Microbial communities and denitrification mechanisms of pyrite autotrophic denitrification coupled with three-dimensional biofilm electrode reactor.

Denitrification is of great significance for low C/N wastewater treatment. In this study, pyrite autotrophic denitrification (PAD) was coupled with a three-dimensional biofilm electrode reactor (BER) to enhance denitrification. The effect of current on denitrification was extensively studied. The nitrate removal of the PAD-BER increased by 14.90% and 74.64% compared to the BER and the PAD, respectively. In addition, the electron utilization, extracellular polymeric substances secretion, and denitrification enzyme activity (NaR and NiR) were enhanced in the PAD-BER. The microbial communities study displayed that Dokdonella, Hydrogenophaga, Nitrospira, and Terrimonas became the main genera for denitrification. Compared with the PAD and the BER, the abundance of the key denitrification genes narG, nirK, nirS, and nosZ were all boosted in the PAD-BER. This study indicated that the enhanced autotrophic denitrifiers and denitrification genes were responsible for the improved denitrification in the PAD-BER. PRACTITIONER POINTS: PAD-BER displayed higher nitrate removal, EPS, NAR, and NIR activity. The three types of denitrification (HD, HAD, and PAD) and their contribution percentage in the PAD-BER were analyzed. HAD was dominant among the three denitrification processes in PAD-BER. Microbial community composition and key denitrification genes were tested to reveal the denitrification mechanisms.

Calcined pyrite accelerates sulfur metabolic and electron transfer in driving targeted microbial fuel cell denitrification.

The sulfur powder as electron donor in driving dual-chamber microbial fuel cell denitrification (S) process has the advantages in economy and pollution-free to treat nitrate-contained groundwater. However, the low efficiency of electron utilization in sulfur oxidation (ACE) is the bottleneck to this method. In this study, the addition of calcined pyrite to the S system (SCP) accelerated electron generation and intra/extracellular transfer efficiency, thereby improving ACE and denitrification performance. The highest nitrate removal rate reached to 3.55 ± 0.01 mg N/L/h in SCP system, and the ACE was 103 % higher than that in S system. More importantly, calcined pyrite enhanced the enrichment of functional bacteria (Burkholderiales, Thiomonas and Sulfurovum) and functional genes which related to sulfur metabolism and electron transfer. This study was more effective in removing nitrate from groundwater without compromising the water quality.

Hydrology controls sulfuric acid-mediated weathering in an orogenic regime of southwestern Taiwan.

Chemical weathering is a pivotal geochemical process that shapes the carbon cycling and climates in the critical zone. Among its critical drivers, river discharge holds a particular significance, especially in the orogenic landscapes. Here, we examined the impact of discharge on mineral weathering in southwestern (SW) Taiwan by analyzing river water chemistry across a wide discharge range. Current observations indicated that carbonate contributes significantly to total weathering (50-80 %), with sulfuric acid accounting for one-half to two-thirds of carbonate weathering. A statistically strong correlation between river discharge and sulfuric acid-mediated carbonate weathering was highlighted, while the silicate weathering remained constant. This relationship suggests an increased influx of fresh minerals, such as pyrite, into the weathering regime as water flow increases. Our model identifies a critical discharge threshold of 4.6 m3 s-1, determining whether mineral weathering acts as a net source or sink of CO2. Consequently, mineral weathering in SW Taiwan acts as a net CO2 sink during dry periods but turns into a net source during wet periods. Through analyzing a decade of daily discharge data, we found mineral weathering in SW Taiwan is a net CO2 source, with a 2.6-fold increase in annual mean discharge causing a 3.8-fold increase in net CO2 flux. This pattern is likely to be applicable to other similar minerals containing mountain-building regions, highlighting the significant role of hydrology in determining weathering sources and their potential impact on the carbon cycle balance.

Overlooked pyrite-mediated heterogeneous Fenton processes: Mechanisms of surface hydroxyl radical generation and associated decontamination performance.

