Transcriptional Activity of Arsenic-Reducing Bacteria and Genes Regulated by Lactate and Biochar during Arsenic Transformation in Flooded Paddy Soil.

Organic substrates and biochar are important in controlling arsenic release from sediments and soils; however, little is known about their impact on arsenic-reducing bacteria and genes during arsenic transformation in flooded paddy soils. In this study, microcosm experiments were established to profile transcriptional activity of As(V)-respiring gene (arrA) and arsenic resistance gene (arsC) as well as the associated bacteria regulated by lactate and/or biochar in anaerobic arsenic-contaminated paddy soils. Chemical analyses revealed that lactate as the organic substrate stimulated microbial reduction of As(V) and Fe(III), which was simultaneously promoted by lactate+biochar, due to biochar's electron shuttle function that facilitates electron transfer from bacteria to As(V)/Fe(III). Sequencing and phylogenetic analyses demonstrated that both arrA closely associated with Geobacter (>60%, number of identical sequences/number of the total sequences) and arsC related to Enterobacteriaceae (>99%) were selected by lactate and lactate+biochar. Compared with the lactate microcosms, transcriptions of the bacterial 16S rRNA gene, Geobacter spp., and Geobacter arrA and arsC genes were increased in the lactate+biochar microcosms, where transcript abundances of Geobacter and Geobacter arrA closely tracked with dissolved As(V) concentrations. Our findings indicated that lactate and biochar in flooded paddy soils can stimulate the active As(V)-respiring bacteria Geobacter species for arsenic reduction and release, which probably increases arsenic bioavailability to rice plants.

Effect of nitrate addition on reductive transformation of pentachlorophenol in paddy soil in relation to iron(III) reduction.

Reductive dechlorination is a crucial pathway for anaerobic biodegradation of highly chlorinated organic contaminants. Under an anoxic environment, reductive dechlorination of organic contaminants can be affected by many redox processes such as nitrate reduction and iron reduction. In the present study, batch incubation experiments were conducted to investigate the effect of nitrate addition on reductive dechlorination of PCP in paddy soil with consideration of iron transformation. Study results demonstrate that low concentrations (0, 0.5 and 1 mM) of nitrate addition can enhance the reductive dechlorination of PCP and Fe(III) reduction, while high concentrations (5, 10, 20 and 30 mM) of nitrate addition caused the contrary. Significant positive correlations between PCP degradation rates and the formation rates of dissolved Fe(II) (pearson correlation coefficients r = 0.965) and HCl-extractable Fe(II) (r = 0.921) suggested that Fe(III) reduction may enhance PCP dechlorination. Furthermore, consistent variation trends of PCP degradation and the abundances of the genus Comamonas, capable of Fe(III) reduction coupled to reductive dechlorination, and of the genus Dehalobacter indicated the occurrence of microbial community variation induced by nitrate addition as a response to PCP dechlorination.

Profiles, sources, and transport of polycyclic aromatic hydrocarbons in soils affected by electronic waste recycling in Longtang, south China.

We studied the profiles, possible sources, and transport of polycyclic aromatic hydrocarbons (PAHs) in soils from the Longtang area, which is an electronic waste (e-waste) recycling center in south China. The sum of 16 PAH concentrations ranged from 25 to 4,300 ng/g (dry weight basis) in the following order: pond sediment sites (77 ng/g), vegetable fields (129 ng/g), paddy fields (180 ng/g), wastelands (258 ng/g), dismantling sites (678 ng/g), and former open burning sites (2,340 ng/g). Naphthalene, phenanthrene, fluoranthene, pyrene, chrysene, and benzo[b]fluoranthene were the dominant PAHs and accounted for approximately 75 % of the total PAHs. The similar composition characteristics of PAHs and the significant correlations among individual, low molecular weight, high molecular weight, and total PAHs were found in all six sampling site types, thus indicating that PAHs originated from similar sources. The results of both isomeric ratios and principal component analyses confirmed that PAHs were mainly derived from the incomplete combustion of e-waste. The former open burning sites and dismantling sites were the main sources of PAHs. Soil samples that were taken closer to the point sources had high PAH concentrations. PAHs are transported via different soil profiles, including those in agricultural fields, and have been detected not only in 0- to 40-cm-deep soil but also in 40 cm to 80 cm-deep soil. PAH concentrations in soils in Longtang have been strongly affected by primitive e-waste recycling, particularly by former open burning activities.

