Chiral separation of propranolol by electrokinetic chromatography using nanodiamonds and human serum albumin as a pseudo-stationary phase in river water.

Propranolol is currently considered as an emerging contaminant in water bodies. In this study, R- and S-propranolol were determined in river samples by electrokinetic chromatography (EKC) using nanodiamonds (NDs) and human serum albumin (HSA) as a pseudo-stationary phase in order to achieve enantioseparation. Previously, river samples were preconcentrated using a column filled with Amberlite® IR-120 and Dowex® 50WX8 resins. The setting up of influential factors such as temperature, voltage, pH, and HSA and NDs concentration is accurately described along this manuscript. A multivariate study and optimization was carried out to obtain the enantioseparation of propranolol (Rs = 2.91), which was reached under the following experimental conditions: voltage of 16 kV, temperature of 16°C, phosphate buffer pH 9.5, NDs of 0.20%, and HSA of 15 µmol l-1 . The recoveries of analytes under optimal conditions were higher than 98%. The limits of detection were 0.85 µg l-1 for R- and S-propranolol. The method was applied to real samples, and the obtained results in three different water sources studied were 1.02, 0.59, and 0.30 µg l-1 for the R-enantiomer and 0.99, 0.54, and 0.28 µg l-1 for the S-enantiomer. The accuracy of the proposed methodology (including bias and precision) has allowed us to propose it as a successful tool for the control of water quality.

Ecotoxicological Methodologies to Evaluate Biomarkers at Different Scales in Neotropical Anurans.

The new questions in ecotoxicology highlight the importance of applying a battery of biomarkers, as this results in ecotoxicological predictions that improve not only the interpretation of the effects of environmental stressors on organisms but also the determination of their possible impact. It is well known that the use of ecotoxicological biomarkers at different levels of organization allows for the prediction of the biological responses of organisms to environmental stressors, which is useful in environmental risk assessment. Nevertheless, it is necessary to consider the optimization of basic procedures, to generate historical data in control groups, and to employ specific bioassays to evaluate responses in organs and tissues in order to elucidate the nature and variation of the effects observed. Therefore, the present work aims to describe several ecotoxicological methodologies employed in all stages of neotropical anurans at different ecological levels and to validate them as useful biomarkers to be used both in wildlife and in laboratory conditions. In this work, these biomarkers were applied at the individual/organismic level (body condition index), histological/physiological level (histopathology, histometric, and pigmentary analyses), biochemical level (oxidative stress enzymes), and genetic level (direct and oxidative damage in DNA by comet assay). Although these methodologies have small variations or modifications depending on the species, these techniques provide effective biomarkers for evaluating the effect of xenobiotics on anurans, which possess certain characteristics that make them useful indicator species of aquatic and terrestrial ecosystems. In conclusion, the battery of biomarkers employed in the present study has proven to be adequate for estimating toxic responses in Neotropical anurans and can be further recommended as bioindicators for identifying the impact of pollutants on the aquatic ecosystems of the region. Finally, it is recommended to achieve the standardization of these important biomarkers for anurans in specific regions as well as to possibly include them in risk assessments and decision-making.

Integral use of sugarcane vinasse for biomass production of actinobacteria: Potential application in soil remediation.

The use of living actinobacteria biomass to clean up contaminated soils is an attractive biotechnology approach. However, biomass generation from cheap feedstock is the first step to ensure process sustainability. The present work reports the ability of four actinobacteria, Streptomyces sp. M7, MC1, A5, and Amycolatopsis tucumanensis, to generate biomass from sugarcane vinasse. Optimal vinasse concentration to obtain the required biomass (more than 0.4 g L-1) was 20% for all strains, either grown individually or as mixed cultures. However, the biomass fraction recovered from first vinasse was discarded as it retained trace metals present in the effluent. Fractions recovered from three consecutive cycles of vinasse re-use obtained by mixing equal amounts of biomass from single cultures or produced as a mixed culture were evaluated to clean up contaminated soil with lindane and chromium. In all cases, the decrease in pesticide was about 50% after 14 d of incubation. However, chromium removal was statistically different depending on the preparation methodology of the inoculum. While the combined actinobacteria biomass recovered from their respective single cultures removed about 85% of the chromium, the mixed culture biomass removed more than 95%. At the end of the reused vinasse cycle, the mixed culture removed more than 70% of the biological oxygen demand suggesting a proportional reduction in the effluent toxicity. These results represent the first integral approach to address a problematic of multiple contaminations, concerning pesticides, heavy metals and a regionally important effluent like vinasse.

Development of nitrocellulose membrane filters impregnated with different biosynthesized silver nanoparticles applied to water purification.

Bactericidal water filters were developed. For this purpose, nitrocellulose membrane filters were impregnated with different biosynthesized silver nanoparticles. Silver nanoparticles (AgNPs) from Aspergillus niger (AgNPs-Asp), Cryptococcus laurentii (AgNPs-Cry) and Rhodotorula glutinis (AgNPs-Rho) were used for impregnating nitrocellulose filters. The bactericidal properties of these nanoparticles against Escherichia coli, Enterococcus faecalis and Pseudomona aeruginosa were successfully demonstrated. The higher antimicrobial effect was observed for AgNPs-Rho. This fact would be related not only to the smallest particles, but also to polysaccharides groups that surrounding these particles. Moreover, in this study, complete inhibition of bacterial growth was observed on nitrocellulose membrane filters impregnated with 1 mg L(-1) of biosynthesized AgNPs. This concentration was able to reduce the bacteria colony count by over 5 orders of magnitude, doing suitable for a water purification device.

