Ecotoxic effect in Allium cepa due to sphalerite weathering arising in calcareous conditions.

The ecotoxic effect of Zn species arising from the weathering of the marmatite-like sphalerite ((Fe, Zn)S) in Allium cepa systems was herein evaluated in calcareous soils and connected with its sulfide oxidation mechanism to determine the chemical speciation responsible of this outcome. Mineralogical analyses (X-ray diffraction patterns, Raman spectroscopy, scanning electron microscopy and atomic force microscopy), chemical study of leachates (total Fe, Zn, Cd, oxidation-reduction potential, pH, sulfates and total alkalinity) and electrochemical assessments (chronoamperometry, chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy) were carried out using (Fe, Zn)S samples to elucidate interfacial mechanisms simulating calcareous soil conditions. Results indicate the formation of polysulfides (Sn2-), elemental sulfur (S0), siderite (FeCO3)-like, hematite (Fe2O3)-like with sorbed CO32- species, gunningite (ZnSO4·H2O)-like phase and smithsonite (ZnCO3)-like compounds in altered surface under calcareous conditions. However, the generation of gunningite (ZnSO4·H2O)-like phase was predominant bulk-solution system. Quantification of damage rates ranges from 75 to 90% of bulb cells under non-carbonated conditions after 15-30 days, while 50-75% of damage level is determined under neutral-alkaline carbonated conditions. Damage ratios are 70.08 and 30.26 at the highest level, respectively. These findings revealed lower ecotoxic damage due to ZnCO3-like precipitation, indicating the effect of carbonates on Zn compounds during vegetable up-taking (exposure). Other environmental suggestions of the (Fe, Zn)S weathering and ecotoxic effects under calcareous soil conditions are discussed.

Influence of oxygen vacancies, surface composition, and crystallite size on the photoelectrochemical oxidation activity of C,N-codoped TiO2 for cefadroxil abatement along with O3.

This study aims the development of photoelectrodes to be incorporated in a photoelectrocatalytic ozonation (PECO) process for tertiary treatment of urban wastewaters, targeting the removal of contaminants of emerging concern (CEC). PECO tests were performed using urban wastewater after secondary treatment fortified with Cefadroxil (CFX, C16H17N3O5S), as target model CEC. Three Nitrogen and Carbon doped TiO2 (CN-TiO2) electrodes were synthesized by anodizing at 50, 70, and 90 V, and calcined. These materials were characterized by X-Ray diffraction and Rietveld refinement, Scanning Electron Microscopy, Diffuse Reflectance Spectroscopy, X-ray photoelectron spectroscopy, chronoamperometry, and electrochemical impedance spectroscopy, to correlate defects with photoactivity. All photoanodes considerably reduced their main bandgaps by the incorporation of C and N species, to enable absorption capacities in the UV region using a Xe lamp. The lowest oxygen vacancy content and largest crystallite size were found for CN-TiO2-70, favoring the reduction of bulk defects that could act as recombination of charge carriers. Therefore, oxygen vacancies affect more the TiO2 photoactivity compared to the crystallite size or the light absorption capacity, confirming that a lower content of vacancies in the material bulk and surface doping significantly influence the activity as detected by Rietveld refinement, DRS, and XPS. The electrochemical techniques confirm that the highest photocurrent was obtained for CN-TiO2-70, whence this photoanode was chosen to carry out the CFX degradation. A point defect model simulating Nyquist plot reveals that the photoactivity depends on the speed to diffuse oxygen vacancies through the TiO2 coating. All abatement processes were followed by high-performance liquid chromatography, and Total Organic Carbon (TOC). At neutral and alkaline conditions, CFX is eliminated to levels below the analytical detection limit after 90 min of treatment (TOC removals of 87 and 91%, respectively), indicating that the coupling between the CN-TiO2-70 photocatalyst and ozone is effective in eliminating the contaminant due to parallel routes forming •OH species. Lower CFX degradation observed at acidic pH (TOC removal of 70%) is assigned to the difficulty of oxidizing protonated CFX species.

