Guo-Xin Sun

Inorganic arsenic in Chinese food and its cancer risk.

Even moderate arsenic exposure may lead to health problems, and thus quantifying inorganic arsenic (iAs) exposure from food for different population groups in China is essential. By analyzing the data from the China National Nutrition and Health Survey (CNNHS) and collecting reported values of iAs in major food groups, we developed a framework of calculating average iAs daily intake for different regions of China. Based on this framework, cancer risks from iAs in food was deterministically and probabilistically quantified. The article presents estimates for health risk due to the ingestion of food products contaminated with arsenic. Both per individual and for total population estimates were obtained. For the total population, daily iAs intake is around 42 μg day(-1), and rice is the largest contributor of total iAs intake accounting for about 60%. Incremental lifetime cancer risk from food iAs intake is 106 per 100,000 for adult individuals and the median population cancer risk is 177 per 100,000 varying between regions. Population in the Southern region has a higher cancer risk than that in the Northern region and the total population. Sensitive analysis indicated that cancer slope factor, ingestion rates of rice, aquatic products and iAs concentration in rice were the most relevant variables in the model, as indicated by their higher contribution to variance of the incremental lifetime cancer risk. We conclude that rice may be the largest contributor of iAs through food route for the Chinese people. The population from the South has greater cancer risk than that from the North and the whole population.

Inorganic arsenic levels in baby rice are of concern

Inorganic arsenic is a chronic exposure carcinogen. Analysis of UK baby rice revealed a median inorganic arsenic content (n=17) of 0.11 mg/kg. By plotting inorganic arsenic against total arsenic, it was found that inorganic concentrations increased linearly up to 0.25 mg/kg total arsenic, then plateaued at 0.16 mg/kg at higher total arsenic concentrations. Inorganic arsenic intake by babies (4-12 months) was considered with respect to current dietary ingestion regulations. It was found that 35% of the baby rice samples analysed would be illegal for sale in China which has regulatory limit of 0.15 mg/kg inorganic arsenic. EU and US food regulations on arsenic are non-existent. When baby inorganic arsenic intake from rice was considered, median consumption (expressed as microg/kg/d) was higher than drinking water maximum exposures predicted for adults in these regions when water intake was expressed on a bodyweight basis.

Biotransformation and Volatilization of Arsenic by Three Photosynthetic Cyanobacteria

Arsenic (As) is a pervasive and ubiquitous environmental toxin that has created worldwide human health problems. However, there are few studies about how organisms detoxify As. Cyanobacteria are capable of both photolithotrophic growth in the light and heterotrophic growth in the dark and are ubiquitous in soils, aquatic systems, and wetlands. In this study, we investigated As biotransformation in three cyanobacterial species (Microcystis sp. PCC7806, Nostoc sp. PCC7120, and Synechocystis sp. PCC6803). Each accumulated large amounts of As, up to 0.39 g kg−1 dry weight, 0.45 g kg−1 dry weight, and 0.38 g kg−1 dry weight when treated with 100 μm sodium arsenite for 14 d, respectively. Inorganic arsenate and arsenite were the predominant species, with arsenate making up >80% of total As; methylated arsenicals were detected following exposure to higher As concentrations. When treated with arsenate for 6 weeks, cells of each cyanobacterium produced volatile arsenicals. The genes encoding the As(III) S-adenosylmethionine methyltransferase (ArsM) were cloned from these three cyanobacteria. When expressed in an As-hypersensitive strain of Escherichia coli, each conferred resistance to arsenite. Two of the ArsM homologs (SsArsM from Synechocystis sp. PCC6803 and NsArsM from Nostoc sp. PCC7120) were purified and were shown to methylate arsenite in vitro with trimethylarsine as the end product. Given that ArsM homologs are widespread in cyanobacteria, we propose that they play an important role in As biogeochemistry.

Survey of arsenic and its speciation in rice products such as breakfast cereals, rice crackers and Japanese rice condiments.

Rice has been demonstrated to be one of the major contributors to arsenic (As) in human diets in addition to drinking water, but little is known about rice products as an additional source of As exposure. Rice products were analyzed for total As and a subset of samples were measured for arsenic speciation using high performance liquid chromatography interfaced with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). A wide range of rice products had total and inorganic arsenic levels that typified those found in rice grain including, crisped rice, puffed rice, rice crackers, rice noodles and a range of Japanese rice condiments as well as rice products targeted at the macrobiotic, vegan, lactose intolerant and gluten intolerance food market. Most As in rice products are inorganic As (75.2-90.1%). This study provides a wider appreciation of how inorganic arsenic derived from rice products enters the human diet.

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C(pw)) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C(pw) of Cd and Zn, increasing the C(pw) of As, and increasing the iron plaque blocking capacity for Cd and Pb.

Spatial distribution of arsenic and temporal variation of its concentration in rice

• In order to gain insights into the transport and distribution of arsenic (As) in intact rice (Oryza sativa) plants and its unloading into the rice grain, we investigated the spatial distribution of As and the temporal variation of As concentration in whole rice plants at different growth stages. To the best of our knowledge, this is the first time that such a study has been performed. • Inductively coupled plasma mass spectroscopy (ICP-MS) and high-performance liquid chromatography (HPLC)-ICP-MS were used to analyze total As concentration and speciation. Moreover, synchrotron-based X-ray fluorescence (SXRF) was used to investigate in situ As distribution in the leaf, internode, node and grain. • Total As concentrations of vegetative tissues increased during the 2 wk after flowering. The concentration of dimethylarsinic acid (DMA) in the caryopsis decreased progressively with its development, whereas inorganic As concentration remained stable. The ratios of As content between neighboring leaves or between neighboring internodes were c. 0.6. SXRF revealed As accumulation in the center of the caryopsis during its early development and then in the ovular vascular trace. • These results indicate that there are different controls on the unloading of inorganic As and DMA; the latter accumulated mainly in the caryopsis before flowering, whereas inorganic As was mainly transported into the caryopsis during grain filling. Moreover, nodes appeared to serve as a check-point in As distribution in rice shoots.

