Differences among active toluene-degrading microbial communities in farmland soils with different levels of heavy metal pollution.

Heavy metals can severely influence the mineralisation of organic pollutants in a compound-polluted environment. However, to date, no study has focused on the effects of heavy metals on the active organic pollutant-degrading microbial communities to understand the bioremediation mechanism. In this study, toluene was used as the model organic pollutant to explore the effects of soils with different levels of heavy metal pollution on organic contaminant degradation in the same area via stable isotope probing (SIP) and 16 S rRNA high-throughput sequencing. Heavy metals can seriously affect toluene biodegradation and regulate the abundance and diversity of microbial communities. SIP revealed a drastic difference in the community structure of active toluene degraders between the unpolluted and heavy metal-polluted soils. All SIP-identified degraders were assigned to nine bacterial classes, among which Alphaproteobacteria, Gammaproteobacteria, and Bacilli were shared by both treatments. Among all active degraders, Nitrospira, Nocardioides, Conexibacteraceae, and Singulisphaera were linked to toluene biodegradation for the first time. Notably, the type of active degrader and microbial diversity were strongly related to biodegradation efficiency, indicating their key role in toluene biodegradation. Overall, heavy metals can affect the microbial diversity and alter the functional microbial communities in soil, thereby influencing the removal efficiency of organic contaminants. Our findings provide novel insights into the biodegradation mechanism of organic pollutants in heavy metal-polluted soils and highlight the biodiversity of microbes involved in toluene biodegradation in compound-polluted environments.

A New Electron Shuttling Pathway Mediated by Lipophilic Phenoxazine via the Interaction with Periplasmic and Inner Membrane Proteins of Shewanella oneidensis MR-1.

Although it has been established that electron mediators substantially promote extracellular electron transfer (EET), electron shuttling pathways are not fully understood. Here, a new electron shuttling pathway was found in the EET process by Shewanella oneidensis MR-1 with resazurin, a lipophilic electron mediator. With resazurin, the genes encoding outer-membrane cytochromes (mtrCBA and omcA) were downregulated. Although cytochrome deletion substantially reduced biocurrent generation to 1-12% of that of wild-type (WT) cells, the presence of resazurin restored biocurrent generation to 168 µA·cm-2 (ΔmtrA/omcA/mtrC), nearly equivalent to that of WT cells (194 µA·cm-2), indicating that resazurin-mediated electron transfer was not dependent on the Mtr pathway. Biocurrent generation by resazurin was much lower in ΔcymA and ΔmtrA/omcA/mtrC/fccA/cctA mutants (4 and 6 µA·cm-2) than in WT cells, indicating a key role of FccA, CctA, and CymA in this process. The effectiveness of resazurin in EET of Mtr cytochrome mutants is also supported by cyclic voltammetry, resazurin reduction kinetics, and in situ c-type cytochrome spectroscopy results. The findings demonstrated that low molecular weight, lipophilic electron acceptors, such as phenoxazine and phenazine, may facilitate electron transfer directly from periplasmic and inner membrane proteins, thus providing new insight into the roles of exogenous electron mediators in electron shuttling in natural and engineered biogeochemical systems.

Aggregation Kinetics of TiO2 Nanoparticles in Human and Artificial Sweat Solutions: Effects of Particle Properties and Sweat Constituents.

Dermal penetration potentials of titanium dioxide nanoparticles (TiO2 NPs) may be affected by aggregation upon contact with sweat. This study investigated the aggregation kinetics of three TiO2 NPs in thirty human sweat samples and four artificial sweat standards. Effects of particle concentration, sweat type, and inorganic (sodium chloride, disodium hydrogen phosphate, and sodium dihydrogen phosphate) and organic (l-histidine, lactic acid, and urea) constituents were examined. Three TiO2 NPs remained colloidally stable in >20/30 human sweat samples and showed significant negative correlations (P < 0.01) between aggregation rates and |zeta potentials|. They aggregated rapidly over 20 min to >750 nm in three artificial sweat standards, while remained more stable in the International-Standard-Organization-pH-5.5 standard. Aggregation behaviors of three TiO2 NPs mostly followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, allowing for determining their critical coagulation concentrations in inorganic constituents (15-491 mM) and Hamaker constants (3.3-7.9 × 10-21 J). Higher concentrations of particles, inorganic constituents, and l-histidine destabilized three TiO2 NPs, whereas urea inhibited aggregation. Three TiO2 NPs adsorbed organic sweat constituents via complexation with amino or carboxyl groups, with isotherms following the Langmuir model. Correlation analyses further suggested that the adsorbed organic constituents may stabilize three TiO2 NPs against aggregation in sweat by steric hindrance.

