Mechanism of extracellular electron transport and reactive oxygen mediated Sb(III) oxidation by Klebsiella aerogenes HC10.

Microbial oxidation and the mechanism of Sb(III) are key governing elements in biogeochemical cycling. A novel Sb oxidizing bacterium, Klebsiella aerogenes HC10, was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation. However, linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive. Here, model phenolic and quinone compounds, i.e., anthraquinone-2,6-disulfonate (AQDS) and hydroquinone (HYD), representing extracellular oxidants secreted by K. aerogenes HC10, were chosen to further study the Sb(III) oxidation mechanism. N2 purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78% of Sb(III) in the metabolite reaction system, while hydroxyl free radicals (·OH) accounted for 15.52%. ·OH and H2O2 are the main driving factors for Sb oxidation. Radical quenching, methanol purification and electron paramagnetic resonance (EPR) analysis revealed that ·OH, superoxide radical (O2•-) and semiquinone (SQ-•) were reactive intermediates of the phenolic induced oxidation process. Phenolic-induced ROS are one of the main oxidants in metabolites. Cyclic voltammetry (CV) showed that electron transfer of quinone also mediated Sb(III) oxidation. Part of Sb(V) was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the incubation system. Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.

Mechanism of efficient adsorption for arsenic in aqueous solution by zeolitic imidazolate framework­8.

Arsenic (As) is one extremely hazardous and carcinogenic metalloid element. Due to mining, metal smelting, and other human activities, the pollution of water (especially groundwater) and soil caused by As is increasingly serious, which badly threatens the environment and human health. In this study, a zeolite imidazolate framework (ZIF-8) was synthesized at room temperature and employed as an adsorbent to facilitate the adsorption of As(III) and As(V) from the solution. The successful synthesis of ZIF-8 was demonstrated by X-ray diffraction (XRD), and scanning electron microscopy (SEM) revealed that its particle size was approximately 80 nm. The adsorption kinetics, adsorption isotherm, solution pH, dose, coexisting ions, and the synonymous elements antimony (Sb) were conducted to study the adsorption of As by ZIF-8 nanoparticles. The maximum saturation adsorption capacity was determined to be 101.47 mg/g and 81.40 mg/g for As(III), and As(V) at initial pH = 7.0, respectively. Apparently, ZIF-8 had a good removal effect on As, and it still maintained a good performance after four cycles. The coexisting ions PO43- and CO32- inhibited the adsorption of both As(III) and As(V). ZIF-8 performed well in removing both As and Sb simultaneously, although the presence of Sb hindered the adsorption of both As(III) and As(V). Both FTIR and XPS indicated the adsorption mechanism of As on ZIF-8: ZIF-8 generates a large amount of Zn-OH on the surface through hydrolysis and partial fracture of Zn-N, both of which form surface complexes with As.

Investigating the use of Aspergillus niger fermentation broth as a washing treatment for arsenic and antimony co-contaminated soil.

High concentrations of arsenic and antimony contamination in soil are a potential risk to the ecological environment and human health. Soil washing can effectively and permanently reduce the soil contamination. This study used Aspergillus niger fermentation broth as a washing agent to remove As and Sb from contaminated soil. Characterization of organic acids in the fermentation broth by high-performance liquid chromatographic (HPLC) and chemically simulated leaching experiments revealed that oxalic acid played a significant role in removing As and Sb from the soil. The effect of washing conditions on the metal removal rate of Aspergillus niger fermentation broth was investigated by batch experiments, and the optimal conditions were determined: no dilution, pH 1, L/S ratio 15:1, and leaching at 25 °C for 3 h. The soils were washed three times under optimal conditions, with 73.78%, 80.84%, and 85.83% removal of arsenic and 65.11%, 76.39%, and 82.06% removal of antimony, respectively. The results of metal speciation distribution in the soil showed that the fermentation broth could effectively remove As and Sb on amorphous Fe/Al hydrous oxides in soil. The analysis of X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) of soils before and after washing showed that the washing of Aspergillus niger fermentation broth had a minor effect on the structural changes of soils. After washing, soil organic matter and soil enzyme activity were increased. Thus, Aspergillus niger fermentation broth shows excellent potential as a washing agent for removing As and Sb from soils.

Contamination characteristics of heavy metals in a small-scale tanning area of southern China and their source analysis.

