Critical role of multiple antibiotics on the denitrification rate in groundwater: Field investigative proof.

The impact of antibiotics on denitrification has emerged as a significant topic; however, there is a dearth of mechanistic understanding regarding the effects of multiple antibiotics at the ng/L level on denitrification in groundwater. This study conducted five field samplings between March 2019 and July 2021 at two representative monitoring wells. The investigation utilized metagenomic sequencing to unveil the antibiotic mechanisms influencing denitrification. Results revealed the detection of 16 out of 64 antibiotics, with a maximum detection frequency and total concentration of 100 % and 187 ng/L, respectively. Additionally, both nitrate and total antibiotic concentrations exhibited a gradual decrease along the groundwater flow direction. Metagenomic evidence indicated that denitrification served as the dominant biogeochemical process controlling nitrate attenuation in groundwater. However, the denitrification capacity experienced significant inhibition in the presence of multiple antibiotics at the ng/L level. This inhibition was attributed to decreases in the relative abundance of dominant denitrifying bacteria (Candidatus_Scalindua, Herminiimonas and unclassified_p_Planctomycetes) and denitrifying functional genes (narGH, nirKS and norB), signifying the pressure exerted by antibiotics on denitrifying bacteria. The variation in antibiotic concentration (∆Cantibiotics) indicated a change in antibiotic pressure on denitrifying bacteria. A larger ∆Cantibiotics corresponded to a greater rebound in the relative abundance of denitrifying functional genes, resulting in a faster denitrification rate (Kdenitrification). Field observations further demonstrated a positive correlation between Kdenitrification and ∆Cantibiotics. Comparatively, a higher Kdenitrification observed at higher ∆Cantibiotics was primarily due to the enrichment of more nondominant denitrifying bacteria carrying key denitrifying functional genes. In conclusion, this study underscores that multiple antibiotics at the ng/L level in groundwater inhibited denitrification, and the degree of inhibition was closely related to ∆Cantibiotics.

Mechanism of Cr(VI) removal by efficient Cr(VI)-resistant Bacillus mobilis CR3.

Cr(VI) is a hazardous environmental pollutant that poses significant risks to ecosystems and human health. We successfully isolated a novel strain of Bacillus mobilis, strain CR3, from Cr(VI)-contaminated soil. Strain CR3 showed 86.70% removal capacity at 200 mg/L Cr(VI), and a good Cr(VI) removal capacity at different pH, temperature, coexisting ions, and electron donor conditions. Different concentrations of Cr(VI) affected the activity of CR3 cells and the removal rate of Cr(VI), and approximately 3.46% of total Cr was immobilized at the end of the reaction. The combination of SEM-EDS and TEM-EDS analysis showed that Cr accumulated both on the cell surface and inside the cells after treatment with Cr(VI). XPS analysis showed that both Cr(III) and Cr(VI) were present on the cell surface, and FTIR results indicated that the presence of Cr on the cell surface was mainly related to functional groups, such as O-H, phosphate, and -COOH. The removal of Cr(VI) was mainly achieved through bioreduction, which primarily occurred outside the cell. Metabolomics analysis revealed the upregulation of five metabolites, including phenol and L-carnosine, was closely associated with Cr(VI) reduction, heavy metal chelation, and detoxification mechanisms. In addition, numerous metabolites were linked to cellular homeostasis exhibited differential expression. Cr(VI) exerted inhibitory effects on the division rate and influenced critical pathways, including energy metabolism, nucleotide metabolism, and amino acid synthesis and catabolism. These findings reveal the molecular mechanism of Cr(VI) removal by strain CR3 and provide valuable insights to guide the remediation of Cr(VI)-contaminated sites.

Exploring the mechanism of enhanced Cr(VI) removal by Lysinibacillus cavernae microcapsules loaded with synthetic nano-hydroxyapatite.