Fulvic Acid-Mediated Interfacial Reactions on Exposed Hematite Facets during Dissimilatory Iron Reduction.

Although the dual role of natural organic matter (NOM) as an electron shuttle and an electron donor for dissimilatory iron (Fe) reduction has been extensively investigated, the underlying interfacial interactions between various exposed facets and NOM are poorly understood. In this study, fulvic acid (FA), as typical NOM, was used and its effect on the dissimilatory reduction of hematite {001} and {100} by Shewanella putrefaciens CN-32 was investigated. FA accelerates the bioreduction rates of hematite {001} and {100}, where the rate of hematite {100} is lower than that of hematite {001}. Secondary Fe minerals were not observed, but the HR-TEM images reveal significant defects. The ATR-FTIR results demonstrate that facet-dependent binding mainly occurs via surface complexation between the surface iron atoms and carboxyl groups of NOM. The spectroscopic and mass spectrometry analyses suggest that organic compounds with large molecular weight, highly aromatic and unsaturated structures, and lower H/C ratios are easily adsorbed on Fe oxides or decomposed by bacteria in FA-hematite {001} treatment after iron reduction. Due to the metabolic processes of cells, a significant number of compounds with higher H/C and medium O/C ratios appear. The Tafel curves show that hematite {100} possessed higher resistance (4.1-2.6 Ω) than hematite {001} (3.5-2.2 Ω) at FA concentrations ranging from 0 to 500 mg L-1, indicating that hematite {100} is less conductive during the electron transfer from reduced FA or cells to Fe oxides than hematite {001}. Overall, the discrepancy in the iron bioreduction of two exposed facets is attributed to both the different electrochemical activities of the Fe oxides and the different impacts on the properties and composition of OM. Our findings shed light on the molecular mechanisms of mutual interactions between FA and Fe oxides with various facets.

Three Silver(I) Coordination Polymers Based on Pyridyl Ligands and Auxiliary Carboxylic Ligands: Luminescence and Efficient Sensing Properties.

Easily producible sensors for harmful industrial waste compounds are of significant interest for both human health and the environment. Three novel coordination polymers, [Ag(µ-aca)(µ4-bztpy)1/2] (1), [Ag(µ-bza)(µ-bpa)] (2), and [Ag2(µ-aca)2(µ-bpa)2]·EtOH·2H2O (3), were assembled in this study by reactions using Ag+ as a node with the pyridyl ligand 1,2,4,5-tetrakis(4-pyridyl)benzene (bztpy) or 9,10-bis(4-pyridyl)anthracene (bpa) and an auxiliary chelating carboxylic ligand. Single-crystal X-ray structural analyses revealed that compound 1 has a 3D framework consisting of 1D [Ag(aca)]∞ chains and bztpy linkers, while 2 and 3 have 2D layered structures consisting of binuclear Ag-carboxylate units and bpa linkers, respectively. Topological studies revealed that 1 has a bbf topology, while 2 and 3 are 2D [4,4] rhombic grids. The compounds were further characterized by powder X-ray diffraction, IR, elemental analysis, thermogravimetric analysis, and a luminescence study. The solids of 1-3 exhibited intense photoluminescent emission with λemmax at ca. 493, 472, and 500 nm, respectively. Remarkably, due to their excellent framework stability, 1 and 2 can act as multiresponsive luminescent sensors for nitrobenzene, Fe3+, and Cr2O72- with a high selectivity and sensitivity ascribed to their quenching effect.