Evaluating oxidation-reduction properties of dissolved organic matter from Chinese milk vetch (Astragalus sinicus L.): a comprehensive multi-parametric study.

Green manuring is a common practice in replenishment of soil organic matter and nutrients in rice paddy field. Owing to the complex interplay of multiple factors, the oxidation--reduction (redox) properties of dissolved organic matter (DOM) from green manure crops are presently not fully understood. In this study, a variety of surrogate parameters were used to evaluate the redox capacity and redox state of DOM derived from Chinese milk vetch (CMV, Astragalus sinicus L.) via microbial decomposition under continuously flooded (CF) and non-flooded (NF) conditions. Additionally, the correlation between the surrogate parameters of CMV-DOM and the kinetic parameters of relevant redox reactions was evaluated in a soil-water system containing CMV-DOM. Results showed that the redox properties of CMV-DOM were substantially different between the fresh and decomposed CMV-DOM treatments. Determination of the surrogate parameters via ultraviolet-visible/Fourier transform infrared absorption spectroscopy and gel permeation chromatography generally provided high-quality data for predicting the redox capacity of CMV-DOM, while the surrogate parameters determined by elemental analysis were suitable for predicting the redox state of CMV-DOM. Depending on the redox capacity and redox state of various moieties/components, NF-decomposed CMV-DOM could easily accelerate soil reduction by shuttling electrons to iron oxides, because it contained more reversible redox-active functional groups (e.g. quinone and hydroquinone pairs) than CF-decomposed CMV-DOM. This work demonstrates that a single index cannot interpret complex changes in multiple factors that jointly determine the redox reactivity of CMV-DOM. Thus, a multi-parametric study is needed for providing comprehensive information on the redox properties of green manure DOM.

Enhancement effect of two ecological earthworm species (Eisenia foetida and Amynthas robustus E. Perrier) on removal and degradation processes of soil DDT.

Effects of two ecological earthworm species (epigeic Eisenia foetida and endogeic Amynthas robustus E. Perrier) with different densities (15 and 30 individuals per kg of soil) on the removal of soil 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) with two pollution levels (2 and 4 mg kg(-1)) were investigated. Concentrations of DDT and its metabolites, including 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE), and 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU), were monitored after 60, 180, and 360 days of incubation. The results obtained showed that both earthworm species can significantly enhance degradation of soil DDT to its metabolites. For E. foetida, the higher earthworm density showed significantly higher rate of DDT degradation than the lower one. Anaerobic reductive dechlorination was the main degradation pathway over 180 days of incubation, while the aerobic dechlorination process was promoted between 180 and 360 days of incubation. Some earthworm amended treatments showed significantly higher microbial biomass carbon and nitrogen than the control, which suggested that earthworms might enhance the microbial degradation of DDT. Both earthworm species would have the potential to be applied to enhance the remediation of agricultural lands polluted by DDT.

Corynebacterium humireducens sp. nov., an alkaliphilic, humic acid-reducing bacterium isolated from a microbial fuel cell.

A novel halotolerant, alkaliphilic, humic acid-reducing bacterium, designated MFC-5(T), was isolated from a microbial fuel cell that was fed continuously with artificial wastewater (pH 10.0). Cells were Gram-positive-staining, facultatively anaerobic, non-fermentative, non-motile rods and had a G+C content of 59.0 mol%. Microbial growth was observed with <13 % (w/v) NaCl (optimum 10 %), at pH 7.0-11.0 (optimum pH 9.0) and at 25-45 °C (optimum 37 °C). Strain MFC-5(T) was active in the anaerobic reduction of a humic acid analogue, anthraquinone-2,6-disulphonate, with lactate, formate, acetate, ethanol or sucrose as the electron donor. The major cellular fatty acids were C(18 : 1)ω9c (42.68 %), C(16 : 0) (33.69 %), C(18 : 0) (7.56 %), C(17 : 1)ω8c (5.14 %) and C(17 : 0) (3.39 %). Phylogenetic analysis demonstrated that strain MFC-5(T) displayed >3 % 16S rRNA gene sequence divergence from its closest relatives. Based on phenotypic, genetic and phylogenetic analysis, a novel species, Corynebacterium humireducens sp. nov., is proposed. The type strain is MFC-5(T) ( = NBRC 106098(T)  = CGMCC 2452(T)  = DSM 45392(T)).

