Microbe-mediated arsenic (As) biotransformation in paddy soils determines the fate of As in soils... more Microbe-mediated arsenic (As) biotransformation in paddy soils determines the fate of As in soils and its availability to rice plants, yet little is known about the microbial communities involved in As biotransformation. Here, we revealed wide distribution, high diversity, and abundance of arsenite (As(III)) oxidase genes (aioA), respiratory arsenate (As(V)) reductase genes (arrA), As(V) reductase genes (arsC), and As(III) S-adenosylmethionine methyltransferase genes (arsM) in 13 paddy soils collected across Southern China. Sequences grouped with As biotransformation genes are mainly from rice rhizosphere bacteria, such as some Proteobacteria, Gemmatimonadales, and Firmicutes. A significant correlation of gene abundance between arsC and arsM suggests that the two genes coexist well in the microbial As resistance system. Redundancy analysis (RDA) indicated that soil pH, EC, total C, N, As, and Fe, C/N ratio, SO4(2-)-S, NO3(-)-N, and NH4(+)-N were the key factors driving diverse micro...
In order to gain insights into the transport and distribution of arsenic (As) in intact rice (Ory... more 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.
Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of... more Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of Duanwu, colloquially known worldwide as the Dragon Boat Day. Arsenic wine is drunk on the morning of the fifth day of the fifth lunar calendar month to commemorate the death of Qu Yuan, a famed Chinese poet who drowned himself in protest of a corrupt government, and to protect against ill fortune. Although realgar minerals are characteristically composed of sparingly soluble tetra-arsenic tetra-sulfides (As(4)S(4)), purity does vary with up to 10% of As being present as non-sulfur bound species, such as arsenate (As(V)) and arsenite (As(III)). Despite, the renewed interest in As speciation and the bioaccessibility of the active As components in realgar based Chinese medicines, little is known about the safety surrounding the cultural practice of drinking As wine. In a series of experiments the speciation and solubility of As in a range of wines were investigated. Furthermore, a simulated gastrointestinal system was employed to predict the impact of digestive processes on As bioavailability. The predominant soluble As species found in all the wines were As(III) and As(V). Based on typical As wine recipes employing 0.1 g realgar mL(-1) wine, the concentration of dissolved As ranged from ca. 100 to 400 mg L(-1) depending on the ethanol content of the preparation: with the As solubility found to be higher in wines with a lower proportion of ethanol. Based on a common 100 mL measure of wine with a concentration of 400 mg As L(-1), the amount of soluble As would equate to around half of the acute minimal lethal dose for adults. This is likely an underestimate of the bioaccessible concentration, as a three-fold increase in bioaccessibility could be observed in the intestinal phase based on the results from the stimulated gastrointestinal system.
Purpose Dissimilatory iron-reducing bacteria have been described by both culture-dependent and -... more Purpose Dissimilatory iron-reducing bacteria have been described by both culture-dependent and -independent methods in various environments, including freshwater, marine sediments, natural wetlands, and contaminated aquifers. However, little is known about iron-reducing microbial communities in paddy soils. The goal of this study was to characterize iron-reducing microbial communities in paddy soil. Moreover, the effect of dissolved and solid-phase iron (III) species on
Journal of Radioanalytical and Nuclear Chemistry, 1998
The partition of uranium(VI) between nitric acid and N,N-dibutyldecanamide (DBDEA) in kerosene ha... more The partition of uranium(VI) between nitric acid and N,N-dibutyldecanamide (DBDEA) in kerosene has been investigated at various concentrations of nitric acid, extractant and salting-out agent LiNO 3. The mechanism of extraction is discussed in the light of the results obtained. The effect of TBP on the extraction of uranium(VI) with DBDEA has also been considered. There is an apparent synergistic effect with these two extractants at low concentration of TBP, however, one sees a decrease in extraction distribution at higher concentration. IR spectra show that there is no apparent interaction between the two kinds of extractants. The stoichiometry of the synergistic extracted species has been determined.