Impacts of Redox Conditions on Arsenic and Antimony Transformation in Paddy Soil: Kinetics and Functional Bacteria.

Arsenic (As) and antimony (Sb) are known carcinogens and are present as contaminants in paddy soils. However, the complicated dynamics of the mobility of these metalloids have not been well understood due to changing redox conditions in paddy soils. Herein, the kinetics of dissolved As and Sb, and functional bacteria/genes were examined in a paddy soil cultured under aerobic and anaerobic conditions. Under aerobic condition, dissolved As(V) and Sb(V) increased constantly due to sulfide oxidation by O2 and bound As and Sb were released. Under anaerobic condition, the reduction of As(V) and Sb(V) occurred, and the mobility of As and Sb were affected by soil redox processes. The bacteria with functional genes aioA and arrA were responsible for the direct As/Sb transformation, while Fe- and N-related bacteria had an indirect effect on the fate of As/Sb via coupling with the redox processes of Fe and N. These findings improve understanding of the mobility of As and Sb in paddy soil systems under different redox conditions.

Enhanced Current Production by Exogenous Electron Mediators via Synergy of Promoting Biofilm Formation and the Electron Shuttling Process.

Exogenous electron mediators (EMs) can facilitate extracellular electron transfer (EET) via electron shuttling processes, but it is still unclear whether and how biofilm formation is affected by the presence of EMs. Here, the impacts of EMs on EET and biofilm formation were investigated in bioelectrochemical systems (BESs) with Shewanella oneidensis MR-1, and the results showed that the presence of five different EMs led to high density current production. All the EMs substantially promoted biofilm formation with 15-36 times higher total biofilm DNA with EMs than without EMs, and they also increased the production of extracellular polymeric substances, which was favorable for biofilm formation. The current decreased substantially after removing EMs from the medium or by replacing electrodes without biofilm, suggesting that both biofilm and EMs are required for high density current production. EET-related gene expression was upregulated with EMs, resulting in the high flux of cell electron output. A synergistic mechanism was proposed: EMs in suspension were quickly reduced by the cells and reoxidized rapidly by the electrode, resulting in a microenvironment with sufficient oxidized EMs for biofilm formation, and thus, besides the well-known electron shuttling process, the EM-induced high biofilm formation and high Mtr gene expression could jointly contribute to the EET and subsequently produce a high density current. This study provides a new insight into EM-enhanced current production via regulating the biofilm formation and EET-related gene expression.

Extracellular Electron Shuttling Mediated by Soluble c-Type Cytochromes Produced by Shewanella oneidensis MR-1.

How metal-reducing bacteria transfer electrons during dissimilatory energy generation under electron acceptor-limited conditions is poorly understood. Here, we incubated the iron and manganese-reducing bacterium Shewanella oneidensis MR-1 without electron acceptors. Removal of soluble extracellular organic compounds (EOCs) dramatically retarded transfer of electrons to an experimental electron acceptor, Cr(VI), by MR-1. However, the return of either high MW (>3000 Da) or low MW (<3000 Da) soluble EOCs produced by MR-1 to washed cells restored Cr(VI) reduction though Cr(VI) reduction was fastest when both size fractions were added together. Spectral and electrochemical characterization of EOCs indicated the presence of flavins and c-type cytochromes (c-Cyts). A model of the kinetics of individual elementary reactions between cells, flavins, released c-Cyts, and Cr(VI), including the direct reduction of flavins, released c-Cyts, and Cr(VI) by cells and the indirect reduction of Cr(VI) by reduced forms of flavins and released c-Cyts, was developed. Model results suggest that released c-Cyts could act as electron mediators to accelerate electron transfer from cells to Cr(VI), and the relative contribution of this pathway was higher than that mediated by flavins. Hence, extracellular c-Cyts produced by MR-1 likely play a role in extracellular electron transfer under electron acceptor-limited conditions. These findings provide new insights into extracellular electron shuttling and the metabolic strategy of metal-reducing bacteria under electron acceptor-limited conditions.

