Extended Battery Compatibility Consideration from an Electrolyte Perspective.

The performance of electrochemical batteries is intricately tied to the physicochemical environments established by their employed electrolytes. Traditional battery designs utilizing a single electrolyte often impose identical anodic and cathodic redox conditions, limiting the ability to optimize redox environments for both anode and cathode materials. Consequently, advancements in electrolyte technologies are pivotal for addressing these challenges and fostering the development of next-generation high-performance electrochemical batteries. This review categorizes perspectives on electrolyte technology into three key areas: additives engineering, comprehensive component analysis encompassing solvents and solutes, and the effects of concentration. By summarizing significant studies, the efficacy of electrolyte engineering is highlighted, and the review advocates for further exploration of optimized component combinations. This review primarily focuses on liquid electrolyte technologies, briefly touching upon solid-state electrolytes due to the former greater vulnerability to electrode and electrolyte interfacial effects. The ultimate goal is to generate increased awareness within the battery community regarding the holistic improvement of battery components through optimized combinations.

Dependence of Biotic and Abiotic H2O2 and •OH Production on the Redox Conditions and Compositions of Sediment during Oxygenation.

Reactive oxygen species (ROS) production in O2-perturbed subsurface environments has been increasingly documented in recent years. However, the constraining conditions under which abiotic and/or biotic mechanisms predominate for ROS production remain ambiguous. Here, we demonstrate that the ROS production mechanism, biotic and abiotic, is determined by sediment redox properties and sediment compositions. Upon the oxygenation of 10 field sediments, the cumulative H2O2 concentrations reached up to 554 µmol/kg within 2 h. The autoclaving sterilization experiments showed that H2O2 could be produced by both biotic and abiotic processes depending on the redox conditions. However, only the abiotic process could produce significant levels of •OH, and the production yield was closely related to the sediment components, particularly sediment Fe(II) and organic matter. Fe(II) bound with organic matter led to high yields of H2O2 and •OH production. Sediment oxygenation contributed to the appearance of H2O2 in groundwater, with the abiotic mechanism producing higher instantaneous H2O2 concentrations than the biotic mechanism. These findings reveal that the redox conditions, compositions, and texture of sediments collectively control abiotic and biotic mechanisms for ROS production, which assists the identification of ROS production hotspots and the understanding of ROS distribution and utilization in the subsurface.

Pyrogenic Carbon Improves Cd Retention during Microbial Transformation of Ferrihydrite under Varying Redox Conditions.

Fe(III) (oxyhydr)oxides are ubiquitous in paddy soils and play a key role in Cd retention. Recent studies report that pyrogenic carbon (PC) may largely affect the microbial transformation processes of Fe(III) (oxyhydr)oxides, yet the impact of PC on the fate of Fe(III) (oxyhydr)oxide-associated Cd during redox fluctuations remains unclear. Here, we investigated the effects of PC on Cd retention during microbial (Shewanella oneidensis MR-1) transformation of Cd(II)-bearing ferrihydrite under varying redox conditions. The results showed that in the absence of PC, microbial reduction of ferrihydrite resulted in Cd release under anoxic conditions and Fe(II) oxidation by oxygen resulted in Cd retention under subsequent oxic conditions. The presence of PC facilitated microbial ferrihydrite reductive dissolution under anoxic conditions, promoted Fe(II) oxidative precipitation under oxic conditions, and inhibited Cd release under both anoxic and oxic conditions. The presence of PC and frequent shifts in redox conditions (i.e., redox cycling) inhibited the transformation of ferrihydrite to highly crystalline goethite and magnetite that exhibited less Cd adsorption. As a result, PC enhanced Cd retention by 41-59% and 55-77% after the redox shift and redox cycling, respectively, while in the absence of PC, Cd retention decreased by 5% after the redox shift and increased by 11% after redox cycling. Sequential extraction analysis revealed that 63-78% of Cd was associated with Fe minerals, while 3-12% of Cd was bound to PC, indicating that PC promoted Cd retention mainly through inhibiting ferrihydrite transformation. Our results demonstrate the great impacts of PC on improving Cd retention under dynamic redox conditions, which is essential for applying PC in remediating Cd-contaminated paddy soils.