[Reactivation of Passivated Biochar/Nanoscale Zero-Valent Iron by an Electroactive Microorganism for Cooperative Hexavalent Chromium Removal and Mechanisms].

Nanoscale zero-valent iron (nZVI) shows excellent reduction of Cr(Ⅵ), but the passivation on its outer surface can restrict its longevity and performance. To tackle this problem, this work introduced Shewanella oneidensis MR-1, a dissimilatory iron-reducing bacterium, into the chemical reduction system of aged nZVI/biochar (B) and Cr(Ⅵ). The potential synergistic effect of Cr(Ⅵ) reduction of aged nZVI/B and MR-1 was systematically investigated under varying conditions. The results indicated that aged nZVI/B and MR-1 exhibited a synergistic effect at a pH of 7, and the removal rate of Cr(Ⅵ) increased by 51.3%. Further research showed that the synergistic effect could be attenuated with the increase in the initial Cr(Ⅵ) concentration and enhanced with the increase in the MR-1 concentration. The XPS spectra confirmed that Cr(Ⅵ) was mainly removed through reduction. The dissimilatory iron-reducing ability of MR-1 played a key role in enhancing the Cr(Ⅵ) reduction. The reductive dissolution of the oxidation layers not only released reactive sites inside the nZVI, but also reduced Cr(Ⅵ) by producing ferrous ions. Moreover, B promoted the reduction by dispersing the nZVI and mediating the extracellular electron transfer. This study provides a new insight into solving the passivation problem of the long-term application of nZVI for Cr(Ⅵ) removal, which is considered a promising solution for synergistically improving the performance of nZVI in environmental remediation.

Microbial fuel cell with an azo-dye-feeding cathode.

Microbial fuel cells (MFCs) were constructed using azo dyes as the cathode oxidants to accept the electrons produced from the respiration of Klebsiella pneumoniae strain L17 in the anode. Experimental results showed that a methyl orange (MO)-feeding MFC produced a comparable performance against that of an air-based one at pH 3.0 and that azo dyes including MO, Orange I, and Orange II could be successfully degraded in such cathodes. The reaction rate constant (k) of azo dye reduction was positively correlated with the power output which was highly dependent on the catholyte pH and the dye molecular structure. When pH was varied from 3.0 to 9.0, the k value in relation to MO degradation decreased from 0.298 to 0.016 micromol min(-1), and the maximum power density decreased from 34.77 to 1.51 mW m(-2). The performances of the MFC fed with different azo dyes can be ranked from good to poor as MO>Orange I>Orange II. Furthermore, the cyclic voltammograms of azo dyes disclosed that the pH and the dye structure determined their redox potentials. A higher redox potential corresponded to a higher reaction rate.

Effects of peptizing conditions on nanometer properties and photocatalytic activity of TiO2 hydrosols prepared by H2TiO3.

TiO2 hydrosols were prepared from metatitanic acid (H2TiO3) by chemical precipitation-peptization method under various peptizing conditions. The effects of peptizing conditions on nanosized properties and photocatalytic activity of TiO2 hydrosols were investigated. The crystal structure, crystallinity, particle size distribution, and transparency (T%) of as-obtained hydrosols were characterized by means of X-ray diffraction, transmission electron microscopy, light-scattering size analyzer, and UV-vis transmittance spectra. The results showed that the properties of hydrosols depended on peptizing conditions including a molar ratio of H+/Ti, temperature, and solid content. The photoactivity of TiO2 hydrosols was evaluated in terms of the degradation of rhodamine B (RhB) in aqueous solution, and formaldehyde (HCHO) and methyl mercaptan (CH3SH) in gaseous phase. The results showed that increase in H+/Ti ranging 0.19-0.75 led to the decrease in particle size and the increase in transparency. With increasing of temperature, particle sizes increased while the transparency and photoactivity decreased steadily when the temperature was higher than 65 degrees C. The particle size, transparency and photoactivity of the hydrosols hardly depended on solid content when it was not less than 2%. It should be confirmed that the hydrosols with higher crystallinity, smaller particle size and higher transparency could have the higher photoactivity for the degradation of RhB, CH3SH, and HCHO. In this study, the optimal peptizing conditions were determined to be H+/Ti=0.75, temperature=65 degrees C and solid content=2-6%.

TiO2 hydrosols with high activity for photocatalytic degradation of formaldehyde in a gaseous phase.