Conduction Band of Hematite Can Mediate Cytochrome Reduction by Fe(II) under Dark and Anoxic Conditions.

While it was recently reported that the conduction band of iron minerals can mediate electron transfer between Fe(II) and different Fe(III) lattice sites during Fe(II)-catalyzed mineral transformation, it is unclear whether such a conduction band mediation pathway occurs in the microbial Fe(II) oxidation system under dark and anoxic subsurface conditions. Here, using cytochrome c (c-Cyts) as a model protein of microbial Fe(II) oxidation, the in vitro kinetics and thermodynamics of c-Cyts reduction by Fe(II) were studied. The results showed that the rates of c-Cyts reduction were greatly enhanced in the presence of the semiconducting mineral hematite (Hem, α-Fe2O3). The electrochemical experiments separating Fe(II) and c-Cyts demonstrated that electrons from Fe(II) to the electrode or from the electrode to c-Cyts could directly penetrate hematite, resulting in enhanced current. Independent photochemical and photoluminescence experiments indicated that c-Cyts could be directly reduced by the conduction band electrons of hematite which were generated under light illumination. In c-Cyts+Fe(II)+Hem, the redox potential of Fe(II)-Hem was shifted from -0.15 to -0.18 V and that of c-Cyts+Hem changed slightly from -0.05 to -0.04 V. For the bulk hematite, Mott-Schottky plots illustrated that the flat band was shifted negatively and positively in the presence of Fe(II) and oxidized c-Cyts, respectively, and the surface electron/charge density was higher in the presence of Fe(II)/c-Cyts. As a consequence, the redox gradients from adsorbed Fe(II) to adsorbed c-Cyts allow electron transfer across the conduction band of hematite and facilitate c-Cyts reduction. This mechanistic study on conduction band-mediating electron transfer could help interpret the role of semiconducting minerals in the microbial Fe(II) oxidation process under dark anoxic conditions.

Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

Xiaoqinglong decoction mitigates nasal inflammation and modulates gut microbiota in allergic rhinitis mice.

Introduction: Allergic rhinitis (AR) is a respiratory immune system disorder characterized by dysregulation of immune responses. Within the context of AR, gut microbiota and its metabolites have been identified as contributors to immune modulation. These microorganisms intricately connect the respiratory and gut immune systems, forming what is commonly referred to as the gut-lung axis. Xiaoqinglong Decoction (XQLD), a traditional Chinese herbal remedy, is widely utilized in traditional Chinese medicine for the clinical treatment of AR. In this study, it is hypothesized that the restoration of symbiotic microbiota balance within the gut-lung axis plays a pivotal role in supporting the superior long-term efficacy of XQLD in AR therapy. Therefore, the primary objective of this research is to investigate the impact of XQLD on the composition and functionality of the gut microbiota in a murine model of AR. Methods: An ovalbumin-sensitized mouse model to simulate AR was utilized, the improvement of AR symptoms after medication was investigated, and high-throughput sequencing was employed to analyze the gut microbiota composition. Results: XQLD exhibited substantial therapeutic effects in AR mice, notably characterized by a significant reduction in allergic inflammatory responses, considerable alleviation of nasal symptoms, and the restoration of normal nasal function. Additionally, following XQLD treatment, the disrupted gut microbiota in AR mice displayed a tendency toward restoration, showing significant differences compared to the Western medicine (loratadine) group. Discussion: This results revealed that XQLD may enhance AR allergic inflammatory responses through the regulation of intestinal microbiota dysbiosis in mice, thus influencing the dynamics of the gut-lung axis. The proposal of this mechanism provides a foundation for future research in this area.

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite.

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. These findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

Electron shuttle-dependent biofilm formation and biocurrent generation: Concentration effects and mechanistic insights.

