Arsenic bioavailability to rice is elevated in Bangladeshi paddy soils

Some paddy soils in the Bengal delta are contaminated with arsenic (As) due to irrigation of As-laden groundwater, which may lead to yield losses and elevated As transfer to the food chain. Whether these soils have a higher As bioavailability than other soils containing either geogenic As or contaminated by mining activities was investigated in a pot experiment. Fourteen soils varying in the source and the degree (4-138 mg As kg 1?1) of As contamination were collected, 10 from Bangladeshi paddy fields (contaminated by irrigation water) and two each from China and the UK (geogenic or mining impacted), for comparison. Bangladeshi soils had higher percentages of the total As extractable by ammonium phosphate (specifically sorbed As) than other soils and also released more As into the porewater upon flooding. Porewater As concentrations increased with increasing soil As concentrations more steeply in Bangladeshi soils, with arsenite being the dominant As species. Rice growth and grain yield decreased markedly in Bangladeshi soils containing > 13 mg As kg 1?1, but not in the other soils. Phosphate-extractable or porewater As was a better indicator of As bioavailability than total soil As. Rice straw As concentrations increased with increasing soil As concentrations; however, As phytotoxicity appeared to result in lower grain As concentrations. The relative proportions of inorganic As and dimethylarsinic acid (DMA) in grain varied among soils, and the percentage DMA was larger in greenhouse-grown plants than grain samples collected from the paddy fields of the same soil and the same rice cultivar, indicating a strong environmental influence on As species found in rice grain. This study shows that Bangladeshi paddy soils contaminated by irrigation had a higher As bioavailability than other soils, resulting in As phytotoxicity in rice and substantial yield losses.     

Arsenic dynamics in porewater of an intermittently irrigated paddy field in Bangladesh

In Bangladesh, irrigation of dry season rice (boro) with arsenic-contaminated groundwater is leading to increased As levels in soils and rice, and to concerns about As-induced yield reduction. Arsenic concentrations and speciation in soil porewater are strongly influenced by redox conditions, and thus by water management during rice growth. We studied the dynamics of As, Fe, P, Si, and other elements in porewater of a paddy field near Sreenagar (Munshiganj), irrigated according to local practice, in which flooding was intermittent. During early rice growth, As porewater concentrations reached up to 500 μg L(-1) and were dominated by As(III), but As release was constrained to the lower portion of the soil above the plow pan. In the later part of the season, soil conditions were oxic throughout the depth range relevant to rice roots and porewater concentrations only intermittently increased to ～150 μg L(-1) As(V) following irrigation events. Our findings suggest that intermittent irrigation, currently advocated in Bangladesh for water-saving purposes, may be a promising means of reducing As input to paddy soils and rice plant exposure to As.     

Organic matter-solid phase interactions are critical for predicting arsenic release and plant uptake in Bangladesh paddy soils

Agroecological zones within Bangladesh with low levels of arsenic in groundwater and soils produce rice that is high in arsenic with respect to other producing regions of the globe. Little is known about arsenic cycling in these soils and the labile fractions relevant for plant uptake when flooded. Soil porewater dynamics of field soils (n = 39) were recreated under standardized laboratory conditions to investigate the mobility and interplay of arsenic, Fe, Si, C, and other elements, in relation to rice grain element composition, using the dynamic sampling technique diffusive gradients in thin films (DGT). Based on a simple model using only labile DGT measured arsenic and dissolved organic carbon (DOC), concentrations of arsenic in Aman (Monsoon season) rice grain were predicted reliably. DOC was the strongest determinant of arsenic solid-solution phase partitioning, while arsenic release to the soil porewater was shown to be decoupled from that of Fe. This study demonstrates the dual importance of organic matter (OM), in terms of enhancing arsenic release from soils, while reducing bioavailability by sequestering arsenic in solution.     

