Occurrence and spatiotemporal distribution of arsenic biotransformation genes in urban dust.

Microbially-mediated arsenic biotransformation plays a pivotal role in the biogeochemical cycling of arsenic; however, the presence of arsenic biotransformation genes (ABGs) in urban dust remains unclear. To investigate the occurrence and spatiotemporal distributions of ABGs, a total of one hundred and eighteen urban dust samples were collected from different districts of Xiamen city, China in summer and winter. Although inorganic arsenic species, including arsenate [As(V)] and arsenite [As(III)], were found to be predominant, the methylated arsenicals, particularly trimethylarsine oxide [TMAs(V)O] and dimethylarsenate [DMAs(V)], were detected in urban dust. Abundant ABGs were identified in urban dust via AsChip analysis (a high-throughput qPCR chip for ABGs), of which As(III) S-adenosylmethionine methyltransferase genes (arsM), As(V) reductase genes (arsC), As(III) oxidase genes (aioA), As(III) transporter genes (arsB), and arsenic-sensing regulator genes (arsR) were the most prevalent, collectively constituting more than 90 % of ABGs in urban dust. Microbes involved in arsenic methylation were assigned to bacteria (e.g., Actinomycetes and Alphaproteobacteria), archaea (e.g., Halobacteria), and eukaryotes (e.g., Chlamydomonadaceae) in urban dust via the arsM amplicon sequencing. Temperature, a season-dependent environmental factor, profoundly affected the abundance of ABGs and the composition of microbes involved in arsenic methylation. This study provides new insights into the presence of ARGs within the urban dust.

Continuous and low-carbon production of biomass flash graphene.

Flash Joule heating (FJH) is an emerging and profitable technology for converting inexhaustible biomass into flash graphene (FG). However, it is challenging to produce biomass FG continuously due to the lack of an integrated device. Furthermore, the high-carbon footprint induced by both excessive energy allocation for massive pyrolytic volatiles release and carbon black utilization in alternating current-FJH (AC-FJH) reaction exacerbates this challenge. Here, we create an integrated automatic system with energy requirement-oriented allocation to achieve continuous biomass FG production with a much lower carbon footprint. The programmable logic controller flexibly coordinated the FJH modular components to realize the turnover of biomass FG production. Furthermore, we propose pyrolysis-FJH nexus to achieve biomass FG production. Initially, we utilize pyrolysis to release biomass pyrolytic volatiles, and subsequently carry out the FJH reaction to focus on optimizing the FG structure. Importantly, biochar with appropriate resistance is self-sufficient to initiate the FJH reaction. Accordingly, the medium-temperature biochar-based FG production without carbon black utilization exhibited low carbon emission (1.9 g CO2-eq g-1 graphene), equivalent to a reduction of up to ~86.1% compared to biomass-based FG production. Undoubtedly, this integrated automatic system assisted by pyrolysis-FJH nexus can facilitate biomass FG into a broad spectrum of applications.

Synergistic Reduction of Arsenic Uptake and Alleviation of Leaf Arsenic Toxicity in Maize (Zea mays L.) by Arbuscular Mycorrhizal Fungi (AMF) and Exogenous Iron through Antioxidant Activity.

Arbuscular mycorrhizal fungi (AMF) play key roles in enhancing plant tolerance to heavy metals, and iron (Fe) compounds can reduce the bioavailability of arsenic (As) in soil, thereby alleviating As toxicity. However, there have been limited studies of the synergistic antioxidant mechanisms of AMF (Funneliformis mosseae) and Fe compounds in the alleviation of As toxicity on leaves of maize (Zea mays L.) with low and moderate As contamination. In this study, a pot experiment was conducted with different concentrations of As (0, 25, 50 mgꞏkg-1) and Fe (0, 50 mgꞏkg-1) and AMF treatments. Results showed that under low and moderate As concentrations (As25 and As50), the co-inoculation of AMF and Fe compound significantly increased the biomass of maize stems and roots, phosphorus (P) concentration, and P-to-As uptake ratio. Moreover, the co-inoculation of AMF and Fe compound addition significantly reduced the As concentration in stem and root, malondialdehyde (MDA) content in leaf, and soluble protein and non-protein thiol (NPT) contents in leaf of maize under As25 and As50 treatments. In addition, co-inoculation with AMF and Fe compound addition significantly increased the activities of catalase (CAT), peroxidase (POD), and superoxide dismutase (SOD) in the leaves of maize under As25 treatment. Correlation analysis showed that stem biomass and leaf MDA content were very significantly negatively correlated with stem As content, respectively. In conclusion, the results indicated that the co-inoculation of AMF and Fe compound addition can inhibit As uptake and promote P uptake by maize under low and moderate As contamination, thereby mitigating the lipid peroxidation on maize leaves and reducing As toxicity by enhancing the activities of antioxidant enzymes under low As contamination. These findings provide a theoretical basis for the application of AMF and Fe compounds in the restoration of cropland soil contaminated with low and moderate As.