Introduction: Electron shuttles (ESs) play a key role in extracellular electron transfer (EET) in Shewanella oneidensis MR-1. However, the quantification relationship between ES concentration, biofilm formation, and biocurrent generation has not been clarified. Methods: In this study, 9,10-anthraquinone-2-sulfonic acid (AQS)-mediated EET and biofilm formation were evaluated at different AQS concentrations in bioelectrochemical systems (BESs) with S. oneidensis MR-1. Results and discussion: Both the biofilm biomass (9- to 17-fold) and biocurrent (21- to 80-fold) were substantially enhanced by exogenous AQS, suggesting the dual ability of AQS to promote both biofilm formation and electron shuttling. Nevertheless, biofilms barely grew without the addition of exogenous AQS, revealing that biofilm formation by S. oneidensis MR-1 is highly dependent on electron shuttling. The biofilm growth was delayed in a BES of 2,000 µM AQS, which is probably because the redundant AQS in the bulk solution acted as a soluble electron acceptor and delayed biofilm formation. In addition, the maximum biocurrent density in BESs with different concentrations of AQS was fitted to the Michaelis-Menten equation (R 2 = 0.97), demonstrating that microbial-catalyzed ES bio-reduction is the key limiting factor of the maximum biocurrent density in BESs. This study provided a fundamental understanding of ES-mediated EET, which could be beneficial for the enrichment of electroactive biofilms, the rapid start-up of microbial fuel cells (MFCs), and the design of BESs for wastewater treatment.

Facet-dependent Fe(II) redox chemistry on iron oxide for organic pollutant transformation and mechanisms.

Fe(II) redox chemistry is a pivotal process of biogeochemical Fe cycle and the transformation of organic pollutants in subsurface aquifers, while its interfacial reactivity on iron oxides with varying surface chemistries remains largely unexplored. In this study, the redox processes of Fe(II) on two hematite with highly exposed {001} and {110} facets and their impacts on the transformation of nitrobenzene were investigated. Results suggest that Fe(II) adsorption is the rate-limiting step of the redox chain reactions, controlling the reduction potential (EH). Nitrobenzene activates the facet electron transfer on hematite, leading to nitrobenzene reduction and Fe(II) oxidation. Moreover, {001} facet exhibits a higher reactivity and electron transport efficiency than {110} facet, which is attributed to a lower site density (0.809 #Fe/nm2) and a lower EH of hematite {001} facet than that of {110} facet. It is worth noting that the facet-dependent reduction activity is more intense at low pH or high Fe(II) activity. A slight dissolution of {110} facet was observed, indicating hematite {001} facet exhibits higher thermodynamic stability than {110} facet. This study confirms the facet-dependent reducing activity of surface bound Fe(II) on hematite, providing a new perspective for in-depth understanding of the interfacial reactions on hematite. The findings of this work broaden the biogeochemical process of Fe cycle in subsurface environments and its impact on the fate of organic pollutants in groundwater.

Hematite-promoted nitrate-reducing Fe(II) oxidation by Acidovorax sp. strain BoFeN1: Roles of mineral catalysis and cell encrustation.

Although nitrate-reducing Fe(II) oxidizing (NRFO) bacteria can grow sustainably in natural environments, numerous laboratory studies suggested that cell encrustation-induced metabolism limitations and cell death occurred more seriously in the absence of natural minerals. Hence, a study on how natural minerals could affect NRFO is warranted. This study examined the impact of hematite on NRFO by Acidovorax sp. BoFeN1 with different electron donors (acetate and Fe(II), acetate alone, and Fe(II) alone) and with nitrate as an electron acceptor. When acetate and Fe(II) were used as the electron donors, the amount of Fe(II) oxidation and nitrate reduction was enhanced in the presence of hematite, whereas no promotion was observed when only acetate was added as an electron donor. Under the conditions with only Fe(II) added as an electron donor, the level of Fe(II) oxidation was increased from 3.07 ± 0.06 to 3.92 ± 0.02 mM in the presence of hematite and nitrate reduction was enhanced. This suggests that hematite promotes microbial nitrate reduction by accelerating the biological oxidation of Fe(II). The main secondary minerals were goethite and lepidocrocite. After adding hematite, the assemblage of iron minerals on the cell surface decreased, and the cell crusts became thinner, indicating that hematite effectively mitigated cell encrustation. Furthermore, hematite accelerated the chemical oxidation of Fe(II) by nitrite. Hence, hematite can promote the NRFO of Acidovorax sp. BoFeN1 via two possible pathways: (i) hematite acts as nucleation sites to mitigate cell encrustation; (ii) hematite catalyzes the biological and chemical oxidation of Fe(II) through the mineral catalysis effects. This study highlights the importance of existing iron minerals on NRFO and sheds light on the survival strategy of NRFO bacteria in anoxic subsurface environments.