In this study, nano-scale hydroxyapatite (HAP) powder was successfully synthesized from waste eggshells and combined with Lysinibacillus cavernae CR-2 to form bio-microcapsules, which facilitated the enhanced removal of Cr(VI) from wastewater. The effects of various parameters, such as bio-microcapsule dosage, HAP dosage, and initial Cr(VI) concentration on Cr(VI) removal, were investigated. Under different treatment conditions, the Cr(VI) removal followed the order of LC@HAP (90.95%) > LC (78.15%) > Free-LC (75.61%) > HAP (6.56%) > NM (0.23%) at the Cr(VI) initial concentration of 50 mg L-1. Relative to other reaction systems, the LC@HAP treatment exhibited a considerable decrease in total Cr content in the solution, with removal rates surpassing 70%. Additionally, the bio-microcapsules maintained significant biological activity after reacting with Cr(VI). Further characterization using SEM, FTIR, XPS, and XRD revealed that the Cr(VI) removal mechanisms by bio-microcapsules primarily involved biological reduction and HAP adsorption. The adsorption of Cr(III) by HAP predominantly occurred through electrostatic interactions and surface complexation, accompanied by an ion exchange process between Cr(III) and Ca(II). Hence, bio-microcapsules, created by combining L. cavernae with HAP, represent a promising emerging material for the enhanced removal of Cr(VI) pollutants from wastewater.

Effect of amino acids on biomineralization of lead ions by Aspergillus niger.

This study investigates the biomineralization of lead ions by Aspergillus niger from aqueous environments, focusing on the dynamic effects of fungal metabolism and biological components. Three biomolecules (glutamate, methionine, and lysine) were used to induce lead oxalate mineralization under lead stress. Comparative experiments were conducted to analyze the growth characteristics and Pb (II) removal ability of A. niger, as well as the morphological and structural properties of the resulting lead oxalate minerals using inductively coupled plasma atomic emission spectroscopy, X-ray powder diffraction, and scanning electron microscopy-energy dispersive spectroscopy techniques. The findings reveal that A. niger plays a crucial role in controlling the mineralization process of Pb (II), with biomineralization experiments demonstrating the specific morphogenesis of lead oxalate over time. Additionally, the inclusion of the three biomolecules in the system indirectly influenced the rate of Pb (II) removal and mineral morphology. These results contribute to a better understanding of A. niger-mediated biomineralization process of lead oxalate and suggest its potential application in the removal of Pb (II) from aqueous environments, particularly in combination with amino acids for enhanced immobilization and mineral recovery. PRACTITIONER POINTS: Fungal activity and amino acids play a crucial role in shaping lead oxalate crystals during water treatment processes. Specific amino acids can effectively delay lead oxalate recrystallization, enhancing the stability and removal efficiency of the crystals. Biomineralization mediated by fungi offers a promising and eco-friendly approach for lead removal and recovery in wastewater treatment. Exploring the influence of organic additives and fungal metabolism on crystal growth provides valuable insights for developing efficient remediation strategies. Further research on the utilization of fungi and amino acids can help with innovative and sustainable wastewater treatment technologies.

Electron transfer rules of minerals under pressure informed by machine learning.

Electron transfer is the most elementary process in nature, but the existing electron transfer rules are seldom applied to high-pressure situations, such as in the deep Earth. Here we show a deep learning model to obtain the electronegativity of 96 elements under arbitrary pressure, and a regressed unified formula to quantify its relationship with pressure and electronic configuration. The relative work function of minerals is further predicted by electronegativity, presenting a decreasing trend with pressure because of pressure-induced electron delocalization. Using the work function as the case study of electronegativity, it reveals that the driving force behind directional electron transfer results from the enlarged work function difference between compounds with pressure. This well explains the deep high-conductivity anomalies, and helps discover the redox reactivity between widespread Fe(II)-bearing minerals and water during ongoing subduction. Our results give an insight into the fundamental physicochemical properties of elements and their compounds under pressure.

Mineral weathering is linked to microbial priming in the critical zone.

Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phenomenon known as the 'priming effect'. Despite its global importance, the relationship of the priming effect to mineral weathering and nutrient release remains unclear. Here we show close linkages between mineral weathering in the critical zone and primed decomposition of SOM. Intensified mineral weathering and rock-derived nutrient release are generally coupled with primed SOM decomposition resulting from "triggered" microbial activity. Fluxes of organic matter products decomposed via priming are linearly correlated with weathering congruency. Weathering congruency influences the formation of organo-mineral associations, thereby modulating the accessibility of organic matter to microbial decomposers and, thus, the priming effect. Our study links weathering with primed SOM decomposition, which plays a key role in controlling soil C dynamics in space and time. These connections represent fundamental links between long-term lithogenic element cycling (= weathering) and rapid turnover of carbon and nutrients (= priming) in soil.

Microbial remediation mechanisms and applications for lead-contaminated environments.

High concentrations of lead (Pb) in agricultural soil and wastewater represent a severe threat to the ecosystem and health of living organisms. Among available removal techniques, microbial remediation has attracted much attention due to its lower cost, higher efficiency, and less impact on the environment; hence, it is an effective alternative to conventional physical or chemical Pb-remediation technologies. In the present review, recent advances on the Pb-remediation mechanisms of bacteria, fungi and microalgae have been reported, as well as their detoxification pathways. Based on the previous researches, microorganisms have various remediation mechanisms to cope with Pb pollution, which are basically categorized into biosorption, bioprecipitation, biomineralization, and bioaccumulations. This paper summarizes microbial Pb-remediation mechanisms, factors affecting Pb removal, and examples of each case are described in detail. We emphatically discuss the mechanisms of microbial immobilization of Pb, which can resist toxicity by synthesizing nanoparticles to convert dissolved Pb(II) into less toxic forms. The tolerance mechanisms of microbes to Pb are discussed at the molecular level as well. Finally, we conclude the research challenges and development prospects regarding the microbial remediation of Pb-polluted environment. The current review provides insight of interaction between lead and microbes and their potential applications for Pb removal.

Reduction, mineralization, and magnetic removal of chromium from soil by using a natural mineral composite.

Reductive immobilization has been a commonly used technique to detoxify Cr(VI) from soil; however, it's challenging to remove the reduced Cr from soil to prevent its re-oxidation. This work explored a natural magnetic composite for the remediation, mineralization, and magnetic removal of Cr(VI) from the soil. It consists of 77% magnetite and 23% pyrrhotite with strong magnetic properties. A series of characterization tests show that composites of magnetite and pyrrhotite are interlaced and closely bonded, and contain no other heavy metals. The Cr(VI) removal rate increases with the decrease in composite particle size. A kinetics study shows that removing Cr(VI) by the composite is likely through both adsorption and reduction. Acidic conditions are more favorable for the immobilization of Cr(VI), at 45.8 mg Cr(VI) removal per g of composite at pH 2. After 100 days of in-situ treatment by the composite, the leaching concentration (TCLP) of Cr(VI)-contaminated soil was 1.95 mg L-1, which was below the EPA limit (5 mg L-1) for hazardous waste. After reduction, the composite was separated from soil by magnetic characteristics, and 58.2% of Cr was found mineralized. The post-treatment Cr-containing composite was analyzed by SEM-EDS, Raman spectra, and XPS. It was found that Cr was mineralized on the surface of the composite in the form of Cr(OH)3, Cr2O3, and FeCr2O4. This indicates that reduction and mineralization of Cr(VI) in the soil can be accomplished through natural magnetic mineral composites and easily separated and removed from the soil, achieving a complete soil cleanup.

Efficient immobilization behavior and mechanism investigation of Pb(II) by Aspergillus tubingensis.

