Assessing the Labile Arsenic Pool in Contaminated Paddy Soils by Isotopic Dilution Techniques and Simple Extractions

Arsenic (As) contamination of paddy soils threatens rice cultivation and the health of populations relying on rice as a staple crop. In the present study, isotopic dilution techniques were used to determine the chemically labile (E value) and phytoavailable (L value) pools of As in a range of paddy soils from Bangladesh, India, and China and two arable soils from the UK varying in the degree and sources of As contamination. The E value accounted for 6.2-21.4% of the total As, suggesting that a large proportion of soil As is chemically nonlabile. L values measured with rice grown under anaerobic conditions were generally larger than those under aerobic conditions, indicating increased potentially phytoavailable pool of As in flooded soils. In an incubation study, As was mobilized into soil pore water mainly as arsenite under flooded conditions, with Bangladeshi soils contaminated by irrigation of groundwater showing a greater potential of As mobilization than other soils. Arsenic mobilization was best predicted by phosphate-extractable As in the soils.

The dynamics of arsenic in four paddy fields in the Bengal delta

Irrigation with arsenic contaminated groundwater in the Bengal Delta may lead to As accumulation in the soil and rice grain. The dynamics of As concentration and speciation in paddy fields during dry season (boro) rice cultivation were investigated at 4 sites in Bangladesh and West Bengal, India. Three sites which were irrigated with high As groundwater had elevated As concentrations in the soils, showing a significant gradient from the irrigation inlet across the field. Arsenic concentration and speciation in soil pore water varied temporally and spatially; higher As concentrations were associated with an increasing percentage of arsenite, indicating a reductive mobilization. Concentrations of As in rice grain varied by 2-7 fold within individual fields and were poorly related with the soil As concentration. A field site employing alternating flooded-dry irrigation produced the lowest range of grain As concentration, suggesting a lower soil As availability caused by periodic aerobic conditions.

The impact of a rice based diet on urinary arsenic

Rice is elevated in arsenic (As) compared to other staple grains. The Bangladeshi community living in the United Kingdom (UK) has a ca. 30-fold higher consumption of rice than white Caucasians. In order to assess the impact of this difference in rice consumption, urinary arsenicals of 49 volunteers in the UK (Bangladeshi n = 37; white Caucasians n = 12) were monitored along with dietary habits. Total urinary arsenic (As(t)) and speciation analysis for dimethylarsinic acid (DMA), monomethylarsonic acid (MA) and inorganic arsenic (iAs) was conducted. Although no significant difference was found for As(t) (median: Bangladeshis 28.4 µg L(-1)) and white Caucasians (20.6 µg L(-1)), the sum of medians of DMA, MA and iAs for the Bangladeshi group was found to be over 3-fold higher (17.9 µg L(-1)) than for the Caucasians (3.50 µg L(-1)). Urinary DMA was significantly higher (p <0.001) in the UK Bangladeshis (median: 16.9 µg DMA L(-1)) than in the white Caucasians (3.16 µg DMA L(-1)) as well as iAs (p <0.001) with a median of 0.630 µg iAs L(-1) for Bangladeshi and 0.250 µg iAs L(-1) for Caucasians. Cationic compounds were significantly lower in the Bangladeshis (2.93 µg L(-1)) than in Caucasians (14.9 µg L(-1)). The higher DMA and iAs levels in the Bangladeshis are mainly the result of higher rice consumption: arsenic is speciated in rice as both iAs and DMA, and iAs can be metabolized, through MA, to DMA by humans. This study shows that a higher dietary intake of DMA alters the DMA/MA ratio in urine. Consequently, DMA/MA ratio as an indication of methylation capacity in populations consuming large quantities of rice should be applied with caution since variation in the quantity and type of rice eaten may alter this ratio.

Identification of tetramethylarsonium in rice grains with elevated arsenic content

Tetramethylarsonium has for the first time been identified in a commercially grown food product, rice, constituting up to 5.8% of the total arsenic in the rice.