Two types of TiO2 hydrosols (TOSO and HTO) were prepared from titanium sulfate (TiOSO4) and metatitanic acid (H2TiO3) by a chemical precipitation-peptization method, respectively. The prepared hydrosols were characterized by means of X-ray diffraction, particle size distribution, scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller and Barret-Joyner-Halender methods. The results showed that the TiO2 hydrosols with an anatase crystal structure had smaller particle sizes, higher surface areas, larger pore volume, and higher transparence than Degussa P-25 suspension. The photocatalytic activity of the TiO2 hydrosols was evaluated for formaldehyde degradation under UVA illumination in a gaseous phase. The results demonstrated that the photocatalytic activity with the catalyst loading of 2mgcm(-2) was ranked as an order of HTO>TOSO>P-25. The photocatalytic activity was further studied using the HTO catalyst under different experimental conditions. The results showed that catalyst loading, relative humidity, and initial concentration could influence the efficiency of HCHO photocatalytic degradation. It was found that a catalyst loading of more than 2mgcm(-2) and a relative humidity of 55% were two essential conditions for achieving the best performance under these experimental conditions. The repeated experiments indicated that the HTO catalyst was reasonably stable and could be repeatedly used for the HCHO oxidation under UVA irradiation. This investigation would be helpful to promote the application of TiO2 photocatalytic technique for indoor air purification.

Roles of different active metal-reducing bacteria in arsenic release from arsenic-contaminated paddy soil amended with biochar.

Although biochar has great potential for heavy metal removal from sediments or soils, its impact on arsenic biogeochemistry in contaminated paddy fields remains poorly characterized. In this study, anaerobic microcosms were established with arsenic-contaminated paddy soil to investigate arsenic transformation as well as the potentially active microbial community and their transcriptional activities in the presence of biochar. The results demonstrated that biochar can simultaneously stimulate microbial reduction of As(V) and Fe(III), releasing high levels of As(III) into the soil solution relative to the control. Total RNAs were extracted to profile the potentially active microbial communities, which suggested that biochar increased the abundance of arsenic- and iron-related bacteria, such as Geobacter, Anaeromyxobacter and Clostridium compared to the control. Reverse transcription, quantitative PCR (RT-qPCR) showed that the abundance of Geobacter transcripts were significantly stimulated by biochar throughout the incubation. Furthermore, significant positive correlations were observed between the abundance of Geobacter transcripts and As(V) concentrations, and between that of Clostridium transcripts and Fe(III) concentrations in biochar-amended microcosms. Our findings suggest that biochar can stimulate the activity of metal-reducing bacteria to promote arsenic mobility. The Geobacter may contribute to As(V) reduction in the presence of biochar, while Clostridium has a role in Fe(III) reduction.

The influence of Si(iv) on the reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples for 2-nitrophenol reduction in γ-Al2O3 suspensions.

In a natural environment, Fe(ii) adsorbed onto the surfaces of natural particles to form various surface complex species can influence the transformation of contaminants. The reductive reactivity of the [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples are close correlated with the surrounding conditions. In this study, we investigated the effects of Si(iv) on the reductive reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples adsorbed onto γ-Al2O3. Experiments were conducted under different conditions to investigate the effects of Si(iv) on the reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples for 2-nitrophenol (2-NP, selected as the model pollutant) reduction in γ-Al2O3 suspensions. Kinetics results revealed that chemical adsorption is the rate limiting step in Fe(ii) and Si(iv) adsorption processes and the reduction of 2-NP is an endothermic reaction. The linear correlations between the reduced peak oxidation potential (E p) (versus SCE) and 2-NP reduction rate (ln k), and between the adsorbed Fe(ii) density (ρ Fe(II)) and ln k, illustrated that E p and ρ Fe(II) are two key factors in the inhibiting effects of Si(iv) on the reductive reactivity of Fe(iii)/Fe(ii) couples on γ-Al2O3. The results of Fe K-edge X-ray absorption spectroscopy revealed that the increase of Si(iv) concentration resulted in the gradual change in the composition of the adsorbed Fe species from pure [triple bond, length as m-dash]AlOFe+ (γ-Al2O3 surface-bound Fe(ii) species with higher reductive reactivity) to a mixture of [triple bond, length as m-dash]AlOFe+ and [triple bond, length as m-dash]SiOFe+ (SiO2 surface-bound Fe(ii) species with lower reductive reactivity), leading to the decrease in ρ Fe(II), the positive shift in E p, the increase in activation energy (E a), and consequently the decrease in the reduction rate (ln k) of 2-NP.

