Metals, pesticides, and emerging contaminants on water bodies from agricultural areas and the effects on a native amphibian.

In the Paraná River lower basin, an important agro-productive area of Argentina, crop fields and cattle breeding activities are common and may affect water quality. So, the aim of this study was to analyze the impacts of cattle breeding and agricultural activities on a stream from Buenos Aires, through physicochemical parameters (metals, pesticides, and emerging contaminants) and ecotoxicological parameters with Rhinella arenarum larvae, a native amphibian species. Three sites were selected on an ordinary plain stream that goes through agricultural fields and a cattle breeding establishment (upstream -S1-, near -S2- and downstream -S3- the establishment). Physicochemical parameters were measured in situ (in water) and in laboratory (in water and sediment samples: metals, pesticides, ivermectin and oxytetracycline). A semi-static chronic toxicity bioassay (504 h) was performed with water samples, and neurotoxicity, oxidative stress and genotoxicity biomarkers were measured after acute exposure (96 h). According to the index, a degradation in the water quality was observed in all sites. Ivermectin (8.03 mg/kg) and oxytetracycline (1.9 mg/kg) were detected in sediment samples from S2. Pesticides were detected in all sites, mainly in water samples: S1 presented the highest variability (7 residues) and in S3 AMPA, glyphosate and acetochlor concentrations were higher (10.3, 22.4 and 23.8 µg/L). Also, all sites significantly produced lethality at chronic exposure. Lethality at 504h was 40% for S1, 56.66% for S2 and 93.33% for S3. At acute exposure, the oxidative stress biomarkers were altered on R. arenarum larvae exposed to all sites and the neurotoxicity biomarkers were altered on larvae exposed to S1 and S3. Water quality was severely degraded by the surrounding agricultural and cattle breeding activities, which may represent a threat to the ecosystems.

Impacts of cattle management and agricultural practices on water quality through different approaches: physicochemical and ecotoxicological parameters.

The intensification of livestock farming can pose risks to the environment due to the increased use of veterinary products and the generation of waste in confined areas. The quality of water bodies near livestock establishments (Areco River (A) and Doblado stream (D), San Antonio de Areco, Buenos Aires, Argentina) was studied by physicochemical parameters, metals, pesticides, emerging contaminants, and lethal and sublethal toxicity (neurotoxicity and oxidative stress) in larvae of the native amphibian Rhinella arenarum. Six sites were selected: upstream (S1A and S1D), at the level (S2A and S2D), and downstream (S3A and S3D) from the establishments. A low concentration of dissolved oxygen was observed in Doblado stream (< 2.34 mg/L). Cu, Mn, V, and Zn exceeded the limits for the protection of aquatic life at various sites. Between 24 and 34 pesticides were detected in all sites, with 2,4-D, atrazine, and metolachlor being the most recurrent. In water and sediment, the concentrations of ivermectin (S2A, 1.32 µg/L and 58.18 µg/kg; S2D, 0.8 µg/L and 85.22 µg/kg) and oxytetracycline (S2A, < 1 mg/L and < 1 mg/kg; S2D, 11.8 mg/L and 39 mg/kg) were higher at sites near the establishments. All sites caused between 30 and 38.3% of lethality and produced neurotoxicity and alterations in the reduced glutathione content. Moreover, larvae exposed to samples from all sites incorporated ivermectin. These results demonstrate the degradation of the studied sites in relation to the agricultural activities of the area, highlighting the need to take measures to protect and preserve aquatic ecosystems.

Assessing the transformation products and fate of Oxytetracycline by simulated aerobic degradation tests.

Oxytetracycline (OTC) is a widely used broad-spectrum antibiotic, whose presence in water and sediments was reported in various regions of the world. The effects of OTC and other tetracyclines on the environment have been intensively studied although many of their transformation products (TPs) formed in the environment and their impact have not been yet fully characterized. Abiotic and biotic degradation tests under aerobic conditions at two pH values were carried out using OTC in artificial water/sediment systems to assess the effect of these variables on the environmental fate of the pollutant. HPLC-MSn was employed to detect and identify the main degradation products and pathways. Several transformations involved in the process were identified including alcohol oxidation, decarbonylation and hydroxylation. Differences in TPs and kinetics were found among degradation conditions, remarking a faster degradation of both OTC and TPs in the presence of microorganisms and at lower pH values. In summary, a total of 44 TPs were detected and structures were proposed for 20 of them, none of them having been previously reported. Furthermore, OTC degradation generated 24 TPs which remained in either solution or sediment, although none of them displayed higher algae toxicity than OTC. These results might be useful for planning future remediation and monitoring strategies.