The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility w... more The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility were examined by iron reducing bacteria enriched from As contaminated paddy soil. To our knowledge, this is the first time to report the impact of microbial iron plaque reduction on As mobility. Iron reduction occurred during the inoculation of iron reducing enrichment culture in the treatments with iron plaque and ferrihydrite as the electron acceptors, respectively. The Fe(II) concentration with the treatment of anthraquinone-2, 6-disulfonic acid (AQDS) and iron reducing bacteria increased much faster than the control. Arsenic released from iron plaque with the iron reduction, and a significant correlation between Fe(II) and total As in culture was observed. However, compared with control, the increasing rate of As was inhibited by iron reducing bacteria especially in the presence of AQDS. In addition, the concentrations of As(III) and As(V) in abiotic treatments were higher than those in the biotic treatments at day 30. These results indicated that both microbial and chemical reductions of iron plaque caused As release from iron plaque to aqueous phase, however, microbial iron reduction induced the formation of more crystalline iron minerals, leading to As sequestration. In addition, the presence of AQDS in solution can accelerate the iron reduction, the As release from iron plaque and subsequently the As retention in the crystalline iron mineral. Thus, our results suggested that it is possible to remediate As contaminated soils by utilizing iron reducing bacteria and AQDS.
Selenium, an essential micronutrient for humans, is insufficient in dietary intake for millions o... more Selenium, an essential micronutrient for humans, is insufficient in dietary intake for millions of people worldwide. Rice as the most popular staple food in the world is one of the dominant selenium (Se) sources for people. The distribution and translocation of Se from soil to grain were investigated in a Serich environment in this study. The Se levels in soils ranged widely from 0.5 to 47.7 mg kg -1 . Selenium concentration in rice bran was 1.94 times higher than that in corresponding polished rice. The total Se concentrations in the rice fractions were in the following order: straw > bran > whole grain > polished rice > husk. Significant linear relationships between different rice fractions were observed with each other, and Se in the soil has a linear relationship with different rice fractions as well. Se concentration in rice can easily be predicted by soil Se concentrations or any rice fractions and vice versa according to their linear relationships. In all rice samples for Se speciation, SeMet was the major Se species, followed by MeSeCys and SeCys. The average percentage for SeMet (82.9%) and MeSeCys (6.2%) was similar in the range of total Se from 2.2 to 8.4 mg kg -1 tested. The percentage of SeCys decreased from 6.3 to 2.8%, although its concentration elevated with the increase in total Se in rice. This could be due to the fact that SeCys is the precursor for the formation of other organic Se compounds. The information obtained may have considerable significance for assessing translocation and accumulation of Se in plant.
Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estua... more Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower 206 Pb/ 207 Pb and higher 208 Pb/ 206 Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for 206 Pb/ 207 Pb and 208 Pb/ 206 Pb, respectively), indicated a significant input of non-indigenous Pb with low 206 Pb/ 207 Pb and high 208 Pb/ 206 Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.
Rice has been demonstrated to be one of the major contributors to arsenic (As) in human diets in ... more 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.
Even moderate arsenic exposure may lead to health problems, and thus quantifying inorganic arseni... more 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.
Toasting friends and family with realgar wines and painting children&... more Toasting friends and family with realgar wines and painting children's foreheads and limbs with the leftover realgar/alcohol slurries is an important customary ritual during the Dragon Boat Festival (DBF); a Chinese national holiday and ancient feast day celebrated throughout Asia. Realgar is an arsenic sulfide mineral, and source of highly toxic inorganic arsenic. Despite the long history of realgar use during the DBF, associated risk to human health by arsenic ingestion or percutaneous adsorption is unknown. To address this urine samples were collected from a cohort of volunteers who were partaking in the DBF festivities. The total concentration of arsenic in the wine consumed was 70 mg L⁻¹ with all the arsenic found to be inorganic. Total arsenic concentrations in adult urine reached a maximum of ca. 550 μg L⁻¹ (mean 220.2 μg L⁻¹) after 16 h post-ingestion of realgar wine, while face painting caused arsenic levels in children's urine to soar to 100 μg L⁻¹ (mean 85.3 μg L⁻¹) 40 h after the initial paint application. The average concentration of inorganic arsenic in the urine of realgar wine drinkers on average doubled 16 h after drinking, although this was not permanent and levels subsided after 28 h. As would be expected in young children, the proportions of organic arsenic in the urine remained high throughout the 88-h monitoring period. However, even when arsenic concentrations in the urine peaked at 40 h after paint application, concentrations in the urine only declined slightly thereafter, suggesting pronounced longer term dermal accumulation and penetration of arsenic. Drinking wines blended with realgar or using realgar based paints on children does result in the significant absorption of arsenic and therefore presents a potentially serious and currently unquantified health risk.
