Arsenic uptake and transport of Pteris vittata L. as influenced by phosphate and inorganic arsenic species under sand cu｜ture

In order to understand the similarity or difference of inorganic As species uptake and transport related to phosphorus in As-hyperaccumulator, uptake and transport of arsenate (As(Ⅴ)) and arsenite (As(Ⅲ)) were studied using Pteris vittata L. under sand culture. Higher concentrations of phosphate were found to inhibit accumulation of arsenate and arsenite in the fronds of P. vittata. The reduction in As accumulation was greater in old fronds than in young fronds, and relatively weak in root and rhizome. Moderate increases, from 0.05 to 0.3 mmol/L, in phosphate reduced uptake of As(Ⅲ) more than As(Ⅴ), while the reverse was observed at high concentrations of phosphate (≥ 1.0 mmol/L). Phosphate apparently reduced As transport and the proportion of As accumulated in fronds of P. vittata when As was supplied as As(Ⅴ). It may in part be due to competition between phosphorus and As(Ⅴ) during transport. In contrast, phosphate had a much smaller effect on As transport when the As was supplied as As(Ⅲ). Therefore, the results from present experiments indicates that a higher concentration of phosphate suppressed As accumulation and transport in P. vittata, especially in the fronds, when exposure to As(Ⅴ); but the suppression of phosphate to As transport in the root or rhizome may be insignificant when P. vittata when exposure to As(Ⅲ) under sand culture conditions. The finding will help to understand the interaction of P and As during their uptake process in P. vittata.     

Arsenic removal from groundwater by acclimated sludge under autohydrogenotrophic conditions

Arsenic in the environment is attracting increasing attention due to its chronic health effects. Although arsenite(As(III)) is generally more mobile and more toxic than arsenate(As(V)), reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation with sulfide or by adsorption or complexation with other metal sulfides. The performance of As(V) bio-reduction under autohydrogenotrophic conditions was investigated with batch experiments. The results showed that As(V) reduction was a biochemical process while both acclimated sludge and hydrogen were essential. Most of the reduced arsenic remained in a soluble form, although 20% was removed with no addition of sulfate, while 82% was removed when sulfate was reduced to sulfide. The results demonstrated that the reduced arsenic was re-sequestered in the precipitates, probably as arsenic sulfides. Kinetic analysis showed that pseudo first-order kinetics described the bio-reduction process better than pseudo second-order. In particular, the influences of pH and temperature on As(V) reduction by acclimated sludge under autohydrogenotrophic conditions and total soluble As removal were examined. The reduction process was highly sensitive to both pH and temperature, with the optimum ranges of pH 6.5–7.0 and 30–40°C respectively. Furthermore, Arrhenius modeling results for the temperature effect indicated that the As(V) reduction trend was systematic. Total soluble As removal was consistent with the trend of As(V) reduction.     

The role of phosphorus in the metabolism of arsenate by a freshwater green alga, Chlorella vulgaris

A freshwater microalga, Chlorella vulgaris, was grown in the presence of varying phosphate concentrations( 10–500 μg/L P) and environmentally realistic concentrations of arsenate(As(Ⅴ))(5–50 μg/L As). Arsenic speciation in the culture medium and total cellular arsenic were measured using AEC-ICP-MS and ICP-DRC-MS, respectively, to determine arsenic biotransformation and uptake in the various phosphorus scenarios. At high phosphate concentration in the culture medium, 100 μg/L P, the uptake and biotransformation of As(Ⅴ) was minimal and dimethylarsonate(DMAs(Ⅴ)) was the dominant metabolite excreted by C. vulgaris, albeit at relatively low concentrations. At common environmental P concentrations, 0–50 μg/L P, the uptake and biotransformation of As(Ⅴ) increased. At these higher As-uptake levels, arsenite(As(Ⅲ)) was the predominant metabolite excreted from the cell. The concentrations of As(Ⅲ) in these low P conditions were much higher than the concentrations of methylated arsenicals observed at the various P concentrations studied. The switchover threshold between the(small) methylation and(large) reduction of As(Ⅴ) occurred around a cellular As concentration of 1 fg/cell. The observed nearly quantitative conversion of As(Ⅴ) to As(Ⅲ) under low phosphate conditions indicates the importance of As(Ⅴ) bio-reduction at common freshwater P concentrations. These findings on the influence of phosphorus on arsenic uptake, accumulation and excretion are discussed in relation to previously published research. The impact that the two scenarios of As(Ⅴ) metabolism, As(Ⅲ) excretion at high As(Ⅴ)-uptake and methylarsenical excretion at low As(Ⅴ)-uptake, have on freshwater arsenic speciation is discussed.     