Pyrite-based Fenton-like processes have been extensively studied for wastewater decontamination; however, most relevant studies placed excessive emphasis on the homogeneous Fenton reaction mediated by aqueous Fe2+, resulting in the proposed technologies facing issues such as additional acid requirements for pH adjustment and excessive iron sludge production. Herein, through in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), custom dual-chamber reactor experiments, and a series of control experiments, significant hydroxyl radical generation was identified during the pyrite/H2O2 process, while the dominant reactive iron species was verified to the structural Fe sites on the pyrite surface, rather than structural Fe(II) in secondary iron minerals and surface adsorbed Fe2+. Consequently, even with significant suppression of the homogeneous Fenton pathway, the pyrite/H2O2 process exhibited significant degradation efficiency for sulfamethoxazole (SMX) at pH 4. Moreover, the pyrite/H2O2 process was found to selectively remove 50 µM of pollutants with high affinity for pyrite (bisphenol A, carbamazepine, nitrobenzene, and SMX), even in the presence of 50-100 mM methanol. Compared to the typical iron-based reductive catalyst (zero-valent iron, ZVI), pyrite mediated a Fenton process with greater potential for practical applications at pH 4, achieving a 43.75-fold reduction in iron sludge production and almost doubling the H2O2 utilization efficiency. Additionally, in contrast to ZVI, minimal iron oxide formed on the pyrite surface during the oxidation process. Thus, after seven cycles of degradation experiments, the decontamination efficiency of the pyrite/H2O2 process remained stable. These findings are crucial for understanding the complex environmental behavior of pyrite in both natural and engineering processes and provide a new perspective for the efficient utilization of pyrite resources as well.

The evolutionary arch of bioenergetics from prebiotic mechanisms to the emergence of a cellular respiratory chain.

This article proposes an evolutionary trajectory for the development of biological energy producing systems. Six main stages of energy producing system evolution are described, from early evolutionary pyrite-pulled mechanism through the Last Universal Common Ancestor (LUCA) to contemporary systems. We define the Last Pure Chemical Entity (LPCE) as the last completely non-enzymatic entity. LPCE could have had some life-like properties, but lacked genetic information carriers, thus showed greater instability and environmental dependence than LUCA. A double bubble model is proposed for compartmentalization and cellularization as a prerequisite to both highly efficient protein synthesis and transmembrane ion-gradient. The article finds that although LUCA predominantly functioned anaerobically, it was a non-exclusive anaerobe, and sulfur dominated metabolism preceded phosphate dominated one.

Highly efficient selective extraction of Li from spent LiNixCoyMnzO2 assisted with activated pyrite in a subcritical water system.

As the strategic importance of Li in the energy sector increases, selective Li extraction technology from spent lithium-ion batteries (LIBs) is attracting increasing attention. Current Li extraction processes typically suffer from lengthy procedures, high costs, and low efficiency. To improve the efficiency of Li extraction, a novel approach to achieve efficient Li recovery is proposed in this study, namely, reacting pyrite (FeS2) with LiNixCoyMnzO2 (NCM) powder in a subcritical water reduction (SWR) system. The reducing solvent environment created by the enhanced reaction of FeS2 with subcritical water converts the high-valent metals in NCM to a low-valent state, causing the collapse of the stable laminar structure and allowing Li+ to be released smoothly. After dual activation through mechanochemical and roasting processes, more than 99 % of Li is preferentially extracted under optimal conditions. Furthermore, Li+ in solution is converted into highly pure Li2CO3, while other metallic elements remain in the residue. Using inexpensive FeS2 for efficient Li extraction without adding additional chemical reagents is a promising approach for recovering spent LIBs.

An evaluation of pyrite as a component of respirable coal dust.

Over the past two decades, the rise in coal worker's pneumoconiosis has prompted research into the effects of respirable coal dust components. This study explores how coal-pyrites produce hydroxyl radicals (•OH), a reactive oxygen species closely associated with particle toxicity, and assesses the ability of safe chemical additives to reduce •OH production at various pH levels. Promising candidates were evaluated in various solutions, including tap and process waters and simulated lung fluid. We employed electrokinetic measurements, infrared and X-ray photoelectron spectroscopies, and ab initio atomistic simulations to analyze particle surfaces. The study also looked at how surface aging affects •OH production. Our results show that •OH generation of the pyrite varies and is catalyzed by elements like silicon, aluminum, and iron in pyrite. Carboxymethyl cellulose was effective in reducing •OH production by targeting surface sulfide and silicon sites and affecting surface hydration and charge. Atmospheric aging was found to increase •OH production, especially in the pyrite with high iron and silicon and low calcium contents, relative to other samples. This highlights the role of the pyrite surface properties and chemical composition, and the solution pH and composition in •OH generation by coal-pyrites.

Low-toxicity natural pyrite on electro-Fenton catalytic reaction in a wide pH range.

