Methylated arsenic (As) species are a common constituent of rice grains accounting for 10-90% of the total As. Recent studies have shown that higher plants are unlikely to methylate As in vivo suggesting that As methylation is a microbial mediated process that occurs in soils prior to plant uptake. In this study, we designed primers according to the conserved essential amino acids and structural motifs of arsenite S-adenosylmethionine methyltransferase (ArsM). We report for the first time the successful amplification of the prokaryotic arsM gene in 14 tested soils with wide ranging As concentrations. The abundance and diversity of the arsM gene in the rice rhizosphere soil and roots were analyzed using the designed primers. Results showed that microbes containing arsM genes were phylogenetically diverse, as revealed by the clone library and terminal restriction fragment length polymorphism (T-RFLP) analysis, and were branched into various phyla. Concentration of methylated As species in the soil solution was elevated in the rhizosphere soil and also by the addition of rice straw into the paddy soil, corresponding to the elevated abundance of the arsM gene in the soil. These results, together with evidence of horizontal gene transfer (HGT) of the arsM gene, suggest the genes encoding ArsM in soils are widespread. These findings demonstrate why most rice, when compared with other cereals, contains unusually high concentrations of methylated As species.

Arsenic (As) uptake by rice is largely determined by As speciation, which is strongly influenced by microbial activities. However, little is known about interactions between root and rhizosphere microbes, particularly on arsenic oxidation and reduction. In this study, two rice cultivars with different radial oxygen loss (ROL) ability were used to investigate the impact of microbially mediated As redox changes in the rhizosphere on As uptake. Results showed that the cultivar with higher ROL (Yangdao) had lower As uptake than that with lower ROL (Nongken). The enhancement of the rhizospheric effect on the abundance of the arsenite (As(III)) oxidase gene (aroA-like) was greater than on the arsenate (As(V)) reductase gene (arsC), and As(V) respiratory reductase gene (arrA), resulting in As oxidation and sequestration in the rhizosphere, particularly for cultivar Yangdao. The community of As(III)-oxidizing bacteria in the rhizosphere was dominated by α-Proteobacteria and β-Proteobacteria and was influenced by rhizospheric effects, rice straw application, growth stage, and cultivar. Application of rice straw into the soil increased As release and accumulation into rice plants. These results highlighted that uptake of As by rice is influenced by microbial processes, especially As oxidation in the rhizosphere, and these processes are influenced by root ROL and organic matter application. ■ INTRODUCTIONArsenic (As) contamination and its health impacts are widespread around the world. 1,2 Large areas of paddy soils are contaminated by As due to irrigation with As-tainted groundwater, mining, and other industrial activities. Rice is particularly efficient in accumulating As, compared with other cereal crops, as a result of its anaerobic growth conditions. 3 This poses potential harm to people through ingestion of rice, especially in Southeast Asia where rice is consumed as the staple food. 4−6 Rhizospheric chemical processes, such as iron oxidation−reduction and iron plaque formation on root surfaces, play an important role in affecting As uptake by rice plants, and they are largely influenced by oxygen release from rice roots. 7,8 The aerated rice rhizosphere and O 2 -releasing root surface are usually coated with iron (Fe) and manganese (Mn) oxides, while As is precipitated with these oxides mainly as arsenate (As(V)). 8,9 In addition to chemical processes, As speciation and mobility in soils, sediments, and natural water systems are mainly driven by microbial transformations. 10−12 Anaerobic bacteria containing the respiratory reductase (ArrA) can use As(V) as the terminal electron acceptor in respiration and conserve energy from this process. 13 Another pathway for microbial As(V) reduction lies in the widespread As detoxification by As(V) reductase (ArsC). 14,15 Arsenite (As(III)) is more weakly bound to most soil minerals than As(V); thus, As(V) reduction results in As release into soil solutions, especially under anaerobic conditions such as paddy soil. 16,17 On the other hand, some heterotrophic as well a...

Methylation of arsenic in soil influences its environmental behavior and accumulation by plants, but little is known about the factors affecting As methylation. As speciation was determined in the pore waters of six soils from diverse geographical locations over 54 days of incubation under flooded conditions. The concentration of methylated As (monomethylarsonic acid, MMA, and dimethylarsinic acid, DMA) varied from 0 to 85 μg L −1 (0 − 69% of the total As in pore water). Two Bangladeshi paddy soils contaminated by irrigation of As-laden groundwater produced large concentrations of inorganic As but relatively little methylated As. Two contaminated paddy soils from China produced a transient peak of DMA during the early phase of incubation. Methylated As represented considerable proportions of the total soluble As in the two uncontaminated soils from the UK and U.S. The copy number of the microbial arsenite methyltransferase gene (arsM) correlated positively with soil pH. However, pore-water methylated As correlated negatively with pH or arsM copy number, and positively with dissolved organic C. GeoChip assay revealed considerable arsM diversity among the six soils, with 27−35 out of 66 sequences in the microarray being detected. As speciation in rice plants grown in the soils generally mirrored that in the pore water. The results suggest that methylated As species in plants originated from the soil and As methylation in soil was influenced strongly by the soil conditions. ■ INTRODUCTIONArsenic (As) is a ubiquitous contaminant in the environment originating from both natural and anthropogenic sources. Because its biogeochemical behavior and toxicity vary greatly among different chemical species, it is important to understand how the speciation of As changes in the environment and what drives such changes. A particularly important case is the paddy rice system because it is now recognized that rice is a major source of As in the human diet. 1 The anaerobic conditions in paddy soils are conducive to the mobilization of arsenite, 2,3 which is taken up inadvertently by rice roots through the strong uptake pathway for silicic acid. 4 Rice grain contains both inorganic As (arsenate and arsenite) and organic As (mostly dimethylarsinic acid, DMA; occasionally also trace amounts of monomethylarsonic acid, MMA, and tetramethylarsonium). 5−9 As speciation in rice varies widely among different riceproducing regions. Market-basket surveys show that Asian rice generally is dominated by inorganic As with DMA typically accounting for about 20% of the total As. [5][6][7]10 In contrast, rice produced in the U.S. and Europe is more variable in As speciation with many samples containing more organic than inorganic As. 5,7,8,10 It is possible that that this geographical pattern reflects the relative bioavailability of inorganic versus organic As in different paddy environments. 10 Compared with inorganic As, methylated As species are more easily accumulated in rice grain. 10 Although pentavalent methylated As species are ...