Arsenic uptake and transport of Pteris vittata L.as influenced by phosphate and inorganic arsenic species under sand culture

In order to understand the similarity or difference of inorganic As species uptake and transport related to phosphorus in As-hyperaccumulator,uptake and transport of arsenate(As(V))and arsenite(As(III))were studied using Pteris vittata L.under sandculture.Higher concentrations of phosphate were found to inhibit accumulation of arsenate and arsenite in the fronds of P.vittata.The reduction in As accumulation was greater in old fronds than in young fronds,and relatively weak in root and rhizome.Moderateincreases,from 0.05 to 0.3 mmol/L,in phosphate reduced uptake of As(III)more than As(V),while the reverse was observed at highconcentrations of phosphate(1.0 mmol/L).Phosphate apparently reduced As transport and the proportion of As accumulated in frondsof P.vittata when As was supplied as As(V).It may in part be due to competition between phosphorus and As(V)during transport.Incontrast,phosphate had a much smaller effect on As transport when the As was supplied as As(III).Therefore,the results from presentexperiments indicates that a higher concentration of phosphate suppressed As accumulation and transport in P.vittata,especially inthe fronds,when exposed to As(V);but the suppression of phosphate to As transport may be insignificant when P.vittata exposed toAs(III)under sand culture conditions.The finding will help to understand the interaction of P and As during their uptake process in P.vittata.     

A review on completing arsenic biogeochemical cycle：Microbial volatilization of arsines in environment

Arsenic （As） is ubiquitous in the environment in the carcinogenic inorganic forms, posing risks to human health in many parts of the world. Many microorganisms have evolved a series of mechanisms to cope with inorganic arsenic in their growth media such as transforming As compounds into volatile derivatives. Bio-volatilization of As has been suggested to play an important role in global As biogeochemical cycling, and can also be explored as a potential method for arsenic bioremediation. This review aims to provide an overview of the quality and quantity of As volatilization by fungi, bacteria, microalga and protozoans. Arsenic bio-volatilization is influenced by both biotic and abiotic factors that can be manipulated/elucidated for the purpose of As bioremediation. Since As bio- volatilization is a resurgent topic for both biogeochemistry and environmental health, our review serves as a concept paper for future research directions.     

Phylogenetic analysis and arsenate reduction e ect of the arsenic-reducing bacteria enriched from contaminated soils at an abandoned smelter site

Microbial reduction of As(V) (i.e., arsenate) plays an important role in arsenic (As) mobilization in aqueous environment. In this study, we investigated As(Ⅴ) reduction characteristics of the bacteria enriched from the arsenic-contaminated soil at an abandoned smelter site. It was found that As(Ⅴ) was completely reduced to As(Ⅲ) (i.e., arsenite) in 21 h. After 3-d incubation, a yellow solid was precipitated and the concentration of As(Ⅲ) decreased sharply. After 150 h incubation, ca. 65% of soluble arsenic was removed from the solution. The analysis of the precipitate by scanning electron microscopy and energy dispersive spectrometer (SEM-EDS) and X-ray diffraction (XRD) revealed that the main component was crystalline arsenic sulfide (ASS). Microbial mediated reduction and mobilization of adsorbed As(Ⅴ) on ferric hydroxide was also examined. In the microcosm slurry experiment, ca. 53% of the adsorbed As(V) was reduced to As(Ⅲ) by the bacteria, which resulted in an appreciable release of arsenic into aqueous phase. The released arsenic was present predominantly as As(Ⅲ). The microbial diversity was analyzed by 16S rDNA-dependent molecular phylogeny. A near-full-length 16S rDNA gene clone library was constructed. The 197 clones were analyzed using RFLP (restriction fragment length polymorphism) and 72 OTUs were obtained, which contributed 51% of the content for total clone number in six OTUs. Six bacterial clones in these six OTUs were selected for sequencing and the sequenced clones were found to belong to the group Caloramator, Clostridium, and Bacillus.     