Tanning industry has been identified as a significant source of heavy metals; however, heavy metals contamination in farmland soil due to small-scale tanning activities remains unstudied. Here, samples from topsoil, profile soil, water and sediments in the vicinity of a small-scale tanning area in Nanning, Guangxi Zhuang Autonomous Region, southern China, were collected to explore the contamination characteristics and source apportionment of Cd, Cr, Hg, As, Cu, Pb, Ni and Zn. The results show that the farmland soil was mainly contaminated by Cr and its content was 33.40-3830.00 mg kg-1. The highest level of Cr, Cd and Hg was above their thresholds, while the average contents of Cd, Cr, Pb and Hg exceeded the corresponding background levels. Moreover, enrichment of Cr in soil profiles and stream sediments were also observed, whose concentrations varied from 11.50 to 2590.00 mg kg-1 and 738.00 to 11,200.00 mg kg-1, respectively. Concentrations of Cr in top soils and soil profiles from farmland surrounding the stream were significantly higher than those from other areas, and the soils surrounding the stream were moderately to heavily polluted. The multivariate statistical analysis indicated that the heavy metals originated from traffic (Cu, Ni, Zn, Hg, and Pb), agriculture (Cr and Cd) and nature (As). Source apportionment with PMF model results showed that the relative contribution rates of heavy metals by traffic, tanning, agriculture, other industrial activities and natural sources were 16.00%, 18.88%, 20.88%, 22.04% and 22.20%, respectively. These findings indicate that small-scale tanning activities could also lead to heavy metal accumulation in the surrounding environment, which requires decision-makers to pay more attention and to develop effective remediation procedures.

Pollution characteristics and source identification of farmland soils in Pb-Zn mining areas through an integrated approach.

Long-term mining activities have caused serious heavy metals contamination of farmland soils. In this study, we investigated the concentrations, distributions, accumulations, potential ecological risk, and sources of eight heavy metals in farmland soils of Pb-Zn mining areas. According to the soil standard GB15618-2018, Cd was the most contaminated, followed by Pb and Zn. The geo-accumulation index showed that Pb, Zn, Cd, and Hg accumulated seriously. The potential risk index indicated that Cd, Hg, and Pb were the main environmental risk elements. An integrated approach combining multivariate statistical analysis, PMF, and GIS mapping was used to analyze the sources of heavy metals. Four main sources were identified and quantified: (1) mining activities source, the main source of Cd (71.09%) and Zn (61.88%); (2) agricultural activities source, dominated by Hg (73.01%); (3) atmospheric deposition sources, with Pb (85.11%) as the main contributor; (4) natural source, characterized by Cr (72.96%), Ni (66.04%), As (55.98%) and Cu (37.70%). This study would help us understand the pollution characteristics and sources of farmland soils in mining areas and provide basic information for the next step of pollution control and remediation.

Immobilization mechanism of antimony by applying zirconium-manganese oxide in soil.

Antimony (Sb) accumulation in soil poses great potential risk to ecological environment, and its mobilization, transformation and bioavailability are controlled by its fractions and species. Hence, it is important to develop functional materials with both adsorption and oxidation that achieve detoxification and control the mobilization of Sb. In this study, the synthesized zirconium­manganese oxide (ZrMn) could extremely promoted the transformation of antimonite [Sb(III)] to antimonate [Sb(V)], induced the bioavailable Sb shift to well-crystallized (hydr)oxides of Mn and residual fractions, and further reduced mobility and bioavailability Sb in soil. The sorption of ZrMn to Sb(III) and antimonate Sb(V) were affected by interfering ions, and to Sb(III) was a heterogeneous adsorption process. Spectroscopic characterization of XPS and FTIR suggested exchange between the hydroxyl groups and Sb was crucial in its retain and forming an electronegative inner-sphere mononuclear or binuclear bridging compound. The oxidation induced the transformation of Mn species in ZrMn, generated Mn(II) and Mn(III) exposing more reactive sites conducive to oxidation and adsorption, thus Mn oxides has a higher adsorption capacity for Sb(III). However, the Zr oxides of ZrMn presented adsorption rather than oxidation. The application of ZrMn could realize the dual effect of Sb oxidation detoxification and adsorption immobilization in soil, which provided references for Sb contaminated soil remediation.

Sb(III) resistance mechanism and oxidation characteristics of Klebsiella aerogenes X.