Disparities in Drinking Water Manganese Concentrations in Domestic Wells and Community Water Systems in the Central Valley, CA, USA.

Over 1.3 million Californians rely on unmonitored domestic wells. Existing probability estimates of groundwater Mn concentrations, population estimates, and sociodemographic data were integrated with spatial data delineating domestic well communities (DWCs) to predict the probability of high Mn concentrations in extracted groundwater within DWCs in California's Central Valley. Additional Mn concentration data of water delivered by community water systems (CWSs) were used to estimate Mn in public water supply. We estimate that 0.4% of the DWC population (2342 users) rely on groundwater with predicted Mn > 300 µg L-1. In CWSs, 2.4% of the population (904 users) served by small CWSs and 0.4% of the population (3072 users) served by medium CWS relied on drinking water with mean point-of-entry Mn concentration >300 µg L-1. Small CWSs were less likely to report Mn concentrations relative to large CWSs, yet a higher percentage of small CWSs exceed regulatory standards relative to larger systems. Modeled calculations do not reveal differences in estimated Mn concentration between groundwater from current regional domestic well depth and 33 m deeper. These analyses demonstrate the need for additional well-monitoring programs that evaluate Mn and increased access to point-of-use treatment for domestic well users disproportionately burdened by associated costs of water treatment.

Dynamics and control mechanisms of inorganic nitrogen removal during wetting-drying cycles: A simulated managed aquifer recharge experiment.

Managed aquifer recharge (MAR) systems can be operated intermittently through wetting-drying cycles to simultaneously improve the water supply and quality. Although MAR can naturally attenuate considerable amounts of nitrogen, the dynamic processes and control mechanisms of nitrogen removal by intermittent MAR remain unclear. This study was conducted in laboratory sandy columns and lasted for 23 d, including four wetting periods and three drying periods. The hydraulic conductivity, oxidation reduction potential (ORP), and leaching concentrations of ammonia nitrogen and nitrate nitrogen of MAR systems were intensively measured to test the hypothesis that hydrological and biogeochemical controls play an essential role in regulating nitrogen dynamics at different stages of wetting-drying cycles. Intermittent MAR functioned as a sink for nitrogen while providing a carbon source to support nitrogen transformations; however, it occasionally became a source of nitrogen under intense flushes of preferential flow. Nitrogen dynamics were primarily controlled by hydrological processes in the initial wetting phase and were further regulated by biogeochemical processes during the subsequent wetting period, supporting our hypothesis. We also observed that a saturated zone could mediate nitrogen dynamics by creating anaerobic conditions for denitrification and buffering the flush effect of preferential flow. The drying duration can also affect the occurrence of preferential flow and nitrogen transformations, which should be balanced when determining the optimal drying duration for intermittent MAR systems.

Labile carbon-induced soil organic matter turnover in a subtropical forest under different redox conditions.

Labile organic carbon (LOC) input strongly affects soil organic matter (SOM) dynamics, including gains and losses. However, it is unclear how redox fluctuations regulate these processes of SOM decomposition and formation induced by LOC input. The objective of this study was to explore the impacts of LOC input on SOM turnover under different redox conditions. Soil samples were collected in a subtropical forest. A single pulse of 13C-labeled glucose (i.e., LOC) was applied to the soil. Soil samples were incubated for 40 days under three redox treatments, including aerobic, anoxic, and 10-day aerobic followed by 10-day anoxic conditions. Results showed that LOC input affected soil priming and 13C-SOM accumulation differently under distinct redox conditions by altering the activities of various microorganisms. 13C-PLFAs (phospholipid fatty acids) were analyzed to determine the role of microbial groups in SOM turnover. Increased activities of fungi and gram-positive bacteria (i.e., the K-strategists) by LOC input could ingest metabolites or residues of the r-strategists (e.g., gram-negative bacteria) to result in positive priming. Fungi could use gram-negative bacteria to stimulate priming intensity via microbial turnover in aerobic conditions first. Reduced activities of K-strategists as a result of the aerobic to anoxic transition decreased priming intensity. The difference in LOC retention in SOM under different redox conditions was mainly attributable to 13C-particulate organic carbon (13C-POC) accumulation. Under aerobic conditions, fungi and gram-positive bacteria used derivatives from gram-negative bacteria to reduce newly formed POC. However, anoxic conditions were not conducive to the uptake of gram-negative bacteria by fungi and gram-positive bacteria, favoring SOM retention. This work indicated that redox-regulated microbial activities can control SOM decomposition and formation induced by LOC input. It is extremely valuable for understanding the contribution of soil affected by redox fluctuations to the carbon cycle.

