Novel insights into the kinetics and mechanism of arsenopyrite bio-dissolution enhanced by pyrite.

Arsenopyrite and pyrite often coexist in metal deposits and tailings, thus simultaneous bioleaching of both sulfides has economic (as well as environmental) significance. Important targets in bio-oxidation operations are high solubilization rates and minimized accumulation of Fe(III)/As-bearing secondary products. This study investigated the role of pyrite bioleaching in the enhancement of arsenopyrite dissolution. At a pyrite to arsenopyrite mass ratio of 1:1, 93.6% of As and 93.0% of Fe were solubilized. The results show that pyrite bio-oxidation can promote arsenopyrite dissolution, enhance S0 bio-oxidation, and inhibit the formation of jarosites, tooeleite, and amorphous ferric arsenate. The dry weight of the pyrite & arsenopyrite residue was reduced by 95.1% after bioleaching, compared to the initial load, while only 5% weight loss was observed when pyrite was absent. A biofilm was formed on the arsenopyrite surface in the presence of pyrite, while a dense passivation layer was observed in the absence of pyrite. As(III) (as As2O3) was a dominant As species in the pyrite & arsenopyrite residue. Novel and detailed findings are presented on arsenopyrite bio-dissolution in the presence of pyrite, and the presented approach could contribute to the development of novel cost-effective extractive bioprocesses. ENVIRONMENTAL IMPLICATION: The oxidation of arsenopyrite presents significant environmental hazards, as it can contribute to acid mine drainage generation and arsenic mobilization from sulfidic mine wastes. Bioleaching is a proven cost-effective and environmentally friendly extractive technology, which has been applied for decades in metal recovery from minerals or tailings. In this work, efficient extraction of arsenic from arsenopyrite bioleaching was presented through coupling the process with bio-oxidation of pyrite, resulting in lowered accumulation of hazardous and metastable Fe(III)/As-bearing secondary phases. The results could help improve current biomining operations and/or contribute to the development of novel cost-effective bioprocesses for metal extraction.

Nitrogen-doped titanium dioxide/schwertmannite nanocomposites as heterogeneous photo-Fenton catalysts with enhanced efficiency for the degradation of bisphenol A.

Potential health risks related to environmental endocrine disruptors (EEDs) have aroused research hotspots at the forefront of water treatment technologies. Herein, nitrogen-doped titanium dioxide/schwertmannite nanocomposites (N-TiO2/SCH) have been successfully developed as heterogeneous catalysts for the degradation of typical EEDs via photo-Fenton processes. Due to the sustainable Fe(III)/Fe(II) conversion induced by photoelectrons, as-prepared N-TiO2/SCH nanocomposites exhibit much enhanced efficiency for the degradation of bisphenol A (BPA; ca. 100% within 60 min under visible irradiation) in a wide pH range of 3.0-7.8, which is significantly higher than that of the pristine schwertmannite (ca. 74.5%) or N-TiO2 (ca. 10.8%). In this photo-Fenton system, the efficient degradation of BPA is mainly attributed to the oxidation by hydroxyl radical (•OH) and singlet oxygen (1O2). Moreover, the possible catalytic mechanisms and reaction pathway of BPA degradation are systematically investigated based on analytical and photoelectrochemical analyses. This work not only provides a feasible means for the development of novel heterogeneous photo-Fenton catalysts, but also lays a theoretical foundation for the potential application of mineral-based materials in wastewater treatment.

Debye Temperature Evaluation for Secondary Battery Cathode of α-SnxFe1-xOOH Nanoparticles Derived from the 57Fe- and 119Sn-Mössbauer Spectra.