Modeling the sulfamethoxazole degradation by active chlorine in a flow electrochemical reactor.

The aim of this study is to propose a continuous physicochemical model accounting for the active chlorine production used to degrade recalcitrant sulfamethoxazole (SMX) in an electrochemical flow reactor. The computational model describes the fluid mechanics and mass transfer occurring in the re/actor, along with the electrode kinetics of hydrogen evolution reaction arising on a stainless steel cathode, and the chloride oxidation on a DSA. Specifically, the anodic contributions assume the heterogeneous nature of the adsorbed chlorine species formed on this surface, which are a model requirement to correctly define the experimental reactor performance and degradation efficiency of the contaminant. The experimental validation conducted at different applied current densities, volumetric flows, and chloride concentrations is adequately explained by the model, thus evidencing some of the phenomena controlling the electrocatalytic chlorine production for environmental applications. The best conditions to eliminate the SMX are proposed based on the theoretical analysis of the current efficiency calculated with the model, and experimentally confirmed. The use of the Ti/RuO2-ZrO2-Sb2O3 anode at the bench scale improves the SMX removal by using electro-generated chlorine species adsorbed on its surface, which remarkably increases the oxidation potential of the system along with chlorine desorbed from the electrode. This is a technological innovation concerning other mediated oxidation methods entirely using oxidants in solution.

Environmental assessment of energy production from anaerobic digestion of pig manure at medium-scale using life cycle assessment.

This study assessed the potential environmental effects of energy production from pig manure treatment by anaerobic digestion at medium-scale based on the Life Cycle Assessment of a farm in Puebla, Mexico. It also compared the results from common practices of biogas flaring and conventional management. The analysis was based on one ton of pig manure in 4 systems: two with energy production, one with biogas flaring, and the last one conventional management. The use of biogas for electricity production combined with composting techniques generated the lowest net impacts on climate change of 272 kg CO2eq and photochemical oxidation of 0.056 kg ethylene eq, while the biogas flaring registered impacts of 344 kg CO2eq and 0.095 kg ethylene eq. The systems with energy production had environmental benefits on fossil resources depletion by avoiding the consumption of -863 MJ and -1608 MJ, but systems that burned biogas required fossil fuel consumption of 246 MJ from the grid. The conventional management generated the greatest environmental impacts, with eutrophication being the most important negative effect due to the manure discharge into water bodies (5.97 kg PO4eq). Sensitivity analysis shown that energy production could generate greater impacts on global warming compared to the case in which manure was used directly in crop fields, if emissions from unintentional releases and a poor digestate management are not avoided. Results are relevant for developing countries in which processes are carried out in rural and semi-industrial areas with lack of technical knowledge and economic resources.

Spatial distribution, mobility and bioavailability of arsenic, lead, copper and zinc in low polluted forest ecosystem in North-western Mexico.

A geochemical-environmental mapping was carried for a low polluted forest in North-western Mexico (Santiago Papasquiaro mining area), as part of the North American forests accounting for environmental behavior of arsenic (As), lead (Pb), zinc (Zn) and copper (Cu) in soil and tree components (stem wood and aciculums). Spectroscopic and microscopic techniques along with standard protocols were used to determine the mineralogical phases containing these elements, and their corresponding spatial distributions in soil and forests and mobility. In soil, total As, Pb, Zn and Cu ranged from 4.9 to 98.3, 19.6 to 768.6, 19.6 to 407.1, and 1.6 to 63.8 mg kg-1, respectively. Ultrafine particles (<5-10 µm) of arsenopyrite and sphalerite (and complex Zn-Fe phase) were the main As and Zn-bearing phases determined by SEM-EDS, respectively. Complex Pb-Cu-Fe and Cu-O oxide-like phases were the only ones containing Pb and Cu, respectively. Mobility was low for Pb, Zn and Cu, whereas a significant mobility was assessed for As. Concentrations vs. depth profiles suggested progressive accumulations of As, Pb, Zn and Cu in top soil. Total As, Pb, Zn and Cu in pine stem wood varied from 11.5 to 184.5, 98.9 to 7359.8, 3242.7 to 22197.3, 689.2 to 7179.6 µg kg-1, respectively. The respective concentrations in the pine needles ranged from 50 to 624.2, 100 to 16353.1, 120 to 46440.9 and 720 to 7200 µg kg-1, indicating an active bioaccumulation of As, Pb, Zn and Cu. A prospective environmental behavior was discussed for As, Pb, Zn and Cu in the low-polluted forest.