Arsenic methylation by an arsenite S-adenosylmethionine methyltransferase from Spirulina platensis

Arsenic-contaminated water is a serious hazard for human health. Plankton plays a critical role in the fate and toxicity of arsenic in water by accumulation and biotransformation.Spirulina platensis(S. platensis), a typical plankton, is often used as a supplement or feed for pharmacy and aquiculture, and may introduce arsenic into the food chain, resulting in a risk to human health. However, there are few studies about how S. platensis biotransforms arsenic. In this study, we investigated arsenic biotransformation by S. platensis. When exposed to arsenite(As(Ⅲ)), S. platensis accumulated arsenic up to 4.1 mg/kg dry weight.After exposure to As(Ⅲ), arsenate(As(Ⅴ)) was the predominant species making up 64% to86% of the total arsenic. Monomethylarsenate(MMA(Ⅴ)) and dimethylarsenate(DMA(Ⅴ))were also detected. An arsenite S-adenosylmethionine methyltransferase from S. platensis(Sp Ars M) was identified and characterized. Sp Ars M showed low identity with other reported Ars M enzymes. The Escherichia coli AW3110 bearing Spars M gene resulted in As(Ⅲ) methylation and conferring resistance to As(Ⅲ). The in vitro assay showed that Sp Ars M exhibited As(Ⅲ) methylation activity. DMA(Ⅴ) and a small amount of MMA(Ⅴ) were detected in the reaction system within 0.5 hr. A truncated Sp Ars M derivative lacking the last 34 residues still had the ability to methylate As(Ⅲ). The three single mutants of Sp Ars M(C59S, C186 S, and C238S) abolished the capability of As(Ⅲ) methylation, suggesting the three cysteine residues are involved in catalysis. We propose that Sp Ars M is responsible for As methylation and detoxification of As(Ⅲ) and may contribute to As biogeochemistry.     

Reduction of nitrate from groundwater: powder catalysts and catalytic membrane

The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4 % to 89.4%.     

Synthesis of a novel ternary HA/Fe-Mn oxides-loaded biochar composite and its application in cadmium(Ⅱ) and arsenic(Ⅴ) adsorption

Cadmium(Cd) and arsenic(As) are two of the most toxic elements. However, the chemical behaviors of these two elements are different, making it challenging to utilize a single adsorbent with high adsorption capacity for both Cd(Ⅱ) and As(Ⅴ) removal. To solve this problem, we synthesized HA/Fe-Mn oxides-loaded biochar(HFMB), a novel ternary material,to perform this task, wherein scanning electron microscopy(SEM) combined with EDS(SEMEDS) was used to characterize its morphological and physicochemical properties. The maximum adsorption capacity of HFMB was 67.11 mg/g for Cd(Ⅱ) and 35.59 mg/g for As(Ⅴ),which is much higher compared to pristine biochar(11.06 mg/g, 0 mg/g for Cd(Ⅱ) and As(Ⅴ),respectively). The adsorption characteristics were investigated by adsorption kinetics and the effects of the ionic strength and pH of solutions. X-ray photoelectron spectroscopy(XPS)and Fourier-transform infrared spectroscopy(FT-IR) revealed that chelation and deposition were the adsorption mechanisms that bound Cd(Ⅱ) to HFMB, while ligand exchange was the adsorption mechanism that bound As(Ⅴ).     