Debye temperatures of α-SnxFe1-xOOH nanoparticles (x = 0, 0.05, 0.10, 0.15 and 0.20, abbreviated as Sn100x NPs) prepared by hydrothermal reaction were estimated with 57Fe- and 119Sn-Mössbauer spectra measured by varying the temperature from 20 to 300 K. Electrical properties were studied by solid-state impedance spectroscopy (SS-IS). Together, the charge-discharge capacity of Li- and Na-ion batteries containing Sn100x NPs as a cathode were evaluated. 57Fe-Mössbauer spectra of Sn10, Sn15, and Sn20 measured at 300 K showed only one doublet due to the superparamagnetic doublet, while the doublet decomposed into a sextet due to goethite at the temperature below 50 K for Sn 10, 200 K for Sn15, and 100 K for Sn20. These results suggest that Sn10, Sn15 and Sn20 had smaller particles than Sn0. On the other hand, 20 K 119Sn-Mössbauer spectra of Sn15 were composed of a paramagnetic doublet with an isomer shift (δ) of 0.24 mm s-1 and quadrupole splitting (∆) of 3.52 mm s-1. These values were larger than those of Sn10 (δ: 0.08 mm s-1, ∆: 0.00 mm s-1) and Sn20 (δ: 0.10 mm s-1, ∆: 0.00 mm s-1), suggesting that the SnIV-O chemical bond is shorter and the distortion of octahedral SnO6 is larger in Sn15 than in Sn10 and Sn20 due to the increase in the covalency and polarization of the SnIV-O chemical bond. Debye temperatures determined from 57Fe-Mössbauer spectra measured at the low temperature were 210 K, 228 K, and 250 K for Sn10, Sn15, and Sn20, while that of α-Fe2O3 was 324 K. Similarly, the Debye temperature of 199, 251, and 269 K for Sn10, Sn15, and Sn20 were estimated from the temperature-dependent 119Sn-Mössbauer spectra, which were significantly smaller than that of BaSnO3 (=658 K) and SnO2 (=382 K). These results suggest that Fe and Sn are a weakly bound lattice in goethite NPs with low crystallinity. Modification of NPs and addition of Sn has a positive effect, resulting in an increase in DC conductivity of almost 5 orders of magnitude, from a σDC value of 9.37 × 10-7 (Ω cm)-1 for pure goethite Sn (Sn0) up to DC plateau for samples containing 0.15 and 0.20 Sn (Sn15 and Sn20) with a DC value of ~4 × 10-7 (Ω cm)-1 @423 K. This non-linear conductivity pattern and levelling at a higher Sn content suggests that structural modifications have a notable impact on electron transport, which is primarily governed by the thermally activated via three-dimensional hopping of small polarons (SPH). Measurements of SIB performance, including the Sn100x cathode under a current density of 50 mA g-1, showed initial capacities of 81 and 85 mAh g-1 for Sn0 and Sn15, which were larger than the others. The large initial capacities were measured at a current density of 5 mA g-1 found at 170 and 182 mAh g-1 for Sn15 and Sn20, respectively. It is concluded that tin-goethite NPs are an excellent material for a secondary battery cathode and that Sn15 is the best cathode among the studied Sn100x NPs.

Machine learning-based soil quality assessment for enhancing environmental monitoring in iron ore mining-impacted ecosystems.

In November 2015, a catastrophic rupture of the Fundão dam in Mariana (Brazil), resulted in extensive socio-economic and environmental repercussions that persist to this day. In response, several reforestation programs were initiated to remediate the impacted regions. However, accurately assessing soil health in these areas is a complex endeavor. This study employs machine learning techniques to predict soil quality indicators that effectively differentiate between the stages of recovery in these areas. For this, a comprehensive set of soil parameters, encompassing 3 biological, 16 chemical, and 3 physical parameters, were evaluated for samples exposed to mining tailings and those unaffected, totaling 81 and 6 samples, respectively, which were evaluated over 2 years. The most robust model was the decision tree with a restriction of fewer levels to simplify the tree structure. In this model, Cation Exchange Capacity (CEC), Microbial Biomass Carbon (MBC), Base Saturation (BS), and Effective Cation Exchange Capacity (eCEC) emerged as the most pivotal factors influencing model fitting. This model achieved an accuracy score of 92% during training and 93% during testing for determining stages of recovery. The model developed in this study has the potential to revolutionize the monitoring efforts conducted by regulatory agencies in these regions. By reducing the number of parameters that necessitate evaluation, this enhanced efficiency promises to expedite recovery monitoring, simultaneously enhancing cost-effectiveness while upholding the analytical rigor of assessments.

Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes.

The presence of oxyanions, such as nitrate (NO3-) and phosphate (PO43-), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear. We used synchrotron scattering methods and cryogenic transmission electron microscopy to investigate the effects of NO3- outer-sphere complexes and PO43- inner-sphere complexes on the mechanism of Gt and Hm formation from Fh. Our TEM results indicated that Gt particles form through a two-step model in which Fh particles first transform to Gt nanoparticles and then crystallographically align and grow to larger particles by oriented attachment (OA). In contrast, for the formation of Hm, imaging shows that Fh particles first aggregate and then transform to Hm through interface nucleation. This is consistent with our X-ray scattering results, which demonstrate that NO3- outer-sphere and PO43- inner-sphere complexes promote the formation of Gt and Hm, respectively. These results have implications for understanding the coupled interactions of oxyanions and iron oxy-hydroxides in Earth-surface environments.

Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

Dual-functional heterogeneous Fenton catalyst Cu/Ti co-doped Fe3O4@FeOOH for cyanide-containing wastewater treatment: Preparation, performance and mechanism.

The dual-functional heterogeneous Fenton catalyst Cu/Ti co-doped iron-based Fenton catalyst (Cu/Ti -Fe3O4@FeOOH, FCT) were successfully prepared by precipitation oxidation method and characterized by XRD, XPS and XAFS. The prepared Cu/Ti co-doped Fe3O4@FeOOH nanoparticles consisted of goethite nanorods and magnetite rod octahedral particles, with Cu and Ti replacing Fe in the catalyst crystal structure, leading to the formation of the goethite structure. The heterogeneous Fenton catalyst FCT exhibited excellent degradation activity for cyanide in wastewater and showed different reaction mechanisms at varying pH levels. When treating 100 mL of 12 mg L-1 NaCN solution, complete degradation occurred within 40 min at 30 °C and pH ranging from 6.5 to 12.5 without external energy. Compared to Fe3O4, FCT shows superior degradation activity for cyanide. The surface Cu(Ⅰ) facilitated the electron transfer and significantly improved the catalytic activity of the catalyst. Additionally, the magnetic properties of the Ti-doped catalyst samples were greatly enhanced compared to the Cu@FeOOH catalyst doped with Cu, making them favorable for recycling and reuse. FCT maintains 100% degradation of cyanogen after three cycles, indicating its excellent stability. Furthermore, electron spin resonance spectroscopy, free radical quenching experiments and fluorescence probe techniques using terephthalic acid (TA) and benzoic acid (BA) confirmed that the presence of •OH and FeⅣ=O reactive species was responsible for the catalysts exhibiting different mechanisms at different pH conditions. Compared with other heterogeneous Fenton catalysts, FCT exhibits intentional degradation activity for cyanide-containing wastewater under different acid-base conditions, which greatly broadened the pH range of the heterogeneous Fenton reaction.

Extending beyond individual caves: a graph theory approach broadening conservation priorities in Amazon iron ore caves.

The Amazon is renowned worldwide for its biological significance, but it also harbors substantial mineral reserves. Among these, the ferruginous geosystems of the region are critical for iron ore extraction, accounting for 10% of Brazil's export revenue. Additionally, this region holds a significant speleological heritage with more than 1,000 caves. However, cave conservation efforts are often in conflict with land use, necessitating mediation through environmental regulations. While conservation decisions typically consider only the caves' characteristics, such an approach fails to account for the interactions among cave communities and their surrounding landscape. This poses a challenge to reserve design for cave conservation purposes. To address this issue, we assessed the predictors that influence the similarity among cave communities, suggesting the use of this parameter as a proxy for subterranean connectivity. Applying graph theory, we proposed a tool to aid in the selection of priority caves for conservation purposes. Our study involved the sampling of invertebrates in 69 iron ore caves and analyzing 28 environmental variables related to these subterranean habitats and adjacent landscape. Our analysis revealed that landscape and habitat characteristics are more important than geographical distance in determining patterns of similarity among caves. Our graph approach highlighted densely interconnected clusters based on similarity. However, specific caves stood out for harboring exclusive fauna and/or exhibiting habitat specificity, making them unique in the study area. Thus, we recommend prioritizing cave clusters for conservation, assembling both singular caves and others that influence them. It is crucial to note that protocols for the protection of subterranean biodiversity must consider measures that encompass both the caves and the surrounding landscape. Our methodology provides insights into the connectivity among caves, identifies existing groups, highlights singular (or unique) cavities that require preservation, and recognizes those influencing these unique habitats. This methodological advancement is crucial for the development of better conservation policies for the speleological heritage in areas under constant economic pressure.