Unsaturated zone arsenic distribution and implications for groundwater contamination

Arsenic compounds have been applied at the land surface as pesticides in agricultural areas globally. The purpose of this study was to evaluate the fate of anthropogenic arsenic applications related to agriculture, using arsenic applications on cotton in the southern High Plains (SHP), Texas, as a case study and examining possible linkages with contamination of the underlying Ogallala aquifer in this region, where 36% of wells exceed the new EPA 10 microg/L standard. Unsaturated zone soil samples were collected from boreholes beneath natural ecosystems (grassland/ shrubland) to provide a control (no arsenic application) (5 profiles) and cotton cropland (20 profiles) for analyses of water-extractable arsenic, vanadium, phosphate, chloride, and nitrate. Natural ecosystem profiles have high arsenic concentrations at depth (maximum of 7.2-69.6 microg As/ kg dry soil at 5.9-21.4 m depth) that are attributed to a geologic source. Most profiles beneath cotton cropland have high arsenic concentrations within the upper meter (profile means 1.7 to 31.6 microg/kg) that correlate with phosphate (r = 0.70, p < 0.01) and are attributed to anthropogenic arsenic application associated with phosphate fertilizer application. High arsenic concentrations at >1 m depth (profile means < or =36.3 microg/kg) found in cropland profiles are attributed to a geologic source because of similarity with profiles beneath natural ecosystems, lack of correlation with phosphate, and pore-water ages that predate anthropogenic arsenic application in many profiles. GIS analyses showed poor correlations between groundwater arsenic and percent cultivated land (r = -0.15, p < 0.01), groundwater nitrate (r = 0.30, p < 0.01), and water table depth (r= -0.31, p < 0.01), further supporting the idea that anthropogenic-derived arsenic in the shallow subsurface is not linked to groundwater arsenic contamination in this region.     

Increase in rice grain arsenic for regions of Bangladesh irrigating paddies with elevated arsenic in groundwaters

Concern has been raised by Bangladeshi and international scientists about elevated levels of arsenic in Bengali food, particularly in rice grain. This is the first inclusive food market-basket survey from Bangladesh, which addresses the speciation and concentration of arsenic in rice, vegetables, pulses, and spices. Three hundred thirty aman and boro rice, 94 vegetables, and 50 pulse and spice samples were analyzed for total arsenic, using inductivity coupled plasma mass spectrometry (ICP-MS). The districts with the highest mean arsenic rice grain levels were all from southwestern Bangladesh: Faridpur (boro) 0.51 > Satkhira (boro) 0.38 > Satkhira (aman) 0.36 > Chuadanga (boro) 0.32 > Meherpur (boro) 0.29 microg As g(-1). The vast majority of food ingested arsenic in Bangladesh diets was found to be inorganic; with the predominant species detected in Bangladesh rice being arsenite (AsIII) or arsenate (AsV) with dimethyl arsinic acid (DMAV) being a minor component. Vegetables, pulses, and spices are less important to total arsenic intake than water and rice. Predicted inorganic arsenic intake from rice is modeled with the equivalent intake from drinking water for a typical Bangladesh diet. Daily consumption of rice with a total arsenic level of 0.08 microg As g(-1) would be equivalent to a drinking water arsenic level of 10 microg L(-1).     

Arsenic in rice: I. Estimating normal levels of total arsenic in rice grain

High levels of arsenic (As) in rice grain are a potential concern for human health. Variability in total As in rice was evaluated using 204 commercial rice samples purchased mostly in retail stores in upstate New York and supplemented with samples from Canada, France, Venezuela, and other countries. Total As concentration in rice varied from 0.005 to 0.710 mg kg(-1). We combined our data set with literature values to derive a global "normal" range of 0.08-0.20 mg kg(-1) for As concentration in rice. The mean As concentrations for rice from the U.S. and Europe (both 0.198 mg kg(-1)) were statistically similar and significantly higher than rice from Asia (0.07 mg kg(-1)). Using two large data sets from Bangladesh, we showed that As contaminated irrigation water, but not soil, led to increased grain As concentration. Wide variability found in U.S. rice grain was primarily influenced by region of growth rather than commercial type, with rice grown in Texas and Arkansas having significantly higher mean As concentrations than that from California (0.258 and 0.190 versus 0.133 mg kg(-1)). Rice from one Texas distributor was especially high, with 75% of the samples above the global "normal" range, suggesting production in an As contaminated environment.     