Enhanced Formation of 6PPD-Q during the Aging of Tire Wear Particles in Anaerobic Flooded Soils: The Role of Iron Reduction and Environmentally Persistent Free Radicals.

Rapid urbanization drives increased emission of tire wear particles (TWPs) and the contamination of a transformation product derived from tire antioxidant, termed as N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q), with adverse implications for terrestrial ecosystems and human health. However, whether and how 6PPD-Q could be formed during the aging of TWPs in soils remains poorly understood. Here, we examine the accumulation and formation mechanisms of 6PPD-Q during the aging of TWPs in soils. Our results showed that biodegradation predominated the fate of 6PPD-Q in soils, whereas anaerobic flooded conditions were conducive to the 6PPD-Q formation and thus resulted in a ∼3.8-fold higher accumulation of 6PPD-Q in flooded soils than wet soils after aging of 60 days. The 6PPD-Q formation in flooded soils was enhanced by Fe reduction-coupled 6PPD oxidation in the first 30 days, while the transformation of TWP-harbored environmentally persistent free radicals (EPFRs) to superoxide radicals (O2•-) under anaerobic flooded conditions further dominated the formation of 6PPD-Q in the next 30 days. This study provides significant insight into understanding the aging behavior of TWPs and highlights an urgent need to assess the ecological risk of 6PPD-Q in soils.

Aluminum adsorption and antimonite oxidation dominantly regulate antimony solubility in soils.

Soil antimony (Sb) contamination occurs globally due to natural processes and human activities. Total Sb concentration in soils fails to assess its ecological risk, while determined by the concentration of available Sb, which is readily for biological uptake. Available Sb in different soils varied significantly according to soil properties. However, so far it is unknown how soil properties regulate Sb availability, and no model has been established to predict it through soil properties. In this study, 19 soils spiked with antimonite [Sb(III)] were used to identify the major factors controlling Sb availability and establish its predicting models. The results showed that available Sb in different soils varied largely depending on the contents of free aluminum (fAl), free iron (fFe) and electric conductivity (EC), which explained 33%, 27% and 24.9% of the total variation, respectively. During the first 42 days of soil aging, fAl and EC effectively predicted the concentrations of available Sb with R2 = 0.64, while during the later stages (70-150 d) of soil aging, fAl content was the unique parameter employed into the predicting model (R2 = 0.53). These results firstly demonstrate that the content of free aluminum (fAl) is the most important factor regulating Sb availability in soils, although the content of fAl is much lower than that of fFe. This finding can help to develop new remediation materials for Sb-contaminated soils. The prediction models can provide promising tools of assessing the ecological risk. In addition, Sb availability was also affected by the oxidation of Sb(III). After 150 days aging, 1-61% of Sb(III) was oxidized to pentavalent Sb [Sb(V)], which was significantly positively correlated with available Sb, suggesting that Sb(III) oxidization mobilizes Sb in soils. All these findings would help to understand Sb migration and transformation in soils, and to develop new strategies for remediating Sb-contaminated soils.

Multiple Effects of Humic Components on Microbially Mediated Iron Redox Processes and Production of Hydroxyl Radicals.