Hydrogeochemical characterization and natural background level determination of selected inorganic substances in groundwater from a semi-confined aquifer in Midwestern Burkina Faso, West Africa.

Hydrogeochemical processes that govern selected inorganic substances distribution in a semi-confined aquifer were characterized using traditional hydrogeochemical approaches and natural background levels (NBLs). Saturation indices and bivariate plots were used to investigate the effects of water-rock interactions on natural evolution of the groundwater chemistry, whereas Q-mode hierarchical cluster analysis and one-way analysis of variance classified the groundwater samples into three distinct groups. To highlight the groundwater status, NBLs and threshold values (TVs) of the substances were calculated using pre-selection method. Piper's diagram showed that the Ca-Mg-HCO3 water type was the only hydrochemical facies of the groundwaters. Although all samples, except a borewell with a high NO3- concentration, had major ion and transition metal concentrations within the World Health Organization's recommended guideline values for drinking water, Cl-, NO3- and PO43- exhibited scattered distribution patterns, reflecting their nonpoint anthropogenic sources in the groundwater system. The bivariate and saturation indices revealed that silicate weathering and possible gypsum and anhydrite dissolution contributed to the groundwater chemistry. In contrast, NH4+, FeT and Mn abundance appeared to be influenced by redox conditions. Strong positive spatial correlations between pH, FeT, Mn and Zn suggested that mobility of these metals was controlled by pH. The relative high F- concentrations in lowland areas may imply the impact of evaporation on this ion's abundance. Contrary to TVs of HCO3-, those of Cl-, NO3-, SO42-, F- and NH4+ were below the guideline values, confirming the influence of chemical weathering on the groundwater chemistry. Based on the present findings, further studies that take into account more inorganic substances are required for NBLs and TVs determination in the area, thereby setting up a robust sustainable management plan for the regional groundwater resources.

Visualization and quantification of carbon "rusty sink" by rice root iron plaque: Mechanisms, functions, and global implications.

Paddies contain 78% higher organic carbon (C) stocks than adjacent upland soils, and iron (Fe) plaque formation on rice roots is one of the mechanisms that traps C. The process sequence, extent and global relevance of this C stabilization mechanism under oxic/anoxic conditions remains unclear. We quantified and localized the contribution of Fe plaque to organic matter stabilization in a microoxic area (rice rhizosphere) and evaluated roles of this C trap for global C sequestration in paddy soils. Visualization and localization of pH by imaging with planar optodes, enzyme activities by zymography, and root exudation by 14 C imaging, as well as upscale modeling enabled linkage of three groups of rhizosphere processes that are responsible for C stabilization from the micro- (root) to the macro- (ecosystem) levels. The 14 C activity in soil (reflecting stabilization of rhizodeposits) with Fe2+ addition was 1.4-1.5 times higher than that in the control and phosphate addition soils. Perfect co-localization of the hotspots of ß-glucosidase activity (by zymography) with root exudation (14 C) showed that labile C and high enzyme activities were localized within Fe plaques. Fe2+ addition to soil and its microbial oxidation to Fe3+ by radial oxygen release from rice roots increased Fe plaque (Fe3+ ) formation by 1.7-2.5 times. The C amounts trapped by Fe plaque increased by 1.1 times after Fe2+ addition. Therefore, Fe plaque formed from amorphous and complex Fe (oxyhydr)oxides on the root surface act as a "rusty sink" for organic matter. Considering the area of coverage of paddy soils globally, upscaling by model revealed the radial oxygen loss from roots and bacterial Fe oxidation may trap up to 130 Mg C in Fe plaques per rice season. This represents an important annual surplus of new and stable C to the existing C pool under long-term rice cropping.