Arsenic in rice: II. Arsenic speciation in USA grain and implications for human health

Rice is a potentially important route of human exposure to arsenic, especially in populations with rice-based diets. However, arsenic toxicity varies greatly with species. The initial purpose of the present study was to evaluate arsenic speciation in U.S. rice. Twenty-four samples containing high levels of arsenic and produced in different regions of the U.S were selected from a previous market-basket survey. Arsenite and dimethyl arsinic acid (DMA) were the major species detected. DMA increased linearly with increasing total As but arsenite remained fairly constant at approximately 0.1 mg kg(-1), showing that rice high in As was dominated by DMA. A similar result was obtained when our data was combined with other published speciation studies for U.S. rice. However, when all published speciation data for rice was analyzed a second population dominated by inorganic As and lower levels of DMA was found. We thus categorized rice into DMA and Inorganic As types. Rice from the U.S. was predominantly the DMA type, as were single samples from Australia and China, whereas rice from Asia and Europe was the Inorganic As type. We suggest that methylation of As occurs within rice and that genetic differences lead to the two rice types. Insufficient understanding of DMA toxicity precludes a firm assessment of the relative health risks associated with the two rice types but, based on current knowledge, we suggest that the DMA rice type is likely to be less of a health risk than the Inorganic As rice type and, on this basis, rice from the U.S. may be safer than rice from Asia and Europe.     

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.     

Variation in arsenic speciation and concentration in paddy rice related to dietary exposure

Ingestion of drinking water is not the only elevated source of arsenic to the diet in the Bengal Delta. Even at background levels, the arsenic in rice contributes considerably to arsenic ingestion in subsistence rice diets. We set out to survey As speciation in different rice varieties from different parts of the globe to understand the contribution of rice to arsenic exposure. Pot experiments were utilized to ascertain whether growing rice on As contaminated soil affected speciation and whether genetic variation accounted for uptake and speciation. USA long grain rice had the highest mean arsenic level in the grain at 0.26 microg As g(-1) (n = 7), and the highest grain arsenic value of the survey at 0.40 microg As g(-1). The mean arsenic level of Bangladeshi rice was 0.13 microg As g(-1) (n = 15). The main As species detected in the rice extract were AsIII, DMAV, and AsV. In European, Bangladeshi, and Indian rice 64 +/- 1% (n = 7), 80 +/- 3% (n = 11), and 81 +/- 4% (n = 15), respectively, of the recovered arsenic was found to be inorganic. In contrast, DMAV was the predominant species in rice from the USA, with only 42 +/- 5% (n = 12) of the arsenic being inorganic. Pot experiments show that the proportions of DMAV in the grain are significantly dependent on rice cultivar (p = 0.026) and that plant nutrient status is effected by arsenic exposure.     

Arsenic in soil and irrigation water affects arsenic uptake by rice: complementary insights from field and pot studies

Groundwater rich in arsenic (As) is extensively used for dry season boro rice cultivation in Bangladesh, leading to long-term As accumulation in soils. This may result in increasing levels of As in rice straw and grain, and eventually, in decreasing rice yields due to As phytotoxicity. In this study, we investigated the As contents of rice straw and grain over three consecutive harvest seasons (2005-2007) in a paddy field in Munshiganj, Bangladesh, which exhibits a documented gradient in soil As caused by annual irrigation with As-rich groundwater since the early 1990s. The field data revealed that straw and grain As concentrations were elevated in the field and highest near the irrigation water inlet, where As concentrations in both soil and irrigation water were highest. Additionally, a pot experiment with soils and rice seeds from the field site was carried out in which soil and irrigation water As were varied in a full factorial design. The results suggested that both soil As accumulated in previous years and As freshly introduced with irrigation water influence As uptake during rice growth. At similar soil As contents, plants grown in pots exhibited similar grain and straw As contents as plants grown in the field. This suggested that the results from pot experiments performed at higher soil As levels can be used to assess the effect of continuing soil As accumulation on As content and yield of rice. On the basis of a recently published scenario of long-term As accumulation at the study site, we estimate that, under unchanged irrigation practice, average grain As concentrations will increase from currently ～0.15 mg As kg(-1) to 0.25-0.58 mg As kg(-1) by the year 2050. This translates to a 1.5-3.8 times higher As intake by the local population via rice, possibly exceeding the provisional tolerable As intake value defined by FAO/WHO.     