Multielemental analysis in vegetable edible oils by inductively coupled plasma mass spectrometry after solubilisation with tetramethylammonium hydroxide.

Trace metals have negative effects on the oxidative stability of edible oils and they are important because of possibility for oils characterisation. A single-step procedure for trace elemental analysis of edible oils is presented. To this aim, a solubilisation with tetramethylammonium hydroxide (TMAH) was assayed prior to inductively coupled plasma mass spectrometry detection. Small amounts of TMAH were used, resulting in high elemental concentrations. This method was applied to edible oils commercially available in Argentine. Elements present in small amounts (Cu, Ge, Mn, Mo, Ni, Sb, Sr, Ti, and V) were determined in olive, corn, almond and sunflower oils. The limits of detection were between 0.004 µg g(-1) for Mn and Sr, and 0.32 µg g(-1) for Sb. Principal components analysis was used to correlate the content of trace metals with the type of oils. The two first principal components retained 91.6% of the variability of the system. This is a relatively simple and safe procedure, and could be an attractive alternative for quality control, traceability and routine analysis of edible oils.

Determination of chemical oxygen demand by a flow injection method based on microwave digestion and chromium speciation coupled to inductively coupled plasma optical emission spectrometry.

The present paper evaluates the applicability of a new FIA system for COD determination. The new system, flow injection microwave solid phase extraction by means of activated carbon (FI-MW-SPE), consists of a digestion circuit, placed in a home MW oven, coupled to an ICP-OES spectrophotometer. Doehlert experimental design was used to speed up the optimization of different experimental variables studied for assisted digestion methods. The method provided a high throughput of about 18 samples h(-1). To assess the accuracy of analytical methods linear regression, elliptic joint confidence region (EJCR) was used. A large linear range of 2.78-850 mg O(2) L(-1) with an excellent detection limit of 0.94 mg O(2) L(-1) was obtained. The interference by high chloride concentration was studied, and values below 3000 mg Cl(-) ions L(-1), allowed the estimation of COD load without any masking agents. COD values for various types of wastewater samples were correlated with those obtained by standard manual methods. Moreover, interferences due to matrix nature are absent; since matrix is washed out of the column before Cr (III) is eluted. This method reduces the time, reagent volume, hazardous emission, external contamination, with a good reproducibility and accuracy.

Water quality assessment, by statistical analysis, on rural and urban areas of Chocancharava River (Río Cuarto), Córdoba, Argentina.

Water quality has degraded dramatically in the Chocancharava River (Río Cuarto, Córdoba, Argentina) due to point and non-point sources. This paper aims to assess spatial and temporal variations of physical and chemical parameters of the river. Six sampling sites and six sampling campaigns were developed. During the period 2007-2008, wet and dry seasons were included. A statistical analysis was carried out with 23 physical and chemical variables. Then, a new statistical analysis was carried out including the Riparian Corridors Quality Index and the physical and chemical variables (24 variables). Considering a multivariate system, analysis of variance, principal component analysis and cluster analysis were used. From the statistical analysis, the river was divided into two zones with different degrees of contamination. The most polluted zone is due to pollution inputs of urban, industrial and agricultural sources. This area showed a remarkable deterioration in water quality, mainly due to wastewater discharges. According to Riparian Quality, better results were found in sections of poor water quality, due to the fact that the river bank forest was less degraded downstream of the sewage discharge.

Influence of urbanization and tourist activities on the water quality of the Potrero de los Funes River (San Luis - Argentina).

A study of the water quality of the Potrero de los Funes River (San Luis - Argentina) was carried out in order to evaluate the possible effect of the anthropogenic activities on the river developed in the homonymous town. Samples were collected during the period March 2000-November 2005 at three selected sampling sites (RP(1), RP(2) and RP(3)). Different physicochemical and bacteriological parameters (turbidity, pH, conductivity, suspended solids, alkalinity, potassium, sodium, calcium, magnesium, chlorides, nitrates, phosphates, sulphates, chemical oxygen demand (COD), 5-day biological oxygen demand (BOD(5)), dissolved oxygen, total coliforms, Escherichia coli and total heterotrophic bacteria) were analysed according to the Standard Method for the Examination of Water and Wastewater. When comparing the values of total coliforms, E. coli, total heterotrophic bacteria, COD, BOD(5) and phosphates from the zone without anthropogenic influence (RP(1)) and the urban zones (RP(2) and RP(3)) an important variation in the parameters was observed. These results indicate that the urban activity produces a serious and negative effect on the water quality, thus constituting a sanitary risk and may have a major impact on the trophic status of the Potrero de los Funes dam. As case study, we report on the use of General Quality Index (GQI) to evaluate spatial and seasonal changes in the water quality of Potrero de los Funes River. Results revealed a significant degradation of the water quality at RP(2) and RP(3).