The resource utilization of natural pyrite not only reduces secondary pollution but also brings certain environmental benefits. However, the green and efficient use of pyrite presents certain challenges. In this study, a novel electro-Fenton (EF) system was constructed utilizing copper modified graphite felt (GF/Cu) as cathode and natural pyrite (com-FeS2) as catalyst. The results demonstrated that the system exhibited a remarkable stability over an extensive pH range (3.0-10.0) and remained effective even under adverse environmental conditions, such as high salinity or elevated antibiotic concentration. After optimizing the reaction conditions, 0.2 mM sulfamerazine (SMZ) was almost completely degraded within 1.5 h. The results highlighted the catalytic role of Fe(II) on the com-FeS2 surface. Combined with quenching experiments and quantitative analysis of reactive oxygen species (ROS), the removal of SMZ was primarily attributed to the generation of •OH, ordered by 1O2 > â€¢O2- > â€¢OHads, a possible degradation pathway was proposed by HR-LC-MS. The biological toxicity after the reaction was detected, and the introduction of polyvinylpyrrolidone (PVP) was beneficial to reduce the biological toxicity of iron dissolution. This work provides new insights into the green and efficient resource utilization of natural pyrite and significantly expands the pH applicability range of the Fenton process, demonstrating the large-scale industrial application potential of pyrite.

A Novel Fabrication of Hematite Nanoparticles via Recycling of Titanium Slag by Pyrite Reduction Technology.

An enormous quantity of titanium slag has caused not merely serious environment pollution, but also a huge waste of iron and sulfur resources. Hence, recycling iron and sulfur resources from titanium slag has recently been an urgent problem. Herein, hematite nanoparticles were fabricated through a pyrite reduction approach using as-received titanium slag as the iron source and pyrite as the reducing agent in an nitrogen atmosphere. The physicochemical properties of the hematite nanoparticles were analyzed using multiple techniques such as X-ray diffraction pattern, ultraviolet-visible spectrophotometry, and scanning electron microscopy. The best synthesis conditions for hematite nanoparticles were found at 550 °C for 30 min with the mass ratio of 14:1 for titanium slag and pyrite. The results demonstrated that hematite nanoparticles with an average particle diameter of 45 nm were nearly spherical in shape. The specific surface area, pore volume, and pore size estimated according to the BET method were 19.6 m2/g, 0.117 cm3/g, and 0.89 nm, respectively. Meanwhile, the fabricated hematite nanoparticles possessed weak ferromagnetic behavior and good absorbance in the wavelength range of 200 nm-600 nm, applied as a visible light responsive catalyst. Consequently, these results show that hematite nanoparticles formed by the pyrite reduction technique have a promising application prospect for magnetic material and photocatalysis.

Screening the Performance of a Reverse Osmosis Pilot-Scale Process That Treats Blended Feedwater Containing a Nanofiltration Concentrate and Brackish Groundwater.

A two-stage pilot plant study has been completed that evaluated the performance of a reverse osmosis (RO) membrane process for the treatment of feedwater that consisted of a blend of a nanofiltration (NF) concentrate and brackish groundwater. Membrane performance was assessed by monitoring the process operation, collecting water quality data, and documenting the blended feedwater's impact on fouling due to microbiological or organic means, plugging, and scaling, or their combination. Fluorescence and biological activity reaction tests were used to identify the types of organics and microorganisms present in the blended feedwater. Additionally, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were used to analyze suspended matter that collected on the surfaces of cartridge filters used in the pilot's pretreatment system. SEM and EDS were also used to evaluate solids collected on the surfaces of 0.45 µm silver filter pads after filtering known volumes of NF concentrate and RO feedwater blends. Water quality analyses confirmed that the blended feedwater contained little to no dissolved oxygen, and a significant amount of particulate matter was absent from the blended feedwater as defined by silt density index and turbidity measurements. However, water quality results suggested that the presence of sulfate, sulfide, iron, anaerobic bacteria, and humic acid organics likely contributed to the formation of pyrite observed on some of the membrane surfaces autopsied at the conclusion of pilot operations. It was determined that first-stage membrane productivity was impacted by the location of cartridge filter pretreatment; however, second-stage productivity was maintained with no observed flux decline during the entire pilot operation's timeline. Study results indicated that the operation of an RO process treating a blend of an NF concentrate and brackish groundwater could maintain a sustainable and productive operation that provided a practical minimum liquid discharge process operation for the NF concentrate, while the dilution of RO feedwater salinity would lower overall production costs.