Reliability of a commercial kit to test groundwater for arsenic in Bangladesh

A comparison of field and laboratory measurements of arsenic in groundwater of Araihazar, Bangladesh, indicates that the most widely used field kit correctly determined the status of 88% of 799 wells relative to the local standard of 50 microg/L As. Additional tests showthatthe inconsistencies, mainly underestimates in the 50-100 microg/L As range, can be avoided by increasing the reaction time from 20 to 40 min. Despite this limitation, the field data already compiled for millions of wells by the Bangladesh Arsenic Mitigation and Water Supply Project, in combination with information on well location and depth, should prove to be extremely useful to prioritize interventions in thousands of affected villages.     

Scorodite dissolution kinetics: implications for arsenic release

We have measured the rate of scorodite (FeAsO4.2H2O) dissolution over an environmentally relevant range of pH and temperature conditions. Dissolution rates, calculated using arsenic (As) as the reaction progress variable, were slowest at pH 3 and increased with both decreasing and increasing pH. Comparison of the pH-dependence of the dissolution rates with a scorodite stability diagram suggests that our measurements of dissolution rate at pH 2 reflect congruent dissolution, and those at and above pH 3 reflect incongruent dissolution. Because As was used as the reaction progress variable, and recognizing that As may adsorb to iron hydroxides during incongruent dissolution of scorodite, the derived rates may be underestimated. The pH and temperature dependence of scorodite dissolution rates determined in these experiments have implications for the stability of scorodite at field sites and also for the potential use of scorodite to sequester As. Although scorodite dissolution is slow, it can be enhanced by up to a half order of magnitude by increases in pH and temperature.     

Fish for human consumption: risk of contamination by mercury

Total mercury concentrations were measured in the muscle of different kinds of fish: megrim (Lepidorhombus boscii), common sole (Solea vulgaris), striped mullet (Mullus barbatus), anglerfish (Lophius piscatorius), and black-bellied angler (Lophius budegassa     

Arsenic and lead in foods: a potential threat to human health in Bangladesh

The non-carcinogenic and carcinogenic risk of arsenic and lead to adults and children via daily dietary intake of food composites in Bangladesh was estimated. The target hazard quotients (THQs), hazard index (HI) and target carcinogenic risk (TR) were calculated to evaluate the non-carcinogenic and carcinogenic health risk from arsenic and lead. Most of the individual food composites contain a considerable amount of arsenic and lead. The highest mean concentrations of arsenic were found in cereals (0.254 mg kg^–1 fw) and vegetables (0.250 mg kg^–1 fw), and lead in vegetables (0.714 mg kg^–1 fw) and fish (0.326 mg kg^–1 fw). The results showed the highest THQs of arsenic in cereals and lead in vegetables for both adults and children which exceeded the safe limit (> 1) indicating that cereals and vegetables are the main food items contributing to the potential health risk. The estimated TR from ingesting dietary arsenic and lead from most of the foods exceeded 10^?6, indicating carcinogenic risks for all adult people of the study area.     

Rice field geochemistry and hydrology: an explanation for why groundwater irrigated fields in Bangladesh are net sinks of arsenic from groundwater

Irrigation of rice fields in Bangladesh with arsenic-contaminated groundwater transfers tens of cubic kilometers of water and thousands of tons of arsenic from aquifers to rice fields each year. Here we combine observations of infiltration patterns with measurements of porewater chemical composition from our field site in Munshiganj Bangladesh to characterize the mobility of arsenic in soils beneath rice fields. We find that very little arsenic delivered by irrigation returns to the aquifer, and that recharging water mobilizes little, if any, arsenic from rice field subsoils. Arsenic from irrigation water is deposited on surface soils and sequestered along flow paths that pass through bunds, the raised soil boundaries around fields. Additionally, timing of flow into bunds limits the transport of biologically available organic carbon from rice fields into the subsurface where it could stimulate reduction processes that mobilize arsenic from soils and sediments. Together, these results explain why groundwater irrigated rice fields act as net sinks of arsenic from groundwater.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 1. Irrigation water