Microbially mediated iron redox processes are of great significance in the biogeochemical cycles of elements, which are often coupled with soil organic matter (SOM) in the environment. Although the influences of SOM fractions on individual reduction or oxidation processes have been studied extensively, a comprehensive understanding is still lacking. Here, using ferrihydrite, Shewanella oneidensis MR-1, and operationally defined SOM components including fulvic acid (FA), humic acid (HA), and humin (HM) extracted from black soil and peat, we explored the SOM-mediated microbial iron reduction and hydroxyl radical (•OH) production processes. The results showed that the addition of SOM inhibited the transformation of ferrihydrite to highly crystalline iron oxides. Although FA and HA increased Fe(II) production over four times on average due to complexation and their high electron exchange capacities, HA inhibited 30-43% of the •OH yield, while FA had no significant influence on it. Superoxide (O2•-) was the predominant intermediate in •OH production in the FA-containing system, while one- and two-electron transfer processes were concurrent in HA- and HM-containing systems. These findings provide deep insights into the multiple mechanisms of SOM in regulating microbially mediated iron redox processes and •OH production.

Sustainable removal of soil arsenic by naturally-formed iron oxides on plastic tubes.

Arsenic (As) pollution in paddy fields is a major threat to rice safety. Existing As remediation techniques are costly, require external chemical addition and degrade soil properties. Here, we report the use of plastic tubes as a recyclable tool to precisely extract As from contaminated soils. Following insertion into flooded paddy soils, polyethylene tube walls were covered by thin but massive Fe coatings of 76.9-367 mg Fe m-2 in 2 weeks, which adsorbed significant amounts of As. The formation of tube-wall Fe oxides was driven by local Fe-oxidizing bacteria with oxygen produced by oxygenic phototrophs (e.g., Cyanobacteria) or diffused from air through the tube wall. The tubes with As-bound Fe oxides can be easily separated from soil and then washed and reused. We tested the As removal efficiency in a pot experiment to remove As from ~ 20 cm depth/40 kg soils in a 2-year experiment and achieved an overall removal efficiency of 152 mg As m-2 soil year-1, comparable to phytoremediation with the As hyperaccumulator Pteris vittata. The cost of Fe hooks was estimated at 8325 RMB ha-1 year-1, and the profit of growing rice (around 16080 RMB ha-1 year-1 can be still maintained. The As accumulated in rice tissues was markedly decreased in the treatment (>11.1 %). This work provides a low-cost and sustainable soil remediation method for the targeted removal of As from soils and a useful tool for the study and management of the biogeochemical Fe cycle in paddy soils.

Widespread occurrence of microplastics in marine bays with diverse drivers and environmental risk.

Microplastic contamination in the sediment of marine bays has attracted widespread attention, whereas the distribution, sedimentation, morphology and risk of microplastics at regional scale remain poorly understood. By introducing a data mining framework into microplastic research, we compiled a microplastic dataset of 649 samples from 24 bays to enhance the understanding of geographical difference and drivers, transfer, composition profile and environmental risk of sedimental microplastics. Microplastic abundance varied from 0.72 to 1963.96 items/kg dry weight, with higher concentrations mainly occurring in East Asian bays. The spatial pattern in abundance was driven by the river plastic emissions, aquaculture production and hydrodynamic condition. A significantly positive correlation between microplastic abundance in water and sediment was found, and microplastic sedimentation was related to polymer density, hydrodynamic conditions and sediment properties. The dominant shape and polymer of sedimental microplastics were fiber and polypropylene, respectively, and the similarity of microplastic composition decreased with increasing geographical distance. The environmental risks of microplastics were partitioned into three classes (Rank II-Rank IV) with a two-dimensional assessment system considering the bioavailability and toxicity of microplastics, and Asian bays were identified as potential high-risk areas. To reduce the environmental risk of sedimental microplastics in bays, priority should be given to the removal of microfibers, and control measures depend on the risk classes and dominant polymers. Microplastic abundance and composition were significantly affected by methodological choices regarding sampling, pretreatment and identification, suggesting a unified methodology is essential to further enhance our knowledge on the distribution and risk of microplastics in marine bays.

Deciphering the impact of urban built environment density on respiratory health using a quasi-cohort analysis of 5495 non-smoking lung cancer cases.

