Distinguishing the contributions of different smelting emissions to the spatial risk footprints of toxic elements in soil using PMF, Bayesian isotope mixing models, and distance-based regression.

Toxic element pollution of soils emanating from smelting operations is an escalating global concern due to its severe impact on ecosystems and human health. In this study, soil samples were collected and analyzed to quantify the risk contributions and delineate the spatial risk footprints from smelting emissions for 8 toxic elements. A comprehensive health risk contribution and delineation framework was utilized, consisting of Positive matrix factorization (PMF), spatial interpolation, an advanced Bayesian isotope mixing model via Mixing Stable Isotope Analysis in R (MixSIAR), and distance-based regression. The results showed that the mean concentrations of As, Cd, Cu, Hg, Pb, and Zn exceeded the background levels, indicating substantial contamination. Three sources were identified using the PMF model and confirmed by spatial interpolation and MixSIAR, with contributions ranked as follows: industrial wastewater discharge and slag runoff from the smelter site (48.9 %) > natural geogenic inputs from soil parent materials (26.7 %) > atmospheric deposition of dust particles from smelting operations (24.5 %). Among the identified sources, smelter runoff posed the most significant risk, accounting for 97.9 % of the non-carcinogenic risk (NCR) and 59.9 % of the carcinogenic risk (CR). Runoff also drove NCR and CR exceedances at 7.8 % and 4.7 % of sites near the smelter, respectively. However, atmospheric deposition from smelting emissions affected soils across a larger 0.8 km radius. Although it posed lower risks, contributing just 1.1 % to NCR and 22.6 % to CR due to the limited elevation of toxic elements, deposition reached more distant soils. Spatial interpolation and distance-based regression delineated high NCR and CR exposure hotspots within 1.4 km for runoff and 0.8 km for deposition, with exponentially diminishing risks at further distances. These findings highlight the need for pathway-specific interventions that prioritize localized wastewater containment and drainage controls near the smelter while implementing broader regional air pollution mitigation measures.

Elucidating the impacts of cobalt (II) ions on extracellular electron transfer and pollutant degradation by anodic biofilms in bioelectrochemical systems during industrial wastewater treatment.

Electrogenic biofilms in bioelectrochemical systems (BES) are critical in wastewater treatment. Industrial effluents often contain cobalt (Co2+); however, its impact on biofilms is unknown. This study investigated how increasing Co2+ concentrations (0-30 mg/L) affect BES biofilm community dynamics, extracellular polymeric substances, microbial metabolism, electron transfer gene expression, and electrochemical performance. The research revealed that as Co2+ concentrations increased, power generation progressively declined, from 345.43 ± 4.07 mW/m2 at 0 mg/L to 160.51 ± 0.86 mW/m2 at 30 mg/L Co2+. However, 5 mg/L Co2+ had less effect. The Co2+ removal efficiency in the reactors fed with 5 and 10 mg/L concentrations exceeded 99% and 94%, respectively. However, at 20 and 30 mg/L, the removal efficiency decreased substantially, likely because of reduced biofilm viability. FTIR indicated the participation of biofilm functional groups in Co2+ uptake. XPS revealed Co2+ presence in biofilms as CoO and Co(OH)2, indicating precipitation also aided removal. Cyclic voltammetry and electrochemical impedance spectroscopy tests revealed that 5 mg/L Co2+ had little impact on the electrocatalytic activity, while higher concentrations impaired it. Furthermore, at a concentration of 5 mg/L Co2+, there was an increase in the proportion of the genus Anaeromusa-Anaeroarcus, while the genus Geobacter declined at all tested Co2+ concentrations. Additionally, higher concentrations of Co2+ suppressed the expression of extracellular electron transfer genes but increased the expression of Co2+-resistance genes. Overall, this study establishes how Co2+ impacts electrogenic biofilm composition, function, and treatment efficacy, laying the groundwork for the optimized application of BES in remediating Co2+-contaminated wastewater.

Release characteristics of heavy metals from electrolytic manganese residue under varying environmental factors.