Suppressing Surface Oxidation of Pyrite FeS2 by Cobalt Doping in Lithium Sulfur Batteries.

Lithium-sulfur batteries have emerged as a promising energy storage device due to ultra-high theoretical capacity, but the slow kinetics of sulfur and polysulfide shuttle hinder the batteries' further development. Here, the 10% cobalt-doped pyrite iron disulfide electrocatalyst deposited on acetylene black as a separator coating in lithium-sulfur batteries is reported. The adsorption rate to the intermediate Li2S6 is significantly improved while surface oxidation of FeS2 is inhibited: iron oxide and sulfate, thus avoiding FeS2 electrocatalyst deactivation. The electrocatalytic activity has been evaluated in terms of electronic resistivity, lithium-ion diffusion, liquid-liquid, and liquid-solid conversion kinetics. The coin batteries exhibit ultra-long cycle life at 1 C with an initial capacity of 854.7 mAh g-1 and maintained at 440.8 mAh g-1 after 920 cycles. Furthermore, the separator is applied to a laminated pouch battery with a sulfur mass of 326 mg (3.7 mg cm-2) and retained the capacity of 590 mAh g-1 at 0.1 C after 50 cycles. This work demonstrates that FeS2 electrocatalytic activity can be improved when Co-doped FeS2 suppresses surface oxidation and provides a reference for low-cost separator coating design in pouch batteries.

Pyrite-stimulated bio-reductive immobilization of perrhenate: Insights from integrated biotic and abiotic perspectives.

Microbes possessing electron transfer capabilities hold great promise for remediating subsurface contaminated by redox-active radionuclides such as technetium-99 (99TcO4-) through bio-transformation of soluble contaminants into their sparingly soluble forms. However, the practical application of this concept has been impeded due to the low electron transfer efficiency and long-term product stability under various biogeochemical conditions. Herein, we proposed and tested a pyrite-stimulated bio-immobilization strategy for immobilizing ReO4- (a nonradioactive analogue of 99TcO4-) using sulfate-reducing bacteria (SRB), with a focus on pure-cultured Desulfovibrio vulgaris. Pyrite acted as an effective stimulant for the bio-transformation of ReO4-, boosting the removal rate of ReO4- (50 mg/L) in a solution from 2.8 % (without pyrite) to 100 %. Moreover, the immobilized products showed almost no signs of remobilization during 168 days of monitoring. Dual lines of evidence were presented to elucidate the underlying mechanisms for the pyrite-enhanced bio-activity. Transcriptomic analysis revealed a global upregulation of genes associated with electron conductive cytochromes c network, extracellular tryptophan, and intracellular electron transfer units, leading to enhanced ReO4- bio-reduction. Spectroscopic analysis confirmed the long-term stability of the bio-immobilized products, wherein ReO4- is reduced to stable Re(IV) oxides and Re(IV) sulfides. This work provides a novel green strategy for remediation of radionuclides- or heavy metals-contaminated sites.

New insights into the controversy of reactive mineral-controlled arsenopyrite dissolution and arsenic release.

Serious arsenic (As) contaminations could commonly result from the oxidative dissolution of As-containing sulfide minerals, such as arsenopyrite (FeAsS). Pyrite (Py) and calcite (Cal) are two typically co-existing reactive minerals and represent different geological scenarios. Previous studies have shown that a high proportion of Py can generate a stronger galvanic effect and acid dissolution, thereby significantly promoting the release of arsenic. However, this conclusion overlooks calcite's antagonistic effect on the release of As in the natural environment. That antagonistic effect could remodel the linear relationship of pyrite on the oxidative dissolution of arsenopyrite, thus altering the environmental risk of As. We examined As release from arsenopyrite along a gradient of Py to Cal molar ratios (Py:Cal). The results showed that the lowest As release from arsenopyrite was surprisingly found in co-existing Py and Cal systems than in the singular Cal system, let alone in the singular Py system. This phenomenon indicated an interesting possibility of Py assistance to Cal inhibition of As release, though Py has always been regarded as a booster, also evidenced in this research, for As release from arsenopyrite. In singular systems of Py and Cal, As continued to be released for 60 days. However, in co-existing Py and Cal systems, As was released non-linearly in three stages over time: initial release (0-1 Day), immobilization (1-15 Days), and subsequent re-release (>15 Days). This is a new short-term natural attenuation stage for As, but over time, this stage gradually collapses. During the re-release stage (> 15 Days), a higher molar ratio of Py:Cal (increasing from 1:9 to 9:1) results in a lower rate constant k (mg·L-1·h-1) of As release (range from 0.0011 to 0.0002), and a higher abundance of secondary minerals formed (up to 26 mg/g goethite and hematite at Py: Cal=9:1). This demonstrates that increasing the Py:Cal molar ratio results in the formation of more secondary minerals which compensate for the higher potential antagonistic mechanisms generated by pyrites, such as acid dissolution and galvanic effect. These results explain the mechanisms of the high-risk characteristics of As both in acidic mine drainage and karst aquifers and discover the lowest risk in pyrite and calcite co-existing regions. Moreover, we emphasize that reactive minerals are important variables that can't be ignored in predicting As pollution in the future.