Arsenic (As) methylation in aquatic microbes plays a major role in the biogeochemistry of As. Pro... more Arsenic (As) methylation in aquatic microbes plays a major role in the biogeochemistry of As. Protozoa, especially the free-living freshwater species, are important players in aquatic ecological health. In this study, an arsenite (As(III)) methyltransferase, TpyArsM, was identified and characterized in a freeliving protozoan, Tetrahymena pyriformis. In order to confirm its function, TpyarsM gene was knocked-out in Tetrahymena and was also heterologously expressed in hypersensitive E. coli; these events resulted in expected decreases in As tolerance and methylation ability, respectively. In-vitro tests revealed that purified TpyArsM protein methylated inorganic As to mono-and di-methylarsenate, and also had the novel property of producing trimethylarsenite (TMA(III)) and dimethylarsine (Me 2 AsH) gases. This new methyltransferase gene, identified in a species near the base of the food web, has enriched our knowledge of As methyltransferases and has great potential for bioremediation of As-contaminated environments.
A triphenyltin (TPT)-decomposing strain, Pseudomonas aeruginosa CGMCC 1.860, was screened out. It... more A triphenyltin (TPT)-decomposing strain, Pseudomonas aeruginosa CGMCC 1.860, was screened out. It secreted an unknown TPT-decomposing factor into the medium, later shown to be pyochelin, even in the presence of 100 M iron. To our knowledge, this is the first report of organotin decomposition by pyochelin.
Pyochelin (PCH), a kind of siderophore secreted by Pseudomonas aeruginosa, was recently found to ... more Pyochelin (PCH), a kind of siderophore secreted by Pseudomonas aeruginosa, was recently found to have triphenyltin (TPT)-decomposing capacity. In this work, significant augmentation of TPT decomposition by ferripyochelin (FePCH), the chelating compound of PCH with iron, was demonstrated in Tris-HCl buffer (pH 8.0). The generation of hydroxyl radical (HO·) in the presence of FePCH was observed. Inhibition of HO· generation by adding catalase and HO· scavengers (methanol and dimethyl sulfoxide) decreased TPT decomposition, while an increase in HO· formation in the presence of H 2 O 2 enhanced its decomposition. Our findings indicated that HO· generated in the reaction system was responsible for the enhanced TPT decomposition by FePCH versus PCH. The existence of the TPT-pyochelin-iron ternary complex was demonstrated by electron spray ionization-mass spectrometry, tandem mass spectrometry, and 1 H nuclear magnetic resonance. On the basis of the above results, HO· produced in the presence of FePCH was deduced to be in close proximity to TPT and has more opportunity to attack the Sn-C bond, which resulted in the enhanced organotin decomposition. The information obtained may have considerable environmental significance.
Synechocysis sp. PCC6803 is a unicellular blue alga which ubiquitously exists in aquatic system a... more Synechocysis sp. PCC6803 is a unicellular blue alga which ubiquitously exists in aquatic system and is considered to play a role in arsenic cycling. Our results showed that Synechocysis can accumulate arsenic as much as 1.0 and 0.9 gkg −1 DW when exposed to 0.5 mM arsenate and arsenite for 14 days, respectively. In addition, arsenic species in cells were assayed under different exposure conditions and it was found that inorganic arsenic, including arsenate and arsenite, is the dominant species. Organic methylated arsenicals can only be detected exposed to higher arsenic concentration range (100-500 μM). Arsenate is the dominant arsenic species and presents more than 80% of the total arsenic in cells. Efflux of both arsenate and arsenite was observed. When treated with 2.67 μM arsenite, Synechocysis can rapidly oxidize arsenite to arsenate and accumulate As rapidly. The observed arsenic oxidation in solute is solely caused by cellular oxidation. Given the robust ability of As accumulation, it can serve as a phytoremediation organism to efficiently remove arsenic from aquatic environments.
Rice is more elevated in arsenic than all other grain crops tested to date, with whole grain (bro... more Rice is more elevated in arsenic than all other grain crops tested to date, with whole grain (brown) rice having higher arsenic levels than polished (white). It is reported here that rice bran, both commercially purchased and specifically milled for this study, have levels of inorganic arsenic, a nonthreshold, class 1 carcinogen, reaching concentrations of ∼1 mg/kg dry weight, around 10-20 fold higher than concentrations found in bulk grain. Although pure rice bran is used as a health food supplement, perhaps of more concern is rice bran solubles, which are marketed as a superfood and as a supplement to malnourished children in international aid programs. Five rice bran solubles products were tested, sourced from the United States and Japan, and were found to have 0.61-1.9 mg/kg inorganic arsenic. Manufactures recommend ∼20 g servings of the rice bran solubles per day, which equates to a 0.012-0.038 mg intake of inorganic arsenic. There are no maximum concentration levels (MCLs) set for arsenic or its species in food stuffs. EU and U.S. water regulations, set at 0.01 mg/L total or inorganic arsenic, respectively, are based on the assumption that 1 L of water per day is consumed, i.e., 0.01 mg of arsenic/ day. At the manufacturers recommended rice bran solubles consumption rate, inorganic arsenic intake exceeds 0.01 mg/ day, remembering that rice bran solubles are targeted at malnourished children and that actual risk is based on mg kg -1 day -1 intake.
Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arseni... more Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arsenic (As) accumulation, speciation and tolerance of the rootless duckweed Wolffia globosa and its potential for As phytofiltration. • When grown with 1 µM arsenate, W. globosa accumulated two to 10 times more As than four other duckweed or Azolla species tested. W. globosa was able to accumulate > 1000 mg As kg −1 in frond dry weight (DW), and tolerate up to 400 mg As kg −1 DW. At the low concentration range, uptake rate was similar for arsenate and arsenite, but at the high concentration range, arsenite was taken up at a faster rate. • Arsenite was the predominant As species (c. 90% of the total extractable As) in both arsenate-and arsenite-exposed duckweed. W. globosa was more resistant to external arsenate than arsenite, but showed a similar degree of tolerance internally. W. globosa decreased arsenate in solution rapidly, but also effluxed arsenite.
An extensive data set of total arsenic analysis for 901 polished (white) grain samples, originati... more An extensive data set of total arsenic analysis for 901 polished (white) grain samples, originating from 10 countries from 4 continents, was compiled. The samples represented the baseline (i.e., notspecifically collected from arsenic contaminated areas), and all were for market sale in major conurbations. Median total arsenic contents of rice varied 7-fold, with Egypt (0.04 mg/kg) and India (0.07 mg/kg) having the lowest arsenic content while the U.S. (0.25 mg/kg) and France (0.28 mg/kg) had the highest content. Global distribution of total arsenic in rice was modeled by weighting each country's arsenic distribution by that country's contribution to global production. A subset of 63 samples from Bangladesh, China, India, Italy, and the U.S. was analyzed for arsenic species. The relationship between inorganic arsenic contentversus total arsenic contentsignificantly differed among countries, with Bangladesh and India having the steepest slope in linear regression, and the U.S. having the shallowest slope. Using country-specific rice consumption data, daily intake of inorganic arsenic was estimated and the associated internal cancer risk was calculated using the U.S. Environmental Protection Agency (EPA) cancer slope. Median excess internal cancer risks posed by inorganic arsenic ranged 30-fold for the 5 countries examined, being 0.7 per 10,000 for Italians to 22 per 10,000 for Bangladeshis, when a 60 kg person was considered.
For up to 1 billion people worldwide, insufficient dietary intake of selenium (Se) is a serious h... more For up to 1 billion people worldwide, insufficient dietary intake of selenium (Se) is a serious health constraint. Cereals are the dominant Se source for those on low protein diets, as typified by the global malnourished population. With crop Se content constrained largely by underlying geology, regional soil Se variations are often mirrored by their locally grown staples. Despite this, the Se concentrations of much of the world's rice, the mainstay of so many, is poorly characterized, for both total Se content and Se speciation. In this study, 1092 samples of market sourced polished rice were obtained. The sampled rice encompassed dominant rice producing and exporting countries. Rice from the U.S. and India were found to be the most enriched, while mean average levels were lowest in Egyptian rice: ∼32-fold less than their North American equivalents. By weighting country averages by contribution to either global production or export, modeled baseline values for both were produced. Based on a daily rice consumption of 300 g day -1 , around 75% of the grains from the production and export pools would fail to provide 70% of daily recommended Se intakes. Furthermore, Se localization and speciation characterization using X-ray fluorescence (µ-XRF) and X-ray absorption near edge structure (µ-XANES) techniques were investigated in a Se-rich sample. The results revealed that the large majority of Se in the endosperm was present in organic forms.
An iron-reducing bacterial strain was isolated from a paddy soil and identified as a member of th... more An iron-reducing bacterial strain was isolated from a paddy soil and identified as a member of the Aeromonas group by 16S rRNA gene sequence analysis. When the cells were growing with dissolved Fe(III) as the electron acceptor in the presence of As(V), Fe(II) minerals (siderite and vivianite) were formed and dissolved. As was removed efficiently from solution. When the cells were growing with the Fe(III) hydroxide mineral (ferrihydrite) as the electron acceptor in the presence of As(V), ferrihydrite was reduced and dissolved As(V) concentrations decreased sharply. The present study results demonstrated first that members of the Aeromonas group can reduce Fe(III) in paddy soils and second that iron reduction does not necessarily lead to arsenic mobilization. However, As immobilization can occur in environments that contain significant concentrations of counterions such as bicarbonate and phosphate.