Arsenic (As) methylation and volatilization in soil can be increased after organic matter (OM) amendment, though the factors influencing this are poorly understood. Herein we investigate how amended OM influences As speciation as well as how it alters microbial processes in soil and soil solution during As volatilization. Microcosm experiments were conducted on predried and fresh As contaminated paddy soils to investigate microbial mediated As speciation and volatilization under different OM amendment conditions. These experiments indicated that the microbes attached to OM did not significantly influence As volatilization. The arsine flux from the treatment amended with 10% clover (cloveramended treatment, CT) and dried distillers grain (DDG) (DDG-amended treatment, DT2) were significantly higher than the control. Trimethylarsine (TMAs) was the dominant species in arsine derived from CT, whereas the primary arsine species from DT2 was TMAs and arsine (AsH 3 ), followed by monomethylarsine (MeAsH 2 ). The predominant As species in the soil solutions of CT and DT2 were dimethylarsinic acid (DMAA) and As(V), respectively. OM addition increased the activities of arseniteoxidizing bacteria (harboring aroA-like genes), though they did not increase or even decrease the abundance of arsenite oxidizers. In contrast, the abundance of arsenate reducers (carrying the arsC gene) was increased by OM amendment; however, significant enhancement of activity of arsenate reducers was observed only in CT. Our results demonstrate that OM addition significantly increased As methylation and volatilization from the investigated paddy soil. The physiologically active bacteria capable of oxidization, reduction, and methylation of As coexisted and mediated the As speciation in soil and soil solution.

a b s t r a c tThe abundance and distribution of antibiotics and antibiotic resistance genes (ARGs) in soils from six parks using reclaimed water in Beijing, China, were characterized. Three classes of commonly used antibiotics (tetracycles, quinolones, and sulfonamides) were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The highest concentrations of tetracyclines and quinolones were 145.2 mg kg À1 and 79.2 mg kg À1 , respectively. Detected tetG, tetW, sulI, and sulII genes were quantified by quantitative PCR. ARGs exhibited various abundances for different park soils. The integrase gene (intI1) as an indicator of horizontal gene transfer potential was also detected in high abundance, and had significant positive correlation with tetG, sulI, and sulII genes, suggesting that intI1 may be involved in ARGs dissemination. Both sulII and intI1 clones had high homology with some classes of pathogenic bacteria, such as Klebsiella oxytoca, Acinetobacter baumannii, Shigella flexneri, which could trigger potential public health concern.

Recent studies have shown that higher plants are unable to methylate arsenic (As), but it is not known whether methylated As species taken up by plants can be volatilized. Rice (Oryza sativa L.) plants were grown axenically or in a nonsterile soil using a two-chamber system. Arsenic transformation and volatilization were investigated. In the axenic system, uptake of As species into rice roots was in the order of arsenate (As(V)) > monomethylarsonic acid (MMAs(V)) > dimethylarsinic acid (DMAs(V)) > trimethylarsine oxide (TMAs-(V)O), but the order of the root-to-shoot transport index (Ti) was reverse. Also, volatilization of trimethylarsine (TMAs) from rice plants was detected when plants were treated with TMAs(V)O but not with As(V), DMAs(V), or MMAs(V). In the soil culture, As was volatilized mainly from the soil. Small amounts of TMAs were also volatilized from the rice plants, which took up DMAs(V), MMAs(V), and TMAs(V)O from the soil solution. The addition of dried distillers grain (DDG) to the soil enhanced As mobilization into the soil solution, As methylation and volatilization from the soil, as well as uptake of different As species and As volatilization from the rice plants. Results show that rice is able to volatilize TMAs after the uptake of TMAs(V)O but not able to convert inorganic As, MMAs(V) or DMAs(V) into TMAs and that the extent of As volatilization from rice plants was much smaller than that from the flooded soil.

a b s t r a c t 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 biovolatilization is a resurgent topic for both biogeochemistry and environmental health, our review serves as a concept paper for future research directions.

The Calvin cycle is known to be the major pathway for CO2 fixation, but our current understanding of its occurrence and importance in paddy soils is poor. In this study, the diversity of three ribulose-1,5-bisphosphate carboxylase/oxygenase large-subunit genes (cbbLG, cbbLR, cbbM) was investigated by clone library, T-RFLP, qPCR, and enzyme assay in five paddy soils in China. The cbbLG sequences revealed a relatively low level of diversity and were mostly related to the sequences of species from Thiobacillus. In contrast, highly diverse cbbLR and cbbM sequences were dispersed on the phylogenetic trees, and most of them were distantly related to known sequences, even forming separate clusters. Abundances of three cbbL genes ranged from 10(6) to 10(9) copies g(-1) soil, and cbbLR outnumbered cbbM and cbbLG in all soil samples, indicating that cbbLR may play a more important role than other two cbbL genes. Soil properties significantly influenced cbbL diversity in five paddy soils, of which clay content, C/N ratio, CEC, pH, and SOC correlated well with variations in microbial composition and abundance. In summary, this study provided a comparison of three cbbL genes, advancing our understanding of their role in carbon sequestration and nutrient turnover in the paddy soil.