Augmenting atrazine and hexachlorobenzene degradation under different soil redox conditions in a bioelectrochemistry system and an analysis of the relevant microorganisms.

Soil microbial fuel cells (MFCs) are a sustainable technology that degrades organic pollutants while generating electricity. However, there have been no detailed studies of the mechanisms of pollutant degradation in soil MFCs. In this study, the effects of external resistance and electrode effectiveness on atrazine and hexachlorobenzene (HCB) degradation were evaluated, the performance of soil MFCs in the degradation of these pollutants under different soil redox conditions was assessed, and the associated microorganisms in the anode were investigated. With an external resistance of 20Ω, the degradation efficiencies of atrazine and HCB were 95% and 78%, respectively. The degradation efficiency, degradation rate increased with decreasing external resistance, while the half-life decreased. There were different degradation trends for different pollutants under different soil redox conditions. The fastest degradation rate of atrazine was in the upper MFC section (aerobic), whereas that of HCB was in the lower MFC section (anaerobic). The results showed that electrode effectiveness played a significant role in pollution degradation. In addition, the microbial community analysis demonstrated that Proteobacteria, especially Deltaproteobacteria involved in current generation was extremely abundant (27.49%) on soil MFC anodes, although the percentage abundances of atrazine degrading Rhodocyclaceae (8.77%), Desulfitobacterium (0.64%), and HCB degrading Desulfuromonas (0.73%), were considerably lower. The results of the study suggested that soil MFCs can enhance the degradation of atrazine and HCB, and bioelectrochemical reduction was the main mechanism for the pollutants degradation.

Denitrification potential in the subsurface environment in the Manawatu River catchment, New Zealand: Indications from oxidation-reduction conditions, hydrogeological factors, and implications for nutrient management.

A sound understanding of the effects of hydrogeological factors on loss, transport and transformation of farm nutrients is essential for predicting their impacts on ecosystem health of receiving waters. We assessed the potential of groundwater to attenuate nitrate through denitrification, and the distribution of this potential across the Tararua Groundwater Management Zone (GWMZ) in the Manawatu River catchment, New Zealand. We combined a number of methods in an unprecedented manner to confirm findings and obtain supporting evidence for the features that determine the subsurface denitrification characteristics. Our results showed that the denitrification characteristics of groundwater varied considerably in the Tararua GWMZ. The southern part of the Tararua GWMZ contained mainly oxic groundwater with low potential to denitrify, whereas the middle and northern parts of the Tararua GWMZ contained reduced groundwater with high denitrification potential. The hydrogeological features that influence denitrification potential in groundwater were identified as soil texture and drainage class, and the aquifer material or rock type. Low dissolved oxygen levels and nitrate concentrations were found in groundwater where the combinations of soil and rock types had poor drainage characteristics as opposed to higher concentrations in groundwater under well-drained soils and rocks (e.g. gravels). Intensive pastoral farming over well-drained soils and rocks showed high nitrate concentration in groundwater. This spatial variability in denitrification potential of groundwater offers a targeted management of nutrients runoff and leaching from pastoral lands to reduce their impacts on receiving surface waters.

Impact of hydroquinone used as a redox effector model on potential denitrification, microbial activity and redox condition of a cultivable soil.

