Silicate Mineral Impacts on the Uptake and Storage of Arsenic and Plant Nutrients in Rice (Oryza sativa L.)

Arsenic-contaminated rice grain may threaten human health globally. Since H₃AsO₃⁰ is the predominant As species found in paddy pore-waters, and H₄SiO₄⁰ and H₃AsO₃⁰ share an uptake pathway, silica amendments have been proposed to decrease As uptake and consequent As concentrations in grains. Here, we evaluated the impact of two silicate mineral additions differing in solubility (+Si_L, diatomaceous earth, 0.29 mM Si; +Si_H, Si-gel, 1.1 mM Si) to soils differing in mineralogy on arsenic concentration in rice. The +Si_L addition either did not change or decreased As concentration in pore-water but did not change or increased grain-As levels relative to the (+As–Si) control. The +Si_H addition increased As in pore-water, but it significantly decreased grain-As relative to the (+As–Si) control. Only the +Si_H addition resulted in significant increases in straw- and husk-Si. Total grain- and straw-As was negatively correlated with pore-water Si, and the relationship differed between two soils exhibiting different mineralogy. These differing results are a consequence of competition between H₄SiO₄⁰ and H₃AsO₃⁰ for adsorption sites on soil solids and subsequent plant-uptake, and illustrate the importance of Si mineralogy on arsenic uptake

Arsenic, Lead, and Cadmium in U.S. Mushrooms and Substrate in Relation to Dietary Exposure

Wild mushrooms can absorb high quantities of metal­(loid)­s, yet the concentration, speciation, and localization of As, Pb, and Cd in cultivated mushrooms, particularly in the United States, are unresolved. We collected 40 samples of 12 types of raw mushrooms from 2 geographic locations that produce the majority of marketable U.S. mushrooms and analyzed the total As, Pb, and Cd content, the speciation and localization of As in select samples, and assessed the metal sources and substrate-to-fruit transfer at one representative farm. Cremini mushrooms contained significantly higher total As concentrations than Shiitake and localized the As differently; while As in Cremini was distributed throughout the fruiting body, it was localized to the hymenophore region in Shiitake. Cd was significantly higher in Royal Trumpet than in White Button, Cremini, and Portobello, while no difference was observed in Pb levels among the mushrooms. Concentrations of As, Pb, and Cd were less than 1 μg g^–1 d.w. in all mushroom samples, and the overall risk of As, Cd, and Pb intake from mushroom consumption is low in the U.S. However, higher percentages of tolerable intake levels are observed when calculating risk based on single serving-sizes or when substrate contains elevated levels of metal­(loid)­s

How Rice (<i>Oryza sativa</i> L.) Responds to Elevated As under Different Si-Rich Soil Amendments

Several strategies exist to mitigate As impacts on rice and each has its set of trade-offs with respect to yield, inorganic As content in grain, and CH₄ emissions. The addition of Si to paddy soil can decrease As uptake by rice but how rice will respond to elevated As when soil is amended with Si-rich materials is unresolved. Here, we evaluated yield impacts and grain As content and speciation in rice exposed to elevated As in response to different Si-rich soil amendments including rice husk, rice husk ash, and CaSiO₃ in a pot study. We found that As-induced yield losses were alleviated by Husk amendment, partially alleviated by Ash amendment, and not affected by CaSiO₃ amendment. Furthermore, Husk was the only tested Si-amendment to significantly decrease grain As concentrations. Husk amendment was likely effective at decreasing grain As and improving yield because it provided more plant-available Si, particularly during the reproductive and ripening phases. Both Husk and Ash provided K, which also played a role in yield improvement. This study demonstrates that while Si-rich amendments can affect rice uptake of As, the kinetics of Si dissolution and nutrient availability can also affect As uptake and toxicity in rice

Arsenic Concentrations in Paddy Soil and Rice and Health Implications for Major Rice-Growing Regions of Cambodia