Resistant bacteria are potential natural materials for the bioremediation of soil metalloid pollution. A strain isolated from farmland soil chronically exposed to Sb was identified as K. aerogenes X with high antimonite [Sb(III)] tolerance and oxidation ability. The resistance mechanism of K. aerogenes X and its extracellular polymeric substances (EPS), antioxidant enzymes, and oxidation characteristics in Sb(III) stress were investigated in this study by stress incubation experiments and FTIR. The biotoxicity of Sb was limited by the binding of the organic compounds in EPS, and the anionic functional groups (e.g., amino, carboxyl and hydroxyl groups, etc.) present in the cell envelope were the components primarily responsible for the metalloid-binding capability of K. aerogenes X. The K. aerogenes X can oxidize Sb(III), and its metabolites induce changes in reactive oxygen species (ROS), catalase (CAT), total superoxide dismutase (SOD) and glutathione s-transferase (GSH-S) activity, indicating that the resistance mechanisms of K. aerogenes X are mediated by oxidative stress, EPS restriction and cell damage. Oxidation of Sb(III) is driven by interactions in intracellular oxidation, cell electron transport, extracellular metabolism including proteins and low molecular weight components (LMWs). LMWs (molecular weight <3 kDa) are the main driving factor of Sb(III) oxidation. In addition, Sb resistance genes arsA, arsB, arsC, arsD and acr3 and potential oxidation gene arsH were identified in K. aerogenes X. Owing to its natural origin, high tolerance and oxidation ability, K. aerogenes X could serve as a potential bioremediation material for the mitigation of Sb(III) in contaminated areas.

Remediation of Soil in a Deserted Arsenic Plant Site Using Synthesised MgAlFe-LDHs.

Layered double hydroxides (LDHs) are promising soil contamination amendment agents for its efficient absorbing abilities. However, the application of LDHs in remediation of heavy metal contaminated soil are to be developed. In this study, we synthesized MgAlFe-LDHs by introducing Fe3+ into interlayer of the MgAl-LDHs using co-precipitation method. X-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR) and scanning electron microscope (SEM) were employed to characterized the micro structure of MgAlFe-LDHs. And then pot incubation and pilot experiments were conducted to investigate the heavy metal removal efficiencies of MgAlFe-LDHs and its potential being applicated in As contaminated soil amendment from a deserted arsenic plant site. Incubation experiments showed that the MgAlFe-LDHs had a higher removal efficiency on arsenic contaminated soil compared to other agents. And the results of pilot experiments indicated that the MgAlFe-LDHs can immobilize up to 90% of the As in soil with 5% (w/w) addition. Based on the results above, MgAlFe-LDHs are promising materials amending the heavy metal contaminated soil with practical application value.

Promoted oxidation of polycyclic aromatic hydrocarbons in soils by dual persulfate/calcium peroxide system.

In situ chemical oxidations (ISCO) have been demonstrated as effective ways for remediating soils contaminated with organic pollutants by complete mineralization. This work aims to develop a technology for the oxidation remediation of soils contaminated with Polycyclic Aromatic Hydrocarbons (PAHs) using a dual calcium peroxide (CP)/persulfate (PS) oxidant system activated by oxalic acid (OA)-chelating Fe2+. The dual peroxide system was set up, and the effects of 5 single factors (i.e., CP dosage, PS dosage, Fe2+ dosage, OA concentration, and soil/water ratio) on PAHs degradation were studied using the single-factor experiment. The response surface method was then introduced to obtain the optimized experimental conditions (CP dosage, PS dosage, OA concentration) of the dual peroxide system. The result shows that the dual peroxide system significantly increased the PAHs degradation and the maximum PAHs degradation efficiency (70.8%) was achieved by the dual peroxide system under optimal conditions (PS dosage, CP concentration, Fe2+/PS ratio, and Fe2+/OA ratio was 8.89 g/kg, 0.18 mol/L, 1/4 and 0.62) at neutral soil condition. This study is an illustration of the promising efficiency of the dual peroxide system for PAH oxidation in the neutral soil and has great potential for remediation of PAHs contaminated farmland soils.

Remediation of Cd, Pb and as Co-contaminated Paddy Soil by Applying Different Amendments.

The current study investigated the efficiency of sepiolite (SE), sodium humate (HS), microbial fertilizer (JF) and SE combined with JF/HS in a ratio of 2:1 (w/w) (JF-2SE and HS-2SE) on Cd, Pb and As bioavailability in field trials with rice (Oryza sativa L.). The results showed that all the amendments remarkably decreased (p < 0.05) the contents of available Cd and available Pb in soil. Only JF-2SE treatment reduced available As concentration in soil. All the amendments were found to effectively reduce (p < 0.05) the contents of As in brown rice. Both JF-2SE and HS-2SE co-applications reduced the concentrations of Cd in brown rice to 0.108 and 0.135 mg kg-1, and that of Pb reduced to 0.2 and 0.175 mg kg-1, which met the national standard limit of China. Thus, the co-application of JF/HS-2SE can be a promising remediation strategy in Cd, Pb and As co-contaminated paddy soil.

