Microaerobic iron oxidation and carbon assimilation and associated microbial community in paddy soil

Iron oxidation is a prevalent and important biogeochemical process in paddy soil,but little is known about whether and how microbially mediated iron oxidation is coupled with carbon assimilation,particularly under microaerobic conditions.Here,we investigated kinetics of CO_2 assimilation and Fe(Ⅱ)oxidation in an incubation experiment with paddy soil under suboxic conditions,and profiled the associated microbial community using DNA-stable isotope probing and 16S r RNA gene-based sequencing.The results showed that CO_2 assimilation and Fe(II)oxidation in the gradient tubes were predominantly mediated by the microbes enriched in the paddy soil,primarily Azospirillum and Magnetospirillum,as their relative abundances were higher in the^( 13)C heavy fractions compared to^( 12)C heavy fractions.This study provided direct evidence of chemoautotrophic microaerophiles linking iron oxidation and carbon assimilation at the oxic–anoxic interface in the paddy soil ecosystem.

Fractionation characteristics of rare earth elements(REEs) linked with secondary Fe, Mn, and Al minerals in soils

Soil secondary minerals are important scavengers of rare earth elements(REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs(La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs(LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs(HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs.The substantial fractions of REEs in soils extracted byoxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile(10 %–30 %), which were similar to the mass fraction of Fe(10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation.

The in situ spectral methods for examining redox status of c-type cytochromes in metal-reducing/oxidizing bacteria

The membrane-associated c-type cytochromes(c-Cyts) have been well known as the key enzymes mediating extracellular electron transfer to terminal electron acceptors, resulting in biogeochemical elemental transformation, contaminant degradation, and nutrient cycling. Although c-Cyts-mediated metal reduction or oxidation have been mainly investigated with the purified proteins of metal reducing/oxidizing bacteria, the in vivo behavior of c-Cyts is still unclear, given the difficulty in measuring the proteins of intact cells. Fortunately, the in situ spectroscopy would be ideal for measuring the reaction kinetics of c-Cyts in intact cells under noninvasive physiological conditions. It can also help the establishment of kinetic/thermodynamic models of extracellular electron transfer processes, which are essential to understand the electron transfer mechanisms at the molecular scale. This review briefly summarizes the current advances in spectral methods for examining the c-Cyts in intact cells of dissimilatory metal reducing bacteria and Fe(Ⅱ)-oxidizing bacteria.

Electrochemical and spectroscopic characteristics of dissolved organic matter in a forest soil profile

Dissolved organic matter （DOM） represents one of the most mobile and reactive organic compounds in ecosystem and plays an important role in the fate and transport of soil organic pollutants, nutrient cycling and more importantly global climate change. Electrochemical methods were first employed to evaluate DOM redox properties, and spectroscopic approaches were utilized to obtain information concerning its composition and structure. DOM was extracted from a forest soil profile with five horizons. Differential pulse voltammetry indicated that there were more redox-active moieties in the DOM from upper horizons than in that from lower horizons. Cyclic voltammetry further showed that these moieties were reversible in electron transfer. Chronoamperometry was employed to quantify the electron transfer capacity of DOM, including electron acceptor capacity and electron donor capacity, both of which decreased sharply with increasing depth. FT-IR, UV-Vis and fluorescence spectra results suggested that DOM from the upper horizons was enriched with aromatic and humic structures while that from the lower horizons was rich in aliphatic carbon, which supported the findings obtained by electrochemical approaches. Electrochemical approaches combined with spectroscopic methods were applied to evaluate the characteristics of DOM extracted along a forest soil profile. The electrochemical properties of DOM, which can be rapidly and simply obtained, provide insight into the migration and transformation of DOM along a soil profile and will aid in better understanding of the biogeochemical role of DOM in natural environments.

A study of electron-shuttle mechanism in Klebsiella pneumoniae based-microbial fuel cells

In microbial fuel cell (MFC), the rate of electron transfer to anode electrode is a key intrinsic limiting factor on the power output of MFCs. Using Klebsiella pneumoniae (K. pneumoniae) strain L17 as biocatalyst, we studied the mechanism of electron shuttle via self-producing mediator in a cubic air-chamber MFC. To eliminate the influence of biofilm mechanism, the anode electrode was coated with microfiltration membrane (0.22 μm). Data showed that the microfiltration membrane coated and uncoated MFCs achieved the maximum voltage outputs of 316.2 and 426.2 mV after 270 and 120 h, respectively. When the medium was replaced in MFCs that had the highest power generation, the power output dropped by 62.1% and 8.8%, and required 120 and 48 h to resume the original level in the coated and uncoated MFCs, respectively. The results suggested an electron-shuttle mechanism rather than biofilm mechanism was responsible for electricity generation in the membrane coated MFC. Cyclic voltammetric measurements demonstrated the presence of an electrochemical active compound produced by K. pneumoniae strain L17, which was identified to be 2,6-di-tert-butyl-p-benzoquinon (2,6-DTBBQ) by GC-MS. 2,6-DTBBQ, as a recyclable electron shuttle, could transfer electrons between K. pneumoniae L17 and the anode electrode.