Arsenic influence on genetic variation in grain trace-element nutrient content in Bengal delta grown rice

It has previously been shown that across different arsenic (As) soil environments, a decrease in grain selenium (Se), zinc (Zn), and nickel (Ni) concentrations is associated with an increase in grain As. In this study we aim to determine if there is a genetic element for this observation or if it is driven by the soil As environment. To determine the genetic and environmental effect on grain element composition, multielement analysis using ICP-MS was performed on rice grain from a range of rice cultivars grown in 4 different field sites (2 in Bangladesh and 2 in West Bengal). At all four sites a negative correlation was observed between grain As and grain Ni, while at three of the four sites a negative correlation was observed between grain As and grain Se and grain copper (Cu). For manganese, Ni, Cu, and Se there was also a significant genetic interaction with grain arsenic indicating some cultivars are more strongly affected by arsenic than others.

Getting to the bottom of arsenic standards and guidelines

Public health policy for arsenic needs to better reflect the ability to detect the risk(s).

Arsenic as a food chain contaminant:mechanisms of plant uptake and metabolism and mitigation strategies

Arsenic (As) is an environmental and food chain contaminant. Excessive accumulation of As, particularly inorganic arsenic (As(i)), in rice (Oryza sativa) poses a potential health risk to populations with high rice consumption. Rice is efficient at As accumulation owing to flooded paddy cultivation that leads to arsenite mobilization, and the inadvertent yet efficient uptake of arsenite through the silicon transport pathway. Iron, phosphorus, sulfur, and silicon interact strongly with As during its route from soil to plants. Plants take up arsenate through the phosphate transporters, and arsenite and undissociated methylated As species through the nodulin 26-like intrinsic (NIP) aquaporin channels. Arsenate is readily reduced to arsenite in planta, which is detoxified by complexation with thiol-rich peptides such as phytochelatins and/or vacuolar sequestration. A range of mitigation methods, from agronomic measures and plant breeding to genetic modification, may be employed to reduce As uptake by food crops.

Arsenic shoot-grain relationships in field grown rice cultivars

Arsenic (As) accumulation in rice grains is a risk to human health. The mechanism of transfer of As from the shoot into the grain during grain filling is unknown at present. In this study As speciation in the shoot and grains at maturity were examined, and the relationships between phosphorus (P) and As, and silicon (Si) and As were established in a wide range of cultivars grown in As contaminated field trials in Bangladesh and China. No correlations were observed between shoot and grain speciation, with the inorganic form comprising 93.0-97.0% of As in the shoot and 63.0-83.7% in the grains. The percentage of dimethylarsinic acid (DMA) was between 1.4 and 6.6% in the shoot and 14.6 and 37.0% in the grains; however, the concentrations were comparable, ranging from 0.07 to 0.26 mg kg(-1) in the shoots and 0.03 to 0.25 mg kg(-1) in the grains. A positive correlation was observed between shoot As and shoot Si, however, no correlation was observed between shoot Si and grain As. A significant negative correlation was observed between shoot P and grain As concentrations. These results suggest that the translocation of As into the grain from the shoots is potentially using P rather than Si transport mechanisms. The findings also indicate that inorganic As and DMA translocation to the grain differ considerably.

Arsenic accumulation and phosphorus status in two rice (Oryza sativa L.) cultivars surveyed from fields in South China

The consumption of paddy rice (Oryza sativa L.) is a major inorganic arsenic exposure pathway in S.E. Asia. A multi-location survey was undertaken in Guangdong Province, South China to assess arsenic accumulation and speciation in 2 rice cultivars, one an Indica and the other a hybrid Indica. The results showed that arsenic concentrations in rice tissue increased in the order grain <husk <straw <root. Rice grain arsenic content of 2 rice cultivars was significant different and correlated with phosphorus concentration and molar ratio of P/As in shoot, being higher for the Indica cultivar than for the hybrid Indica, which suggests altering shoot phosphorus status as a promising route for breeding rice cultivars with reduced grain arsenic. Speciation of grain arsenic, performed using HPLC-ICP-MS, identified inorganic arsenic as the dominant arsenic species present in the rice grain.