Changes in biooxidation mechanism and transient biofilm characteristics by As(V) during arsenopyrite colonization with Acidithiobacillus thiooxidans.

Chemical and surface analyses are carried out using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM-EDS), atomic force microscopy (AFM), confocal laser scanning microscopy (CLSM), glow discharge spectroscopy (GDS) and extracellular surface protein quantification to thoroughly investigate the effect of supplementary As(V) during biooxidation of arsenopyrite by Acidithiobacillus thiooxidans. It is revealed that arsenic can enhance bacterial reactions during bioleaching, which can strongly influence its mobility. Biofilms occur as compact-flattened microcolonies, being progressively covered by a significant amount of secondary compounds (S n2- , S0, pyrite-like). Biooxidation mechanism is modified in the presence of supplementary As(V), as indicated by spectroscopic and microscopic studies. GDS confirms significant variations between abiotic control and biooxidized arsenopyrite in terms of surface reactivity and amount of secondary compounds with and without As(V) (i.e. 6 µm depth). CLSM and protein analyses indicate a rapid modification in biofilm from hydrophilic to hydrophobic character (i.e. 1-12 h), in spite of the decrease in extracellular surface proteins in the presence of supplementary As(V) (i.e. stressed biofilms).

Assessment of biofilm changes and concentration-depth profiles during arsenopyrite oxidation by Acidithiobacillus thiooxidans.

Biofilm formation and evolution are key factors to consider to better understand the kinetics of arsenopyrite biooxidation. Chemical and surface analyses were carried out using Raman spectroscopy, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), glow discharge spectroscopy (GDS), and protein analysis (i.e., quantification) in order to evaluate the formation of intermediate secondary compounds and any significant changes arising in the biofilm structure of Acidithiobacillus thiooxidans during a 120-h period of biooxidation. Results show that the biofilm first evolves from a low cell density structure (1 to 12 h) into a formation of microcolonies (24 to 120 h) and then finally becomes enclosed by a secondary compound matrix that includes pyrite (FeS2)-like, S n2-/S0, and As2S3 compounds, as shown by Raman and SEM-EDS. GDS analyses (concentration-depth profiles, i.e., 12 h) indicate significant differences for depth speciation between abiotic control and biooxidized surfaces, thus providing a quantitative assessment of surface-bulk changes across samples (i.e. reactivity and /or structure-activity relationship). Respectively, quantitative protein analyses and CLSM analyses suggest variations in the type of extracellular protein expressed and changes in the biofilm structure from hydrophilic (i.e., exopolysaccharides) to hydrophobic (i.e., lipids) due to arsenopyrite and cell interactions during the 120-h period of biooxidation. We suggest feasible environmental and industrial implications for arsenopyrite biooxidation based on the findings of this study.

Assessment of arsenic and fluorine in surface soil to determine environmental and health risk factors in the Comarca Lagunera, Mexico.