Effect of competing solutes on arsenic（Ⅴ） adsorption using iron and aluminum oxides

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe_2O_3 and AL_2O_3.The test results indicate that chloride,nitrate and sulfate did not have detectable effects,and that selenium(Ⅳ)(Se(Ⅳ))and vanadium(Ⅴ)(V(Ⅴ)) showed slight effects on the adsorption of As(Ⅴ)with Fe_2O_3.The results also showed that adsorption of As(Ⅴ)on AL_2O_3 was not affected by chloride and nitrate anions,but slightly by Se(Ⅳ)and V(Ⅴ)ions.Unlike the adsorption of As(Ⅴ)with Fe_2O_3,that with Fe_2O_3 was affected by the presence of sulfate in water solutions.Both phosphate and silica have significant adverse effects on the adsorption of As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.Compared to the other tested anions,phosphate anion was found to be the most prominent solute affecting the As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.In general,Fe_2O_3 has a better performance than Al_2O_3 in removal of As(Ⅴ)within a water environment where multi competing solutes are present.     

Effect of microbial mediated iron plaque reduction on arsenic mobility in paddy soil

The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility were examined by iron reducing bacteria enriched from As contaminated paddy soil. To our knowledge, this is the first time to report the impact of microbial iron plaque reduction on As mobility. Iron reduction occurred during the inoculation of iron reducing enrichment culture in the treatments with iron plaque and ferrihydrite as the electron acceptors, respectively. The Fe(II) concentration with the treatment of anthraquinone-2, 6-disulfonic acid (AQDS) and iron reducing bacteria increased much faster than the control. Arsenic released from iron plaque with the iron reduction, and a significant correlation between Fe(II) and total As in culture was observed. However, compared with control, the increasing rate of As was inhibited by iron reducing bacteria especially in the presence of AQDS. In addition, the concentrations of As(III) and As(V) in abiotic treatments were higher than those in the biotic treatments at day 30. These results indicated that both microbial and chemical reductions of iron plaque caused As release from iron plaque to aqueous phase, however, microbial iron reduction induced the formation of more crystalline iron minerals, leading to As sequestration. In addition, the presence of AQDS in solution can accelerate the iron reduction, the As release from iron plaque and subsequently the As retention in the crystalline iron mineral. Thus, our results suggested that it is possible to remediate As contaminated soils by utilizing iron reducing bacteria and AQDS.     

Shewanella oneidensis MR-1异化还原Fe(III)介导的As(III)氧化转化

在实验室模拟条件下,研究了Shewanella oneidensis MR-1作用下Fe(III)还原和As(III)氧化动力学及其影响因素.结果表明,Fe(III)被还原为Fe(II)的同时伴随着As(III)氧化为As(V);S. oneidensis MR-1 在含低浓度As(III)培养基上生长良好,在高浓度培养基上生长被抑制;As(III)通过制约菌体的生长与活性来抑制Fe(III)异化还原.同样,适量浓度的Fe(III)含量对As(III)氧化转化有很强的促进作用,但是过高浓度的Fe(III)浓度使得溶液中产生过多的Fe(II),从而对As(III)氧化转化有一定程度的抑制作用.此外,弱碱环境更有利于As(III)氧化转化.     

Accelerated anaerobic dechlorination of DDT in slurry with Hydragric Acrisols using citric acid and anthraquinone-2,6-disulfonate (AQDS)

The application of electron donor and electron shuttle substances has a vital influence on electron transfer,thus may affect the reductive dechlorination of 1,1,1-trichoro-2,2-bis(p-chlorophenyl)ethane(DDT) in anaerobic reaction systems.To evaluate the roles of citric acid and anthraquinone-2,6-disulfonate(AQDS) in accelerating the reductive dechlorination of DDT in Hydragric Acrisols that contain abundant iron oxide,a batch anaerobic incubation experiment was conducted in a slurry system with four treatments of(1) control,(2) citric acid,(3) AQDS,and(4) citric acid + AQDS.Results showed that DDT residues decreased by 78.93%–92.11% of the initial quantities after 20 days of incubation,and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane(DDD) was the dominant metabolite.The application of citric acid accelerated DDT dechlorination slightly in the first 8 days,while the methanogenesis rate increased quickly,and then the acceleration effect improved after the 8th day while the methanogenesis rate decreased.The amendment by AQDS decreased the Eh value of the reaction system and accelerated microbial reduction of Fe(III) oxides to generate Fe(II),which was an efficient electron donor,thus enhancing the reductive dechlorination rate of DDT.The addition of citric acid + AQDS was most efficient in stimulating DDT dechlorination,but no significant interaction between citric acid and AQDS on DDT dechlorination was observed.The results will be of great significance for developing an efficient in situ remediation strategy for DDT-contaminated sites.     