OBJECTIVES: To understand the mechanism of Pb(II) immobilized by Pb(II)-tolerant microbes. RESULTS: Aspergillus tubingensis isolated from the lead-zine mine was investigated through surface morphology observation and multiple experimental analysis in order to elucidate the Pb(II) biosorption and immobilization behavior. The maximum Pb(II) uptake capacity of A. tubingensis was about 828.8 mg L-1. Fourier transform-infrared spectra and environmental scanning electron microscope indicated that a large number of functional groups (carboxyl, phosphoryl and sulfydryl, etc.) participated in Pb(II) binding on the cell surface. Raman and X-ray diffraction, field emission high-resolution transmission electron microscopy and X-ray absorption fine structure investigation revealed that the Pb(II) loaded on the surface of the fungus could be transformed into PbCO3 and PbS nanocrystals. Meanwhile, Pb(II) transported into the cell would be oxidized to form lead oxide minerals (Pb2O3.333) over time. CONCLUSIONS: This study has important implications for an in-depth understanding of Pb(II) removal by A. tubingensis and provides guidance for remediating lead-polluted environment using microorganisms.

Effect of Photoreduction of Semiconducting Iron Mineral-Goethite on Microbial Community in the Marine Euphotic Zone.

Marine euphotic zone is the pivotal region for interplay of light-mineral-microorganism and elements cycle, in which semiconducting minerals exist widely and iron-bearing goethite is a typical and widespread one. In this work, we have conducted in-depth researches on the effect of ferrous [Fe(II)] ions dissolved by photoreduction of goethite on microbial community structure and diversity. The mineral phase, structure and morphology of synthesized goethite were characterized by Raman, X-ray diffraction (XRD), energy disperse spectroscopy (EDS), environmental scanning electron microscope (ESEM), and atomic force microscope (AFM). Photoelectrochemical measurements tested photoelectric response and redox activity of goethite, having proved its significant property of photoelectric response with 44.11% increment of the average photocurrent density relative to the dark current density. The photoreduction experiments of goethite were conducted under light condition in simulated seawater. It has suggested the photoreduction of goethite could occur and Fe(III) was reduced to Fe(II). The dissolved Fe(II) from the photoreduction of goethite under light condition was nearly 11 times than that group without light after a 10-day reaction. Furthermore, results of microbial community sequencing analysis indicated that dissolved Fe(II) could affect the structure and regulate the decrease of microbial community diversity. The emergence of dominant bacteria associated with iron oxidation and transport protein has suggested their obvious selectivity and adaptability in the environment with adding dissolved Fe(II). This work revealed the photoreduction process of semiconducting goethite was remarkable, giving rise to a non-negligible dissolved Fe(II) and its selective effect on the structure, diversity, as well as the function of microbial community. This light-induced interaction between minerals and microorganisms may also further regulate correlative metabolic pathways of carbon cycle in the marine euphotic zone.

An Overlooked Natural Hydrogen Evolution Pathway: Ni2+ Boosting H2 O Reduction by Fe(OH)2 Oxidation during Low-Temperature Serpentinization.

Natural hydrogen (H2 ) has gained considerable attentions as a renewable energy resource to mitigate the globally increasing environmental concerns. Low-temperature serpentinization (<200 °C) as a typical water-rock reaction is a major source of the natural H2 . However, the reaction mechanism and the controlling step to product H2 remained unclear, which hinders the further utilization of natural H2 . Herein, we demonstrated that the H2 production rate could be determined by the Fe(OH)2 oxidation during low-temperature serpentinization. Moreover, the co-existence of Ni2+ could largely enhance the H2 production kinetics. With the addition of only 1 % Ni2+ , the H2 production rate was remarkably enhanced by about two orders of magnitude at 90 °C. D2 O isotopic experiment and theoretical calculations revealed that the enhanced H2 production kinetics could be attributed to the catalytic role of Ni2+ to promote the reduction of H2 O.

Enhanced mechanism of extracellular electron transfer between semiconducting minerals anatase and Pseudomonas aeruginosa PAO1 in euphotic zone.