Arsenic limits Trace Mineral Nutrition (Selenium, Zinc, and Nickel) in Bangladesh Rice Grain

A reconnaissance of 23 paddy fields, from three Bangladesh districts, encompassing a total of 230 soil and rice plant samples was conducted to identify the extent to which trace element characteristics in soils and irrigation waters are reflected by the harvested rice crop. Field sites were located on two soil physiographic units with distinctly different As soil baseline and groundwater concentrations. For arsenic (As), both straw and grain trends closely fitted patterns observed for the soils and water. Grain concentration characteristics for selenium (Se), zinc (Zn), and nickel (Ni), however, were markedly different. Regressions of shoot and grain As against grain Se, Zn, and Ni were highly significant (P <0.001), exhibiting a pronounced decline in grain trace-nutrient quality with increasing As content. To validate this further, a pot experiment cultivar screening trial, involving commonly cultivated high yielding variety (HYV) rice grown alongside two U.S. rice varieties characterized as being As tolerant and susceptible, was conducted on an As-amended uniform soil. Findings from the trial confirmed that As perturbed grain metal(loid) balances, resulting in severe yield reductions in addition to constraining the levels of Se, Zn, and Ni in the grain.

Environmental and genetic control of arsenic accumulation and speciation in rice grain:comparing a range of common cultivars grown in contaminated sites across Bangladesh, China, and India

The concentration of arsenic (As) in rice grains has been identified as a risk to human health. The high proportion of inorganic species of As (As(i)) is of particular concern as it is a nonthreshold, class 1 human carcinogen. To be able to breed rice with low grain As, an understanding of genetic variation and the effect of different environments on genetic variation is needed. In this study, 13 cultivars grown at two field sites each in Bangladesh, India, and China are evaluated for grain As. There was a significant site, genotype, and site by genotype interaction for total grain As. Correlations were observed only between sites in Bangladesh and India, not between countries or within the Chinese sites. For seven cultivars the As was speciated which revealed significant effects of site, genotype, and site by genotype interaction for percentage As(i). Breeding low grain As cultivars that will have consistently low grain As and low As(i), over multiple environments using traditional breeding approaches may be difficult, although CT9993-5-10-1-M, Lemont, Azucena, and Te-qing in general had low grain As across the field sites.

Quantitative and qualitative trapping of arsines deployed to assess loss of volatile arsenic from paddy soil

Arsenic volatilization in the environment is thought to be an important pathway for transfer from terrestrial pools to the atmosphere. However, this phenomenon is not well characterized due to inherent sampling issues in trapping, quantifying and qualifying these arsine gases; including arsine (AsH(3)), monomethyl arsine (MeAsH(2)), dimethyl arsine (Me(2)AsH) and trimethyl arsine (TMAs). To quantify and qualify arsines in air we developed a novel technique based on silver nitrate impregnated silica gel filled tubes. The method was characterized by measuring the recovery of trapped arsines after elution of this chemo-trap with hot boiling diluted nitric acid. Results from three separate experiments, measured by ICP-MS, showed that the method is reproducible and quantitative. Arsine species recovery ranged from 80.1 to 95.6%, with limit of detection as low as 3.8 ng per chemo-trap tube. Moreover, HPLC-ICP-MS analysis of hot boiling water eluted traps showed that the corresponding oxy ions of the arsines were formed with the As-C bonds of the molecule intact, hence, allowing qualification of trapped arsine species. A microcosm study examining volatile arsenic evolution from field contaminated Bangladeshi paddy soils (24.2 mg/kg arsenic) was used to show the application of silver nitrate chemo-trapping approach. Traps were placed on the inlet and the outlet of microcosms containing the soils that were either (cattle derived) manured or not, or flooded or not, in a factorial design. The headspace was purged with air at a flow rate of 12 mL/min. Results showed that as much as 320 ng of arsenic (0.014% of total soil content) could be emitted in a 3 week period for manured and flooded soils and that TMAs was the dominant species evolved, with lesser quantities of Me(2)AsH. No volatile arsenic evolution was observed for nonmanured treatments, and arsine release from the nonflooded, manured treatment was much less than the flooded treatment.