Quinone-mediated dissimilatory iron reduction of hematite: Interfacial reactions on exposed {001} and {100} facets.

Although quinone-mediated bioreduction of iron oxides has been investigated extensively, little is known about the interfacial interactions between quinone and various exposed facets. In this study, the reduction of hematite {001} and {100} by Shewanella putrefaciens CN-32 with anthraquinone-2,6-disulfonate (AQDS) was investigated. The added AQDS can enhance the bioreduction of both hematite {001} and {100}, with hematite {001} showing a higher reduction degree than hematite {100}. No significant secondary iron oxides were found, but defects were observed in HR-TEM images. AQDS sorption was higher on hematite {001} (0.13 µM m-2) than hematite {100} (0.1 µM m-2). Electron transfer rate between hematite {001} and AQDS (19.6 s-1) was higher than hematite {100} (18.2 s-1). Tafel curves revealed that hematite {001} possesses lower resistance (3.5-2.4 Ω) than hematite {100} (4.1-2.9 Ω) with AQDS from 0 to 400 µM, indicating that hematite {001} is more favorable for electron transfer from cells or anthrahydroquinone-2,6,-disulfonate (AH2QDS) to Fe oxide. In addition to the well-known electron shuttling role of AQDS, the higher adsorption sites and electrochemical activity of hematite {001} over {100} jointly contributed to the enhanced iron bioreduction. The findings provide a mechanistic understanding of the interactions between quinone and various facets of iron oxides.

Distinct biofilm formation regulated by different culture media: Implications to electricity generation.

Biofilm of Shewanella oneidensis MR-1 is extensively studied as it can transform organic compounds directly into electricity. Although revealing the biofilm regulation mechanism is crucial for enhancing bio-current, studies regarding the mechanism by which the culture condition affects biofilm formation are still lacking. The biofilm formation of S. oneidensis MR-1 in two typical media with same electron donor was investigated in this study. Bio-electricity increased 1.8 times in medium with phosphate-buffered saline (PBS) than in piperazine-1,4-bisethanesulfonic acid (PIPES). Biofilm total protein has 1.5-fold of difference between two media at day 3, and biofilm structures also differed; a fluffy biofilm with curled cells was formed in medium with PBS, whereas a compact, ordered, and closely attached biofilm was formed in medium with PIPES. Transcriptome studies clarified that the expression of genes beneficial for cell aggregation [e.g., aggA (2.3 fold), bpfA (2.8 fold) and csgB (3.9 fold)] in medium with PIPES was significantly upregulated, thus provided an explanation for the specific biofilm structure. Buffer concentration was proved to be a critical factor impacted cell morphology and current generation. The maximum current density in 30 mM of PBS and PIPES is 165 and 159 µA·cm-2 respectively, but it increased to 327 and 274 µA·cm-2 in 200 mM of PBS and PIPES. This study provides new insights into the mechanism of medium-dependent biofilm regulation, which will be beneficial for developing simple and efficient strategies to enhance bio-electricity generation.

Influence of Incubation Temperature on 9,10-Anthraquinone-2-Sulfonate (AQS)-Mediated Extracellular Electron Transfer.

