Search

A field and market basket study (~1300 samples) of locally grown fruits and vegetables from historically mined regions of southwest (SW) England (Cornwall and Devon), and as reference, a market basket study of similarly locally grown produce from the northeast (NE) of Scotland (Aberdeenshire) was conducted to determine the concentration of total and inorganic arsenic present in produce from these two geogenically different areas of the U.K. On average 98.5% of the total arsenic found was present in the inorganic form. For both the market basket and the field survey, the highest total arsenic was present in open leaf structure produce (i.e., kale, chard, lettuce, greens, and spinach) being most likely to soil/dust contamination of the open leaf structure. The concentration of total arsenic in potatoes, swedes, and carrots was lower in peeled produce compared to unpeeled produce. For baked potatoes, the concentration of total arsenic in the skin was higher compared to the total arsenic concentration of the potato flesh, this difference in localization being confirmed by laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS). For all above ground produce (e.g., apples), peeling did not have a significant effect on the concentration of total arsenic present.

Triphenyltin (TPhT) is a biocide used worldwide in agriculture, especially in rice crop farming. The distribution and dissipation of TPhT in rice fields, as well as uptake of TPhT and other phenyltin compounds (monophenyltin, MPhT, and diphenyltin, DPhT) is still unknown at present. In this study, speciation analysis of phenyltin compounds was carried out in soil and water from a rice field where TPhT was applied during rice seeding according to legal application rates in Brazil. The results indicate the degradation of biocide and distribution of tin species into soil and water. To evaluate whether TPhT is taken up by plants, rice plants were exposed to three different TPhT application rates in a controlled mesocosm during 7 weeks. After this period, tin speciation was determined in soil, roots, leaves, and grains of rice. Degradation of TPhT was observed in soil, where DPhT and MPhT were detected. MPhT, DPhT, and TPhT were also detected in the roots of plants exposed to all TPhT application rates. Only TPhT was detected in leaves and at relatively low concentration, suggesting selective transport of TPhT in the xylem, in contrast to DPhT and MPhT. Concentration of phenyltin species in rice grains was lower than the limit of detection, suggesting that rice plants do not have the capability to take up TPhT from soil and transport it to the grains.

Arsenic (As) occurs in a variety of different chemical forms, among them volatile (gaseous) species, usually referred to as arsine and methylarsines. Here we demonstrate that arsine and methylarsines are stable in air in concentrations at the μg/L gas level. We determined half-lives of approximately 8 h under daytime conditions (UV light) for all methylated arsines, while the same species were found to be considerably more stable in night-time (dark) conditions. Arsine (AsH₃) showed under both day and night-time conditions, considerably higher stabilities than methylated arsines. We show here that volatile As species seem stable enough to travel considerable distances in the atmosphere from a point source before converting into nonvolatile, oxidized compounds. Also, the degradation pathway leading to the conversion to nonvolatile compounds was investigated using computational chemistry. Arsine and methylarsines' reactions with the hydroxyl radical (•OH) as well as As-C and As-H bonds strengths in the species studied were modeled. Results showed that conversion could not be explained by H abstraction, nor by OH addition. Moreover, it was found that As-C and As-H bonds strengths are not the determining factor responsible for the decrease in stability with ascending methylation of the different volatile arsine species, as previously suggested.

The biogeochemical cycle of arsenic (As) has been extensively studied over the past decades because As is an environmentally ubiquitous, nonthreshold carcinogen, which is often elevated in drinking water and food. It has been known for over a century that micro-organisms can volatilize inorganic As salts to arsines (arsine AsH(3), mono-, di-, and trimethylarsines, MeAsH(2), Me(2)AsH, and TMAs, respectively), but this part of the As cycle, with the exception of geothermal environs, has been almost entirely neglected because of a lack of suited field measurement approaches. Here, a validated, robust, and low-level field-deployable method employing arsine chemotrapping was used to quantify and qualify arsines emanating from soil surfaces in the field. Up to 240 mg/ha/y arsines was released from low-level polluted paddy soils (11.3 ± 0.9 mg/kg As), primarily as TMAs, whereas arsine flux below method detection limit was measured from a highly contaminated mine spoil (1359 ± 212 mg/kg As), indicating that soil chemistry is vital in understanding this phenomenon. In microcosm studies, we could show that under reducing conditions, induced by organic matter (OM) amendment, a range of soils varied in their properties, from natural upland peats to highly impacted mine-spoils, could all volatilize arsines. Volatilization rates from 0.5 to 70 μg/kg/y were measured, and AsH(3), MeAsH(2), Me(2)AsH, and TMAs were all identified. Addition of methylated oxidated pentavalent As, namely monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), to soil resulted in elevated yearly rates of volatilization with up to 3.5% of the total As volatilized, suggesting that the initial conversion of inorganic As to MMAA limits the rate of arsine and methylarsines production by soils. The nature of OM amendment altered volatilization quantitatively and qualitatively, and total arsines release from soil showed correlation between the quantity of As and the concentration of dissolved organic carbon (DOC) in the soil porewater. The global flux of arsines emanating from soils was estimated and placed in the context of As atmospheric inputs, with arsines contributing from 0.9 to 2.6% of the global budget.

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.

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.

Quantification and speciation of volatile selenium (Se) fluxes in remote areas has not been feasible previously, due to the absence of a simple and easily transportable trapping technique that preserves speciation. This paper presents a chemo-trapping method with nitric acid (HNO3) for volatile Se species, which preserves speciation of trapped compounds. The recovery and speciation of dimethylselenide (DMSe) and dimethyl diselenide (DMDSe) entrained through both concentrated nitric acid and hydrogen peroxide (H2O2) were compared by HPLC-ICP-MS and HPLC-HG-AFS analyses. It was demonstrated that trap reproducibility was better for nitric acid and a recovery of 65.2 +/- 1.9% for DMSe and 81.3 +/- 3.9% for DMDSe was found in nitric acid traps. HPLC-ES-MS identified dimethyl selenoxide (DMSeO) as the trapped product of DMSe. Methylseleninic acid (MSA) was identified to be the single product of DMDSe trapping. These oxidized derivatives have a high stability and low volatility, which makes nitric acid a highly attractive trapping liquid for volatile Se species and enables reconstruction of the speciation of those species. The presented trapping method is simple, quantifiable, reproducible, and robust and can potentially be applied to qualitatively and quantitatively study Se volatilization in a wide range of natural environments.

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.

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.

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.

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 approximately 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 approximately 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.

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As in the outer grain of brown rice was confirmed by laser ablation ICP-MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (micro-XANES) and bulk extraction followed by anion exchange HPLC-ICP-MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n=39) and brown (n=45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.