Design of saccharide based organic binder for low-grade iron ore pelletization using atomistic simulations and machine learning methods.

Inorganic binders like bentonite, used for pelletization of low-grade iron ore, generate iron ore slimes with comparatively high silica and alumina content necessitating extra steps for their removal during iron making process. This demands the usage of organic binders as full or partial replacement of bentonite for iron ore pelletization. In this work, adsorption of organic binders with saccharides skeleton and -H, -OH, -CH2OH and -CH2CH2OH as polar substituents, on goethite surface was studied using density functional theory, molecular dynamics and machine learning. It was observed that adsorption energy of binders on goethite surface had weak dependence on number of hydrogen bonds between them. With this favorable interaction in mind, a library containing 64 organic binders was constructed and adsorption energy of 30 of these binders was computed using molecular dynamics, followed by training of a linear regression model, which was then used to predict the adsorption energy of rest of the binders in the library. It was found that the introduction of -CH2CH2OH at R2 position resulted in statistically significant higher adsorption energy. Binder34 and Binder44 were identified as viable candidates for both goethite and hematite ore pelletization and adsorption of their n-mers on goethite and hematite surfaces was also quantified.

Enhanced dewaterability of food waste digestate by biochar/potassium ferrate treatments: Performance and mechanisms.

The combined process of biochar (BC) and potassium ferrate (PF) offers a fascinating technique for efficient dewatering of digestate. However, the effects of BC/PF treatment on the dewaterability and mechanisms of FWD are still unknown. This study aimed to reveal the impact mechanisms of BC/PF treatment on digestate dewatering performance. Experimental results indicated that BC/PF treatment significantly enhanced the dewaterability of digestate, with the minimum specific resistance to filtration of (1.05 ± 0.02) × 1015 m·kg-1 and water content of 57.52 ± 0.51% being obtained at the concentrations of 0.018 g·g-1 total solid (TS) BC300 and 0.20 g·g-1 TS PF, which were 8.60% and 13.59% lower than PF treatment, respectively. BC/PF treatment proficiently reduced the fractal dimension, bound water content, apparent viscosity, and gel-like network structure strength of digestate, as well as increased the floc size and zeta potential of digestate. BC/PF treatment promoted the conversion of extracellular polymeric substances (EPS) fractions from inner EPS to soluble EPS, increased the fluorescence intensity of the dissolved compounds, and enhanced the hydrophobicity of proteins. Mechanisms investigations showed that BC/PF enhanced dewatering through non-reactive oxygen species pathways, i.e., via strong oxidative intermediate irons species Fe(V)/Fe(IV). BC/PF treatment enhanced the solubilization of nutrients, the inactivation of fecal coliforms, and the mitigation of heavy metal toxicity. The results suggested that BC/PF treatment is an effective digestate dewatering technology which can provide technological supports to the closed-loop treatment of FWD.

Photocatalytic degradation of fluoranthene in soil suspension by TiO2/α-FeOOH with enhanced charge transfer capacity.