Interactively interfacial reaction of iron-reducing bacterium and goethite for reductive dechlorination of chlorinated organic compounds

The interactively interfacial reactions between the iron-reducing bacterium (Shewanella decolorationis, S12) and iron oxide (α-FeOOH) were investigated to determine reductive dechlorination transformation of chlorinated organic compounds (chloroform and pentachlorophenol). The results showed that the interactive system of S12+ α-FeOOH exhibited relatively high dechlorination rate. By comparison, the S12 biotic system alone had no obvious dechlorination, and the α-FeOOH abiotic system showed low dechlorination rate. The enhanced dechlorination of chloroform and pentachlorophenol in the interactive system of S12+α-FeOOH was derived from the promoted generation of adsorbed Fe(Ⅱ) by S12. A decrease in redox potential of the Fe(Ⅲ)/Fe(Ⅱ) couple in the interactive reaction system was determined by cyclic voltammetry. Our results will give new insight into interactively interfacial reaction between iron-reducing bacterium and iron oxides for degradation of chlorinated organic compounds under anaerobic condition.

Adsorption of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite

The adsorption behavior of 2-mercaptobenzothiazole onto organo-bentonite was investigated. Natural bentonite from Gaozhou in Guangdong Province, China was collected. Organo-bentonite was prepared by intercalation of cetyltrimethyl ammonium bromide into the natural bentonite. The physicochemical properties of the prepared organo-bentonite were characterized by X-ray diffraction, N2 adsorption-desorption isotherm and Fourier transform infrared spectroscopy. The results showed that montmorillonite is the main component of the natural bentonite. The basal spacing of the natural bentonite is 1.47 nm, which increased to 1.98 nm on intercalation with cetyltrimethyl ammonium bromide. Moreover, both the surface area and pore volume increased with intercalation. Clear CH2 stretching （3000-2800 cm-1） and scissoring （1480-1450 cm-1） modes of the intercalated surfactants were observed for organo- bentonite. Compared with the pseudo first-order kinetic model, the pseudo second-order kinetic model is more suitable to describe the adsorption kinetics of 2-mercaptobenzothiazole onto organo-bentonite. The adsorption capacity of 2-mercaptobenzothiazole onto organo-bentonite increased with increasing initial concentration of 2-mercaptobenzothiazole, but decreased with increasing adsorbent dosage. The adsorption isotherm of 2-mercaptobenzothiazole onto organo-bentonite fits well with the Langmuir model. The maximum adsorption capacity of organo-bentonite for 2-mercaptobenzothiazole was 33.61 mg/g, indicating that organo-bentonite is a promising adsorbent for 2-mercaptobenzothiazole.

Effect of environmental C/N ratio on activities of lignin-degrading enzymes produced by Phanerochaete chrysosporium

Lignin-degrading enzymes secreted by white rot fungi play an important role in the degradation of lignin and persistent organic pollutants(POPs).In this study,effect of environmental C/N ratio on the activities of lignin-degrading enzymes,lignin peroxide(Li P)and manganese peroxidase(Mn P),produced by Phanerochaete chrysosporium,a white rot fungus,was investigated.Glucose was used as C source,and ammonium tartrate of different concentrations was used as N source to provide different C/N ratios.Relationships between Li P and Mn P activities and environmental C/N ratio were explored.The results showed that the higher the N source concentration,the faster the mycelium pellets aged.The faster the mycelium dry weight increased,the higher the Li P and Mn P activities.A high C/N ratio was a necessary condition for the secretion of Li P or Mn P.In addition,mycelium dry weight essentially affected enzyme activities.In the 122 C/N ratio and 50 C/N ratio treatments,mycelium dry weight essentially affected Mn P activity and both Li P and Mn P activities,respectively.

Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems

The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments,oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of p H, Fe（II） and Cr（III） on the intermediates and redox rate was investigated. SO42-and elemental S were formed as the major and minor products,respectively, during the oxidation processes. Ferric（hydr） oxides including Fe（OH）3and goethite were formed with low degree of crystallinity. Low p H and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air（oxygen）, and Fe（II） ions played a key role in the redox process. The addition of Fe（II） ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr（III） ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe（II） ions to form a Fe（III）/Fe（II） redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe（II） ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.

Humic acid-enhanced electron transfer of in vivo cytochrome c as revealed by electrochemical and spectroscopic approaches

Out-membrane cytochrome c （Cyt c） plays an important role carrying electrons from the inside of microbes to outside electron acceptors. However, the active sites of Cyt c are wrapped by non- conductive peptide chains, hindering direct extracellular electron transfer （EET）. Humic acids （HA） have been previously proven to efficiently facilitate EET. However, the inherent mechanism of HA- stimulated EET has not been well interpreted. Here, to probe the mechanism behind HA-stimulated EET, we studied the interaction between Cyt c and HA. The attachment of active in vivo Cyt c on a graphite electrode was achieved when MR-1 cells were self-assembled on the electrode surface. Pure horse-heart Cyt c was covalently immobilized on an electrode via 4-aminobenzoic acid to create an active in vitro Cyt c-enriched surface. Cyclic voltammetric measurements and scanning electron microscopy confirmed the immobilization of bacterial cells and pure Cyt c protein. Electrochemical methods revealed that HA could enhance the electrocatalytic current of both in vitro and in vivo Cyt c towards oxygen and thiosulfate, suggesting enhanced EET. The blue-shifted soret band in the UV-Vis spectra and changes in the excitation/emission matrix fluorescence spectra demonstrated that Cyt c interacted with HA to form organic complexes via electrostatic or hydrogen-bonding interactions. The results will help understand electron shuttle-stimulated EET and develop bacteria- based bioremediation and bioenergy technologies.

Reply to comments on “Adsorption of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite” by Yuhshan Ho

There were several first-order kinetic equations used and cited by previous publications （Do,an et al., 2007; Eftekhari et al., 2010; Lagergren, 1898; Kannan and Sundaram, 2001;Ozcan et al., 2006）：