Focusing the marine euphotic zone, which is the pivotal region for interaction of solar light-mineral-microorganism and the elements cycle, we have conducted the research on the mechanism of semiconducting minerals promoting extracellular electron transfer with microorganisms in depth. Therein, anatase which is one of the most representative semiconducting minerals in marine euphotic zone was selected. The mineralogical characterization of anatase was identified by ESEM, AFM, EDS, Raman, XRD, and its semiconducting characteristics was determined by UV-Vis and Mott-Schottky plots. Determined by the electrochemical measurement of I-t curves, the photocurrent density of anatase was more prominent than dark current density. Pseudomonas aeruginosa PAO1 was widely distributed in the euphotic zone, and its mutants of operons deficient in biosynthesis pyocyanin (Δphz1Δphz2) and pili deficient (ΔpilA) were employed in this study. I-t curves indicated that both direct and indirect extracellular electron transfer processes occurred between anatase and PAO1. The indirect electron transfer depending on pyocyanin secreted by PAO1 was the main electron transfer mode. This work demonstrated the light-driven extracellular electron transfer and further revealed the photo-catalyzed mechanisms between anatase and PAO1 in marine euphotic zone.

Removal of lead ions in an aqueous solution by living and modified Aspergillus niger.

An indigenous lead-tolerant fungal strain was isolated from lead-contaminated soil and identified as Aspergillus niger, via 18S rRNA gene sequencing. We determined the adsorption and accumulation of Pb(II) by living A. niger and the adsorption of Pb(II) via modified A. niger. This strain resisted and removed 96.21%-100% Pb(II) ranging from 2 to 8 mmol/L Pb(II). Pb-containing particles were observed outside of the cell, and lead was detected inside the cell under scanning electron microscopy and transmission electron microscopy. The process of measuring the adsorption ability of modified fungal biomass, freeze-dried, high-temperature, and alkali-treated fungal samples was analyzed; they adsorbed 25.02%, 8.76%, and 15.05% Pb(II) under 8 mmol/L Pb(II) in 43, 10, and 10 hr, respectively. These three types of modified A. niger fit the pseudo-second-order model equation well. PRACTITIONER POINTS: Isolation and identification of effective Pb(II) removal strain from the soil around Dexing lead-zinc mine. The ability of living and modified Aspergillus niger to remove Pb(II) in an aqueous environment was evaluated. Lead distributions inside and outside the cell were analyzed by SEM and TEM. Kinetic models for modified biomass adsorbing Pb(II) were made for describing adsorption process.

A Comparative Study of Pathological Nanomineral Aggregates with Distinct Morphology in Human Aortic Atherosclerotic Plaques.

Calcification exists in atherosclerotic plaques in the form of nanomineral aggregates and is closely related to the development of atherosclerosis. Spheroidal and massive calcification are two major types of calcification found in atherosclerotic tissue. However, the exact difference between these two types of calcification is still not clear. Samples composed entirely of spheroidal calcifications and massive calcifications were isolated from aortic atherosclerotic plaques and tested using both bulk and microscopic analysis techniques. Scanning electron microscopy and transmission electron microscopy showed that spheroidal calcifications had a core-shell structure. Massive calcifications were composed of randomly arranged nanocrystals. Synchrotron radiation X-ray diffraction, Raman spectroscopy and selected area electron diffraction showed amorphous calcium phosphate, whitlockite and carbonate hydroxyapatite all existing in spheroidal calcification, while massive calcification only consisted of carbonate hydroxyapatite. We conclude that amorphous calcium phosphate may act as a precursor phase of spheroidal calcifications that eventually transforms into a crystalline phase, while whitlockite in lesions could aggravate the progression of atherosclerosis.

Photoreduction of inorganic carbon(+IV) by elemental sulfur: Implications for prebiotic synthesis in terrestrial hot springs.

Terrestrial hydrothermal systems have been proposed as alternative birthplaces for early life but lacked reasonable scenarios for the supply of biomolecules. Here, we show that elemental sulfur (S0), as the dominant mineral in terrestrial hot springs, can reduce carbon dioxide (CO2) into formic acid (HCOOH) under ultraviolet (UV) light below 280 nm. The semiconducting S0 is indicated to have a direct bandgap of 4.4 eV. The UV-excited S0 produces photoelectrons with a highly negative potential of -2.34 V (versus NHE, pH 7), which could reduce CO2 after accepting electrons from electron donors such as reducing sulfur species. Simultaneously, UV light breaks sulfur bonds, benefiting the adsorption of charged carbonates onto S0 and assisting their photoreduction. Assuming that terrestrial hot springs covered 1% of primitive Earth's surface, S0 at 10 µM could have produced maximal 109 kg/year HCOOH within 10-cm-thick photic zones, underlying its remarkable contributions to the accumulation of prebiotic biomolecules.