In this microcosm study, we analyzed the effect produced by hydroquinone on the expression of soil biological denitrification, in relation to the redox state of the soil, both in terms of intensity factor (Eh') and capacity factor (amount of oxidized or reduced compounds). The supplementation of an Argiudoll soil with hydroquinone decreased the soil apparent reduction potential (Eh') and soil dehydrogenase activity (formazan production from tetrazolium chloride reduction; redox capacity factor), the relationship between both factors being highly significative, r=0.99 (p<0.001). The bacterial population (measured by colony forming units) increased, and the production of N2O was greater (p<0.001) at 200 and 400µg/g dry soil doses. Furthermore, there was an inverse relationship between soil dehydrogenase activity and the number of bacteria (r=-0.82; p<0.05), increased denitrification activity and changes in the CO2/N2O ratio value. These results suggest that hydroquinone at supplemented doses modified the soil redox state and the functional structure of the microbial population. Acetate supplementation on soil with hydroquinone, to ensure the availability of an energy source for microbial development, confirmed the tendency of the results obtained with the supplementation of hydroquinone alone. The differences observed at increased doses of hydroquinone might be explained by differences on the hydroquinone redox species between treatments.

Seagrass-mediated rhizosphere redox gradients are linked with ammonium accumulation driven by diazotrophs.

Seagrasses can enhance nutrient mobilization in their rhizosphere via complex interactions with sediment redox conditions and microbial populations. Yet, limited knowledge exists on how seagrass-derived rhizosphere dynamics affect nitrogen cycling. Using optode and gel-sampler-based chemical imaging, we show that radial O2 loss (ROL) from rhizomes and roots leads to the formation of redox gradients around below-ground tissues of seagrass (Zostera marina), which are co-localized with regions of high ammonium concentrations in the rhizosphere. Combining such chemical imaging with fine-scale sampling for microbial community and gene expression analyses indicated that multiple biogeochemical pathways and microbial players can lead to high ammonium concentration within the oxidized regions of the seagrass rhizosphere. Symbiotic N2-fixing bacteria (Bradyrhizobium) were particularly abundant and expressed the diazotroph functional marker gene nifH in Z. marina rhizosphere areas with high ammonium concentrations. Such an association between Z. marina and Bradyrhizobium can facilitate ammonium mobilization, the preferred nitrogen source for seagrasses, enhancing seagrass productivity within nitrogen-limited environments. ROL also caused strong gradients of sulfide at anoxic/oxic interfaces in rhizosphere areas, where we found enhanced nifH transcription by sulfate-reducing bacteria. Furthermore, we found a high abundance of methylotrophic and sulfide-oxidizing bacteria in rhizosphere areas, where O2 was released from seagrass rhizomes and roots. These bacteria could play a beneficial role for the plants in terms of their methane and sulfide oxidation, as well as their formation of growth factors and phytohormones. ROL from below-ground tissues of seagrass, thus, seems crucial for ammonium production in the rhizosphere via stimulation of multiple diazotrophic associations. IMPORTANCE: Seagrasses are important marine habitats providing several ecosystem services in coastal waters worldwide, such as enhancing marine biodiversity and mitigating climate change through efficient carbon sequestration. Notably, the fitness of seagrasses is affected by plant-microbe interactions. However, these microscale interactions are challenging to study and large knowledge gaps prevail. Our study shows that redox microgradients in the rhizosphere of seagrass select for a unique microbial community that can enhance the ammonium availability for seagrass. We provide first experimental evidence that Rhizobia, including the symbiotic N2-fixing bacteria Bradyrhizobium, can contribute to the bacterial ammonium production in the seagrass rhizosphere. The release of O2 from rhizomes and roots also caused gradients of sulfide in rhizosphere areas with enhanced nifH transcription by sulfate-reducing bacteria. O2 release from seagrass root systems thus seems crucial for ammonium production in the rhizosphere via stimulation of multiple diazotrophic associations.

Reconstructing a 300-year history of phosphorus cycle in west Chaohu Lake, China.