Microbe-mediated arsenic (As) biotransformation in paddy soils determines the fate of As in soils... more Microbe-mediated arsenic (As) biotransformation in paddy soils determines the fate of As in soils and its availability to rice plants, yet little is known about the microbial communities involved in As biotransformation. Here, we revealed wide distribution, high diversity, and abundance of arsenite (As(III)) oxidase genes (aioA), respiratory arsenate (As(V)) reductase genes (arrA), As(V) reductase genes (arsC), and As(III) S-adenosylmethionine methyltransferase genes (arsM) in 13 paddy soils collected across Southern China. Sequences grouped with As biotransformation genes are mainly from rice rhizosphere bacteria, such as some Proteobacteria, Gemmatimonadales, and Firmicutes. A significant correlation of gene abundance between arsC and arsM suggests that the two genes coexist well in the microbial As resistance system. Redundancy analysis (RDA) indicated that soil pH, EC, total C, N, As, and Fe, C/N ratio, SO4(2-)-S, NO3(-)-N, and NH4(+)-N were the key factors driving diverse micro...
In order to gain insights into the transport and distribution of arsenic (As) in intact rice (Ory... more 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.
Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of... more Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of Duanwu, colloquially known worldwide as the Dragon Boat Day. Arsenic wine is drunk on the morning of the fifth day of the fifth lunar calendar month to commemorate the death of Qu Yuan, a famed Chinese poet who drowned himself in protest of a corrupt government, and to protect against ill fortune. Although realgar minerals are characteristically composed of sparingly soluble tetra-arsenic tetra-sulfides (As(4)S(4)), purity does vary with up to 10% of As being present as non-sulfur bound species, such as arsenate (As(V)) and arsenite (As(III)). Despite, the renewed interest in As speciation and the bioaccessibility of the active As components in realgar based Chinese medicines, little is known about the safety surrounding the cultural practice of drinking As wine. In a series of experiments the speciation and solubility of As in a range of wines were investigated. Furthermore, a simulated gastrointestinal system was employed to predict the impact of digestive processes on As bioavailability. The predominant soluble As species found in all the wines were As(III) and As(V). Based on typical As wine recipes employing 0.1 g realgar mL(-1) wine, the concentration of dissolved As ranged from ca. 100 to 400 mg L(-1) depending on the ethanol content of the preparation: with the As solubility found to be higher in wines with a lower proportion of ethanol. Based on a common 100 mL measure of wine with a concentration of 400 mg As L(-1), the amount of soluble As would equate to around half of the acute minimal lethal dose for adults. This is likely an underestimate of the bioaccessible concentration, as a three-fold increase in bioaccessibility could be observed in the intestinal phase based on the results from the stimulated gastrointestinal system.
Purpose Dissimilatory iron-reducing bacteria have been described by both culture-dependent and -... more Purpose Dissimilatory iron-reducing bacteria have been described by both culture-dependent and -independent methods in various environments, including freshwater, marine sediments, natural wetlands, and contaminated aquifers. However, little is known about iron-reducing microbial communities in paddy soils. The goal of this study was to characterize iron-reducing microbial communities in paddy soil. Moreover, the effect of dissolved and solid-phase iron (III) species on
Journal of Radioanalytical and Nuclear Chemistry, 1998
The partition of uranium(VI) between nitric acid and N,N-dibutyldecanamide (DBDEA) in kerosene ha... more The partition of uranium(VI) between nitric acid and N,N-dibutyldecanamide (DBDEA) in kerosene has been investigated at various concentrations of nitric acid, extractant and salting-out agent LiNO 3. The mechanism of extraction is discussed in the light of the results obtained. The effect of TBP on the extraction of uranium(VI) with DBDEA has also been considered. There is an apparent synergistic effect with these two extractants at low concentration of TBP, however, one sees a decrease in extraction distribution at higher concentration. IR spectra show that there is no apparent interaction between the two kinds of extractants. The stoichiometry of the synergistic extracted species has been determined.
The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility w... more The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility were examined by iron reducing bacteria enriched from As contaminated paddy soil. To our knowledge, this is the first time to report the impact of microbial iron plaque reduction on As mobility. Iron reduction occurred during the inoculation of iron reducing enrichment culture in the treatments with iron plaque and ferrihydrite as the electron acceptors, respectively. The Fe(II) concentration with the treatment of anthraquinone-2, 6-disulfonic acid (AQDS) and iron reducing bacteria increased much faster than the control. Arsenic released from iron plaque with the iron reduction, and a significant correlation between Fe(II) and total As in culture was observed. However, compared with control, the increasing rate of As was inhibited by iron reducing bacteria especially in the presence of AQDS. In addition, the concentrations of As(III) and As(V) in abiotic treatments were higher than those in the biotic treatments at day 30. These results indicated that both microbial and chemical reductions of iron plaque caused As release from iron plaque to aqueous phase, however, microbial iron reduction induced the formation of more crystalline iron minerals, leading to As sequestration. In addition, the presence of AQDS in solution can accelerate the iron reduction, the As release from iron plaque and subsequently the As retention in the crystalline iron mineral. Thus, our results suggested that it is possible to remediate As contaminated soils by utilizing iron reducing bacteria and AQDS.