Simultaneous Fe(III) reduction and ammonia oxidation process in Anammox sludge

In recent years, there have been a number of reports on the phenomenon in which ferric iron (Fe(III)) is reduced to ferrous iron [Fe(II)] in anaerobic environments, accompanied by simultaneous oxidation of ammonia to NO₂^-, NO₃^-, or N₂. However, studies on the relevant reaction characteristics and mechanisms are rare. Recently, in research on the effect of Fe(III) on the activity of Anammox sludge, excess ammonia oxidization has also been found. Hence, in the present study, Fe(III) was used to serve as the electron acceptor instead of NO₂^-, and the feasibility and characteristics of Anammox coupled to Fe(III) reduction (termed Feammox) were investigated. After 160days of cultivation, the conversion rate of ammonia in the reactor was above 80%, accompanied by the production of a large amount of NO₃^- and a small amount of NO₂^-. The total nitrogen removal rate was up to 71.8%. Furthermore, quantities of Fe(II) were detected in the sludge fluorescence in situ hybridization (FISH) and denaturated gradient gel electrophoresis (DGGE) analyses further revealed that in the sludge, some Anammox bacteria were retained, and some microbes were enriched during the acclimatization process. We thus deduced that in Anammox sludge, Fe(III) reduction takes place together with ammonia oxidation to NO₂^- and NO₃^- along with the Anammox process.     

不同Fe(III)对活性污泥异化铁还原及除磷影响研究

以SBBR反应器活性污泥作为铁还原菌菌种来源,采用兼性厌氧/严格厌氧恒温培养试验,投加不同Fe(III)考察各条件下的异化铁还原能力,同时比较对磷的去除效果.结果表明:2种条件下Fe(III)还原能力具有较好的一致性,依次为:Fe(OH)3>氧化铁皮>青矿>红矿,其中严格厌氧条件下较好.同时,除磷效果与其呈正相关,富集培养至7d, Fe(OH)3及氧化铁皮体系出水磷浓度均达到2mg/L以下,之后继续降低,最终达到0.5mg/L以下.结合异化铁还原除磷机理,可以证明,不同Fe(III)表面吸附作用对TP的去除贡献较小,其主要作用为铁还原菌驱动下的化学沉淀去除.     

Bacterial reduction and release of adsorbed arsenate on Fe(Ⅲ)-, Al- and coprecipitated Fe(Ⅲ)/Al-hydroxides

Mobilization of arsenic under anaerobic conditions is of great concern in arsenic contaminated soils and sediments. Bacterial reduction of As(V) and Fe(Ⅲ) influences the cycling and partitioning of arsenic between solid and aqueous phase. We investigated the impact of bacterially mediated reductions of Fe(Ⅲ)/Al hydroxides-bound arsenic(V) and iron(Ⅲ) oxides on arsenic release. Our results suggested that As(V) reduction occurred prior to Fe(Ⅲ) reduction, and Fe(Ⅲ) reduction did not enhance the release of arsenic. Instead, Fe(Ⅲ) hydroxides retained their dissolved concentrations during the experimental process, even though the new iron mineral-magnetite formed. In contrast, the release of reduced As(Ⅲ) was promoted greatly when aluminum hydroxides was incorporated. Thus, the substitution of aluminum hydroxides may be responsible for the release of arsenic in the contaminated soils and sediments, since aluminum substitution of Fe(Ⅲ) hydroxides universally occurs under natural conditions.     