Genome Analysis of a Marine Bacterium Halomonas sp. and Its Role in Nitrate Reduction under the Influence of Photoelectrons.

The solar light response and photoelectrons produced by widespread semiconducting mineral play important roles in biogeochemical cycles on Earth's surface. To explore the potential influence of photoelectrons generated by semiconducting mineral particles on nitrate-reducing microorganisms in the photic zone, a marine heterotrophic denitrifier Halomonas sp. strain 3727 was isolated from seawater in the photic zone of the Yellow Sea, China. This strain was classified as a Halomonadaceae. Whole-genome analysis indicated that this strain possessed genes encoding the nitrogen metabolism, i.e., narG, nasA, nirBD, norZ, nosB, and nxr, which sustained dissimilatory nitrate reduction, assimilatory nitrate reduction, and nitrite oxidation. This strain also possessed genes related to carbon, sulfur, and other metabolisms, hinting at its substantial metabolic flexibility. A series of microcosm experiments in a simulative photoelectron system was conducted, and the results suggested that this bacterial strain could use simulated photoelectrons with different energy for nitrate reduction. Nitrite, as an intermediate product, was accumulated during the nitrate reduction with limited ammonia residue. The nitrite and ammonia productions differed with or without different energy electron supplies. Nitrite was the main product accounting for 30.03% to 68.40% of the total nitrogen in photoelectron supplement systems, and ammonia accounted for 3.77% to 8.52%. However, in open-circuit systems, nitrite and ammonia proportions were 26.77% and 11.17%, respectively, and nitrogen loss in the liquid was not observed. This study reveals that photoelectrons can serve as electron donors for nitrogen transformation mediated by Halomonas sp. strain 3727, which reveals an underlying impact on the nitrogen biogeochemical cycle in the marine photic zone.

Removal mechanism of Pb(II) by Penicillium polonicum: immobilization, adsorption, and bioaccumulation.

Currently, lead (Pb) has become a severe environmental pollutant and fungi hold a promising potential for the remediation of Pb-containing wastewater. The present study showed that Penicillium polonicum was able to tolerate 4 mmol/L Pb(II), and remove 90.3% of them in 12 days through three mechanisms: extracellular immobilization, cell wall adsorption, and intracellular bioaccumulation. In this paper. the three mechanisms were studied by Raman, X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results indicated that Pb(II) was immobilized as lead oxalate outside the fungal cell, bound with phosphate, nitro, halide, hydroxyl, amino, and carboxyl groups on the cell wall, precipitated as pyromorphite [Pb5(PO4)3Cl] on the cell wall, and reduced to Pb(0) inside the cell. These combined results provide a basis for additionally understanding the mechanisms of Pb(II) removal by P. polonicum and developing remediation strategies using this fungus for lead-polluted water.

Mineralogical characteristics and photocatalytic properties of natural sphalerite from China.

Different natural sphalerites have a range of photocatalytic properties that can potentially be exploited for environmental remediation purposes. To develop value in the exploitation of sphalerite, samples were collected from 19 ore deposits in China and characterized for their mineralogical and photocatalytic properties. X-ray diffraction (XRD) and electron probe micro analysis (EPMA) measurements indicated that all the natural sphalerites from various localities crystallized in cubic phases with various chemical compositions. The substitution of Fe for Zn ranged from 0.235% to 14.826% by weight, Mn from 0.004% to 4.868%, Cu from 0.009% to 5.529% and Cd from 0.133% to 1.576%. As Fe became more abundant, the color of natural sphalerite darkened, becoming almost black; and higher Fe content was associated with stronger visible light absorption. Photoluminescence spectra showed emission mainly related to S-vacancies and progressively decreasing fluorescence intensity with increasing Fe content. Tests of the photocatalytic degradation of methyl orange indicated that the sample with the highest Cd content but moderate Fe content had the highest photocatalytic activity. Specifically, the degradation of Methyl Orange (30 mg/L) attained 82.11% efficiency under visible light irradiation for 4 hr of natural sphalerite with 4.262% Fe and 1.576% Cd. Overall, the Fe content in sphalerite was found to contribute to the visible light absorption ability and the recombination rate of photo-generated electrons and holes, while substitution by Cd was observed to have a greater effect on the photocatalytic properties. These findings provide a scientific basis for the profitable utilization of base metal resources like sphalerite.

