Methylated and inorganic thioarsenates have recently been reported from paddy fields besides the better-known oxyarsenates. Methylated thioarsenates are highly toxic for humans, yet their uptake, ...transformation, and translocation in rice plants is unknown. Here, hydroponic experiments with 20 day old rice plants showed that monomethylmonothioarsenate (MMMTA), dimethylmonothioarsenate (DMMTA), and monothioarsenate (MTA) were taken up by rice roots and could be detected in the xylem. Total arsenic (As) translocation from roots to shoots was higher for plants exposed to DMMTA, MTA, and dimethylarsenate (DMAV) compared to MMMTA and monomethylarsenate (MMAV). All thioarsenates were partially transformed in the presence of rice roots, but processes and extents differed. MMMTA was subject to abiotic oxidation and largely dethiolated to MMAV already outside the plant, probably due to root oxygen loss. DMMTA and MTA were not oxidized abiotically. Crude protein extracts showed rapid enzymatic reduction for MTA but not for DMMTA. Our study implies that DMMTA has the highest potential to contribute to total As accumulation in grains either as DMAV or partially as DMMTA. DMMTA has once been detected in rice grains using enzymatic extraction. By routine acid extraction, DMMTA is determined as DMAV and thus escapes regulation despite its toxicity.
Inorganic and methylated thioarsenates have recently been reported to contribute substantially to arsenic (As) speciation in paddy-soil pore waters. Here, we show that thioarsenates can also ...accumulate in rice grains and rice products. For their detection, a method was developed using a pepsin–pancreatin enzymatic extraction followed by chromatographic separation at pH 13. From 54 analyzed commercial samples, including white, parboiled and husked rice, puffed rice cakes, and rice flakes, 50 contained dimethylmonothioarsenate (DMMTA) (maximum 25.6 μg kg–1), 18 monothioarsenate (MTA) (maximum 5.6 μg kg–1), 14 dimethyldithioarsenate (DMDTA) (maximum 2.8 μg kg–1), and 5 dithioarsenate (DTA) (maximum 2.3 μg kg–1). Additionally, we show that the commonly used nitric acid extraction transforms MTA to arsenite and DMMTA and DMDTA to dimethylarsenate (DMA). Current food guidelines do not require an analysis of thioarsenates in rice and only limit the contents of inorganic oxyarsenic species (including acid-extraction-transformed MTA), but not DMA (including acid-extraction-transformed DMMTA and DMDTA).
Inorganic and methylated thioarsenates have recently been reported to form in paddy soil pore waters and accumulate in rice grains. Among them, dimethylmonothioarsenate (DMMTA) is particularly ...relevant because of its high cytotoxicity and potential misidentification as nonregulated dimethylarsenate (DMA). Studying DMMTA uptake and flag leaf, grain, and husk accumulation in rice plants during grain filling, substantial dethiolation to DMA was observed with only 8.0 ± 0.1, 9.1 ± 0.6, and 1.4 ± 0.2% DMMTA remaining, respectively. More surprisingly, similar shares of DMMTA were observed in control experiments with DMA, indicating in planta DMA thiolation. Exposure of different rice seedling varieties to not only DMA but also to arsenite and monomethylarsenate (MMA) revealed in planta thiolation as a common process in rice. Up to 35 ± 7% DMA thiolation was further observed in the shoots and roots of the model plant Arabidopsis thaliana. Parameters determining the ratio and kinetics of thiolation versus dethiolation are unknown, yet, but less DMA thiolation in glutathione-deficient mutants compared to wild-type plants suggested glutathione concentration as one potential parameter. Our results demonstrate that pore water is not the only source for thioarsenates in rice grains and that especially the currently nonregulated DMA needs to be monitored as a potential precursor of DMMTA formation inside rice plants.