Around 38% of the area of Bangladesh is irrigated with groundwater to grow dry season crops, most importantly boro rice. Due to high As concentrations in many groundwaters, over 1000 tons of As are thus transferred to arable soils each year, creating a potential risk for future food production. We studied the reactions and changing speciation of As, Fe, P, and other elements in initially anoxic water during and after irrigation and the resulting spatial distribution of As input to paddy soils near Sreenagar (Munshiganj), 30 km south of Dhaka, in January and April 2005 and February 2006. The irrigation water had a constant concentration of 397 +/- 7 microg L(-1) As (approximately 84% As(III)), 11 +/- 0.1 mg L(-1) Fe, and 2 +/- 0.1 mg L(-1) P. During the fast flow along the longest irrigation channel (152 m) As, Fe, and P speciation changed, but total concentrations did not decrease significantly, indicating that As input to fields was independent of the length of the irrigation channels. In contrast, during slow water flow across the fields, As, Fe, and P concentrations decreased strongly with increasing distance from the water inlet, due to formation and settling of As- and P-bearing Fe aggregates and by adsorption to soil minerals. Total As concentrations in field water were approximately 3 times higher close to the inlet than in the opposite field corner shortly after irrigation, and decreased to below 35 microg L(-1) over the next 72 h. The laterally heterogeneous transfer of As, Fe, and P from irrigation waterto soil has important consequences for their distribution in irrigated fields and needs to be considered in sampling and in assessing the dynamics and mass balances of As fluxes among irrigation water, soil, and floodwater.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 2. Paddy soil

Arsenic-rich groundwater from shallow tube wells is widely used for the irrigation of boro rice in Bangladesh and West Bengal. In the long term this may lead to the accumulation of As in paddy soils and potentially have adverse effects on rice yield and quality. In the companion article in this issue, we have shown that As input into paddy fields with irrigation water is laterally heterogeneous. To assess the potential for As accumulation in soil, we investigated the lateral and vertical distribution of As in rice field soils near Sreenagar (Munshiganj, Bangladesh) and its changes over a 1 year cycle of irrigation and monsoon flooding. At the study site, 18 paddy fields are irrigated with water from a shallow tube well containing 397 +/- 7 microg L(-1) As. The analysis of soil samples collected before irrigation in December 2004 showed that soil As concentrations in paddy fields did not depend on the length of the irrigation channel between well and field inlet. Within individual fields, however, soil As contents decreased with increasing distance to the water inlet, leading to highly variable topsoil As contents (11-35 mg kg(-1), 0-10 cm). Soil As contents after irrigation (May 2005) showed that most As input occurred close to the water inlet and that most As was retained in the top few centimeters of soil. After monsoon flooding (December 2005), topsoil As contents were again close to levels measured before irrigation. Thus, As input during irrigation was at least partly counteracted by As mobilization during monsoon flooding. However, the persisting lateral As distribution suggests net arsenic accumulation over the past 15 years. More pronounced As accumulation may occur in regions with several rice crops per year, less intense monsoon flooding, or different irrigation schemes. The high lateral and vertical heterogeneity of soil As contents must be taken into account in future studies related to As accumulation in paddy soils and potential As transfer into rice.     

The contribution of tropical chillies to ascorbic acid consumption

Eight common types of African chillies readily available in the markets, were examined for their ascorbic acid content. These included two species of Capsicum annum L., both the fresh and the dry varieties (Ata-rodo and Tatase). Other types studied included the fresh and dry varieties of two species of Capsicum frutescens L. (Sombo and Ata wewe). The ascorbate value in the raw samples ranged from 4·6 ± 0·3% in the dry sample of one of the varieties of Capsicum frutescens L. (dry Sombo) to 55·1 ± 1·5% in the fresh variety of one of the Capsicum frutescens L. species (fresh Ata wewe).After cooking for a 25-min period there was a loss of vitamin C of between 66% and 98·3% in chillie sauce made from fresh and dry chillies, respectively. Considering that an adult consumes 240 g of fresh chillie sauce a day, this provides (despite cooking loss) about 80% of the ascorbate requirement. This contribution is quite appreciable and should be recognised in practice since the conventional sources of vitamin C (fruits and vegetables) are often either expensive or not available.