稻田NO3-还原耦合As(III)氧化过程及微生物群落特征

以华南稻田土壤为研究对象通过构建微宇宙体系,研究了淹水稻田自养硝酸盐还原耦合As（III）氧化过程及其微生物群落结构组成.结果表明,NO₃^-的添加促进了稻田土壤中As（III）的氧化,在未添加NO₃^-的处理（Soil+As（III））以及灭菌处理（Sterilized soil+As（III）+NO₃^-）中As（III）未发生明显的氧化;在Soil+As（III）+NO₃^-处理中,NO₃^-有少量被还原,而在Soil+NO₃^-处理中,NO₃^-没有被还原.通过16S rRNA高通量分析在NO₃^-还原耦合As（III）氧化体系中微生物群落结构特征,在Soil+As（III）+NO₃^-处理中shannon指数相对较低为8.19,土壤微生物群落多样性降低,其中在门水平上主要优势菌群为变形菌门Proteobacteria（33%）、绿弯菌门Chloroflexi（11%）、浮霉菌门Planctomycetes（12%）;在属水平上主要的优势菌属为Gemmatimonas（7.4%）以及少量的Singulisphaera、Thermomonas、Bacillus.NO₃^-的添加能够促进稻田土壤中自养As（III）氧化,并且影响着稻田土壤中微生物群落组成.     

Bioreduction of vanadium (V) in groundwater by autohydrogentrophic bacteria: Mechanisms and microorganisms

As one of the transition metals, vanadium (V) (V(V)) in trace amounts represents an essential element for normal cell growth, but becomes toxic when its concentration is above 1 mg/L. V(V) can alter cellular differentiation, gene expression, and other biochemical and metabolic phenomena. A feasible method to detoxify V(V) is to reduce it to V(IV), which precipitates and can be readily removed from the water. The bioreduction of V(V) in a contaminated groundwater was investigated using autohydrogentrophic bacteria and hydrogen gas as the electron donor. Compared with the previous organic donors, H₂ shows the advantages as an ideal electron donor, including nontoxicity and less production of excess biomass. V(V) was 95.5% removed by biochemical reduction when autohydrogentrophic bacteria and hydrogen were both present, and the reduced V(IV) precipitated, leading to total-V removal. Reduction kinetics could be described by a first-order model and were sensitive to pH and temperature, with the optimum ranges of pH 7.5–8.0 and 35–40°C, respectively. Phylogenetic analysis by clone library showed that the dominant species in the experiments with V(V) bioreduction belonged to the β-Proteobacteria. Previously known V(V)-reducing species were absent, suggesting that V(V) reduction was carried out by novel species. Their selective enrichment during V(V) bioreduction suggests that Rhodocyclus, a denitrifying bacterium, and Clostridium, a fermenter known to carry out metal reduction, were responsible for V(V) bioreduction.     

Arsenic biotransformation in industrial wastewater treatment residue: Effect of co-existing Shewanella sp. ANA-3 and MR-1

Shewanella sp. ANA-3 with the respiratory arsenate reductase (ArrAB) and MR-1 with ferric reduction ability always coexist in the presence of high arsenic (As)-containing waste residue. However, their synergistic impacts on As transformation and mobility remain unclear. To identify which bacterium, ANA-3 or MR-1, dominates As mobility in the coexisting environment, we explored the As biotransformation in the industrial waste residue in the presence of Shewanella sp. ANA-3 and MR-1. The incubation results show that As(III) was the main soluble species, and strain ANA-3 dominated As mobilization. The impact of ANA-3 was weakened by MR-1, probably due to the survival competition between these two bacteria. The results of micro X-ray fluorescence and X-ray photoelectron spectroscopy analyses further reveal the pathway for ANA-3 to enhance As mobility. Strain ANA-3 almost reduced 100% surface-bound Fe(III), and consequently led to As(V) release. The dissolved As(V) was then reduced to As(III) by ANA-3. The results of this study help to understand the fate of arsenic in the subsurface and highlight the importance of the safe disposal of high As-containing industrial waste.