Synergistic promotion of antimony transformation in the interaction of Acidithiobacillus ferrooxidans and pyrite by driving the formation of reactive oxygen species and secondary minerals.

As one of the important microorganisms in the mining area, the role of iron-sulfur oxidizing microorganisms in antimony (element symbolized as Sb) migration and transformation in mining environments has been largely neglected for a long time. Therefore, the processes of the typical iron-sulfur oxidizing bacterium Acidithiobacillus ferrooxidans (A. ferrooxidans) and pyrite interaction coupled with the migration and transformation of Sb were investigated in this paper. The bio-oxidation process of pyrite by A. ferrooxidans not only accelerates the oxidation rate of Sb(III) to Sb(V) (62.93% of 10 mg L-1 within 4 h), but also promotes the adsorption and precipitation of Sb (32.89 % of 10 mg L-1 within 96 h), and changes in the dosage of minerals, Sb concentration, and pH value affect the conversion of Sb. The characterization results show that the interaction between A. ferrooxidans and pyrite produces a variety of reactive species, such as H2O2 and •OH, resulting in the oxidation of Sb(III). In addition, A. ferrooxidans mediates the formation of stereotyped iron-sulfur secondary minerals that can act as a major driver of Sb (especially Sb(V)) adsorption or co-precipitation. This study contributes to the further understanding of the diversified biogeochemical processes of iron-sulfur oxidizing bacteria-iron-sulfur minerals-toxic metals in mining environments and provides ideas for the development of in-situ treatment technologies for Sb.

Natural pyrite and ascorbic acid co-enhance periodate activation for inactivation of antibiotic resistant bacteria and inhibition of resistance genes transmission: A green disinfection process dominated by singlet oxygen.

The transmission of antibiotic resistance genes (ARGs) and the propagation of antibiotic resistant bacteria (ARB) threaten public health security and human health, and greener and more efficient disinfection technologies are expected to be discovered for wastewater treatment. In this study, natural pyrite and ascorbic acid (AA) were proposed as environmental-friendly activator and reductant for periodate (PI) activation to inactivate ARB. The disinfection treatment of PI/pyrite/AA system could inactivate 5.62 log ARB within 30 min, and the lower pH and higher PI and natural pyrite dosage could further boost the disinfection efficiency. The 1O2 and SO4•- were demonstrated to be crucial for the inactivation of ARB in PI/pyrite/AA system. The disinfection process destroyed the morphological structure of ARB, inducing oxidative stress and stimulating the antioxidant system. The PI/pyrite/AA system effectively reduced the intracellular and extracellular DNA concentration and ARGs abundance, inhibiting the propagation of ARGs. The presence of AA facilitated the activation of PI with natural pyrite and significantly increased the concentration of Fe2+ in solution. The reusability of natural pyrite, the safety of the disinfection by-products and the inhibition of ARB regeneration indicated the application potential of PI/pyrite/AA system in wastewater disinfection.

Superior nitrate and chromium reduction synergistically driven by multiple electron donors: Performance and the related biochemical mechanism.