Arsenic is one of the most relevant environmental pollutants and human health threats. Several arsenic species occur in soil pore waters. Recently, it was discovered that these include inorganic and ...organic thioarsenates. Among the latter, dimethylmonothioarsenate (DMMTA) is of particular concern because in mammalian cells, its toxicity was found to exceed even that of arsenite. We investigated DMMTA toxicity for plants in experiments with Arabidopsis thaliana and indeed observed stronger growth inhibition than with arsenite. DMMTA caused a specific, localized deformation of root epidermal cells. Toxicity mechanisms apparently differ from those of arsenite since no accumulation of reactive oxygen species was observed in DMMTA-exposed root tips. Also, there was no contribution of the phytochelatin pathway to the DMMTA detoxification as indicated by exposure experiments with respective mutants and thiol profiling. RNA-seq analysis found strong transcriptome changes dominated by stress-responsive genes. DMMTA was taken up more efficiently than the methylated oxyarsenate dimethylarsenate and highly mobile within plants as revealed by speciation analysis. Shoots showed clear indications of DMMTA toxicity such as anthocyanin accumulation and a decrease in chlorophyll and carotenoid levels. The toxicity and efficient translocation of DMMTA within plants raise important food safety issues.
Thioarsenates have recently been detected in rice and rice-based products, with particularly high contents in puffed rice cakes. Here, we show that puffing rice can cause almost complete ...transformation of dimethylarsenate (DMA) to dimethyldithioarsenate (DMDTA) and dimethylmonothioarsenate (DMMTA). Analysis of puffed rice cakes after 3 months of non-sealed storage at room temperature showed transformation of DMDTA mainly into DMMTA. From a food safety perspective, this likely represents an increased risk because DMMTA is highly cytotoxic and misidentified as non-regulated DMA by routine acid extractions. Analysis of 80 commercial puffed rice cakes confirmed widespread occurrence of thioarsenates. The sum of non-regulated, but potentially toxic DMMTA and DMDTA reached values up to 537 µg·kg-1 and 241 µg·kg-1 for generic and infant-labeled rice cakes, respectively. Our results highlight the importance of better understanding (de)thiolation processes along the rice cake-production chain and potentially revising current thresholds set for iAs to include DMMTA and DMDTA.
Accumulation of inorganic arsenic (iAs) and dimethylarsenate (DMA) in rice threatens human health and rice yield, respectively. We studied the yet unclear interactions of soil sulfate amendment and ...water management for decreasing As accumulation in rice grain in a pot experiment. We show that soil sulfate amendment (+200 mg S/kg soil) decreased grain iAs by 44% without clearly increasing grain DMA under intermittent flooding from booting stage to maturation. Under continuous flooding during this period, sulfate amendment decreased grain iAs only by 25% but increased grain DMA by 68%. The mechanisms of sulfate amendment effects on grain iAs were not explained by porewater composition or in-planta As sequestration but were allocated to the rhizosphere. Grain iAs closely correlated with As in the root iron-plaque (r = 0.92) which was effectively decreased by sulfate amendment and may have acted as an iAs source for rice uptake. Although both sulfate amendment and intermittent flooding substantially increased porewater DMA concentrations, it was the continuous flooding, irrespective of sulfate amendment, that resulted in rice straighthead disease with 47–55% less yield and 258–320% more DMA in grains than intermittent flooding. This study suggests that combining soil sulfate amendment and intermittent flooding can help to secure the quantity and quality of rice produced in As-affected areas. Our results also imply the key role of rhizosphere processes in controlling both iAs and DMA accumulation in rice which should be elucidated in the future.
•Under intermittent flooding, sulfate amendment decreased grain iAs by 44%.•Under continuous flooding, sulfate amendment decreased grain iAs only by 25%.•Only under continuous flooding, sulfate amendment clearly increased grain DMA.•Porewater chemistry and plant As distribution cannot explain grain iAs or DMA.•Rhizosphere processes are proposed to control both grain iAs and DMA.
Arsenic (As) occurrence in rice is a serious human health threat. Worldwide, regulations typically limit only carcinogenic inorganic As, but not possibly carcinogenic dimethylated oxyarsenate (DMA). ...However, there is emerging evidence that “DMA”, determined by routine acid-based extraction and analysis, hides a substantial share of dimethylated thioarsenates that have similar or higher cytotoxicities than arsenite. Risk assessments characterizing the in vivo toxicity of rice-derived dimethylated thioarsenates are urgently needed. In the meantime, either more sophisticated methods based on enzymatic extraction and separation of dimethylated oxy- and thioarsenates have to become mandatory or total As should be regulated.