INTRODUCTION: Lung cancer is a major health concern and is influenced by air pollution, which can be affected by the density of urban built environment. The spatiotemporal impact of urban density on lung cancer incidence remains unclear, especially at the sub-city level. We aimed to determine cumulative effect of community-level density attributes of the built environment on lung cancer incidence in high-density urban areas. METHODS: We selected 78 communities in the central city of Shanghai, China as the study site; communities included in the analysis had an averaged population density of 313 residents per hectare. Using data from the city cancer surveillance system, an age-period-cohort analysis of lung cancer incidence was performed over a five-year period (2009-2013), with a total of 5495 non-smoking/non-secondhand smoking exposure lung cancer cases. Community-level density measures included the density of road network, facilities, buildings, green spaces, and land use mixture. RESULTS: In multivariate models, built environment density and the exposure time duration had an interactive effect on lung cancer incidence. Lung cancer incidence of birth cohorts was associated with road density and building coverage across communities, with a relative risk of 1·142 (95 % CI: 1·056-1·234, P = 0·001) and 1·090 (95 % CI: 1·053-1·128, P < 0·001) at the baseline year (2009), respectively. The relative risk increased exponentially with the exposure time duration. As for the change in lung cancer incidence over the five-year period, lung cancer incidence of birth cohorts tended to increase faster in communities with a higher road density and building coverage. CONCLUSION: Urban planning policies that improve road network design and building layout could be important strategies to reduce lung cancer incidence in high-density urban areas.

Embedded Health Risk from Arsenic in Globally Traded Rice.

International food trade is fundamental to global food security but with often negative consequences in the producing country. We propose a method of quantifying flows of inorganic arsenic (iAs) and embedded increased lifetime cancer risks (EHR) at a global scale, where negative impacts are felt on the importing country. Computations were made for 153 countries. Vietnam exports the most iAs embedded in rice (796 kg/year) followed by India (788 kg/year), Thailand (485 kg/year), and the United States (323 kg/year). We show that continental China, Indonesia, and Malaysia have the highest imports of iAs (292, 174, and 123 kg/year, respectively). Bangladesh ranks highest in EHR followed by Vietnam and Cambodia (150, 141, and 111 per 100,000, respectively). Countries that depend exclusively on imported rice are importing a substantial amount of risk, as, e.g., Kiribati and Solomon Islands (57 and 53 per 100,000, respectively). We discuss the potential policy options for reducing population dietary health risks by well-balanced apportioning of rice sources. This study targets policy design solutions based on health gains, rather than on safe levels of the risk factor alone.

Viral diversity and potential environmental risk in microplastic at watershed scale: Evidence from metagenomic analysis of plastisphere.

Microplastics (MPs) have been considered as a new vector for the long-distance transport of pathogens in aquatic ecosystems. However, the composition of viral communities attached on MPs and their environmental risk are largely unknown. Here, we profiled the viral diversity and potential risk in five different MPs collected from the Beilun River based on metagenomic analysis. Nearly 2863 million raw reads were produced and assembled, and annotation resulted in the identification of 1719 different species of viruses in MPs. Viruses in polypropylene (PP) displayed the highest diversity, with about 250 specific viruses detected. Source tracking of viruses in MPs by the fast expectation-maximization microbial source tracking method (FEAST) demonstrated that viruses in upstream and downstream MPs are two major sources of viruses in estuary. Furthermore, the MP-type-dependent potential environmental risk of viruses was significant based on both antibiotic resistance genes (ARGs) and virulence factors (VFs) detected in viral metagenomes, and PP was confirmed with the highest potential environmental risk. This study reveals the high diversity and potential environmental risk of viruses in different MPs, and provides an important guidance for future environmental monitoring and understanding the potential risks associated with both viral transmission and MPs pollution.

Global meta-analysis of microplastic contamination in reservoirs with a novel framework.