High levels of manganese (Mn) and other heavy metals from electrolytic manganese residue (EMR) stockpiled would be released into the environment under natural conditions. A batch-leaching test was carried out to investigate the release characteristics of heavy metals from EMR with different storage times under simulated environmental conditions such as acid rain with different pH (3.0, 4.5, 5.6, and 7.0) at contact times of 1, 2, 4, 6, and 12 h; liquid to solid ratio (L/S) (5:1, 10:1, 20:1, and 30:1); and temperature (15, 25, 35, and 45 °C). The results showed that low pH (3.0 and 4.5) and high temperature (35 and 45 °C) could significantly promote heavy metal leaching from EMRs and increasing the L/S ratio above 20:1 mL/g significantly decreased heavy metal leachate concentrations due to dilution effect. Cr, Mn, and Pb concentrations in leachate increased almost continuously throughout the leaching process, while Zn decreased slightly at the 12th hour. Meanwhile, heavy metal concentrations in EMR1 (fresh EMR) were higher than in EMR2 (out stockpiled for more than 3 months). The concentrations of Mn, Pb, and Zn in leachates from EMRs at pH 3.0 and 4.5 leaching far exceeded the allowable maximum discharge concentrations for pollutants of the integrated wastewater discharge standard in China (GB8978-1996) by 57.5-59.0, 1.3-4.3, and 1.1-1.8 and 53.5-56.0, 3.04-7.25, and 1.0-1.91 times, respectively. Additionally, the Mn concentrations from both EMR leachates at pH 7.0 were above the national safe emission threshold. The morphological structure of EMRs changed after leaching, and XRD analysis showed the disappearance of MnO2, SiO2, FeS2, and CaSO4. The XPS revealed that Cr, Mn, Pb, and Zn existed as Cr3+, MnO, PbSO4, and ZnSiO3, respectively, after leaching. The study concluded that Mn, Pb, and Zn from EMRS leached by acid rain might pose a high potential environmental risk. Therefore, developing appropriate disposal techniques for EMR is necessary to prevent heavy metal pollution.

Heterotrophic anodic denitrification coupled with cathodic metals recovery from on-site smelting wastewater with a bioelectrochemical system inoculated with mixed Castellaniella species.

Although Castellaniella species are crucial for denitrification, there is no report on their capacity to carry out denitrification and anode respiration simultaneously in a bioelectrochemical system (BES). Herein, the ability of a mixed inoculum of electricigenic Castellaniella species to perform simultaneous denitrification and anode respiration coupled with cathodic metals recovery was investigated in a BES. Results showed that 500 mg/L NO3--N significantly decreased power generation, whereas 100 and 250 mg/L NO3--N had a lesser impact. The single-chamber MFCs (SCMFCs) fed with 100 and 250 mg/L NO3--N concentrations achieved a removal efficiency higher than 90% in all cycles. In contrast, the removal efficiency in the SCMFCs declined dramatically at 500 mg/L NO3--N, which might be attributable to decreased microbial viability as revealed by SEM and CLSM. EPS protein content and enzymatic activities of the biofilms decreased significantly at this concentration. Cyclic voltammetry results revealed that the 500 mg/L NO3--N concentration decreased the redox activities of anodic biofilms, while electrochemical impedance spectroscopy showed that the internal resistance of the SCMFCs at this concentration increased significantly. In addition, BES inoculated with the Castellaniella species was able to simultaneously perform heterotrophic anodic denitrification and cathodic metals recovery from real wastewater. The BES attained Cu2+, Hg2+, Pb2+, and Zn2+ removal efficiencies of 99.86 ± 0.10%, 99.98 ± 0.014%, 99.98 ± 0.01%, and 99.17 ± 0.30%, respectively, from the real wastewater. Cu2+ was bio-electrochemically reduced to Cu0 and Cu2O, whereas Hg0 and HgO constituted the Hg species recovered via bioelectrochemical reduction and chemical deposition, respectively. Furthermore, Pb2+ and Zn2+ were bio-electrochemically reduced to Pb0 and Zn0, respectively. Over 89% of NO3--N was removed from the BES anolyte during the recovery of the metals. This research reveals promising denitrifying exoelectrogens for enhanced power generation, NO3--N removal, and heavy metals recovery in BES.

Antimony oxidation and whole genome sequencing of Phytobacter sp. X4 isolated from contaminated soil near a flotation site.