Metal-Pseudomonas veronii 2E Interactions as Strategies for Innovative Process Developments in Environmental Biotechnology.

The increase of industrial discharges is the first cause of the contamination of water bodies. The bacterial survival strategies contribute to the equilibrium restoration of ecosystems being useful tools for the development of innovative environmental biotechnologies. The aim of this work was to study the Cu(II) and Cd(II) biosensing, removal and recovery, mediated by whole cells, exopolymeric substances (EPS) and biosurfactants of the indigenous and non-pathogenic Pseudomonas veronii 2E to be applied in the development of wastewater biotreatments. An electrochemical biosensor was developed using P. veronii 2E biosorption mechanism mediated by the cell surface associated to bound exopolymeric substances. A Carbon Paste Electrode modified with P. veronii 2E (CPEM) was built using mineral oil, pre-washed graphite power and 24 h-dried cells. For Cd(II) quantification the CPEM was immersed in Cd(II) (1-25 µM), detected by Square Wave Voltammetry. A similar procedure was used for 1-50 µM Cu(II). Regarding Cd(II), removal mediated by immobilized EPS was tested in a 50 ml bioreactor with 0.13 mM Cd(II), pH 7.5. A 54% metal retention by EPS was achieved after 7 h of continuous operation, while a 40% was removed by a control resin. In addition, surfactants produced by P. veronii 2E were studied for recovery of Cd(II) adsorbed on diatomite, obtaining a 36% desorption efficiency at pH 6.5. Cu(II) adsorption from a 1 mM solution was tested using P. veronii 2E purified soluble EPS in 50 mL- batch reactors (pH = 5.5, 32°C). An 80% of the initial Cu(II) was retained using 1.04 g immobilized EPS. Focusing on metal recovery, Cu nanoparticles (NPs) biosynthesis by P. veronii 2E was carried out in Cu(II)-PYG Broth at 25°C for 5 days. Extracellular CuNPs were characterized by UV-Vis spectral analysis while both extracellular and intracellular NPs were analyzed by SEM and TEM techniques. Responses of P. veronii 2E and its products as biosurfactants, bound and soluble EPS allowed Cu(II) and Cd(II) removal, recovery and biosensing resulting in a multiple and versatile tool for sustainable wastewater biotreatments.

In situ synchrotron radiation X-ray scattering study on the effect of a stearic sucrose ester on polymorphic behavior of a new sunflower oil variety.

The effect of the stearic sucrose ester (SE) S-170 on crystallization behavior and polymorphism of two stearins obtained from a new variety of high stearic high oleic sunflower oil was studied by pulsed nuclear magnetic resonance (p-NMR), small (SAXS) and wide (WAXS) angle X-ray scattering using synchrotron light and differential scanning calorimetry (DSC). p-NMR studies showed that there is always a crystallization temperature below which SE S-170 accelerated crystallization and above which SE S-170 delayed nucleation and growth. The effect of SE S-170 strongly depended on supercooling. It was efficient as a seed for high supercooling (low crystallization temperatures) but this efficiency diminished at low supercooling (temperatures close to the melting point) when few crystals were formed. SAXS and WAXS results demonstrated that depending on crystallization temperature SE S-170 promoted crystallization of α and ß forms with more polymorphic similarity and inhibited occurrence of ß' forms especially the ß'2 polymorph. However, in some conditions SE S-170 favored crystallization of ß'1 polymorph. DSC experiments showed that SE S-170 significantly diminished total melting enthalpies when the effect was a delay in crystallization. For other conditions no significant differences were found in melting temperatures or total melting enthalpies. When stearins were stored at 25°C, crystallization in the ß2 form was promoted. Depending on crystallization temperature, polymorphic forms ß'1 and ß2 may be obtained as the main polymorphic forms. This is very relevant from the technological point of view. Depending on the application, SE S-170 may help obtain the required polymorphic form: ß'1 form for spreads and ß2 polymorph for chocolate production.