Microplastic contamination in reservoirs is receiving increasing attention worldwide. However, a holistic understanding of the occurrence, drivers, and potential risks of microplastics in reservoirs is lacking. Building on a systematic review and meta-analysis of 30 existing publications, we construct a global microplastic dataset consisting of 440 collected samples from 43 reservoirs worldwide which we analyze through a framework of Data processing and Multivariate statistics (DM). The purpose is to provide comprehensive understanding of the drivers and mechanisms of microplastic pollution in reservoirs considering three different aspects: geographical distribution, driving forces, and ecological risks. We found that microplastic abundance varied greatly in reservoirs ranging over 2-6 orders of magnitude. Small-sized microplastics (< 1 mm) accounted for more than 60% of the total microplastics found in reservoirs worldwide. The most frequently detected colors, shapes, and polymer types were transparent, fibers, and polypropylene (polyester within aquatic organisms), respectively. Geographic location, seasonal variation and land-use type were main factors influencing microplastic abundance. Detection was also dependent on analytical methods, demonstrating the need for reliable and standardized methods. Interaction of these factors enhanced effects on microplastic distribution. Microplastics morphological characteristics and their main drivers differed between environmental media (water and sediment) and were more diverse in waters compared to sediments. Similarity in microplastic morphologies decreased with increasing geographic distance within the same media. In terms of risks, microplastic pollution and potential ecological risk levels are high in reservoirs and current policies to mitigate microplastic pollution are insufficient. Based on the DM framework, we identified temperate/subtropical reservoirs in Asia as potential high-risk areas and offer recommendations for analytical methods to detect microplastics in waters and sediments. This framework can be extended and applied to other multi-scale and multi-attribute contaminants, providing effective theoretical guidance for reservoir ecosystems pollution control and management.

Impact of Urbanization on Antibiotic Resistome in Different Microplastics: Evidence from a Large-Scale Whole River Analysis.

Microplastics (MPs) are becoming ubiquitous in environments and viewed as carriers of antibiotic resistance genes (ARGs). Rivers connecting differently urbanized areas contribute a significant input of MPs and ARGs to the environment. However, a systematic study assessing the role of urbanization in shaping antibiotic resistome and mobilome in riverine MPs is lacking. Here, we conducted a large-scale study by placing five types of MPs (polyethylene, polypropylene, polystyrene, polyethylene-fiber, and polyethylene-fiber-polyethylene) into Beilun River with an urbanization gradient. A total of 314 ARGs and 57 mobile genetic elements (MGEs) were detected in MPs by high-throughput quantitative polymerase chain reaction (PCR). The ARGs in MPs showed a clear spatial distribution with the abundance increased by 2 orders of magnitude from rural to urban regions. A holistic analysis of 13 socioeconomic and environmental factors identified that urbanization predominantly contributed to both the abundance and potential MGE-mediated dissemination of ARGs in riverine MPs. Notably, MPs types were found to significantly affect the resistome and dissemination risk of ARGs, with polypropylene being the preferred substrates to acquire and spread ARGs. This work highlights the necessity of controlling MPs and ARGs pollution in urban areas and provides an important guide for the future usage and disposal of plastics.

Bioavailable arsenic and amorphous iron oxides provide reliable predictions for arsenic transfer in soil-wheat system.

The application of current soil quality standards based on total arsenic (As) fails to assess the ecological risks of soil arsenic or to ensure the safety of crops and foods. In this study, bioavailable arsenic instead of total arsenic was applied to improve predictive models for arsenic transfer from soil to wheat (Triticum turgidum L.). The stepwise multiple-linear regression analysis showed that bioavailable arsenic and amorphous iron oxides (FeOX) were the two most important factors contributing to arsenic accumulation in wheat grain, with the explained percentage of variation being up to 82%. Compared with the bioavailable arsenic extracted by NH4H2PO4, bioavailable arsenic extracted by HNO3 from soils generated better predictions of the amount of arsenic in grain. The best reliable model was log[Asgrain] = 0.917 log[HNO3-As] - 0.452 log[FeOX] - 1.507 (R2 = 0.82, P <  0.001). Consistently, bioavailable arsenic and FeOX were also the key factors to predict arsenic accumulation in wheat straw, leaves and spikes. Our prediction models was successfully verified for three independent soils. Our results highlight the role of soil bioavailable heavy metals in predicting their transfer in soil-plant systems and can be used to improve existing Chinese soil quality standards.

Metabolic Inactivity and Re-awakening of a Nitrate Reduction Dependent Iron(II)-Oxidizing Bacterium Bacillus ferrooxidans.