The electron shuttling process has been recognized as an important microbial respiration process. Because the incubation temperature can influence both the reactivity of electron mediators and cell growth, it may also affect the electron-shuttle-mediated extracellular electron transfer (EET) process. Here, the effect of incubation temperature (22-38°C) was investigated in a bioelectrochemical system (BES) using Shewanella oneidensis MR-1 and 50 µM of 9,10-anthraquinone-2-sulfonate (AQS). We found that current generation increased as the temperature was increased from 22 to 34°C and then decreased sharply at 38°C. The biofilm biomass, as indicated by the total protein extracted from the electrode, increased as the temperature increased from 22 to 34°C and then decreased at 38°C, mirroring the current generation results. These results were further confirmed by increasing the temperature slowly, step-by-step, in a single BES with a constant biofilm biomass, suggesting that the EET rates could be substantially influenced by temperature, even with the same biofilm. The effects of temperature on the AQS bioreduction rate, c-type cytochrome (c-Cyts)-bound-cofactor-mediated EET, the AQS mid-point potential, and the AQS diffusion coefficient were studied. From these results, we were able to conclude that temperature influenced the EET rates by changing the c-Cyts-bound-cofactor-mediated EET process and the AQS bioreduction rate, and that the change in biofilm formation was a dominant factor influencing the overall EET rates. These findings should contribute to the fundamental understanding of EET processes. Moreover, optimization of the operating parameters for current generation will be helpful for the practical application of bioelectrochemical techniques.

Quantifying Redox Dynamics of c-Type Cytochromes in a Living Cell Suspension of Dissimilatory Metal-reducing Bacteria.

To quickly and accurately quantify the redox dynamics of c-type cytochromes (c-Cyts) in a living cell suspension, diffuse-transmission UV/visible (DT-UV/Vis) and normal UV/Vis spectroscopy were used to record spectra of c-Cyts in living Shewanella oneidensis MR-1 bacteria. DT-UV/Vis showed a higher absorbance of c-Cyts and lower background compared with normal UV/Vis, because interference from cell surface scattering was removed. The extinction coefficients of oxidized c-Cyts (410 nm) and reduced c-Cyts (419 and 552 nm) were observed. Using this method and the obtained c-Cyts extinction coefficients, the redox transformation kinetics of c-Cyts under anoxic conditions were successfully examined in the presence of various electron acceptors, including 9,10-anthraquinone-2,6-disulfonic acid, Cr(VI), Fe(III) citrate and oxygen. Therefore, the in situ spectral analysis of outer-membrane proteins of intact cells using DT-UV/Vis spectroscopy appears a promising method for investigating microbial metal reduction processes in living cell systems.

Reductive transformation of tetrabromobisphenol A by sulfidated nano zerovalent iron.

Recent studies showed that sulfidated nano zerovalent iron (S-nZVI) is a better alternative to non-sulfidated nano zerovalent iron (NS-nZVI) commonly used for contaminated site remediation. However, its reactivity with different halogenated pollutants such as tetrabromobisphenol A (TBBPA) remains unclear. In this study, we explored the reductive transformation of TBBPA by S-nZVI and compared it with that by NS-nZVI. The results showed that over 90% of the initial TBBPA (20 mg L(-1)) was transformed by S-nZVI within 24 h of reaction, which was 1.65 times as high as that for NS-nZVI. The TBBPA transformation by S-nZVI was well described by a pseudo-first-order kinetic model, whilst that by NS-nZVI was well fitted by a three-parameter single exponential decay model. After 11 weeks of aging, S-nZVI was still able to transform up to 56% of the initial TBBPA within 24 h of reaction; by contrast, the two-week aged NS-nZVI lost more than 95% of its original capacity to transform TBBPA. Moreover, S-nZVI showed only an approximately 20% decrease in its capacity to transform TBBPA in the seventh cycle, while NS-nZVI was no longer able to transform TBBPA in the fourth cycle. XPS analysis suggested the formation of FeS layer on S-nZVI surface and electrochemical analysis revealed an elevated electron transfer capacity of S-nZVI, which were likely responsible for the superior performances of S-nZVI in TBBPA transformation. While the transformation rate of TBBPA by S-nZVI decreased with increasing initial concentration of TBBPA, it showed an increasing trend with increasing S/Fe ratio and initial concentration of S-nZVI. The study indicated that S-nZVI has the potential to be a promising alternative to NS-nZVI for remediation of TBBPA-contaminated aquatic environments.