Total, bioaccessible and mobile concentrations of arsenic and fluorine are determined in polluted surface soil within the Comarca Lagunera region using standardized protocols to obtain a full description of the environmental behavior for these elements. The composition of mineral phases associated with them is evaluated with microscopic and spectroscopic techniques. Mineralogical characterizations indicate that ultra-fine particles (<1-5 µm) including mimetite-vanadite (Pb5(AsO4)3Cl, Pb5(AsO4, VO4)3Cl)-like, lead arseniate (Pb3(AsO4)2)-like and complex arsenic-bearing compounds are main arsenic-bearing phases, while fluorite (CaF2) is the only fluorine-bearing phase. Total fluorine and arsenic concentrations in surface soil range from 89.75 to 926.63 and 2.7-78.6 mg kg-1, respectively, exceeding in many points a typical baseline value for fluorine (321 mg kg-1), and trigger level criterion for arsenic soil remediation (20 mg kg-1); whereas fluoride and arsenic concentrations in groundwater vary from 0.24 to 1.8 mg L-1 and 0.12-0.650 mg L-1, respectively. The main bioaccessible percentages of soil in the gastric phase (SBRC-G) are estimated for arsenic from 1 to 63%, and this parameter in the intestinal phase (SBRC-I) fluorine from 2 to 46%, suggesting human health risks for this region. While a negligible/low mobility is found in soil for arsenic (0.1-11%), an important mobility is determined for fluorine (2-39%), indicating environmental risk related to potential fluorine release. The environmental and health risks connected to arsenic and fluorine are discussed based on experimental data.

Chemical and surface analysis during evolution of arsenopyrite oxidation by Acidithiobacillus thiooxidans in the presence and absence of supplementary arsenic.

Bioleaching of arsenopyrite presents a great interest due to recovery of valuable metals and environmental issues. The current study aims to evaluate the arsenopyrite oxidation by Acidithiobacillus thiooxidans during 240h at different time intervals, in the presence and absence of supplementary arsenic. Chemical and electrochemical characterizations are carried out using Raman, AFM, SEM-EDS, Cyclic Voltammetry, EIS, electrophoretic and adhesion forces to comprehensively assess the surface behavior and biooxidation mechanism of this mineral. These analyses evidence the formation of pyrite-like secondary phase on abiotic control surfaces, which contrast with the formation of pyrite (FeS2)-like, orpiment (As2S3)-like and elementary sulfur and polysulfide (Sn(2-)/S(0)) phases found on biooxidized surfaces. Voltammetric results indicate a significant alteration of arsenopyrite due to (bio)oxidation. Resistive processes determined with EIS are associated with chemical and electrochemical reactions mediated by (bio)oxidation, resulting in the transformation of arsenopyrite surface and biofilm direct attachment. Charge transfer resistance is increased when (bio)oxidation is performed in the presence of supplementary arsenic, in comparison with lowered abiotic control resistances obtained in its absence; reinforcing the idea that more stable surface products are generated when As(V) is in the system. Biofilm structure is mainly comprised of micro-colonies, progressively enclosed in secondary compounds. A more compact biofilm structure with enhanced formation of secondary compounds is identified in the presence of supplementary arsenic, whereby variable arsenopyrite reactivity is linked and attributed to these secondary compounds, including Sn(2-)/S(0), pyrite-like and orpiment-like phases.

Arsenopyrite weathering under conditions of simulated calcareous soil.

Mining activities release arsenopyrite into calcareous soils where it undergoes weathering generating toxic compounds. The research evaluates the environmental impacts of these processes under semi-alkaline carbonated conditions. Electrochemical (cyclic voltammetry, chronoamperometry, EIS), spectroscopic (Raman, XPS), and microscopic (SEM, AFM, TEM) techniques are combined along with chemical analyses of leachates collected from simulated arsenopyrite weathering to comprehensively examine the interfacial mechanisms. Early oxidation stages enhance mineral reactivity through the formation of surface sulfur phases (e.g., S n (2-)/S(0)) with semiconductor properties, leading to oscillatory mineral reactivity. Subsequent steps entail the generation of intermediate siderite (FeCO3)-like, followed by the formation of low-compact mass sub-micro ferric oxyhydroxides (α, γ-FeOOH) with adsorbed arsenic (mainly As(III), and lower amounts of As(V)). In addition, weathering reactions can be influenced by accessible arsenic resulting in the formation of a symplesite (Fe3(AsO4)3)-like compound which is dependent on the amount of accessible arsenic in the system. It is proposed that arsenic release occurs via diffusion across secondary α, γ-FeOOH structures during arsenopyrite weathering. We suggest weathering mechanisms of arsenopyrite in calcareous soil and environmental implications based on experimental data.