Arsenic in cooked rice: Effect of chemical, enzymatic and microbial processes on bioaccessibility and speciation in the human gastrointestinal tract

Rice, used as staple food for half of the world population, can easily accumulate arsenic (As) into its grain, which often leads to As contamination. The health risk induced by presence of As in food depends on its release from the food matrix, i.e., its bioaccessibility. Using an in vitro gastrointestinal simulator, we incubated two types of cooked rice (total As: 0.389 and 0.314 mg/kg). Arsenic bioaccessibility and speciation changes were determined upon gastrointestinal digestion. Washing with deionized water and cooking did not result in changes of As speciation in the rice although the arsenic content dropped by 7.1-20.6%. Arsenic bioaccessibility of the cooked rice in the small intestine ranged between 38 and 57%. Bioaccessibility slightly increased during digestion in the simulated small intestine and decreased with time in the simulated colon. Significant speciation changes were noted in the simulated colon, with trivalent monomethylarsonate (MMA(III)) becoming an important species.

Arsenic biotransformation and volatilization in transgenic rice

• Biotransformation of arsenic includes oxidation, reduction, methylation, and conversion to more complex organic arsenicals. Members of the class of arsenite (As(III)) S-adenosylmethyltransferase enzymes catalyze As(III) methylation to a variety of mono-, di-, and trimethylated species, some of which are less toxic than As(III) itself. However, no methyltransferase gene has been identified in plants. • Here, an arsM gene from the soil bacterium Rhodopseudomonas palustris was expressed in Japonica rice (Oryza sativa) cv Nipponbare, and the transgenic rice produced methylated arsenic species, which were measured by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). • Both monomethylarsenate (MAs(V)) and dimethylarsenate (DMAs(V)) were detected in the roots and shoots of transgenic rice. After 12 d exposure to As(III), the transgenic rice gave off 10-fold greater volatile arsenicals. • The present study demonstrates that expression of an arsM gene in rice induces arsenic methylation and volatilization, theoretically providing a potential stratagem for phytoremediation.

Pathways and relative contributions to arsenic volatilization from rice plants and paddy soil.

Recent studies have shown that higher plants are unable to methylate arsenic (As), but it is not known whether methylated As species taken up by plants can be volatilized. Rice (Oryza sativa L.) plants were grown axenically or in a nonsterile soil using a two-chamber system. Arsenic transformation and volatilization were investigated. In the axenic system, uptake of As species into rice roots was in the order of arsenate (As(V)) > monomethylarsonic acid (MMAs(V)) > dimethylarsinic acid (DMAs(V)) > trimethylarsine oxide (TMAs(V)O), but the order of the root-to-shoot transport index (Ti) was reverse. Also, volatilization of trimethylarsine (TMAs) from rice plants was detected when plants were treated with TMAs(V)O but not with As(V), DMAs(V), or MMAs(V). In the soil culture, As was volatilized mainly from the soil. Small amounts of TMAs were also volatilized from the rice plants, which took up DMAs(V), MMAs(V), and TMAs(V)O from the soil solution. The addition of dried distillers grain (DDG) to the soil enhanced As mobilization into the soil solution, As methylation and volatilization from the soil, as well as uptake of different As species and As volatilization from the rice plants. Results show that rice is able to volatilize TMAs after the uptake of TMAs(V)O but not able to convert inorganic As, MMAs(V) or DMAs(V) into TMAs and that the extent of As volatilization from rice plants was much smaller than that from the flooded soil.

Arsenic Speciation and Volatilization from Flooded Paddy Soils Amended with Different Organic Matters

Arsenic (As) methylation and volatilization in soil can be increased after organic matter (OM) amendment, though the factors influencing this are poorly understood. Herein we investigate how amended OM influences As speciation as well as how it alters microbial processes in soil and soil solution during As volatilization. Microcosm experiments were conducted on predried and fresh As contaminated paddy soils to investigate microbial mediated As speciation and volatilization under different OM amendment conditions. These experiments indicated that the microbes attached to OM did not significantly influence As volatilization. The arsine flux from the treatment amended with 10% clover (clover-amended treatment, CT) and dried distillers grain (DDG) (DDG-amended treatment, DT2) were significantly higher than the control. Trimethylarsine (TMAs) was the dominant species in arsine derived from CT, whereas the primary arsine species from DT2 was TMAs and arsine (AsH(3)), followed by monomethylarsine (MeAsH(2)). The predominant As species in the soil solutions of CT and DT2 were dimethylarsinic acid (DMAA) and As(V), respectively. OM addition increased the activities of arsenite-oxidizing bacteria (harboring aroA-like genes), though they did not increase or even decrease the abundance of arsenite oxidizers. In contrast, the abundance of arsenate reducers (carrying the arsC gene) was increased by OM amendment; however, significant enhancement of activity of arsenate reducers was observed only in CT. Our results demonstrate that OM addition significantly increased As methylation and volatilization from the investigated paddy soil. The physiologically active bacteria capable of oxidization, reduction, and methylation of As coexisted and mediated the As speciation in soil and soil solution.