chronic exposure (15 days) of Odontesthes bonariensis to 1 and 10mgL(-1) of formulated glyphosate did not affect brain AEC. However, the highest concentration of the herbicide produced a significant decrease in liver and muscle AEC manifesting adverse sublethal effects on the energy metabolism. These results suggest the usefulness of AEC as a biomarker of fish glyphosate exposure.

Circannual rhythms of acetylcholinesterase (AChE) activity in the freshwater fish Cnesterodon decemmaculatus.

The use of biomarkers as a tool to assess responses of organisms exposed to pollutants in toxicity bioassays, as well as in aquatic environmental risk assessment protocols, requires the understanding of the natural fluctuation of the particular biomarker. The aim of this study was to characterize the intrinsic variations of acetylcholinesterase (AChE) activity in tissues of a native freshwater teleost fish to be used as biomarker in toxicity tests, taking into account both seasonal influence and fish size. Specific AChE activity was measured by the method of Ellman et al. (1961) in homogenates of fish anterior section finding a seasonal variability. The highest activity was observed in summer, decreasing significantly below 40% in winter. The annual AChE activity cycle in the anterior section was fitted to a sinusoidal function with a period of 11.2 months. Moreover, an inverse relationship between enzymatic activity and the animal size was established. The results showed that both the fish length and seasonal variability affect AChE activity. AChE activity in fish posterior section showed a similar trend to that in the anterior section, while seasonal variations of the activity in midsection were observed but differences were not statistically significant. In addition, no relationship between AChE and total tissue protein was established in the anterior and posterior sections suggesting that the circannual rhythms observed are AChE-specific responses. Results highlight the importance of considering both the fish size and season variations to reach valid conclusions when AChE activity is employed as neurotoxicity biomarker.

Adsorption of Cu(II), Zn(II), Cd(II) and Pb(II) by dead Avena fatua biomass and the effect of these metals on their growth.

The biosorption of copper(II), zinc(II), cadmium(II) and lead(II) from aqueous solutions by dead Avena fatua biomass and the effect of these metals on the growth of this wild oat were investigated. Pseudo-first- and second-order and intra-particle diffusion models were applied to describe the kinetic data and to evaluate the rate constants. The adsorption kinetics of all the metals follows a pseudo-second-order model. The adsorption capacity was determined, and the Freundlich and Langmuir models were applied. The experimental data obtained for all the metals are best described by the Langmuir model. A. fatua was characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and zeta potential. The results obtained evidence the presence of Zn(II), Cu(II), Cd(II) or Pb(II) on the surface of the weed. The growth of A. fatua was affected by the presence of all metals. The decrease in the growth rate with increasing metal concentration was more noticeable for zinc.

Impact of the invasive mussel Limnoperna fortunei on glyphosate concentration in water.

The use of glyphosate has increased dramatically during the past years around the world. Microbial communities are altered when glyphosate reaches water bodies. The freshwater golden mussel Limnoperna fortunei is an invasive species that has rapidly dispersed since it was introduced in Argentina two decades ago. Mussels alter aquatic conditions through their filtrating activity by increasing water clarity and nutrient recycling. We aim to evaluate the potential capacity of the golden mussel to reduce glyphosate concentration in water, in laboratory conditions. Firstly, the evasive response of mussels to glyphosate (10, 20, and 40 mg l⁻¹) was evaluated and a toxicity test was carried out for these concentrations. A three-week experiment was then performed to assess glyphosate variation under mussel presence for two mussel sizes. Finally, mussels' role on glyphosate concentration was evaluated considering different mussel parts (living organisms and empty shells) through another three-week experiment. Laboratory experiments were performed in triplicate using 2-l microcosms. An initial glyphosate concentration between 16 and 19 mg l⁻¹ was used, and when mussels or valvae were added, 20 organisms per aquaria were used. Samples were obtained at days 0, 1, 2, 4, 8, 14, and 21. Glyphosate decreased by 40% under large mussel presence in both experiments, and was reduced by 25% in empty shell treatments. We believe that part of the herbicide that disappears from the water column is adsorbed in valvae surface, while another proportion is being mineralized by microbial communities in shells' biofilm. The mechanisms by which living mussels increase glyphosate dissipation would be degradation, possibly mediated by bacteria associated to mussel's metabolism. Glyphosate half-life depended on mussel and valvae presence and varied with mussel size. L. fortunei presence (either alive or as empty valvae) alters glyphosate concentration in water. We provide preliminary observations from laboratory experiments, with strong potential ecological consequences, about two stressors that could be acting jointly on the environment.

Glyphosate as an acetylcholinesterase inhibitor in Cnesterodon decemmaculatus.