Polycyclic aromatic hydrocarbons (PAHs) in soil are potentially harmful to human health. However, the use of photocatalysis technology to treat soil contaminated with PAHs remains challenging. Therefore, TiO2/α-FeOOH composite photocatalyst has been synthesized by hydrothermal method and sol-gel method and applied to photocatalytic degradation of fluoranthene in soil. The morphology, elements, crystal structure, optical properties, electrochemical characteristics, and photocatalytic activity of TiO2/α-FeOOH have been characterized. Results showed that TiO2 is tightly fixed on the surface of α-FeOOH, and TiO2/α-FeOOH had higher photocatalytic activity on photocatalytic degradation of fluoranthene in soil under simulated sunlight. The degradation efficiency of TiO2/α-FeOOH is 3.0 and 4.8 times higher than that of TiO2 and α-FeOOH, respectively. This is attributed to enhanced photocatalytic ability by enhancing the transfer capacity of electrons and holes and broadening the spectrum absorption range. The highest degradation efficiency was achieved when the pH of the soil is neutral, the ratio of water/soil is 10:1, and the dosage of catalyst is 50 mg/g. In addition, it was proved that •O2-, h+, and 1O2 are the main active substances in the photocatalysis of TiO2/α-FeOOH. The possible mechanism of a Z-type electron transfer structure was also proposed. The degradation products of fluoranthene were detected, and the degradation pathway was deduced.

Chemical Mineralization of AMD into Schwertmannite Fixing Iron and Sulfate Ions by Structure and Adsorption: Paving the Way for Enhanced Mineralization Capacity.

Abundant iron and sulfate resources are present in acid mine drainage. The synthesis of schwertmannite from AMD rich in iron and sulfate could achieve the dual objectives of resource recovery and wastewater purification. However, schwertmannite cannot emerge spontaneously due to the Gibbs free energy greater than 0. This results in the iron and sulfate in AMD only being able to use the energy generated by oxidation in the coupling reaction to promote the formation of minerals, but this only achieved partial mineralization, which limited the remediation of AMD through mineralization. In order to clarify the mechanism of iron and sulfate removal by the formation of schwertmannite in AMD, kinetic and thermodynamic parameters were crucial. This work used H2O2 oxidation of Fe2+ as a coupling reaction to promote the formation of schwertmannite from 64.4% of iron and 15.7% of sulfate in AMD, and determined that 99.7% of the iron and 89.9% of sulfate were immobilized in the schwertmannite structural, and only a small fraction was immobilized by the adsorption of schwertmannite, both of which were consistent with second-order kinetics models. The thermodynamic data suggested that reducing the concentration of excess sulfate ions or increasing the energy of the system may allow more iron and sulfate to be immobilized by forming schwertmannite. Experimental verification using the reaction of potassium bicarbonate with the acidity in solution to increase the energy in the system showed that the addition of potassium bicarbonate effectively promoted the formation of schwertmannite from Fe3+ and SO42-. It provided a theoretical and research basis for the direct synthesis of schwertmannite from Fe3+ and SO42- rich AMD for the removal of contaminants from water and the recovery of valuable resources.

Multi-level FeCo/N-doped carbon nanosheet for peroxymonosulfate oxidation and sterilization inactivation.

Magnetic carbon-based catalysts with environmental friendliness have exhibited prominent effects on advanced oxidation processes. Herein, a multi-level FeCo/N-doped carbon nanosheet (FeCo/CNS) was synthesized by facile impregnation iron-cobalt salt onto cotton and followed by confined pyrolysis. We identified excellent advantages of the modified FeCo/CNS materials: (i) The convenience of the synthesis method and (ii) The dual effect of sterilization and contaminant degradation achieved through the FeCo/CNS-activated Peroxymonosulfate (PMS). The comparative experimental showed that FeCo/CNS could provide favorable catalytic performance, completely removing bisphenol A (BPA) and tetracycline (TC) within 5 min. Moreover, the potent sterilization properties against Staphylococcus aureus and Escherichia coli were also verified. Analysis of the degradation pathway confirmed the existence of intermediates, and toxicological research demonstrated that the toxicity of the degradation intermediates of BPA gradually decreased over time. Our research provided an excellent application of FeCo/CNS in PMS oxidation and sterilization inactivation.