Arsenic speciation in Japanese rice drinks and condiments

Rice has been demonstrated to be one of the major contributors to inorganic arsenic (i-As) intake in humans. However, little is known about rice products as additional source of i-As exposure. In this study, misos, syrups and amazake (a fermented sweet rice drink) produced from rice, barley and millet were analysed for total arsenic (t-As) and a subset of samples were also analyzed for As speciation. Rice based products displayed a higher i-As content than those derived from barley and millet. Most of the t-As in the rice products studied was inorganic (63-83%), the remainder being dimethylarsinic acid. Those who regularly consume rice drinks and condiments, such as the Japanese population and those who follow health conscious diets based on the Japanese cuisine, could reach up to 23% of the World Health Organization's Provisional Tolerable Daily Intake of i-As, by only consuming these kinds of products. This study provides a wide appreciation of how i-As derived from rice based products enters the human diet and how this may be of concern to populations who are already exposed to high levels of i-As through consumption of foods such as rice and seaweed.

Grain unloading of arsenic species in rice

Rice (Oryza sativa) is the staple food for over half the world's population yet may represent a significant dietary source of inorganic arsenic (As), a nonthreshold, class 1 human carcinogen. Rice grain As is dominated by the inorganic species, and the organic species dimethylarsinic acid (DMA). To investigate how As species are unloaded into grain rice, panicles were excised during grain filling and hydroponically pulsed with arsenite, arsenate, glutathione-complexed As, or DMA. Total As concentrations in flag leaf, grain, and husk, were quantified by inductively coupled plasma mass spectroscopy and As speciation in the fresh grain was determined by x-ray absorption near-edge spectroscopy. The roles of phloem and xylem transport were investigated by applying a +/- stem-girdling treatment to a second set of panicles, limiting phloem transport to the grain in panicles pulsed with arsenite or DMA. The results demonstrate that DMA is translocated to the rice grain with over an order magnitude greater efficiency than inorganic species and is more mobile than arsenite in both the phloem and the xylem. Phloem transport accounted for 90% of arsenite, and 55% of DMA, transport to the grain. Synchrotron x-ray fluorescence mapping and fluorescence microtomography revealed marked differences in the pattern of As unloading into the grain between DMA and arsenite-challenged grain. Arsenite was retained in the ovular vascular trace and DMA dispersed throughout the external grain parts and into the endosperm. This study also demonstrates that DMA speciation is altered in planta, potentially through complexation with thiols.

Identification of low inorganic and total grain arsenic rice cultivars from Bangladesh

For the world's population, rice consumption is a major source of inorganic arsenic (As), a nonthreshold class 1 carcinogen. Reducing the amount of total and inorganic As within the rice grain would reduce the exposure risk. In this study, grain As was measured in 76 cultivars consisting of Bangladeshi landraces, improved Bangladesh Rice Research Institute (BRRI) cultivars, and parents of permanent mapping populations grown in two field sites in Bangladesh, Faridpur and Sonargaon, irrigated with As-contaminated tubewell water. Grain As ranged from 0.16 to 0.74 mg kg(-1) at Faridpur and from 0.07 to 0.28 mg kg(-1) at Sonargaon. Highly significant cultivar differences were detected and a significant correlation (r = 0.802) in the grain As between the two field sites was observed, indicating stable genetic differences in As accumulation. The cultivars with the highest concentration of grain As were the Bangladeshi landraces. Landraces with red bran had significantly more grain As than the cultivars with brown bran. The percent of inorganic As decreased linearly with increasing total As, but genetic variation within this trend was identified. A number of local cultivars with low grain As were identified. Some tropical japonica cultivars with low grain As have the potential to be used in breeding programs and genetic studies aiming to identify genes which decrease grain As.