Anthropogenic activities could significantly increase nutrients loading, especially phosphorus (P), into aquatic systems, leading to eutrophication and disturbance of ecosystems. Detailed investigation of P cycling and its controlling factors in modern lakes could help understand mechanisms behind eutrophication, thus provide suggestions for future environmental management. Here, we investigate evolution history of P and iron (Fe) cycling over the last ∼300 years in west Chaohu Lake, a typical eutrophic lake in East China. The combination of 210Pb-137Cs dating and elemental analysis demonstrates drastic escalation of P input and organic carbon burial since 1960s, coincided with the rapid growth of human population near this region. P phase partitioning data indicate that Fe-bound P (PFe) is the predominant P pool of sediments in Chaohu Lake, which also regulates the evolving trend of reactive P (Preac). Moreover, the highest fraction of PFe is consistent with observations via P K-edge X-ray absorption near edge structure (P XANES). In addition, Fe speciation results show a principal contribution of Fe (hydr)oxides (Feox) and negligible presence of pyrite, suggesting a generally oxygenated depositional environment, where P could be preferentially sequestrated in sediments in association with Fe oxide minerals. Relatively high molar organic carbon/organic P (Corg/Porg) but low Corg/Preac ratios also support limited recycling of Preac in west Chaohu Lake. This study reveals that human activities play an important role in leading to the eutrophication of Chaohu Lake. Future environmental management could utilize the coupling of P and Fe oxides to remove P from water column.

Lateral redox variability in ca. 1.9 Ga marine environments indicated by organic carbon and nitrogen isotope compositions.

The stepwise oxygenation of Earth's surficial environment is thought to have shaped the evolutionary history of life. Microfossil records and molecular clocks suggest eukaryotes appeared during the Paleoproterozoic, perhaps shortly after the Great Oxidation Episode at ca. 2.43 Ga. The mildly oxygenated atmosphere and surface oceans likely contributed to the early evolution of eukaryotes. However, the principal trigger for the eukaryote appearance and a potential factor for their delayed expansion (i.e., intermediate ocean redox conditions until the Neoproterozoic) remain poorly understood, largely owing to a lack of constraints on marine and terrestrial nutrient cycling. Here, we analyzed redox-sensitive element contents and organic carbon and nitrogen isotope compositions of relatively low metamorphic-grade (greenschist facies) black shales preserved in the Flin Flon Belt of central Canada to examine open-marine redox conditions and biological activity around the ca. 1.9 Ga Flin Flon oceanic island arc. The black shale samples were collected from the Reed Lake area in the eastern part of the Flin Flon Belt, and the depositional site was likely distal from the Archean cratons. The black shales have low Al/Ti ratios and are slightly depleted in light rare-earth elements relative to the post-Archean average shale, which is consistent with a limited contribution from felsic igneous rocks in Archean upper continental crust. Redox conditions have likely varied between suboxic and euxinic at the depositional site of the studied section, as suggested by variable U/Al and Mo/Al ratios. Organic carbon and nitrogen isotope compositions of the black shales are approximately -23‰ and +13.7‰, respectively, and these values are systematically higher than those of broadly coeval continental margin deposits (approximately -30‰ for δ13Corg and +5‰ for δ15Nbulk). These elevated values are indicative of high productivity that led to enhanced denitrification (i.e., a high denitrification rate relative to nitrogen influx at the depositional site). Similar geochemical patterns have also been observed in the modern Peruvian oxygen minimum zone where dissolved nitrogen compounds are actively lost from the reservoir via denitrification and anammox, but the large nitrate reservoir of the deep ocean prevents exhaustion of the surface nitrate pool. Nitrogen must have been widely bioavailable in the ca. 1.9 Ga oceans, and its supply to upwelling zones must have supported habitable environments for eukaryotes, even in the middle of oceans around island arcs.

Modeling groundwater redox conditions at national scale through integration of sediment color and water chemistry in a machine learning framework.