The toxic effect of sublethal concentrations (1, 17.5 and 35 mg L(-1)) of pure glyphosate was evaluated on acetylcholinesterase (AChE) activity in the fish species, Cnesterodon decemmaculatus. Acute bioassays (96 h) under laboratory conditions were conducted and homogenates for each specimen corresponding to the anterior, middle and posterior body sections were performed. Fish survival was 100%, even at the highest concentration tested (35 mg L(-1)), in accordance with the low lethal toxicity reported for glyphosate. However, a significant inhibitory effect on AChE activity was recorded even for the lowest herbicide concentration tested (1 mg L(-1)), in the homogenates corresponding to the anterior body section. The inhibition ranged from 23 to 36%. The analytical determination of glyphosate in assay media by ion chromatography, was used to verify its stability. These results indicate that AChE-a neurotoxicity biomarker-in C. decemmaculatus may be affected by exposure to environmentally relevant concentrations of glyphosate.

Copper, zinc, cadmium and lead biosorption by Gymnogongrus torulosus. Thermodynamics and kinetics studies.

Gymnogongrus torulosus adsorption efficiency for cadmium(II), copper(II), lead(II) and zinc(II) were studied in batch mode in different acidic conditions. The adsorbent removal efficiency was determined as a function of contact time, initial metal ions concentration, pH and temperature. G. torulosus was characterized by SEM, water adsorption surface area and EDS. The Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models have been applied and results showed that the biosorption process was better described by the Langmuir model. Kinetic experiments demonstrated that fast metal uptakes follow a pseudo-second-order kinetic model and that intra-particle diffusion and/or chemisorption were the rate-limiting steps. Experimental results show that G. torulosus isotherm followed the biosorption series, Cu>Cd∼Zn∼Pb. Biosorption capacities were affected by solution parameters. The maximum metal uptake (qmax) increased with increasing pH. The affinity constant, qmax, and the pseudo-second-order kinetic constants were calculated for the adsorption of all studied metals onto G. torulosus. The Gibbs free energy of the adsorption process as well as the process enthalpy and entropy were calculated from experimental results.

Glyphosate behavior at soil and mineral-water interfaces.

Adsorption isotherms and surface coverage of glyphosate, N-phosphonomethylglycine (PMG), in aqueous suspensions of three Argentine soils with different mineralogical composition were measured as a function of PMG concentration and pH. Zeta potential curves for PMG/soils system were also determined. Montmorillonite and soil sample surface charges were negative and increased as the amount of adsorbed PMG increased, showing that the surface complexes are more negative than those formed during the surface protonation. PMG adsorption on soils were described using Langmuir isotherms and the affinity constants, and the maximum surface coverage was estimated at pH 4 and 7 using a two-term Langmuir isotherm, the mineralogical composition percentages, and maximum surface coverage and Langmuir constants for pure minerals. The influence of organic matter (OM) and iron content of soils on the PMG adsorption was evaluated. The surface coverage of PMG decreased when the OM and iron content decreased for minerals and soils.

The impact of particle-bound cadmium on bioavailability and bioaccumulation: A pragmatic approach.

Studying the bioavailability of sediment-bound contaminants is complicated by many reasons, such as the variable composition of the particles, their temporal variations, the low levels of contaminant concentrations, their partitioning between diverse aqueous and particulate phases, and the variety of uptake routes that may involved with the biota. Therefore, simple and innovative methodologies should be tested as analogues for natural sediments. Among them, a diverse selection of artificial particles with well-defined surface properties, in the presence and absence of commercially available humic acids, has been proposed and used to investigate the bioavailability of several organic pollutants. For this work, this model was applied to investigate the uptake and accumulation of cadmium by the freshwater oligochaete Lumbriculus variegatus. The results showed that the uptake of the metal depended on the free dissolved Cd(II) species, while the contribution from the particles was negligible. Thus, the extent of cadmium bioaccumulated from each test system could be predicted as a function of the rate of absorption of the free dissolved Cd(II) species. These species were calculated either from the particle-water partition coefficients, or by using the MINEQL+ computer program. In general, the estimated accumulation levels were in good agreement with the experimental results.

Oxidation of cysteine and glutathione by soluble polymeric MnO2.

The kinetics of reduction of soluble polymeric MnO2 by cysteine and glutathione has been studied in the pH range of 4.0-9.0. The concentration of thiols was varied between 1 and 2 mM, while the MnO2 concentration was varied between 2 and 12 microM. In this pH range, the reaction products were identified as Mn(II) and the corresponding disulfides (cystine and glutathione disulfide). Cysteic or cysteine sulfonic acid was formed only when pH < 2. Experimental data indicate that the rate law over the pH range of 4-9 is first-order in both MnO2 and thiol concentration. Eyring plots for both thiols reacting with MnO2 indicate that the reaction is associative (deltaS(double dagger) approximately -160 J mol(-1) K(-1)) and proceeds via an inner-sphere redox process. The reaction proceeds via the formation of two different inner-sphere complexes [triple bond]Mn(IV)SR- and [triple bond]Mn(IV)SR and their further reaction to products. Both surface species are linked to each other via acid-base equilibria, and the rate constant decreases as pH increases. The presence of two ligand surface species is determined using surface complexation modeling. A reaction mechanism in agreement with the experimental results is proposed.