Microorganisms capable of anaerobic nitrate-dependent Fe(II) (ferrous iron) oxidation (ANDFO) contribute significantly to iron and nitrogen cycling in various environments. However, lab efforts in continuous cultivation of ANDFO strains suffer from loss of activity when ferrous iron is used as sole electron donor. Here, we used a novel strain of nitrate-dependent Fe(II)-oxidizing bacterium Bacillus ferroxidians as a model and focused on the physiological activity of cells during ANDFO. It was shown that B. ferrooxidans entered a metabolically inactive state during ANDFO. B. ferrooxidans exhibited nitrate reduction coupled with Fe(II) oxidation, and the activity gradually declined and was hardly detected after 48-h incubation. Propidium monoazide (PMA) assisted 16S rRNA gene real-time PCR suggested that a large number of B. ferrooxidans cells were alive during incubation. However, 2H(D)-isotope based Raman analysis indicated that the cells were metabolically inactive after 120-h of ANDFO. These inactive cells re-awakened in R2A medium and were capable of growth and reproduction, which was consistent with results in Raman analysis. Scanning electron microscopy (SEM) observation and x-ray diffraction (XRD) revealed the formation of Fe minerals in close proximity of cells in the Fe(II)-oxidizing medium after Fe(II) oxidation. Overall, our results demonstrated that continued ANDFO can induce a metabolically inactive state in B. ferrooxidans, which was responsible for the loss of activity during ANDFO. This study provides an insight into the ANDFO process and its contribution to iron and nitrogen cycling in the environments.

Fate of Labile Organic Carbon in Paddy Soil Is Regulated by Microbial Ferric Iron Reduction.

Global paddy soil is the primary source of methane, a potent greenhouse gas. It is therefore highly important to understand the carbon cycling in paddy soil. Microbial reduction of iron, which is widely found in paddy soil, is likely coupled with the oxidation of dissolved organic matter (DOM) and suppresses methanogenesis. However, little is known about the biotransformation of small molecular DOM accumulated under flooded conditions and the effect of iron reduction on the biotransformation pathway. Here, we carried out anaerobic incubation experiments using field-collected samples amended with ferrihydrite and different short-chain fatty acids. Our results showed that less than 20% of short-chain fatty acids were mineralized and released to the atmosphere. Using Fourier transform ion cyclotron resonance mass spectrometry, we further found that a large number of recalcitrant molecules were produced during microbial consumption of these short-chain fatty acids. Moreover, the biotransformation efficiency of short-chain fatty acids decreased with the increasing length of carbon chains. Ferrihydrite addition promoted microbial assimilation of short-chain fatty acids as well as enhanced the activation and biotransformation of indigenous stable carbon in the soil replenished with formate. This study demonstrates the significance of ferrihydrite in the biotransformation of labile DOM and promotes a more comprehensive understanding of the coupling of iron reduction and carbon cycling in paddy soils.

Manure and Doxycycline Affect the Bacterial Community and Its Resistome in Lettuce Rhizosphere and Bulk Soil.

Manure application to agricultural soil introduces antibiotic residues and increases the abundance of antibiotic-resistant bacteria (ARB) carrying antibiotic resistance genes (ARGs), often located on mobile genetic elements (MGEs). The rhizosphere is regarded as a hotspot of microbial activity and gene transfer, which can alter and prolong the effects of organic fertilizers containing antibiotics. However, not much is known about the influence of plants on the effects of doxycycline applied to soil via manure. In this study, the effects of manure spiked with or without doxycycline on the prokaryotic community composition as well as on the relative abundance of ARGs and MGEs in lettuce rhizosphere and bulk soil were investigated by means of a polyphasic cultivation-independent approach. Samples were taken 42 days after manure application, and total community DNA was extracted. Besides a pronounced manure effect, doxycycline spiking caused an additional enrichment of ARGs and MGEs. High-throughput quantitative PCR revealed an increase in tetracycline, aminoglycoside, and macrolide-lincosamide-streptogramin B (MLSB) resistance genes associated with the application of manure spiked with doxycycline. This effect was unexpectedly lower in the rhizosphere than in bulk soil, suggesting a faster dissipation of the antibiotic and a more resilient prokaryotic community in the rhizosphere. Interestingly, the tetracycline resistance gene tetA(P) was highly enriched in manure-treated bulk soil and rhizosphere, with highest values observed in doxycycline-treated bulk soil, concurring with an enrichment of Clostridia. Thus, the gene tetA(P) might be a suitable marker of soil contamination by ARB, ARGs, and antibiotics of manure origin. These findings illustrate that the effects of manure and doxycycline on ARGs and MGEs differ between rhizosphere and bulk soil, which needs to be considered when assessing risks for human health connected to the spread of ARGs in the environment.

