Native Desmodesmus sp. and Chlorella sp. isolated from the Reconquista River display a different binding preference for Cu(II) and Zn(II).

The present work was developed to study the metal removal performance of unicellular algae isolated from the Reconquista River and to evaluate the effect of the presence of more than one metal in the removal process. Thus, native species of unicellular algae were isolated from the highly contaminated Reconquista River. All of the isolates were classified, at genus level, based on their morphological appearance. Nine isolates were screened for their Zn(II) removal capacities. Chlorella sp. RR5 and Desmodesmus sp. RR7 were selected based on their removal performance, and their potential in the remediation of multiple metals was analyzed. Therefore, zinc (Zn(II)), copper (Cu(II)), and chromium (Cr(VI)) removal was evaluated in mono- and multi-metallic solutions. Biosorption capacities were high (0.8-1.8 mmol g-1) for Zn(II) and Cu(II) in mono-metallic solutions. Removal capacities decreased up to 48% in multi-metallic solutions. Interestingly, when multi-metallic systems were considered, each strain showed a metal preference. Chlorella sp. removed better Cu(II) meanwhile Desmodesmus sp. showed a preference for Zn(II). Thus, a metal-binding selectivity in each strain was determined. Chromium (VI) remediation was almost null in the conditions analyzed in this work. Fourier transformation infrared spectroscopy (FT-IR) analysis showed that polysaccharides were the main functional group involved in metal adsorption and, in some cases, also the carboxylates played an important role. Overall, we were able to analyze a new source of algal diversity and perform a metal removal characterization of them, leading to the identification of a metal selectivity based on the characteristics of the tested algal strains.

Debaryomyces hansenii F39A as biosorbent for textile dye removal.

Many industries generate a considerable amount of wastewater containing toxic and recalcitrant dyes. The main objective of this research was to examine the biosorption capacity of Reactive Blue 19 and Reactive Red 141 by the Antarctic yeast Debaryomyces hansenii F39A biomass. Some variables, including pH, dye concentration, amount of adsorbent and contact time, were studied. The equilibrium sorption capacity of the biomass increased with increasing initial dye concentration up to 350mg/l. Experimental isotherms fit the Langmuir model and the maximum uptake capacity (qmax) for the selected dyes was in the range of 0.0676-0.169mmol/g biomass. At an initial dye concentration of 100mg/l, 2g/l biomass loading and 20±1°C, D. hansenii F39A adsorbed around 90% of Reactive Red 141 and 50% of Reactive Blue 19 at pH 6.0. When biomass loading was increased (6g/l), the uptake reached up to 90% for Reactive Blue 19. The dye uptake process followed a pseudo-second-order kinetics for each dye system. As seen throughout this research study, D. hansenii has the potential to efficiently and effectively remove dyes in a biosorption process and may be an alternative to other costly materials.

Wiring Up Along Electrodes for Biofilm Formation.

Millimeter-length cables of bacteria were discovered growing along a graphite-rod electrode serving as an anode of a microbial electrolysis cell (MEC). The MEC had been inoculated with a culture of Fe-reducing microorganisms enriched from a polluted river sediment (Reconquista river, Argentina) and was operated at laboratory controlled conditions for 18 days at an anode poised potential of 240 mV (vs. Ag/AgCl), followed by 23 days at 480 mV (vs. Ag/AgCl). Anode samples were collected for scanning electron microscopy, phylogenetic and electrochemical analyses. The cables were composed of a succession of bacteria covered by a membranous sheath and were distinct from the known "cable-bacteria" (family Desulfobulbaceae). Apparently, the formation of the cables began with the interaction of the cells via nanotubes mostly located at the cell poles. The cables seemed to be further widened by the fusion between them. 16S rRNA gene sequence analysis confirmed the presence of a microbial community composed of six genera, including Shewanella, a well-characterized electrogenic bacteria. The formation of the cables might be a way of colonizing a polarized surface, as determined by the observation of electrodes extracted at different times of MEC operation. Since the cables of bacteria were distinct from any previously described, the results suggest that bacteria capable of forming cables are more diverse in nature than already thought. This diversity might render different electrical properties that could be exploited for various applications.

Kinetic and equilibrium adsorption of two post-harvest fungicides onto copper-exchanged montmorillonite: synergic and antagonistic effects of both fungicides' presence.

The simultaneous adsorption of both imazalil (IMZ) and thiabendazole (TBZ) fungicides in a Cu2+-exchanged Mt was studied in this work. Kinetic studies were used to determine the rate law which describes the adsorption of individual fungicides onto the adsorbent. Adsorption isotherm of individual and combined fungicides was done to evaluate synergic or antagonistic effects. The Mt-Cu material considerably improved TBZ and/or IMZ adsorption from aqueous suspensions with respect to raw Mt, leading to removal efficiencies higher than 99% after 10 min of contact time for TBZ and IMZ Ci = 15 and 40 mg/L, respectively, when a solid dosage = 1 g/L was used. The adsorption sites involved were determined by a combination of X-ray diffraction (XRD) determinations and electron paramagnetic resonance (EPR), indicating that fungicides were bonded to Cu2+ cations, while the rate limiting step was the formation of coordination bonds. The adsorption mechanism proposed is that of ligand exchange between water and fungicide molecules in the metal coordination sphere. The single-crystal structure for the IMZ-Cu2+ complex indicated that four molecules were bounded to the copper centers, while two molecules of TBZ are bounded to copper explaining the higher IMZ uptake capacity for the Mt-Cu material. Graphical abstract.