Prevalent occupational exposures and risk of lung cancer among women: Results from the application of the Canadian Job-Exposure Matrix (CANJEM) to a combined set of ten case-control studies.

BACKGROUND: Worldwide, lung cancer is the second leading cause of cancer death in women. The present study explored associations between occupational exposures that are prevalent among women, and lung cancer. METHODS: Data from 10 case-control studies of lung cancer from Europe, Canada, and New Zealand conducted between 1988 and 2008 were combined. Lifetime occupational history and information on nonoccupational factors including smoking were available for 3040 incident lung cancer cases and 4187 controls. We linked each reported job to the Canadian Job-Exposure Matrix (CANJEM), which provided estimates of probability, intensity, and frequency of exposure to each selected agent in each job. For this analysis, we selected 15 agents (cleaning agents, biocides, cotton dust, synthetic fibers, formaldehyde, cooking fumes, organic solvents, cellulose, polycyclic aromatic hydrocarbons from petroleum, ammonia, metallic dust, alkanes C18+, iron compounds, isopropanol, and calcium carbonate) that had lifetime exposure prevalence of at least 5% in the combined study population. For each agent, we estimated lung cancer risk in each study center for ever-exposure, by duration of exposure, and by cumulative exposure, using separate logistic regression models adjusted for smoking and other covariates. We then estimated the meta-odds ratios using random-effects meta-analysis. RESULTS AND CONCLUSIONS: None of the agents assessed showed consistent and compelling associations with lung cancer among women. The following agents showed elevated odds ratio in some analyses: metallic dust, iron compounds, isopropanol, and organic solvents. Future research into occupational lung cancer risk factors among women should prioritize these agents.

The role of plants in ironstone evolution: iron and aluminium cycling in the rhizosphere.

The Carajás plateaus in Brazil host endemic epilithic vegetation ("campo rupestre") on top of ironstone duricrusts, known as canga. This capping rock is primarily composed of iron(III) oxide minerals and forms a physically resistant horizon. Field observations reveal an intimate interaction between canga's surface and two native sedges (Rhynchospora barbata and Bulbostylis cangae). These observations suggest that certain plants contribute to the biogeochemical cycling of iron. Iron dissolution features at the root-rock interface were characterised using synchrotron-based techniques, Raman spectroscopy and scanning electron microscopy. These microscale characterisations indicate that iron is preferentially leached in the rhizosphere, enriching the comparatively insoluble aluminium around root channels. Oxalic acid and other exudates were detected in active root channels, signifying ligand-controlled iron oxide dissolution, likely driven by the plants' requirements for goethite-associated nutrients such as phosphorus. The excess iron not uptaken by the plant can reprecipitate in and around roots, line root channels and cement detrital fragments in the soil crust at the base of the plants. The reprecipitation of iron is significant as it provides a continuously forming cement, which makes canga horizons a 'self-healing' cover and contributes to them being the world's most stable continuously exposed land surfaces. Aluminium hydroxide precipitates ("gibbsite cutans") were also detected, coating some of the root cavities, often in alternating layers with goethite. This alternating pattern may correspond with oscillating oxygen concentrations in the rhizosphere. Microbial lineages known to contain iron-reducing bacteria were identified in the sedge rhizospheric microbiome and likely contribute to the reductive dissolution of iron(III) oxides within canga. Drying or percolation of oxygenated water to these anaerobic niches have led to iron mineralisation of biofilms, detected in many root channels. This study sheds light on plants' direct and indirect involvement in canga evolution, with possible implications for revegetation and surface restoration of iron mine sites.

Influence of iron (hydr)oxide mineralogy and contents in aquifer sediments on dissolved organic carbon attenuations during aquifer storage and recovery.