Coupling metabolisms of arsenic and iron with humic substances through microorganisms in paddy soil.

Humic acid (HA) and fulvic acid (FA) are dominating humic substances (HS) in soil. In this study, the effects of HA and FA addition (0.2%-1.5%) on arsenic (As) mobility and microbial community composition in paddy soil were investigated. FA significantly increased the concentrations of As (12-fold), iron (Fe; 20-fold), manganese (Mn; 3-fold) and acetic acid (3-fold) in soil porewater, and also caused significant enrichment of Desulfitobacterium (41-fold). Furthermore, the FA addition significantly increased the relative abundance of Bathyarchaeota (4-fold), a microorganism that is suggested to be important for FA degradation. In contrast, HA slightly increased As (1.2-fold) in porewater, had little effect on Fe, Mn and acetic acid, and 1.5% HA addition significantly decreased As in porewater at day 14 (45%). Both HA and FA addition promoted As methylation. HA increased dimethylarsenate concentration and FA increased monomethylarsenate concentration in porewater. These results highlight the contrasting effects of different (HA vs. FA) organic substances on As fate in paddy soil and advance our understanding of the associations among As, Fe and organic substances through microorganisms in paddy soil.

Mobile Incubator for Iron(III) Reduction in the Gut of the Soil-Feeding Earthworm Pheretima guillelmi and Interaction with Denitrification.

Diets of soil-feeding earthworms contain abundant nitrate and iron(III) oxides, which are potential electron acceptors for mineralization of organic compounds. The earthworm gut provides an ideal habitat for ingested iron(III)-reducing microorganisms. However, little is known about iron(III) reduction and its interaction with other processes in the guts of earthworms. Here, we determined the dynamics of iron(III) and revealed its interaction with the turnover of organic acids and nitrate in the gut of the earthworm Pheretima guillelmi. Samples from gut contents combined with anoxic incubation were used for chemical analysis and 16S rRNA based Illumina sequencing. Chemical analysis showed that higher ratios of iron(II)/iron(III), nitrite/nitrate, and more abundant organic acids were contained in the in vivo gut of the earthworm P. guillelmi than those in the in situ soil. A higher rate of iron(III) reduction was detected in treatments of microcosmic incubation with gut contents (IG gut) than that with soil (IG soil), and nitrate reduction occurred earlier than iron(III) reduction in both treatments. Potential iron(III) reducers were dominated by fermentative genera Clostridium, Bacillus, and Desulfotomaculum in the treatment of IG gut, while they were dominated by dissimilatory iron(III)-reducing genera Geobacter in the treatment of IG soil. The iron(III)-reducing microbial community shared several genera with denitrifers in the treatment of IG gut, revealing a close link between iron(III) reduction and denitrification in the gut of earthworms. Collectively, our findings demonstrated that iron(III) reduction occurred along the gut and provided novel insights into the great contribution of earthworm gut microbiota on Fe and the associated C and N cycling in soil environments.

Identification of Steps in the Pathway of Arsenosugar Biosynthesis.

Arsenosugars are arsenic-containing ribosides that play a substantial role in arsenic biogeochemical cycles. Arsenosugars were identified more than 30 years ago, and yet their mechanism of biosynthesis remains unknown. In this study we report identification of the arsS gene from the cyanobacterium Synechocystis sp. PCC 6803 and show that it is involved in arsenosugar biosynthesis. In the Synechocystis sp. PCC 6803 ars operon, arsS is adjacent to the arsM gene that encodes an As(III) S-adenosylmethionine (SAM) methyltransferase. The gene product, ArsS, contains a characteristic CX3CX2C motif which is typical for the radical SAM superfamily. The function of ArsS was identified from a combination of arsS disruption in Synechocystis sp. PCC 6803 and heterologous expression of arsM and arsS in Escherichia coli. Both genes are necessary, indicating a multistep pathway of arsenosugar biosynthesis. In addition, we demonstrate that ArsS orthologs from three other freshwater cyanobacteria and one picocyanobacterium are involved in arsenosugar biosynthesis in those microbes. This study represents the identification of the first two steps in the pathway of arsenosugar biosynthesis. Our discovery expands the catalytic repertoire of the diverse radical SAM enzyme superfamily and provides a basis for studying the biogeochemistry of complex organoarsenicals.