Water management in paddy soils can effectively reduce the soil-to-rice grain transfer of either As or Cd, but not of both elements simultaneously due to the higher mobility of As under reducing and ...Cd under oxidizing soil conditions. Limestone amendment, the common form of liming, is well known for decreasing Cd accumulation in rice grown on acidic soils. Sulfate amendment was suggested to effectively decrease As accumulation in rice, especially under intermittent soil flooding. To study the unknown effects of combined sulfate and limestone amendment under intermittent flooding for simultaneously decreasing As and Cd in rice, we performed a pot experiment using an acidic sandy loam paddy soil. We also included a clay loam paddy soil to study the role of soil texture in low-As rice production under intermittent flooding. We found that liming not only decreased rice Cd concentrations but also greatly decreased dimethylarsenate (DMA) accumulation in rice. We hypothesize that this is due to suppressed sulfate reduction, As methylation, and As thiolation by liming in the sulfate-amended soil and a higher share of deprotonated DMA at higher pH which is taken up less readily than protonated DMA. Decreased gene abundance of potential soil sulfate-reducers by liming further supported our hypothesis. Combined sulfate and limestone amendment to the acidic sandy loam soil produced rice with 43% lower inorganic As, 72% lower DMA, and 68% lower Cd compared to the control soil without amendment. A tradeoff between soil aeration and water availability was observed for the clay loam soil, suggesting difficulties to decrease As in rice while avoiding plant water stress under intermittent flooding in fine-textured soils. Our results suggest that combining sulfate amendment, liming, and intermittent flooding can help to secure rice safety when the presence of both As and Cd in coarse-textured soils is of concern.
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•Combined soil sulfate and limestone amendment decreased iAs, DMA, and Cd in rice.•Liming decreased DMA in rice by >70% by decreasing protonated DMA in porewater.•It is trickier to control rice As in a more clayey soil under intermittent flooding.
The fate of plastic waste and a sustainable use of synthetic polymers is one of the major challenges of the twenty first century. Waste valorization strategies can contribute to the solution of this ...problem. Besides chemical recycling, biological degradation could be a promising tool. Among the high diversity of synthetic polymers, polyurethanes are widely used as foams and insulation materials. In order to examine bacterial biodegradability of polyurethanes, a soil bacterium was isolated from a site rich in brittle plastic waste. The strain, identified as
sp. by 16S rRNA gene sequencing and membrane fatty acid profile, was able to grow on a PU-diol solution, a polyurethane oligomer, as the sole source of carbon and energy. In addition, the strain was able to use 2,4-diaminotoluene, a common precursor and putative degradation intermediate of polyurethanes, respectively, as sole source of energy, carbon, and nitrogen. Whole genome sequencing of the strain revealed the presence of numerus catabolic genes for aromatic compounds. Growth on potential intermediates of 2,4-diaminotoluene degradation, other aromatic growth substrates and a comparison with a protein data base of oxygenases present in the genome, led to the proposal of a degradation pathway.
Environmental forensics is the application of knowledge from geosciences and chemistry in a legal setting, e.g., to determine the origin and consequences of contamination events. Teaching ...environmental forensics requires reactivating prior knowledge from different fields of natural sciences, filling knowledge gaps, and connecting pieces of scientific evidence to form logical chains of arguments. Here, we present a cooperative teaching format that successfully covers the challenges of interdisciplinary teaching while further developing learners’ soft skills. Through role-playing in a mock trial of a famous hexavalent chromium Cr(VI) contamination case in California, learners choose to team with the town of Hinkley, as the plaintiff team, or with Pacific Gas & Electric (PG&E), the company accused of the contamination, as the defense team. After introductory sessions, the teams summarize facts, and build and present arguments to support their claims regarding the formation of the Cr(VI) plume, the impact on the population’s health, and remediation efforts taken by PG&E. These arguments are delivered in front of their peers and instructors, acting as judges, in a mock trial. Here, we summarize different modalities that have been tested over the past 10 years regarding role assignment and team building. This teaching format has been shown to be successful in engaging learners with the scientific aspects of the case-based trial while helping them become critical about information they are confronted with, delivering arguments in structured ways, defending their points of view, and improving communication skills on a peer- and layperson-level.
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