Sustainable Immobilization of Arsenic by Man-Made Aerenchymatous Tissues in Paddy Soil.

Arsenic (As) is a major environmental pollutant and poses a significant health risk to humans through rice consumption. Elevating the soil redox potential (Eh) has been shown to reduce As bioavailability and decrease As accumulation in rice grains. However, sustainable methods for managing the Eh of rice paddies are lacking. To address this issue, we propose a new approach that uses man-made aerenchymatous tissues (MAT) to increase soil Eh by mimicking O2 release from wet plant roots. Our study demonstrated that the MAT method sustainably increased the soil Eh levels from -119 to -80.7 mV (∼30%), over approximately 100 days and within a radius of around 5 cm from the surface of the MAT. Moreover, it resulted in a significant reduction (-28.5% to -63.3%) in dissolved organic carbon, Fe, Mn, and As concentrations. MAT-induced Fe(III) (oxyhydr)oxide minerals served as additional adsorption sites for dissolved As in soil porewater. Furthermore, MAT promoted the oxidation of arsenite to the less mobile arsenate by significantly enhancing the relative abundance of the aioA gene (130% increase in the 0-5 cm soil zone around MAT). The decrease in As bioavailability significantly reduced As accumulation in rice grains (-30.0%). This work offers a low-cost and sustainable method for mitigating As release in rice paddies by addressing the issue of soil Eh management.

pH dependence of arsenic speciation in paddy soils: The role of distinct methanotrophs.

Arsenic (As) is a priority environmental pollutant in paddy field. The coupling of arsenate (As(V)) reduction with anaerobic methane (CH4) oxidation was recently demonstrated in paddy soils and has been suggested to serve as a critical driver for As transformation and mobilization. However, whether As(V)-dependent CH4 oxidation is driven by distinct methanotrophs under different pH conditions remains unclear. Here, we investigated the response of As(V)-dependent CH4 oxidation to pH shifts (pH 5.5-8.0) by employing isotopically labelled CH4. Furthermore, the underlying mechanisms were also investigated in well-controlled anoxic soil suspension incubations. Our results showed that As(V)-dependent CH4 oxidation is highly sensitive to pH changes (1.6-6.8 times variation of arsenite formation). A short-term (0-10 d) pH shift from near-neutral pH to acidic conditions (i.e., pH 5.5, -85% arsenite formation) had an inhibitory effect on As(V)-dependent CH4 oxidation. However, prolonged acidic conditions (i.e., >15 d) had no significant influence on As(V)-dependent CH4 oxidation. The microbial analyses indicated that As reduction in paddies can be driven by anaerobic CH4 oxidation archaea (ANME) and methanotrophs. And, methanotrophs may serve as a critical driver for As(V)-dependent CH4 oxidation. Moreover, type I methanotrophs Methylobacter were more active in oxidizing CH4 than type II methanotrophs Methylocystis when the pH ≥ 6.5. However, Methylocystis had a higher tolerance to soil acidification than Methylobacter. This study illustrates that As(V)-dependent CH4 oxidation could be dominated by distinct methanotrophs along with pH shifts, which eventually enhances As release in paddy soils.

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.

Simultaneous measurement of aqueous redox-sensitive elements and their species across the soil-water interface.

The redox-sensitive elements, such as iron, manganese, sulfur, phosphorus, and arsenic, shift their speciation every millimeter (mm) across the soil-water interface in the flooded soil environments. Monitoring of element speciation at this high-resolution (HR) within the SWI is still difficult. The key challenge lies in obtaining sufficient porewater samples at specific locations along the soil gradient for downstream analysis. Here with an optimized inductively coupled plasma mass spectrometry (ICP-MS) method and a HR porewater sampler, we demonstrate mm-scale element profiles mapping across the SWI in paddy soils. High-concentrations of iron and manganese (> 10 mg/L) were measured by ICP-MS in an extended dynamic range mode to avoid signal overflow. The iron profile along the SWI generated by the ICP-MS method showed no significant difference (p < 0.05) compared to that measured independently using a colorimetric method. Furthermore, four arsenic (arsenite, arsenate, monomethylarsonic and dimethylarsinic acid), two phosphorus (phosphite and phosphate) and two sulfur (sulfide and sulfate) species were separated in 10 min by ion chromatography -ICP-MS with the NH4HCO3 mobile phase. We verified the technique using paddy soils collected from the field, and present the mm-scale profiles of iron, manganese, and arsenic, phosphorus, sulfur species (relative standard deviation < 8%). The technique developed in this study will significantly promote the measurement throughput in limited samples (e.g. 100 µL) collected by HR samplers, which would greatly facilitate redox-sensitive elements biogeochemical cycling in saturated soils.