Nitrate and Cr(VI) are the typical and prevalent co-contaminants in the groundwater, how to synchronously and effectively diminish them has received growing attention. The most problem that currently limits the nitrate and Cr(VI) reduction technology for groundwater remediation is with emphasis on exploring the optimal electron donors. This study investigated the feasibility of utilizing the synergistical effect of inorganic electron donors (pyrite, sulfur) and inherently limited organics to promote synchronous nitrate and Cr(VI) removal, which meets the requirement of naturally low-carbon and eco-friendly technologies. The NO3--N and Cr(VI) removal efficiencies in the pyrite and sulfur involved mixotrophic biofilter (PS-BF: approximately 90.8 ± 0.6% and 99.1 ± 2.1%) were substantially higher than that in a volcanic rock supported biofilter (V-BF: about 49.6% ± 2.8% and 50.0% ± 9.3%), which was consistent with the spatial variations of their concentrations. Abiotic and biotic batch tests directly confirmed the decisive role of pyrite and sulfur for NO3--N and Cr(VI) removal via chemical and microbial pathways. A server decline in sulfate production correlated with decreasing COD consumption revealed that there was sulfur disproportionation induced by limited organics. Metagenomic analysis suggested that chemoautotrophic microbes like Sulfuritalea and Thiobacillus were key players responsible for sulfur oxidation, nitrate and Cr(VI) reduction. The metabolic pathway analysis suggested that genes encoding functional enzymes related to complete denitrification, S oxidation, and dissimilatory sulfate reduction were upregulated, however, genes encoding Cr(VI) reduction enzymes (e.g. chrA, chrR, nemA, and azoR) were downregulated in PS-BF, which further explained the synergistical effect of multiple electron donors. These findings provide insights into their potential cooperative interaction of multiple electron donors on greatly promoting nitrate and Cr(VI) removal and have implications for the remediation technology of nitrate and Cr(VI) co-contaminated groundwater.

Tourmaline/pyrite dual mineral photocatalysis with a powerful surface electric field for efficient antibiotic removal.

Pyrite (FeS2) has garnered attention due to its narrow bandgap, high light absorption, and low cost. However, the rapid recombination of charge carriers hinders its practical application. Surface electric field is a unique characteristic of tourmaline, which can induce effective separation of photo generated electrons and holes. This study successfully combined two directly mined natural minerals, tourmaline and pyrite, to form TFS. Characterization and experiments show that the surface electric field of tourmaline can significantly enhance the photocatalytic activity of TFS. Tetracycline (TC, 50 ppm) was degraded by 95% with 60 min, and the TFS reaction rate constant reached 0.0439 min-1, which is 6.1 times and 17.3 times higher than that of tourmaline and FeS2. Additionally, it significantly improved light absorption and charge carrier separation capabilities. After simulating various natural environmental factors, TFS demonstrated practicality. Considered analysis of active substances and detection revealed that h+ and 1O2 radicals are significant contributors, and the photocatalytic mechanism was proposed. Furthermore, the transformation pathways and toxicity of metabolites were studied. This research offers further inspiration and insights for improving photocatalytic material performance and the green governance environment of natural resources.

Association of rare earth elements with secondary mineral phases formed during alkalinization of acid mine drainage.

Rare Earth Elements (REE) are present in acid mine drainage (AMD) in micromolar concentrations and AMD discharge may lead to an environmental risk. Alkaline Passive Treatment Systems (PTS) are often used to treat AMD and trap toxic trace elements. This study was set up to identify mechanisms by which REE are trapped in or on secondary phases formed in a PTS. Batch alkalinization experiments were performed to simulate PTS by sequentially increasing the pH of AMD collected from the Tharsis mining area inside the Iberian Pyrite Belt and synthetic AMD water samples via CaCO3 addition. The solids that precipitated up to pH ~4 and between pH 4-6 were collected and characterized by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in combination with Scanning Electron Microscope/Energy Dispersive X-ray spectroscopy (SEM/EDX) and synchrotron-based X-ray Absorption Spectroscopy (XAS) and synchrotron-based Micro-X-ray Fluorescence (µ-XRF). Results reveal that REE are mostly scavenged between pH 4-6 in association with Al and Fe phases, whereas a smaller fraction is scavenged at pH ~4 by association with gypsum. Synchrotron-based analysis evidences the incorporation of La3+ into the gypsum structure by substituting Ca2+, indicating a co-precipitation mechanism with gypsum occurring mainly at low pH. Results from parallel adsorption and co-precipitation tests suggest that the REE scavenging between pH 4-6 could be due to a combination of adsorption and co-precipitation on Al(OH)3 and ferrihydrite. This implies that in PTS, REE would be mainly found in Al- (and Fe-) oxyhydroxides occurring in deeper layers of the PTS, i.e., where higher pH-values occur, though a small fraction, especially the light REE, could also be found incorporated into gypsum in the upper layers.