Redox conditions play a crucial role in determining the fate of many contaminants in groundwater, impacting ecosystem services vital for both the aquatic environment and human water supply. Geospatial machine learning has previously successfully modelled large-scale redox conditions. This study is the first to consolidate the complementary information provided by sediment color and water chemistry to enhance our understanding of redox conditions in Denmark. In the first step, the depth to the first redox interface is modelled using sediment color from 27,042 boreholes. In the second step, the depth of the first redox interface is compared against water chemistry data at 22,198 wells to classify redox complexity. The absence of nitrate containing water below the first redox interface is referred to as continuous redox conditions. In contrast, discontinuous redox conditions are identified by the presence of nitrate below the first redox interface. Both models are built using 20 covariate maps, encompassing diverse hydrologically relevant information. The first redox interface is modelled with a mean error of 0.0 m and a root-mean-squared error of 8.0 m. The redox complexity model attains an accuracy of 69.8 %. Results indicate a mean depth to the first redox interface of 8.6 m and a standard deviation of 6.5 m. 60 % of Denmark is classified as discontinuous, indicating complex redox conditions, predominantly collocated in clay rich glacial landscapes. Both maps, i.e., first redox interface and redox complexity are largely driven by the water table and hydrogeology. The developed maps contribute to our understanding of subsurface redox processes, supporting national-scale land-use and water management.

Simultaneous natural attenuation of Cr(VI) and nitrate in the hyporheic zone sediments from an upstream tributary of the Jinsha River in the Sichuan Basin.

The coexistence of hexavalent chromium (Cr(VI)) and nitrate (NO3-) in groundwater and surface water presents a considerable challenge for the natural attenuation of these two contaminants because their interactions in nature remain contentious. This study investigated the interplay between Cr(VI) and NO3- in hyporheic zone (HZ) sediments by integrating Cr(VI) reduction kinetics, NO3- transformation, microbial community structure, and a three-rate model. The concurrent natural attenuation of Cr(VI) and NO3- in the sediments was significantly influenced by their initial concentrations and redox conditions. The reduction of low concentrations of Cr(VI) (37.1 and 96.2 µM) was slightly enhanced by NO3-, while inhibitory effects were observed at high concentrations of Cr(VI) (200.0 µM). However, except for an initial low concentration of Cr(VI) (37.1 µM) and NO3- (450 µM), the reduction of NO3- was adversely affected by Cr(VI). The reduction rates and efficiencies of Cr(VI) and NO3- were noticeably lower under aerobic conditions than under anaerobic conditions. This phenomenon can be attributed to the presence of O2, which decreased the selectivity of sediments-associated Fe(II) towards Cr(VI) and NO3- and induced alterations in the microbial community structure, leading to subsequent changes in NO3- transformation. Furthermore, the three-rate model represents a robust approach for elucidating the reduction of Cr(VI) in the presence of co-contaminants, such as NO3- contamination under diverse redox conditions. This study provides further insights into the interaction mechanism between Cr(VI) and NO3- within the HZ, necessitating the consideration of the microbial toxicity of Cr(VI) and electron competition among Cr(VI), NO3-, and O2.

Influence of redox condition and inoculum on micropollutant biodegradation by soil and activated sludge communities.

Micropollutant biodegradation is selected by the interplay among environmental conditions and microbial community composition. This study investigated how different electron acceptors, and different inocula with varying microbial diversity, pre-exposed to distinct redox conditions and micropollutants, affect micropollutant biodegradation. Four tested inocula comprised of agricultural soil (Soil), sediment from a ditch in an agricultural field (Ditch), activated sludge from a municipal WWTP (Mun AS), and activated sludge from an industrial WWTP (Ind AS). Removal of 16 micropollutants was investigated for each inoculum under aerobic, nitrate reducing, iron reducing, sulfate reducing, and methanogenic conditions. Micropollutant biodegradation was highest under aerobic conditions with removal of 12 micropollutants. Most micropollutants were biodegraded by Soil (n = 11) and Mun AS inocula (n = 10). A positive correlation was observed between inoculum community richness and the number of different micropollutants a microbial community initially degraded. The redox conditions to which a microbial community had been exposed appeared to positively affect micropollutant biodegradation performance more than pre-exposure to micropollutants. Additionally, depletion of the organic carbon present in the inocula resulted in lower micropollutant biodegradation and overall microbial activities, suggesting that i) an additional carbon source is needed to promote micropollutant biodegradation; and ii) overall microbial activity can be a good indirect indicator for micropollutant biodegradation activity. These results could help to develop novel micropollutant removal strategies.