Simultaneous alleviation of cadmium and arsenic accumulation in rice by applying zero-valent iron and biochar to contaminated paddy soils.

The fates of cadmium (Cd) and arsenic (As) in paddy fields are generally opposite; thus, the inconsistent transformation of Cd and As poses large challenges for their remediation. In this study, the impacts of zero valent iron (ZVI) and/or biochar amendments on Cd and As bioavailability were examined in pot trials with rice. Comparison with the untreated soil, both Cd and As accumulation in different rice tissues decreased significantly in the ZVI-biochar amendments and the Cd and As accumulation in rice decreased with increasing ZVI contents. In particular, the concentrations of Cd (0.15 ± 0.01 mg kg-1) and As (0.17 ± 0.01 mg kg-1) in rice grains were decreased by 93% and 61% relative to the untreated soil, respectively. A sequential extraction analysis indicated that with increasing Fe ratios in the ZVI-biochar mixtures, bioavailable Cd and As decreased, and the immobilized Cd and As increased. Furthermore, high levels of Fe, Cd, and As were detected in Fe plaque of the ZVI-biochar amendments in comparison with the single biochar or single ZVI amendments. The ZVI-biochar mixture may have a synergistic effect that simultaneously reduces Cd and As bioavailability by increasing the formation of amorphous Fe and Fe plaque for Cd and As immobilization. The single ZVI amendment significantly decreased As bioavailability, while the single biochar amendment significantly reduced the bioavailability of Cd compared with the combined amendments. Hence, using a ZVI-biochar mixture as a soil amendment could be a promising strategy for safely-utilizing Cd and As co-contaminated sites in the future.

Fe(II)/Cu(II) interaction on goethite stimulated by an iron-reducing bacteria Aeromonas Hydrophila HS01 under anaerobic conditions.

Copper is a trace element essential for living creatures, but copper content in soil should be controlled, as it is toxic. The physical-chemical-biological features of Cu in soil have a significant correlation with the Fe(II)/Cu(II) interaction in soil. Of significant interest to the current study is the effect of Fe(II)/Cu(II) interaction conducted on goethite under anaerobic conditions stimulated by HS01 (a dissimilatory iron reduction (DIR) microbial). The following four treatments were designed: HS01 with α-FeOOH and Cu(II) (T1), HS01 with α-FeOOH (T2), HS01 with Cu(II) (T3), and α-FeOOH with Cu(II) (T4). HS01 presents a negligible impact on copper species transformation (T3), whereas the presence of α-FeOOH significantly enhanced copper aging contributing to the DIR effect (T1). Moreover, the violent reaction between adsorbed Fe(II) and Cu(II) leads to the decreased concentration of the active Fe(II) species (T1), further inhibiting reactions between Fe(II) and iron (hydr)oxides and decelerating the phase transformation of iron (hydr)oxides (T1). From this study, the effects of the Fe(II)/Cu(II) interaction on goethite under anaerobic conditions by HS01 are presented in three aspects: (1) the accelerating effect of copper aging, (2) the reductive transformation of copper, and (3) the inhibition effect of the phase transformation of iron (hydr)oxides.

The effect of erbium on the adsorption and photodegradation of orange I in aqueous Er3+-TiO2 suspension.

Pure TiO(2) and erbium ion-doped TiO(2) (Er(3+)-TiO(2)) catalysts prepared by the sol-gel method were characterized by means of XRD and diffusive reflectance spectra (DRS). The XRD results showed that erbium ion doping could enhance the thermal stability of TiO(2) and inhibit the increase of the crystallite size, and the DRS results showed that the optical absorption edge slightly shifted to red direction owing to erbium ion doping and the Er(3+)-TiO(2) catalysts had three typical absorption peaks located at 490, 523 and 654 nm owing to the transition of 4f electron from (4)I(15/2) to (4)F(7/2), (2)H(11/2) and (4)F(9/2). With a purpose of azo dyes degradation, orange I was used as a model chemical. And the adsorption isotherm, degradation and mineralization of orange I were investigated in aqueous suspension of pure TiO(2) or Er(3+)-TiO(2) catalysts. The results showed that Er(3+)-TiO(2) catalysts had higher adsorption equilibrium constants and better adsorption capacity than pure TiO(2). The adsorption equilibrium constants (K(a)) of Er(3+)-TiO(2) catalysts were about twice of that of pure TiO(2). The maximum adsorption capacity (Q(max)) of 2.0% Er(3+)-TiO(2) catalyst was 13.08x10(-5)mol/g, which was much higher than that of pure TiO(2) with 9.03x10(-5)mol/g. Among Er(3+)-TiO(2) catalysts, 2.0% Er(3+)-TiO(2) catalyst achieved the highest Q(max) and K(a) values. The kinetics of the orange I degradation using different Er(3+)-TiO(2) catalysts were also studied. The results demonstrated that the degradation and mineralization of orange I under both UV radiation and visible light were more efficient with Er(3+)-TiO(2) catalyst than with pure TiO(2), and an optimal dosage of erbium ion at 1.5% achieved the highest degradation rate. The higher photoactivity under visible light might be attributable to the transitions of 4f electrons of Er(3+) and red shifts of the optical absorption edge of TiO(2) by erbium ion doping.