Selenium, an essential micronutrient for humans, is insufficient in dietary intake for millions o... more Selenium, an essential micronutrient for humans, is insufficient in dietary intake for millions of people worldwide. Rice as the most popular staple food in the world is one of the dominant selenium (Se) sources for people. The distribution and translocation of Se from soil to grain were investigated in a Serich environment in this study. The Se levels in soils ranged widely from 0.5 to 47.7 mg kg -1 . Selenium concentration in rice bran was 1.94 times higher than that in corresponding polished rice. The total Se concentrations in the rice fractions were in the following order: straw > bran > whole grain > polished rice > husk. Significant linear relationships between different rice fractions were observed with each other, and Se in the soil has a linear relationship with different rice fractions as well. Se concentration in rice can easily be predicted by soil Se concentrations or any rice fractions and vice versa according to their linear relationships. In all rice samples for Se speciation, SeMet was the major Se species, followed by MeSeCys and SeCys. The average percentage for SeMet (82.9%) and MeSeCys (6.2%) was similar in the range of total Se from 2.2 to 8.4 mg kg -1 tested. The percentage of SeCys decreased from 6.3 to 2.8%, although its concentration elevated with the increase in total Se in rice. This could be due to the fact that SeCys is the precursor for the formation of other organic Se compounds. The information obtained may have considerable significance for assessing translocation and accumulation of Se in plant.
Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estua... more Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower 206 Pb/ 207 Pb and higher 208 Pb/ 206 Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for 206 Pb/ 207 Pb and 208 Pb/ 206 Pb, respectively), indicated a significant input of non-indigenous Pb with low 206 Pb/ 207 Pb and high 208 Pb/ 206 Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.
Rice has been demonstrated to be one of the major contributors to arsenic (As) in human diets in ... more 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.
Even moderate arsenic exposure may lead to health problems, and thus quantifying inorganic arseni... more 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.
Toasting friends and family with realgar wines and painting children&... more Toasting friends and family with realgar wines and painting children's foreheads and limbs with the leftover realgar/alcohol slurries is an important customary ritual during the Dragon Boat Festival (DBF); a Chinese national holiday and ancient feast day celebrated throughout Asia. Realgar is an arsenic sulfide mineral, and source of highly toxic inorganic arsenic. Despite the long history of realgar use during the DBF, associated risk to human health by arsenic ingestion or percutaneous adsorption is unknown. To address this urine samples were collected from a cohort of volunteers who were partaking in the DBF festivities. The total concentration of arsenic in the wine consumed was 70 mg L⁻¹ with all the arsenic found to be inorganic. Total arsenic concentrations in adult urine reached a maximum of ca. 550 μg L⁻¹ (mean 220.2 μg L⁻¹) after 16 h post-ingestion of realgar wine, while face painting caused arsenic levels in children's urine to soar to 100 μg L⁻¹ (mean 85.3 μg L⁻¹) 40 h after the initial paint application. The average concentration of inorganic arsenic in the urine of realgar wine drinkers on average doubled 16 h after drinking, although this was not permanent and levels subsided after 28 h. As would be expected in young children, the proportions of organic arsenic in the urine remained high throughout the 88-h monitoring period. However, even when arsenic concentrations in the urine peaked at 40 h after paint application, concentrations in the urine only declined slightly thereafter, suggesting pronounced longer term dermal accumulation and penetration of arsenic. Drinking wines blended with realgar or using realgar based paints on children does result in the significant absorption of arsenic and therefore presents a potentially serious and currently unquantified health risk.