Arsenic behavior across soil-water interfaces in paddy soils: Coupling, decoupling and speciation.

The sharp redox gradient at soil-water interfaces (SWI) plays a key role in controlling arsenic (As) translocation and transformation in paddy soils. When Eh drops, As is released to porewater from solid iron (Fe) and manganese (Mn) minerals and reduced to arsenite. However, the coupling or decoupling processes operating within the redox gradient at the SWI in flooded paddy soils remain poorly constrained due to the lack of direct evidence. In this paper, we reported the mm-scale mapping of Fe, As and other associated elements across the redox gradient in the SWI of five different paddy soils. The results showed a strong positive linear relationship between dissolved Fe, Mn, As, and phosphorus (P) in 4 out of the 5 paddy soils, indicating the general coupling of these elements. However, decoupling of Fe, Mn and As was observed in one of the paddy soils. In this soil, distinct releasing profiles of Mn, As and Fe were observed, and the releasing order followed the redox ladder. Further investigation of As species showed the ratio of arsenite to total As dropped from 100% to 75.5% and then kept stable along depth of the soil profile, which indicates a dynamic equilibrium between arsenite oxidization and arsenate reduction. This study provides direct evidence of multi-elements' interaction along redox gradient of SWI in paddy soils.

Mitigation effects of the microbial fuel cells on heavy metal accumulation in rice (Oryza sativa L.).

The increase in toxic heavy metal pollutants in rice paddies threatens food safety. There is an urgent need for lnow-cost remediation technology for immobilizing these trace metals. In this study, we showed that the application of the soil microbial fuel cell (sMFC) can greatly reduce the accumulation of Cd, Cu, Cr, and Ni in the rice plant tissue. In the sMFC treatment, the accumulation of Cd, Cu, Cr, and Ni in rice grains was 35.1%, 32.8%, 56.9% and 21.3% lower than the control, respectively. The reduction of these elements in the rice grain was due to their limited mobility in the soil porewater of soils employing the sMFC. The restriction in Cd, Cu, Cr, and Ni bioavailability was ascribed to the sMFC ability to immobilize trace metals through both biotic and abiotic means. The results suggest that the sMFC may be used as a promising technique to limit toxic trace metal bioavailability and translocation in the rice plants.

Soil organic matter amount determines the behavior of iron and arsenic in paddy soil with microbial fuel cells.

Arsenic (As) mobility in paddy soils is mainly controlled by iron (Fe) oxides and iron reducing bacteria (IBR). The Fe reducing bacteria are also considered to be enriched on the anode of soil microbial fuel cells (sMFC). Thus, the sMFC may have an impact on elements' behavior, especially Fe and As, mobilization and immobilization in paddy soils. In this study, we found dissolved organic matter (DOC) abundance was a major determinate for the sMFC impact on Fe and As. In the constructed sMFCs with and without water management, distinctive behaviors of Fe and As in paddy soil were observed, which can be explained by the low or high DOC content under different water management. When the sMFC was deployed without water management, i.e. DOC was abundant, the sMFC promoted Fe and As movement into the soil porewater. The As release into the porewater was associated with the enhanced Fe reduction by the sMFC. This was ascribed to the acidification effect of sMFC anode and the increase of Fe reducing bacteria in the sMFC anode vicinity and associated bulk soil. However, when the sMFC was coupled with alternating dry-wet cycles, i.e. DOC was limited, the Fe and As concentrations in the soil porewater dramatically decreased by up to 2.3 and 1.6 fold, respectively, compared to the controls under the same water management regime. This study implies an environmental risk for the in-situ application of sMFC in organic matter rich wetlands and also points out a new mitigation strategy for As management in paddy soils.

Tracing the Dynamic Changes of Element Profiles by Novel Soil Porewater Samplers with Ultralow Disturbance to Soil-Water Interface.