Evidence for autotrophic growth of purple sulfur bacteria using pyrite as electron and sulfur source.

Purple sulfur bacteria (PSB) are capable of anoxygenic photosynthesis via oxidizing reduced sulfur compounds and are considered key drivers of the sulfur cycle in a range of anoxic environments. In this study, we show that Allochromatium vinosum (a PSB species) is capable of autotrophic growth using pyrite as the electron and sulfur source. Comparative growth profile, substrate characterization, and transcriptomic sequencing data provided valuable insight into the molecular mechanisms underlying the bacterial utilization of pyrite and autotrophic growth. Specifically, the pyrite-supported cell cultures ("py"') demonstrated robust but much slower growth rates and distinct patterns from their sodium sulfide-amended positive controls. Up to ~200-fold upregulation of genes encoding various c- and b-type cytochromes was observed in "py," pointing to the high relevance of these molecules in scavenging and relaying electrons from pyrite to cytoplasmic metabolisms. Conversely, extensive downregulation of genes related to LH and RC complex components indicates that the electron source may have direct control over the bacterial cells' photosynthetic activity. In terms of sulfur metabolism, genes encoding periplasmic or membrane-bound proteins (e.g., FccAB and SoxYZ) were largely upregulated, whereas those encoding cytoplasmic proteins (e.g., Dsr and Apr groups) are extensively suppressed. Other notable differentially expressed genes are related to flagella/fimbriae/pilin(+), metal efflux(+), ferrienterochelin(-), and [NiFe] hydrogenases(+). Characterization of the biologically reacted pyrite indicates the presence of polymeric sulfur. These results have, for the first time, put the interplay of PSB and transition metal sulfide chemistry under the spotlight, with the potential to advance multiple fields, including metal and sulfur biogeochemistry, bacterial extracellular electron transfer, and artificial photosynthesis. IMPORTANCE: Microbial utilization of solid-phase substrates constitutes a critical area of focus in environmental microbiology, offering valuable insights into microbial metabolic processes and adaptability. Recent advancements in this field have profoundly deepened our knowledge of microbial physiology pertinent to these scenarios and spurred innovations in biosynthesis and energy production. Furthermore, research into interactions between microbes and solid-phase substrates has directly linked microbial activities to the surrounding mineralogical environments, thereby enhancing our understanding of the relevant biogeochemical cycles. Our study represents a significant step forward in this field by demonstrating, for the first time, the autotrophic growth of purple sulfur bacteria using insoluble pyrite (FeS2) as both the electron and sulfur source. The presented comparative growth profiles, substrate characterizations, and transcriptomic sequencing data shed light on the relationships between electron donor types, photosynthetic reaction center activities, and potential extracellular electron transfer in these organisms capable of anoxygenic photosynthesis. Furthermore, the findings of our study may provide new insights into early-Earth biogeochemical evolutions, offering valuable constraints for understanding the environmental conditions and microbial processes that shaped our planet's history.

Advanced Monitoring of H2S Injection through the Coupling of Reactive Transport Models and Geophysical Responses.

Hydrogen sulfide (H2S), an environmentally harmful pollutant, is a byproduct of geothermal energy production. To reduce the H2S emissions, H2S-charged water is injected into the basaltic subsurface, where it mineralizes to iron sulfides. Here, we couple geophysical induced polarization (IP) measurements in H2S injection wells and geochemical reactive transport models (RTM) to monitor the H2S storage efforts in the subsurface of Nesjavellir, one of Iceland's most productive geothermal fields. An increase in the IP response after 40 days of injection indicates iron-sulfide formation near the injection well. Likewise, the RTM shows that iron sulfides readily form at circumneutral to alkaline pH conditions, and the iron supply from basalt dissolution limits its formation. Agreement in the trends of the magnitude and distribution of iron-sulfide formation between IP and RTM suggests that coupling the methods can improve the monitoring of H2S mineralization by providing insight into the parameters influencing iron-sulfide formation. In particular, accurate fluid flow parameters in RTMs are critical to validate the predictions of the spatial distribution of subsurface iron-sulfide formation over time obtained through IP observations. This work establishes a foundation for expanding H2S sequestration monitoring efforts and a framework for coupling geophysical and geochemical site evaluations in environmental studies.