Arsenic (As) methylation in aquatic microbes plays a major role in the biogeochemistry of As. Pro... more Arsenic (As) methylation in aquatic microbes plays a major role in the biogeochemistry of As. Protozoa, especially the free-living freshwater species, are important players in aquatic ecological health. In this study, an arsenite (As(III)) methyltransferase, TpyArsM, was identified and characterized in a freeliving protozoan, Tetrahymena pyriformis. In order to confirm its function, TpyarsM gene was knocked-out in Tetrahymena and was also heterologously expressed in hypersensitive E. coli; these events resulted in expected decreases in As tolerance and methylation ability, respectively. In-vitro tests revealed that purified TpyArsM protein methylated inorganic As to mono-and di-methylarsenate, and also had the novel property of producing trimethylarsenite (TMA(III)) and dimethylarsine (Me 2 AsH) gases. This new methyltransferase gene, identified in a species near the base of the food web, has enriched our knowledge of As methyltransferases and has great potential for bioremediation of As-contaminated environments.
A triphenyltin (TPT)-decomposing strain, Pseudomonas aeruginosa CGMCC 1.860, was screened out. It... more A triphenyltin (TPT)-decomposing strain, Pseudomonas aeruginosa CGMCC 1.860, was screened out. It secreted an unknown TPT-decomposing factor into the medium, later shown to be pyochelin, even in the presence of 100 M iron. To our knowledge, this is the first report of organotin decomposition by pyochelin.
Pyochelin (PCH), a kind of siderophore secreted by Pseudomonas aeruginosa, was recently found to ... more Pyochelin (PCH), a kind of siderophore secreted by Pseudomonas aeruginosa, was recently found to have triphenyltin (TPT)-decomposing capacity. In this work, significant augmentation of TPT decomposition by ferripyochelin (FePCH), the chelating compound of PCH with iron, was demonstrated in Tris-HCl buffer (pH 8.0). The generation of hydroxyl radical (HO·) in the presence of FePCH was observed. Inhibition of HO· generation by adding catalase and HO· scavengers (methanol and dimethyl sulfoxide) decreased TPT decomposition, while an increase in HO· formation in the presence of H 2 O 2 enhanced its decomposition. Our findings indicated that HO· generated in the reaction system was responsible for the enhanced TPT decomposition by FePCH versus PCH. The existence of the TPT-pyochelin-iron ternary complex was demonstrated by electron spray ionization-mass spectrometry, tandem mass spectrometry, and 1 H nuclear magnetic resonance. On the basis of the above results, HO· produced in the presence of FePCH was deduced to be in close proximity to TPT and has more opportunity to attack the Sn-C bond, which resulted in the enhanced organotin decomposition. The information obtained may have considerable environmental significance.
Synechocysis sp. PCC6803 is a unicellular blue alga which ubiquitously exists in aquatic system a... more Synechocysis sp. PCC6803 is a unicellular blue alga which ubiquitously exists in aquatic system and is considered to play a role in arsenic cycling. Our results showed that Synechocysis can accumulate arsenic as much as 1.0 and 0.9 gkg −1 DW when exposed to 0.5 mM arsenate and arsenite for 14 days, respectively. In addition, arsenic species in cells were assayed under different exposure conditions and it was found that inorganic arsenic, including arsenate and arsenite, is the dominant species. Organic methylated arsenicals can only be detected exposed to higher arsenic concentration range (100-500 μM). Arsenate is the dominant arsenic species and presents more than 80% of the total arsenic in cells. Efflux of both arsenate and arsenite was observed. When treated with 2.67 μM arsenite, Synechocysis can rapidly oxidize arsenite to arsenate and accumulate As rapidly. The observed arsenic oxidation in solute is solely caused by cellular oxidation. Given the robust ability of As accumulation, it can serve as a phytoremediation organism to efficiently remove arsenic from aquatic environments.
Rice is more elevated in arsenic than all other grain crops tested to date, with whole grain (bro... more Rice is more elevated in arsenic than all other grain crops tested to date, with whole grain (brown) rice having higher arsenic levels than polished (white). It is reported here that rice bran, both commercially purchased and specifically milled for this study, have levels of inorganic arsenic, a nonthreshold, class 1 carcinogen, reaching concentrations of ∼1 mg/kg dry weight, around 10-20 fold higher than concentrations found in bulk grain. Although pure rice bran is used as a health food supplement, perhaps of more concern is rice bran solubles, which are marketed as a superfood and as a supplement to malnourished children in international aid programs. Five rice bran solubles products were tested, sourced from the United States and Japan, and were found to have 0.61-1.9 mg/kg inorganic arsenic. Manufactures recommend ∼20 g servings of the rice bran solubles per day, which equates to a 0.012-0.038 mg intake of inorganic arsenic. There are no maximum concentration levels (MCLs) set for arsenic or its species in food stuffs. EU and U.S. water regulations, set at 0.01 mg/L total or inorganic arsenic, respectively, are based on the assumption that 1 L of water per day is consumed, i.e., 0.01 mg of arsenic/ day. At the manufacturers recommended rice bran solubles consumption rate, inorganic arsenic intake exceeds 0.01 mg/ day, remembering that rice bran solubles are targeted at malnourished children and that actual risk is based on mg kg -1 day -1 intake.
Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arseni... more Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arsenic (As) accumulation, speciation and tolerance of the rootless duckweed Wolffia globosa and its potential for As phytofiltration. • When grown with 1 µM arsenate, W. globosa accumulated two to 10 times more As than four other duckweed or Azolla species tested. W. globosa was able to accumulate > 1000 mg As kg −1 in frond dry weight (DW), and tolerate up to 400 mg As kg −1 DW. At the low concentration range, uptake rate was similar for arsenate and arsenite, but at the high concentration range, arsenite was taken up at a faster rate. • Arsenite was the predominant As species (c. 90% of the total extractable As) in both arsenate-and arsenite-exposed duckweed. W. globosa was more resistant to external arsenate than arsenite, but showed a similar degree of tolerance internally. W. globosa decreased arsenate in solution rapidly, but also effluxed arsenite.
An extensive data set of total arsenic analysis for 901 polished (white) grain samples, originati... more An extensive data set of total arsenic analysis for 901 polished (white) grain samples, originating from 10 countries from 4 continents, was compiled. The samples represented the baseline (i.e., notspecifically collected from arsenic contaminated areas), and all were for market sale in major conurbations. Median total arsenic contents of rice varied 7-fold, with Egypt (0.04 mg/kg) and India (0.07 mg/kg) having the lowest arsenic content while the U.S. (0.25 mg/kg) and France (0.28 mg/kg) had the highest content. Global distribution of total arsenic in rice was modeled by weighting each country's arsenic distribution by that country's contribution to global production. A subset of 63 samples from Bangladesh, China, India, Italy, and the U.S. was analyzed for arsenic species. The relationship between inorganic arsenic contentversus total arsenic contentsignificantly differed among countries, with Bangladesh and India having the steepest slope in linear regression, and the U.S. having the shallowest slope. Using country-specific rice consumption data, daily intake of inorganic arsenic was estimated and the associated internal cancer risk was calculated using the U.S. Environmental Protection Agency (EPA) cancer slope. Median excess internal cancer risks posed by inorganic arsenic ranged 30-fold for the 5 countries examined, being 0.7 per 10,000 for Italians to 22 per 10,000 for Bangladeshis, when a 60 kg person was considered.
For up to 1 billion people worldwide, insufficient dietary intake of selenium (Se) is a serious h... more For up to 1 billion people worldwide, insufficient dietary intake of selenium (Se) is a serious health constraint. Cereals are the dominant Se source for those on low protein diets, as typified by the global malnourished population. With crop Se content constrained largely by underlying geology, regional soil Se variations are often mirrored by their locally grown staples. Despite this, the Se concentrations of much of the world's rice, the mainstay of so many, is poorly characterized, for both total Se content and Se speciation. In this study, 1092 samples of market sourced polished rice were obtained. The sampled rice encompassed dominant rice producing and exporting countries. Rice from the U.S. and India were found to be the most enriched, while mean average levels were lowest in Egyptian rice: ∼32-fold less than their North American equivalents. By weighting country averages by contribution to either global production or export, modeled baseline values for both were produced. Based on a daily rice consumption of 300 g day -1 , around 75% of the grains from the production and export pools would fail to provide 70% of daily recommended Se intakes. Furthermore, Se localization and speciation characterization using X-ray fluorescence (µ-XRF) and X-ray absorption near edge structure (µ-XANES) techniques were investigated in a Se-rich sample. The results revealed that the large majority of Se in the endosperm was present in organic forms.
An iron-reducing bacterial strain was isolated from a paddy soil and identified as a member of th... more An iron-reducing bacterial strain was isolated from a paddy soil and identified as a member of the Aeromonas group by 16S rRNA gene sequence analysis. When the cells were growing with dissolved Fe(III) as the electron acceptor in the presence of As(V), Fe(II) minerals (siderite and vivianite) were formed and dissolved. As was removed efficiently from solution. When the cells were growing with the Fe(III) hydroxide mineral (ferrihydrite) as the electron acceptor in the presence of As(V), ferrihydrite was reduced and dissolved As(V) concentrations decreased sharply. The present study results demonstrated first that members of the Aeromonas group can reduce Fe(III) in paddy soils and second that iron reduction does not necessarily lead to arsenic mobilization. However, As immobilization can occur in environments that contain significant concentrations of counterions such as bicarbonate and phosphate.
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Papers by Guo-xin Sun