In flooded soils, soil-water interface (SWI) is the key zone controlling biogeochemical dynamics. Chemical species and concentrations vary greatly at micro- to cm-scales. Techniques able to track these changing element profiles both in space and over time with appropriate resolution are rare. Here, we report a patent-pending technique, the Integrated Porewater Injection (IPI) sampler, which is designed for soil porewater sampling with minimum disturbance to saturated soil environment. IPI sampler employs a single hollow fiber membrane tube to passively sample porewater surrounding the tube. When working, it can be integrated into the sample introduction system, thus the sample preparation procedure is dramatically simplified. In this study, IPI samplers were coupled to ICP-MS at data-only mode. The limits of detection of IPI-ICP-MS for Ni, As, Cd, Sb, and Pb were 0.12, 0.67, 0.027, 0.029, and 0.074 µg·L-1, respectively. Furthermore, 25 IPI samplers were assembled into an SWI profiler using 3D printing in a one-dimensional array. The SWI profiler is able to analyze element profiles at high spatial resolution (∼2 mm) every ≥24 h. When deployed in arsenic-contaminated paddy soils, it depicted the distributions and dynamics of multiple elements at anoxic-oxic transition. The results show that the SWI profiler is a powerful and robust technique in monitoring dynamics of element profile in soil porewater at high spatial resolution. The method will greatly facilitate studies of elements behaviors in sediments of wetland, rivers, lakes, and oceans.

Relic DNA does not obscure the microbial community of paddy soil microbial fuel cells.

Soil Microbial Fuel Cells (MFCs) are devices that can generate electricity by using the flooded soil's anode respiring microbial consortium. When the MFC starts to work, the microbial community in the anode vicinity rapidly changes. This shift in the microbial community results in many dead cells that may release their DNA (relic DNA) and obscure culture independent estimates of microbial community composition. Although relic DNA is expected to increase in MFCs, the effect of relic DNA has not been investigated in the soil MFCs system. In this study the effect of the MFCs on the soil microbial community composition within the soil profile and the influence of relic DNA were investigated. Microbial community analysis revealed that the MFCs deployment significantly influenced the community composition within the soil profile. The phylum Proteobacteria (34.4% vs 23.6%) and the class Deltaproteobacteria (16.8% vs 5.9%) significantly increased in the MFCs compared to the control, while the phylum Firmicutes (24.0% vs 28.7%) and the class Sphingobacteria (5.3% vs 7.0%) were more abundant in the control. Furthermore, the archaeal phyla Euryarchaeota (40.7% vs 52.3%) and Bathyarchaeota (10.1% vs 17.3%) were significantly lower in the MFCs, whereas the phylum Woesearchaeota (DHVEG6) (24.4% vs 19.4%) was slightly enhanced. Moreover, the results showed that relic DNA can affect the relative abundance of Geobacter and Candidatus Methanoperedens, however, it has no significant effects on the microbial community structure. These results indicate that MFCs can influence the soil microbial community profile, nevertheless the relic DNA generated has minimum effect on the culture independent estimates of microbial community composition.

Arsenic mitigation in paddy soils by using microbial fuel cells.

Arsenic (As) behavior in paddy soils couples with the redox process of iron (Fe) minerals. When soil is flooded, Fe oxides are transformed to soluble ferrous ions by accepting the electrons from Fe reducers. This process can significantly affect the fate of As in paddy fields. In this study, we show a novel technique to manipulate the Fe redox processes in paddy soils by deploying soil microbial fuel cells (sMFC). The results showed that the sMFC bioanode can significantly decrease the release of Fe and As into soil porewater. Iron and As contents around sMFC anode were 65.0% and 47.0% of the control respectively at day 50. The observed phenomenon would be explained by a competition for organic substrate between sMFC bioanode and the iron- and arsenic-reducing bacteria in the soils. In the vicinity of bioanode, organic matter removal efficiencies were 10.3% and 14.0% higher than the control for lost on ignition carbon and total organic carbon respectively. Sequencing of the 16S rRNA genes suggested that the influence of bioanodes on bulk soil bacterial community structure was minimal. Moreover, during the experiment a maximum current and power density of 0.31 mA and 12.0 mWm-2 were obtained, respectively. This study shows a novel way to limit the release of Fe and As in soils porewater and simultaneously generate electricity.