Root adaptation in Echinodorus osiris Rataj plant under cadmium stress.

Cadmium tolerant plant, Echinodorus osiris Rataj, was selected to study its root adaptive mechanism under Cd stress. The change of root porosity, radial oxygen loss (ROL), and iron plaque formation was investigated. Results suggested that Cd treatment decreased 28.6-49.9% of ROL and reduced 13.5-23.3% of root porosity but increased 63.4-147.2% of iron plaque after 21 days, respectively. Under different Cd treatments, the uptake of Cd in root presented quick and mild models while it showed relatively consistent increase in shoot. Correlation analysis demonstrated that Cd concentrations in plant were related negatively with root porosity but had no significant correlation with ROL. There was significant positive correlation between root porosity and ROL; however, they both related negatively with root iron plaque. Moreover, the scanning electron microscopy indicates a barrier to the movement of Cd in endodermis layers.

Physiological mechanisms of a wetland plant (Echinodorus osiris Rataj) to cadmium detoxification.

Physiological responses of Echinodorus osiris Rataj plant under cadmium (Cd) stress (5 and 15 mg L-1) were studied by researching the change of non-enzymatic antioxidants and the exudation of root organic acids. There was a significant increase of ascorbic acid, glutathione, and non-protein thiols in the plant, and the increment was much obvious in roots than that in leaves with increased Cd stress. The accumulation of Cd was associated with mitochondrial structural damages in roots, while the organelle structure, such as chloroplast, in leaves remains intact. In exudates collected from the plants in the treatment with 15 mg L-1 Cd, oxalate, citric, and succinic acids responded intensively than other organic acids.

The ulnar palmar perforator flap: anatomical study and clinical application.

BACKGROUND: Defects sustained at the little finger and the ulnar aspect of the hand are common and pedicled perforator flaps have unique advantages in resurfacing it. The purpose of this study is to reappraise the anatomy of the septocutaneous perforator in the postero-medial aspect of the hand and present our clinical experience in using perforator flaps based on it. METHODS: This study was divided into anatomical study and clinical application. In the anatomical study, 30 preserved upper limbs were used. Clinically, 16 patients with defects at the little finger or the ulnar aspect of the hand underwent reconstruction with flaps based on the perforator from the ulnar palmar artery of little finger. The defects ranged from 2.3 × 1.3 cm(2) to 5.7 × 3.0 cm(2). RESULTS: The septocutaneous perforator was constantly located 1.3 ± 0.3 cm superior to the fifth metacarpophalangeal joint with a diameter of 0.8 ± 0.2 mm. It travelled through the space between the superficial layer and the deep layer of hypothenar muscles, and ramified into three branches before entry into the skin. The ascending branch of the perforator has two patterns of anastomoses with the descending dorsal carpal branch of the ulnar artery: true anastomoses and choked anastomoses. Clinically, flaps in all 16 cases survived uneventfully, and donor sites healed without deformity. CONCLUSION: The location of the perforator at the postero-medial aspect of the hand is consistent; the ulnar palmar perforator flap is particularly suitable to cover defects in the little finger or the ulnar aspect of hand.

Cadmium uptake, chemical forms, subcellular distribution, and accumulation in Echinodorus osiris Rataj.

Phytoremediation is a technology for extracting or inactivating pollutants in soil. Echinodorus osiris (E. osiris) is a fast growing perennial wetland plant that is common in tropical and subtropical areas and has a high tolerance to cadmium (Cd). However, the absorption dynamics, subcellular distribution and accumulation of Cd by E. osiris had not been investigated. In this paper, hydroponic experiments with different levels of Cd(2+) (0, 5.0, 15.0 mg L(-1)) were carried out to determine these characteristics of E. osiris. The results indicated that the Cd absorption rate of Echinodorus osiris decreased over time, and the absorption rate within 0.5-1.0 h was faster than after 1.0 h. In a 6.0 hour time period, the rate of Cd uptake fit a quadratic polynomial curve when E. osiris was grown under the 5 mg L(-1) Cd treatment. However, the rate of Cd uptake by E. osiris fit a cubic polynomial model with the 15 mg L(-1) Cd treatment. In the roots, the ethanol-extractable Cd, water-extractable Cd, and NaCl-extractable Cd were the largest proportions of the total Cd. The HAc-extractable Cd, HCl-extractable Cd, and residual-Cd represented a larger proportion of the total Cd in the leaves which was combined with phosphate including CdHPO4, Cd3 (PO4)2, and oxalic acid. When analyzing the subcellular distribution of Cd in the plant, the soluble fraction containing Cd accounted for the largest part (69.49-88.39%) followed by the Cd bound to the cell wall (8.44-25.62%). Both the lower and the higher Cd treatments demonstrated that compartmentation by the vacuole and cell wall binding were two effective defense mechanisms of the plant. However, the vacuole became the main site for Cd accumulation in the leaves under the 15 mg L(-1) Cd treatment. E. osiris was able to accumulate high concentrations of Cd in both the roots and the leaves. The Cd concentration reached 502.97 mg kg(-1) and 2742.95 mg kg(-1) in the shoots and roots, respectively, after 27 days of cultivation. It was concluded that E. osiris is a potential hyperaccumulator of Cd.