Photoelectric conversion on Earth's surface via widespread Fe- and Mn-mineral coatings.

Sunlight drives photosynthesis and associated biological processes, and also influences inorganic processes that shape Earth's climate and geochemistry. Bacterial solar-to-chemical energy conversion on this planet evolved to use an intricate intracellular process of phototrophy. However, a natural nonbiological counterpart to phototrophy has yet to be recognized. In this work, we reveal the inherent "phototrophic-like" behavior of vast expanses of natural rock/soil surfaces from deserts, red soils, and karst environments, all of which can drive photon-to-electron conversions. Using scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy, and X-ray absorption spectroscopy, Fe and Mn (oxyhydr)oxide-rich coatings were found in rock varnishes, as were Fe (oxyhydr)oxides on red soil surfaces and minute amounts of Mn oxides on karst rock surfaces. By directly fabricating a photoelectric detection device on the thin section of a rock varnish sample, we have recorded an in situ photocurrent micromapping of the coatings, which behave as highly sensitive and stable photoelectric systems. Additional measurements of red soil and powder separated from the outermost surface of karst rocks yielded photocurrents that are also sensitive to irradiation. The prominent solar-responsive capability of the phototrophic-like rocks/soils is ascribed to the semiconducting Fe- and Mn (oxyhydr)oxide-mineral coatings. The native semiconducting Fe/Mn-rich coatings may play a role similar, in part, to photosynthetic systems and thus provide a distinctive driving force for redox (bio)geochemistry on Earth's surfaces.

Natural Extracellular Electron Transfer Between Semiconducting Minerals and Electroactive Bacterial Communities Occurred on the Rock Varnish.

Rock varnish is a thin coating enriched with manganese (Mn) and iron (Fe) oxides. The mineral composition and formation of rock varnish elicit considerable attention from geologists and microbiologists. However, limited research has been devoted to the semiconducting properties of these Fe/Mn oxides in varnish and relatively little attention is paid to the mineral-microbe interaction under sunlight. In this study, the mineral composition and the bacterial communities on varnish from the Gobi Desert in Xinjiang, China were analyzed. Results of principal components analysis and t-test indicated that more electroactive genera such as Acinetobacter, Staphylococcus, Dietzia, and Pseudomonas gathered on varnish bacterial communities than on substrate rock and surrounding soils. We then explored the culture of varnish, substrate and soil samples in media and the extracellular electron transfer (EET) between bacterial communities and mineral electrodes under light/dark conditions for the first time. Orthogonal electrochemical experiments demonstrated that the most remarkable photocurrent density of 6.1 ± 0.4 µA/cm2 was observed between varnish electrode and varnish microflora. Finally, based on Raman and 16S rRNA gene-sequencing results, coculture system of birnessite and Pseudomonas (the major Mn oxide and a common electroactive bacterium in varnish) was established to study underlying mechanism. A steadily growing photocurrent (205 µA at 100 h) under light was observed with a stable birnessite after 110 h. However, only 47 µA was generated in the dark control and birnessite was reduced to Mn2+ in 13 h, suggesting that birnessite helped deliver electrons instead of serving as an electron acceptor under light. Our study demonstrated that electroactive bacterial communities were positively correlated with Fe/Mn semiconducting minerals in varnish, and diversified EET process occurred on varnish under sunlight. Overall, these phenomena may influence bacterial-community structure in natural environments over time.