Mobility of antimony in contrasting surface environments of a mine site: influence of redox conditions and microbial communities.

Microbial processes can influence the complex geochemical behaviour of the toxic metalloid antimony (Sb) in mining environments. The present study is aimed to evaluate the influence of microbial communities on the mobility of Sb from solid phases to water in different compartments and redox conditions of a mining site in southwest (SW) Spain. Samples of surface materials presenting high Sb concentrations, from two weathered mining waste dumps, and an aquatic sediment were incubated in slurries comparing oxic and anoxic conditions. The initial microbial communities of the three materials strongly differed. Incubations induced an increase of microbial biomass and an evolution of the microbial communities' structures and compositions, which diverged in different redox conditions. The presence of active bacteria always influenced the mobility of Sb, except in the neutral pH waste incubated in oxic conditions. The effect of active microbial activities in oxic conditions was dependent on the material: Sb oxic release was biologically amplified with the acidic waste, but attenuated with the sediment. Different bacterial genera involved in Sb, Fe and S oxidation or reduction were present and/or grew during incubation of each material. The results highlighted the wide diversity of microbial communities and metabolisms at the small geographic scale of a mining site and their strong implication in Sb mobility.

Cyanobacterial blooms increase the release of vanadium through iron reduction and dissolved organic matter complexation in the sediment of eutrophic lakes.

Vanadium (V), a hazardous environmental contaminant, can be highly toxic to aquatic or even human life. Nonetheless, knowledge of its redox geochemistry and mobility in sediments, especially those of eutrophic lakes, remains limited. In this study, we combined in situ high-resolution sampling and laboratory simulation experiments for monitoring soluble and labile V to reveal the mobilization mechanism of V in the sediment of Lake Taihu. The results showed that the concentration of soluble V (1.18-5.22 µg L-1) exceeded the long-term ecotoxicology limitation proposed by the government of the Netherlands. The highest value appeared in summer (July to September), with an average concentration of 3.87 µg L-1, which exceeded the short-term exposure limit. The remobilization of V in summer was caused by the combined effect of the reduction of Fe(hydr)oxides and dissolved organic matter (DOM) complexation, which accelerated the release of associated Fe-bound V and increased the solubility of DOM-V. Additionally, V showed high mobility in winter, owing to the species of V(Ⅲ)/V(Ⅳ) being oxidized to V(Ⅴ) with higher solubility. It is noteworthy that the elevated remobilization of V in sediments increases the risk of V release from sediments, which poses the threat of water V pollution in Lake Taihu.

Spatiotemporal characterization of vanadium at the sediment-water interface of a multi-ecological lake.

As an emerging environmentally harmful metal, vanadium (V) deserves significant research attention due to its hazardous concentrations in aquatic environments. However, the research on the characterization of V in sediment-water interface (SWI) remains limited. In this study, seasonal sampling was conducted in algal- and macrophyte-dominated zones via the method of in situ high-resolution diffusive gradients in thin films (DGT). The concentration of dissolved V in water in algal-dominated regions (12 sites) exceeded the long-term ecotoxicology limit of 1.2 µg⋅L-1. Seasonal variations of chemical speciation of V were observed in three ecological sites. DGT-labile V at the SWI exhibited two basic patterns associated with eutrophic status, one showing sharply decreasing gradients in the vicinity of the SWI and the other showing the absence of diffusion gradient. Positive correlations were observed between the water-dissolved V and the DGT-labile V, indicating DGT-labile V is a sensitive indicator for the release of V from sediment into water. Moreover, the mobility of V was influenced by the reduction of Fe(hydr)oxides and complexation with organic matter, in particular, during periods of algal blooms. It is suggested that V contamination at the SWI of algal-dominated zones deserves additional attention.