Aquifer storage and recovery (ASR) is a promising approach for managing water resources that enhances water quality through biogeochemical reactions occurring within aquifers. Iron (hydr)oxides, which are the predominant metallic oxides in soil, play a crucial role in degrading dissolved organic carbon (DOC), primarily through a process known as dissimilatory iron reduction (DIR). However, the efficiency of this reaction varies depending on the mineralogy and composition of the aquifer, and this understanding is essential for adequate water quality in ASR. The objective of this study is to investigate the impact of iron (hydr)oxide on acetate, as an organic carbon source, attenuation during the ASR. To achieve this, three sets of laboratory sediment columns were prepared, each containing a different type of iron (hydr)oxide minerals: ferrihydrite, goethite, and hematite. Following an acclimation period of 28 days to simulate the microcosm within an aquifer, the columns were continuously supplied with the simulated river water spiked with acetate (DOC 40-60 mg L-1), and the acetate concentration in the effluent was monitored. The result revealed that the column containing ferrihydrite achieved 97% acetate attenuation through DIR with anoxic conditions (DO < 0.1 mg L-1), while the goethite and hematite columns exhibited limited attenuation rates of 40 and 50%, respectively. Furthermore, the efficiency of acetate attenuation in the ferrihydrite columns increased with the content of ferrihydrite but experienced a rapidly declined at higher contents (3-4%), possibly due to the partial conversion of ferrihydrite to goethite as a result of the interaction between ferrihydrite and the Fe(II) produced during DIR. Additionally, an analysis of the microbial community demonstrated that microorganisms known to possess the ability to reduce iron (hydr)oxides under anaerobic conditions were abundant in the ferrihydrite columns.

Goethite adaptation prompts alterations in antibiotic susceptibility and suppresses development of antibiotic resistance in bacteria.

Understanding the impact of environmental factors on antibiotic sensitivity and the emergence of antibiotic resistance in microorganism is crucial for antibiotics management and environmental risk assessment. Natural materials, like mineral particles, are prevalent in aquatic and terrestrial ecosystems. However, it remains unclear how microorganism adapt to the physical stress of mineral particles and whether this adaptation influences antibiotic sensitivity and the evolution of antibiotic resistance. In this study, the model bacterium Escherichia coli (E. coli) was exposed to the mineral particle goethite for 30 generations. Adaptive morphogenesis, including an increase in the fraction of spherical bacteria, variations in bacterial mobility, a slightly increased cell membrane thickness, and genome-wide changes in the transcriptomic profile, were observed in adapted E. coli samples to counteract the stress. Moreover, the goethite adapted E. coli showed increased susceptibility to antibiotics including amoxicillin and tetracycline, and decreased susceptibility to kanamycin compared to its ancestral counterparts. These alterations in antibiotic susceptibility in the adapted E. coli were not heritable, as evidenced by the gradual recovery of antibiotic tolerance in cells with the cessation of goethite exposure. Transcriptomic data and a series of experiments suggested that these changes may be associated with variations in cell membrane property and iron metabolism. In addition, the evolution of antibiotic resistance in adapted cells occurred at a slower rate compared to their ancestral counterparts. For instance, E. coli adapted to goethite at a concentration of 1 mg/mL did not acquire antibiotic resistance even after 13 generations, probably due to its poor biofilm-formation capacity. Our findings underscore the occurrence of microbial adaptation to goethite, which influenced antibiotic sensitivity and decelerated the development of resistance in microorganisms. This insight contributes to our comprehension of the natural dynamics surrounding the evolution of antibiotic resistance and opens new perspectives for addressing this issue through nanotechnology-based approaches.

Enhanced Cr(VI) elimination from water by goethite-impregnated activated carbon coupled with weak electric field.