Dependence of bisphenol A photodegradation on the initial concentration of oxalate in the lepidocrocite-oxalate complex system.

To understand the degradation of endocrine disrupting chemicals (EDCs) in natural environment with existence of iron oxides and carboxylic acids, the dependence of bisphenol A (BPA) photodegradation on the initial concentration of oxalate (COX) in lepidocrocite (gamma-FeOOH) aqueous suspension was investigated under both UV and visible lights in this study. Lepidocrocite powder was home-prepared by a hydrothermal process. It was found that BPA degradation was promoted greatly in the presence of oxalate owing to the formation of lepidocrocite-oxalate complex. And there was an optimal COX, which was 2.0 and 2.4 mmol/L, under UV and visible lights, respectively. The first-order kinetic constant, k value increased 38 times from 0.17 x 10(-2) min(-1) in the absence of oxalate to 6.39 x 10(-2) min(-1) in the presence of oxalate with an optimal COX (2.0 mmol/L) under UV irradiation, and almost 306 times from 0.02 x 10(-2) min(-1) in the absence of oxalate to 6.11 x 10(-2) min(-1) in the presence of oxalate with an optimal COX (2.4 mmol/L) under visible irradiation. The BPA degradation rate increased and the first-order kinetic constants decreased with the increase in BPA initial concentration. The dependence of the variation of pH value, total-Fe and Fe2+ during the photoreaction on COX was also investigated. The pH value increased obviously with the reaction time. Total-Fe increased dramatically at the first 5 min and then decreased quickly under UV irradiation and slowly under visible irradiation. The initial concentration of oxalate is a main factor to affect BPA photodegradation in aqueous suspension under both UV and visible lights.

[Impacts of landscape patterns on heavy metal contamination of agricultural top soils in the Pearl River Delta, South China].

Landscape patterns are known to influence many ecological processes, but the relationship between landscape patterns and soil pollution processes is not well understood. Based on 300 top soil samples, land use and cover map for the Pearl River Delta (PRD) of 2005, this study explored the characteristics and spatial pattern of heavy metal contamination of agricultural top soils and examined the impacts of landscape patterns on the heavy metal contamination in the buffers of soil samples. Research methods included geostatistical analysis, landscape pattern analysis, single-factor pollution indices, and Pearson correlation analysis. We found that: 1) out of the 235 agricultural soil samples, 3.8%, 0.4%, 17.0% and 9.4% samples exceeded the Grade II national standard for As, Pb, Cd and Ni concentrations respectively. High pollution levels were found in three cities, Guangzhou, Foshan and Zhongshan; 2) soils in the farmland were more polluted than those in the forest and orchard land, and there were no differences among different agricultural land use types in contamination level of each heavy metal (except Cd); and 3) the proportion, mean patch area as well as the degree of landscape fragmentation, landscape-level structural complexity and aggregation/connectivity of water at the buffer zone were significantly positively correlated with the contamination level of each of the four heavy metals in agricultural top soils. Part of the landscape pattern of urban land in the buffer zone also positively correlated with Pb and Cd levels (P < 0.05). On the contrary, the proportion, mean patch area and aggregation degree of forest land negatively correlated with soil Pb and Ni levels (P < 0.05); and 4) the closer to the industry land were the soil samples, the more polluted the soils were for Pb, Cd and Ni. Only landscape diversity was found to be positively correlated with soil Cd contamination. The study results provide new information and scientific basis for heavy metal pollution control and remediation, especially for agricultural soils in the PRD.