Effects of pollution and bioleaching process on the mineral composition and texture of contaminated sediments of the Reconquista River, Argentina.

In this work, we report on the structural and textural changes in fluvial sediments from Reconquista River´s basin, Argentina, due to processes of contamination with organic matter and remediation by bioleaching. The original uncontaminated matrix showed quartz and phyllosilicates as the main primary mineral constituents and phases of interstratified illite-montmorillonite as secondary minerals. It was found that in contaminated sediments, the presence of organic matter in high concentration causes changes in the specific surface area, particle size distribution, size and distribution of micro and meso, and the morphology of the particles with respect to the uncontaminated sediment. After the bioleaching process, there were even greater changes in these parameters at the level of secondary mineral formation and the appearance of nanoparticles, which were confirmed by SEM. Especially, we found the formation of cementing substances such as gypsum, promoting the formation of macroporous aggregates and the weathering of clay components. Our results indicate that the bioleaching not only decreases the content of metals but also favors the formation of a material with improved characteristics for potential future applications.

Metal bioleaching from anaerobic sediments from Reconquista River basin (Argentina) as a potential remediation strategy.

Anaerobic sediments of urban watercourses are subjected to industrial pollution and frequently tend to accumulate heavy metals. The biocatalyzed oxidation and reduction of sulphur compounds that occur within the sediment are key reactions that determine mobility of metals such as that occurred in mine acidic drainage reactions. The aim of this work was to study the application of these processes using heap leaching technology for the remediation of anaerobic contaminated sediments from Reconquista River basin. The bioleaching potentiality for remediation was demonstrated through batch tests in shake flasks with different pulp densities of anaerobic sediment containing 338 mg kg-1 of Zn and 117 mg kg-1 of Cu. Subsequently, bioleaching heap systems were compiled into columns of 12-cm height and 6-cm diameter, fitted with perlite to improve drainage. In order to assess the effect of elementary sulphur over the mobility of metals from the bioheap to the aqueous solution, increasing concentrations of elementary sulphur (1, 2, 5 % w/w) were added. After 3 months of acidification generated by periodic watering, the extraction of 70 % of the initial Zn and 43 % of the initial Cu was achieved. Polluted sediments from waterways as Reconquista River should not be indiscriminately manipulated if acid drainage is possible. Remediation by a simple and economically viable strategy like heap leaching is feasible.

Degradation alternatives for a commercial fungicide in water: biological, photo-Fenton, and coupled biological photo-Fenton processes.

Imazalil (IMZ) is a widely used fungicide for the post-harvest treatment of citrus, classified as "likely to be carcinogenic in humans" for EPA, that can be only partially removed by conventional biological treatment. Consequently, specific or combined processes should be applied to prevent its release to the environment. Biological treatment with adapted microorganism consortium, photo-Fenton, and coupled biological photo-Fenton processes were tested as alternatives for the purification of water containing high concentration of the fungicide and the coadjutants present in the commercial formulation. IMZ-resistant consortium with the capacity to degrade IMZ in the presence of a C-rich co-substrate was isolated from sludge coming from a fruit packaging company wastewater treatment plant. This consortium was adapted to resist and degrade the organics present in photo-Fenton-oxidized IMZ water solution. Bacteria colonies from the consortia were isolated and identified. The effect of H2O2 initial concentration and dosage on IMZ degradation rate, average oxidation state (AOS), organic acid concentration, oxidation, and mineralization percentage after photo-Fenton process was determined. The application of biological treatment to the oxidized solutions notably decreased the total organic carbon (TOC) in solution. The effect of the oxidation degree, limited by H2O2 concentration and dosage, on the percentage of mineralization obtained after the biological treatment was determined and explained in terms of changes in AOS. The concentration of H2O2 necessary to eliminate IMZ by photo-Fenton and to reduce TOC and chemical oxygen demand (COD) by biological treatment, in order to allow the release of the effluents to rivers with different flows, was estimated.

Bioaccessible heavy metals-sediment particles from Reconquista River induce lung inflammation in mice.

The Reconquista River (RR), one of the most polluted watercourses in Argentina, receives effluent discharges from heavily industrialized and highly populated settlements. During winter and summer, the floodplain remains dry, producing the oxidation of sulfide and organic matter present in the sediment, making heavy metals more bioaccessible. Dispersion of this sediment occurs, and thus harmful effects on the pulmonary health of residents and workers inhabiting the RR bank may take place. The authors characterized the sediment particles of the RR (RR-PM) morphologically by scanning electron microscopy and its elemental composition by energy dispersive X-ray spectroscopy (EDX) and Community Bureau of Reference (BCR) sequential extraction. Furthermore, the authors evaluated its biological impact on the respiratory system of BALB/c mice, generating four groups: control healthy, sensibilized with ovalbumin, exposed to particles, and sensibilized and exposed to particles. Sediment particles of the Reconquista River contained fine particulate matter, with a high concentration of bioaccessible Cu and Zn. The authors found that animal exposure to RR-PM caused polymorphonuclear cell lung infiltration, augmentation of O2(-), increase of proinflammatory cytokines (tumor necrosis factor alpha [TNFα], interleukin-6 [IL-6]) and apoptosis. This adverse response was more dramatic in the sensibilized and exposed to particles group. Even more, they proved the bioaccessible fraction present in the RR-PM to be responsible for these harmful effects. The authors conclude that RR-PM produces an adverse biological impact on the airways of healthy animals, which is largely aggravated in previously sensibilized animals.