A weak electric field (WEF, 2 mA cm-2) was employed to promote Fe(III)/Fe(II) cycle on goethite-impregnated activated carbon (FeOOH@AC) filled in a continuous-flow column for enhanced Cr(VI) elimination from water. Surficial analysis and Cr species distribution showed that α-FeOOH of 0.2-1 µm was successfully synthesized and evenly loaded onto AC. Electron transfer from WEF to α-FeOOH was facilitated with AC as electron shuttles, thereby boosting Fe(III) reduction in the α-FeOOH. The generated Fe(II) reduced Cr(VI) and the resultant Cr(III) subsequently precipitated with OH- and Fe(III) to form Cr(OH)3 and (CrχFe1-χ)(OH)3. Therefore, the WEF-FeOOH@AC column exhibited a much lower Cr(VI) migration rate of 0.0018 cm PV-1 in comparison with 0.0037 cm PV-1 of the FeOOH@AC column, equal to 104 % higher Cr(VI) elimination capacity and 90 % longer column service life-span. Additionally, under different Cr(VI) loadings by varying either seepage velocities or influent Cr(VI) concentrations, the WEF-FeOOH@AC column maintained 1.0-1.5 folds higher Cr(VI) elimination and 0.9-1.4 folds longer longevity than those of the FeOOH@AC column owing to the interaction between FeOOH@AC and WEF. Our research demonstrated that WEF-FeOOH@AC was a potential method to promote Cr(VI) elimination from water and offer an effective strategy to facilitate Fe(III)/Fe(II) cycle in iron oxides.

Study on the removal of fulvic acid in water by potassium ferrate-enhanced iron-manganese co-oxide film and its mechanism.

The previous studies have shown that iron-manganese co-oxide film (MeOx) could simultaneously remove ammonium, manganese ion and bisphenol A. In this study, the removal of fulvic acid (FA) was explored by adding potassium ferrate (K2FeO4) to heighten the catalytic activity of MeOx. After adding about 3.0 mg/L potassium ferrate, the elimination efficiency of 7.0 mg/L FA by the MeOx increased from 20 to 50%. The effects of temperature and ammonium on the elimination of FA were investigated. Higher temperature (above 22 °C) and higher ammonium concentration (above 2.0 mg/L) caused a decrease in FA removal. Most of FA combined with the ferric hydroxide colloid produced by K2FeO4 in water to form macromolecular groups, and they were subsequently absorbed and covered on the surface of MeOx. Scanning electron microscope showed that more viscous flocs appeared on the surface of MeOx, and the film thickness became thicker. Electron energy-dispersive spectrometer analysis revealed a notable increased in the C-O element ratio and a significant decreased in the Mn-Fe element ratio on the surface of MeOx. From Fourier transform infrared spectroscopy, the content of transition metal carbonyl compounds increased in the surface of MeOx. XPS analysis confirmed that the presence of Fe3O4, FeO, Mn2O3 and Mn3O4 along with functional group substances of FA attached on the surface of MeOx. The removal mechanism of FA was studied.

Degradation of enoxacin with different dissociated species during the transformation of ferrihydrite-antibiotic coprecipitates.

Ferrihydrite acts as a natural reservoir for nutrient elements, organic matter, and coexisting pollutants through adsorption and coprecipitation. However, the degradation of emerging fluoroquinolone antibiotics during the transformation of ferrihydrite coprecipitates, especially those with various dissociated species, remains insufficiently explored. In this study, Enoxacin (ENO), employed as a model antibiotic, was introduced to prepare ferrihydrite-ENO coprecipitates. The influence of coprecipitated ENO on the transformation of the ferrihydrite-ENO coprecipitate was investigated across different pH conditions. The results revealed that ferrihydrite-ENO coprecipitates thermodynamically transformed into more stable goethite and/or hematite under all pH conditions. In neutral and alkaline conditions, ENO promoted the transformation of coprecipitates into goethite while hindering hematite formation. Conversely, under acidic conditions, ENO directly obstructed the transformation of coprecipitates into hematite. Different dissociated species of ENO displayed distinct degradation pathways. The cationic form of ENO exhibited a greater tendency for hydroxylation and defluorination, while the zwitterion form leaned toward piperazine ring oxidation, with limited preference for quinolone ring oxidation. The anionic form of ENO exhibited the fastest degradation rate. It is essential to emphasize that the toxicity of the degradation products was intricately connected to the specific reaction sites and the functional groups they acquired post-oxidation. These findings offer fresh insights into the role of antibiotics in coprecipitation, the transformation of ferrihydrite coprecipitates, and the fate of coexisting antibiotics.