Spatial distribution of heavy metals of agricultural soils in Dongguan, China.

Distribution and speciation of heavy metals of agricultural soils(85 surface soil samples and 4 soil profiles) in Dongguan were investigated, while total Cr, Cu, Ni, Pb, Zn(abbreviated as Cr, Cu, Ni, Pb, Zn) and available Cu, Zn(Av-Cu, Av-Zn) were analyzed by a flame absorption spectrophotometer(AAS), and total Cd(Cd) was analyzed using graphite furnace AAS. The content of Cd, Cu and Ni was partially much more than the second grade of GB15618-1995 even though the mean contents of all heavy metal were less than the threshold value of the second grade and only the mean content of Pb was more than the value of national background. Results of descriptive statistic showed that the mean content of heavy metals should depend on land utilization and spatial location at some extent. The heavy metal contents were higher in the Southwest and Northwest than in the Central. In addition, the mean contents of Zn and Pb in Dongguan paddy soils were significantly higher than those of Pearl River Delta(PRD) and Taihu Lake region(TLR). Correlation analyses indicated that there existed significant correlation between Cr and Ni in orchard soils, and among Zn, Cd and Cu, between Av-Cu and Cu, between Av-Zn and Cr, Ni, pH value in vegetable soils, and a weak relationship between Cd, Cu and Pb, between Av-Zn and Zn. Principal component analyses(PCA) showed that the order of importance should be Zn > Pb > Cr > Ni > Cu.

Arsenite oxidation and removal driven by a bio-electro-Fenton process under neutral pH conditions.

The iron-catalyzed oxidation of arsenite (As(III)) associated with Fenton or Fenton-like reactions is one of the most efficient arsenic removal methods. However, the conventional chemical or electro-Fenton systems for the oxidation of As(III) are only efficient under acid conditions. In the present study, a cost-effective and efficient bio-electro-Fenton process was performed for As(III) oxidation in a dual-chamber microbial fuel cell (MFC) under neutral pH conditions. In such a system, the Fenton reagents, including H2O2 and Fe(II), were generated in situ by microbial-driven electro-reduction of O2 and γ-FeOOH, respectively, without an electricity supply. The results indicated that the process was capable of inducing As(III) oxidation with an apparent As(III) depletion first-order rate constant of 0.208 h(-1). The apparent oxidation current efficiency was calculated to be as high as 73.1%. The γ-FeOOH dosage in the cathode was an important factor in determining the system performance. Fourier-transform infrared spectroscopy (FT-IR) analysis indicated that As(V) was bound to the solid surface as a surface complex but not as a precipitated solid phase. The mechanism of bio-E-Fenton reaction for As(III) oxidation was also proposed. The bio-electro-Fenton system makes it potentially attractive method for the detoxification of As(III) from aqueous solution.

The effect of ammonium chloride and urea application on soil bacterial communities closely related to the reductive transformation of pentachlorophenol.

Pentachlorophenol (PCP) is widely distributed in the soil, and nitrogen fertilizer is extensively used in agricultural production. However, studies on the fate of organic contaminants as affected by nitrogen fertilizer application have been rare and superficial. The present study aimed to examine the effect of ammonium chloride (NH4Cl) and urea (CO(NH2)2) application on the reductive transformation of PCP in a paddy soil. The study showed that the addition of low concentrations of NH4Cl/CO(NH2)2 enhanced the transformation of PCP, while the addition of high concentrations of NH4Cl/CO(NH2)2 had the opposite effect. The variations in the abundance of soil microbes in response to NH4Cl/CO(NH2)2 addition showed that both NH4Cl and CO(NH2)2 had inhibitory effects on the growth of dissimilatory iron-reducing bacteria (DIRB) of the genus Comamonas. In contrast, for the genus Shewanella, low concentrations of NH4Cl inhibited growth, and high concentrations of NH4Cl enhanced growth, whereas all concentrations of CO(NH2)2 showed enhancement effects. In addition, consistent patterns of variation were found between the abundances of dechlorinating bacteria in the genus Dehalobacter and PCP transformation rates under NH4Cl/CO(NH2)2 addition. In conclusion, nitrogen application produced variations in the structure of the soil microbial community, especially in the abundance of dissimilatory iron-reducing bacteria and dechlorinating bacteria, which, in turn, affected PCP dechlorination.