Assessment of metals pollution on agricultural soil surrounding a lead-zinc mining area in the Karst region of Guangxi, China.

Soil samples were collected on farmland in a lead-zinc mining area in the Karst region of Guangxi, China. The contamination of the soil by eight metals (Cd, Hg, As, Cu, Pb, Cr, Zn, Ni) was determined. Among all these metals, Cd is the most serious pollutant in this area. Zn, Hg as well asPb can also be measured at high levels, which may affect the crop production. All other metals contributed marginally to the overall soil contamination. Besides the evaluation of single metals, the Nemerow synthetic index indicated that the soil is not suitable for agricultural use.

Effect of biochar amendment on the bioavailability of pesticide chlorantraniliprole in soil to earthworm.

To evaluate the effect of biochar amendment on the bioavailability of chlorantraniliprole (CAP) in soils with different physico-chemical properties, the uptake of CAP from various soils by earthworms was studied. It was observed that the biochar amendment of the soils affected the sorption of CAP, but the magnitude of the sorption enhancement by biochar amendment among the soils was varied, presumably due to the attenuation of the sorptivity of the biochar when amended in the soil. The amendment with biochars leads to a decrease in the bioavailability of CAP in the soils to earthworms, and more prominent for biochar BC850 amendment. In the soil with a CAP concentration of 10 mg kg(-1), the residue of CAP in the earthworm tissues was found to be 9.65 mg kg(-1), in comparison with that the CAP residue was 4.05 mg kg(-1) in BC450 amended soil and 0.59 mg kg(-1) in BC850, respectively. The degree of bioavailability reduction by same level of biochar amendment was different among soils with different properties. The results demonstrate that the properties of soils are important to performance of biochar in soil.

[Impact of biochar amendment on the sorption and dissipation of chlorantraniliprole in soils].

The effects of biochar amendment on sorption and dissipation of chlorantraniliprole (CAP) in 5 different agricultural soils were studied. Red gum wood (Eucalyptus spp.) derived biochar was amended into a black soil, a yellow soil, a red soil, a purplish soil, and a fluvo-aquic soil at the rate of 0.5% (by weight). The sorption and dissipation behaviors of CAP in soils with and without biochar amendment were measured by batch equilibration technique and dissipation kinetic experiment, respectively. The objective was to investigate the impact of biochar application on the environmental fate of pesticides in agricultural soils with different physical-chemical properties, and evaluate the potential ecological impacts of field application of biochar materials. The results showed that biochar application in soils could enhance the sorption of CAP, but the magnitudes were varied among soils with different properties. Amendment of 0.5% (by weight) biochar in the black soil, which have high content of organic matter (4.59%), resulted in an increase of sorption coefficient (K(d)) by 2.17%; while for the fluvo-aquic soil with organic matter content of 1.16%, amendment of biochar at the same level led to an increase of 139.13%. The sorption capacity of biochar was partially suppressed when biochar was mixed with soils. The calculated K(Fbiochar) of biochar after mixed in the black soil, yellow soil, red soil, purplish soil, and fluvo-aquic soil were decreased by 96.94%, 90.6%, 91.31%, 68.26%, and 34.59%, respectively, compared to that of the original biochar. The half-lives of CAP in black soil, yellow soil, red soil, purplish soil, and fluvo-aquic soil were 115.52, 133.30, 154.03, 144.41 and 169.06 d, respectively. In soils amended with biochar, the corresponding half-lives of CAP were extended by 20.39, 35.76, 38.51, 79.19, and 119.75 d, respectively. Similar to the effects of biochar on CAP sorption, in soil with higher content of organic matter, the retardation of CAP dissipation by amending biochar was smaller than that in soil with lower content of organic matter. Our results suggested that application of biochar in soils could enhance the sorption and sequestration of CAP, and retard its soil dissipation, but the magnitudes depended on the organic matter content of the soils.