Despite the global importance of As in rice, research has primarily focused on Bangladesh, India, China, and the United States with limited attention given to other countries. Owing to both indigenous As within the soil and the possible increases arising from the onset of irrigation with groundwater, an assessment of As in rice within Cambodia is needed, which offers a “base-case” comparison against sediments of similar origin that comprise rice paddy soils where As-contaminated water is used for irrigation (e.g., Bangladesh). Here, we evaluated the As content of rice from five provinces (Kandal, Prey Veng, Battambang, Banteay Meanchey, and Kampong Thom) in the rice-growing regions of Cambodia and coupled that data to soil-chemical factors based on extractions of paddy soil collected and processed under anoxic conditions. At total soil As concentrations ranging 0.8 to 18 μg g^–1, total grain As concentrations averaged 0.2 μg g^–1 and ranged from 0.1 to 0.37 with Banteay Meanchey rice having significantly higher values than Prey Veng rice. Overall, soil-extractable concentrations of As, Fe, P, and Si and total As were poor predictors of grain As concentrations. While biogeochemical factors leading to reduction of As­(V)-bearing Fe­(III) oxides are likely most important for predicting plant-available As, husk and straw As concentrations were the most significant predictors of grain-As levels among our measured parameters

Unraveling the Mechanisms of Fe Oxidation and Mn Reduction on Mn Indicators of Reduction in Soil (IRIS) Films

Indicators of reduction in soil (IRIS) devices are low-cost soil redox sensors coated with Fe or Mn oxides, which can be reductively dissolved from the device under suitable redox conditions. Removal of the metal oxide coating from the surface, leaving behind the white film, can be quantified and used as an indicator of reducing conditions in soils. Manganese IRIS, coated with birnessite, can also oxidize Fe(II), resulting in a color change from brown to orange that complicates the interpretation of coating removal. Here, we studied field-deployed Mn IRIS films where Fe oxidation was present to unravel the mechanisms of Mn oxidation of Fe(II) and the resulting minerals on the IRIS film surface. We observed reductions in the Mn average oxidation state when Fe precipitation was evident. Fe precipitation was primarily ferrihydrite (30–90%), but lepidocrocite and goethite were also detected, notably when the Mn average oxidation state decreased. The decrease in the average oxidation state of Mn was due to the adsorption of Mn(II) to the oxidized Fe and the precipitation of rhodochrosite (MnCO3) on the film. The results were variable on small spatial scales (<1 mm), highlighting the suitability of IRIS in studying heterogeneous redox reactions in soil. Mn IRIS also provides a tool to bridge lab and field studies of the interactions between Mn oxides and reduced constituents

Silicon Decreases Dimethylarsinic Acid Concentration in Rice Grain and Mitigates Straighthead Disorder

While root Si transporters play a role in the uptake of arsenite and organic As species dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) in rice (<i>Oryza sativa</i> L.), the impact of Si addition on the accumulation of DMA and MMA in reproductive tissues has not been directly evaluated, particularly in isolation from inorganic As species. Furthermore, DMA and MMA are suspected causal agents of straighthead disorder. We performed a hydroponic study to disentangle the impact of Si on accumulation of DMA and MMA in rice grain. At 5 μM, MMA was toxic to rice, regardless of Si addition, although Si significantly decreased root MMA concentrations. Plants dosed with 5 μM DMA grew well vegetatively but exhibited straighthead disorder at the lowest Si dose, and this DMA-induced yield loss reversed with increasing solution Si. Increasing Si also significantly decreased DMA concentrations in roots, straw, husk, and grain, particularly in mature plants. Si restricted grain DMA through competition for root uptake and downregulation of root Si transporters particularly at later stages of growth when Si uptake was greatest. Our finding that DMA causes straighthead disorder under low Si availability but not under high Si availability suggests Si as a straighthead management strategy

Unraveling the Mechanisms of Fe Oxidation and Mn Reduction on Mn Indicators of Reduction in Soil (IRIS) Films

Indicators of reduction in soil (IRIS) devices are low-cost soil redox sensors coated with Fe or Mn oxides, which can be reductively dissolved from the device under suitable redox conditions. Removal of the metal oxide coating from the surface, leaving behind the white film, can be quantified and used as an indicator of reducing conditions in soils. Manganese IRIS, coated with birnessite, can also oxidize Fe(II), resulting in a color change from brown to orange that complicates the interpretation of coating removal. Here, we studied field-deployed Mn IRIS films where Fe oxidation was present to unravel the mechanisms of Mn oxidation of Fe(II) and the resulting minerals on the IRIS film surface. We observed reductions in the Mn average oxidation state when Fe precipitation was evident. Fe precipitation was primarily ferrihydrite (30–90%), but lepidocrocite and goethite were also detected, notably when the Mn average oxidation state decreased. The decrease in the average oxidation state of Mn was due to the adsorption of Mn(II) to the oxidized Fe and the precipitation of rhodochrosite (MnCO3) on the film. The results were variable on small spatial scales (<1 mm), highlighting the suitability of IRIS in studying heterogeneous redox reactions in soil. Mn IRIS also provides a tool to bridge lab and field studies of the interactions between Mn oxides and reduced constituents