The conversion of the more toxic Sb(III) into less toxic Sb(V) is an effective strategy for the treatment of antimony-contaminated sites. In this study, a strain, Phytobacter sp. X4, which can tolerate high concentrations of antimony and can use nitrate as an electron acceptor for Sb(III) oxidation under anaerobic conditions, was isolated from the deep soil of an antimony mine flotation tailing. Unlike other antimony oxidizing bacteria, X4 oxidized better under high Sb(III) concentration, and the oxidation efficiency of 10 mM Sb(III) reached the maximum at 110 h with 61.8 %. Kinetic study showed X4 yielded a Vmax of 1.093 µM∙min-1 and a Km of 718.2 µM. The genome of Phytobacter sp. X4 consists of a complete circular chromosome and two plasmids. In addition, X4 had more metal(loid)s resistance genes and highly expressed genes than other Phytobacter spp., reflecting its stronger adaptive advantage in harsh survival environments. We also analyzed the origin and evolution of arsB, arsC, and arsH, which may have been transferred horizontally from other species. iscR and arsH may have an important contribution to Sb(III) oxidation. Thus, Phytobacter sp. X4 has a good ability to remediate high antimony-contaminated sites and can be applied to an anaerobic environment.

Effect of nickel (II) on the performance of anodic electroactive biofilms in bioelectrochemical systems.

The impact of nickel (Ni2+) on the performance of anodic electroactive biofilms (EABs) in the bioelectrochemical system (BES) was investigated in this study. Although it has been reported that Ni2+ influences microorganisms in a number of ways, it is unknown how its presence in the anode of a BES affects extracellular electron transfer (EET) of EABs, microbial viability, and the bacterial community. Results revealed that the addition of Ni2+ decreased power output from 673.24 ± 12.40 mW/m2 at 0 mg/L to 179.26 ± 9.05 mW/m2 at 80 mg/L. The metal and chemical oxygen demand removal efficiencies of the microbial fuel cells (MFCs) declined as Ni2+ concentration increased, which could be attributed to decreased microbial viability as revealed by SEM and CLSM. FTIR analysis revealed the involvement of various microbial biofilm functional groups, including hydroxyl, amides, methyl, amine, and carboxyl, in the uptake of Ni2+. The presence of Ni2+ on the anodic biofilms was confirmed by SEM-EDS and XPS analyses. CV demonstrated that the electron transfer performance of the anodic biofilms was negatively correlated with the various Ni2+ concentrations. EIS showed that the internal resistance of the MFCs increased with increasing Ni2+ concentration, resulting in a decrease in power output. High-throughput sequencing results revealed a decrease in Geobacter and an increase in Desulfovibrio in response to Ni2+ concentrations of 10, 20, 40, and 80 mg/L. Furthermore, the various Ni2+ concentrations decreased the expression of EET-related genes. The Ni2+-fed MFCs had a higher abundance of the nikR gene than the control group, which was important for Ni2+ resistance. This work advances our understanding of Ni2+ inhibition on EABs, as well as the concurrent removal of organic matter and Ni2+ from wastewater.

Physiological responses, tolerance efficiency, and phytoextraction potential of Hylotelephium spectabile (Boreau) H. Ohba under Cd stress in hydroponic condition.

A sand hydroponic experiment with different concentrations of 0, 5, 10, 20, 40 mg L-1 Cd was used to study the growth and physiological response of Hylotelephium spectabile (Boreau) H. Ohba. and its phytoextraction potential for Cd. The results showed that total plant biomass under 5 mg L-1 Cd treatment was slightly affected. The content of malondialdehyde (MDA) in leaf exposed to Cd was higher, and the POD and CAT activity exhibited a positive response to the low level of Cd addition (5 mg·L-1). The photosynthesis pigments were slightly inhibited, and the ultrastructure of chloroplast remained intact after treatment with 10 mg L-1 Cd. The maximum leaf Cd content (603 mg·kg-1) was found in 5 mg L-1 Cd treatment, then decreased with the Cd level increased. The maximum Cd content in the shoots far exceeds the threshold level (100 mg kg-1) for a Cd-hyperaccumulator plant with the value of translocation factor (TFshoot/root) for Cd reaching up to 5.62. In conclusion, H. spectabile showed normal growth and physiological response and high shoot Cd accumulation under 5 mg L-1 Cd stress, which made it to be a good candidate for phytoextraction of low-level Cd polluted environment.