Unraveling the Mechanisms of Fe Oxidation and Mn Reduction on Mn Indicators of Reduction in Soil (IRIS) Films

Indicators of reduction in soil (IRIS) devices are low-cost soil redox sensors coated with Fe or Mn oxides, which can be reductively dissolved from the device under suitable redox conditions. Removal of the metal oxide coating from the surface, leaving behind the white film, can be quantified and used as an indicator of reducing conditions in soils. Manganese IRIS, coated with birnessite, can also oxidize Fe(II), resulting in a color change from brown to orange that complicates the interpretation of coating removal. Here, we studied field-deployed Mn IRIS films where Fe oxidation was present to unravel the mechanisms of Mn oxidation of Fe(II) and the resulting minerals on the IRIS film surface. We observed reductions in the Mn average oxidation state when Fe precipitation was evident. Fe precipitation was primarily ferrihydrite (30–90%), but lepidocrocite and goethite were also detected, notably when the Mn average oxidation state decreased. The decrease in the average oxidation state of Mn was due to the adsorption of Mn(II) to the oxidized Fe and the precipitation of rhodochrosite (MnCO3) on the film. The results were variable on small spatial scales (<1 mm), highlighting the suitability of IRIS in studying heterogeneous redox reactions in soil. Mn IRIS also provides a tool to bridge lab and field studies of the interactions between Mn oxides and reduced constituents

Soil Incorporation of Silica-Rich Rice Husk Decreases Inorganic Arsenic in Rice Grain

Arsenic decreases rice yield, and inorganic grain As threatens human health; thus, strategies to decrease rice As are critically needed. Increased plant-available silica (Si) can decrease rice As, yet the source of Si matters. Rice husk, an underutilized and Si-rich byproduct of rice production that contains less labile C and an order of magnitude less As than rice straw, may be an economically viable Si resource to decrease rice As, yet the impact of rice husk incorporation on As in the rice–soil nexus has not been reported. This proof-of-concept study shows that rice husk incorporation to soil (1% w/w) decreases inorganic grain As by 25–50% without negatively affecting grain Cd, yield, or dissolved CH₄ levels. Rice husk is a critical yet perhaps overlooked resource to improve soil quality through enhanced nutrient availability and attenuate human health risks through consumption of As-laden grain

<b>Dataset: High methane concentrations in tidal salt marsh soils: where does the methane go?</b>

Tidal salt marshes produce and emit CH4. Therefore, it is critical to understand the biogeochemical controls that regulate CH4 spatial and temporal dynamics in wetlands. The prevailing paradigm assumes that acetoclastic methanogenesis is the dominant pathway for CH4 production, and higher salinity concentrations inhibit CH4 production in salt marshes. Recent evidence shows that CH4 is produced within salt marshes via methylotrophic methanogenesis, a process not inhibited by sulfate reduction. To further explore this conundrum, we performed measurements of soil-atmosphere CH4 and CO2 fluxes coupled with depth profiles of soil CH4 and CO2 pore water gas concentrations, stable and radioisotopes, pore water chemistry, and microbial community composition to assess CH4 production and fate within a temperate tidal salt marsh. We found unexpectedly high CH4 concentrations up to 145,000 μmol mol-1 positively correlated with S2- (salinity range: 6.6 to 14.5 ppt). Despite large CH4 production within the soil, soil-atmosphere CH4 fluxes were low but with higher emissions and extreme variability during plant senescence (84.3 ± 684.4 nmol m-2 s-1). CH4 and CO2 within the soil pore water were produced from young carbon, with most Δ14C-CH4 and Δ14C-CO2 values at or above modern. We found evidence that CH4 within soils was produced by methylotrophic and hydrogenotrophic methanogenesis. Several pathways exist after CH4 is produced, including diffusion into the atmosphere, CH4 oxidation, and lateral export to adjacent tidal creeks; the latter being the most likely dominant flux. Our findings demonstrate that CH4 production and fluxes are biogeochemically heterogeneous, with multiple processes and pathways that can co-occur and vary in importance over the year. This study highlights the potential for high CH4 production, the need to understand the underlying biogeochemical controls, and the challenges of evaluating CH4 budgets and blue carbon in salt marshes.</p