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.     

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.     

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 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.     

Arsenic contamination of Bangladesh paddy field soils: implications for rice contribution to arsenic consumption

Arsenic contaminated groundwater is used extensively in Bangladesh to irrigate the staple food of the region, paddy rice (Oryza sativa L.). To determine if this irrigation has led to a buildup of arsenic levels in paddy fields, and the consequences for arsenic exposure through rice ingestion, a survey of arsenic levels in paddy soils and rice grain was undertaken. Survey of paddy soils throughout Bangladesh showed that arsenic levels were elevated in zones where arsenic in groundwater used for irrigation was high, and where these tube-wells have been in operation for the longest period of time. Regression of soil arsenic levels with tube-well age was significant. Arsenic levels reached 46 microg g(-1) dry weight in the most affected zone, compared to levels below l0 microg g(-1) in areas with low levels of arsenic in the groundwater. Arsenic levels in rice grain from an area of Bangladesh with low levels of arsenic in groundwaters and in paddy soils showed that levels were typical of other regions of the world. Modeling determined, even these typical grain arsenic levels contributed considerably to arsenic ingestion when drinking water contained the elevated quantity of 0.1 mg L(-1). Arsenic levels in rice can be further elevated in rice growing on arsenic contaminated soils, potentially greatly increasing arsenic exposure of the Bangladesh population. Rice grain grown in the regions where arsenic is building up in the soil had high arsenic concentrations, with three rice grain samples having levels above 1.7 microg g(-1).     

Biogeochemistry of organic and inorganic arsenic species in a forested catchment in Germany

Little is known about the fate and behavior of diffuse inputs of arsenic (As) species in forested catchments which often are the sources of drinking water. The objective of this study was to investigate the mobility and transformation of different As species in forest ecosystems to assess the environmental risk related to the diffuse pollution of As. We determined concentrations and fluxes in precipitation, litterfall, soil solutions (Oa horizon and 20- and 90-cm depth), and runoff of organic and inorganic As species and Astotal in a forest ecosystem in NE-Bavaria, Germany. The concentrations of Astotal were mostly <1 microg As L(-1) in aqueous samples and were highest in forestfloor percolates (7.6 microg As L(-1)). In litterfall, the concentrations of As species never exceeded 0.1 microg As g(-1). Arsenate and arsenite were the prevalent As species in all samples. Organic As species, comprising monomethylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, arsenobetaine, and three unidentified organic As species, were mostly found in throughfall reaching up to 45% of Astotal. The total deposition of Astotal (calculated as throughfall + litterfall) was 5.6 g As ha(-1) yr(-1) with 16% contribution of litterfall. The annual Astotal fluxes were 30 g As ha(-1) yr(-1) for forest floor percolates, 8.0 g As ha(-1) yr(-1) at 20-cm soil depth, and 1.4 g As ha(-1) yr(-1) at 90-cm soil depth. The annual runoff of Astotal from the catchment amounted to 3.8 g As ha(-1) yr(-1). The annual fluxes of total organic As species was highest in total deposition (1.1 g As ha(-1) yr(-1)) and decreased largely with depth in the soil profile. The annual runoff of total organic As species was only 0.08 g As ha(-1) yr(-1). Significant correlations in soil solutions and runoff were found between Astotal and dissolved organic C and Fe. Correlations between Astotal concentrations in runoff and water fluxes were seasonally dependent and with a steeper slope in the growing season than in the dormant season. The elevated concentrations of organic As species in throughfall indicate microbial methylation of As in the phyllosphere, but no evidence for methylation in the soil was found. The mass balance of the catchment points out the strong retention and probable degradation or oxidation of organic As species and arsenite but also to mobilizable pools of Astotal and arsenate. The forest floor is presently a source, whereas the mineral soil is a sink for Astotal and arsenate. The As concentrations in runoff seem to be controlled by As mobilization from forest floor and riparian wetland soils during heavy rain events and superficial flow. The risk for excessment of the drinking water threshold concentrations of As in runoff and soil solutions is considered low at our site.     

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.     

Performance of a household-level arsenic removal system during 4-month deployments in Bangladesh

A simple arsenic removal system was used in Bangladesh by six households for 4 months to treat well water containing 190-750 microg/L As as well as 0.4-20 mg/L Fe and 0.2-1.9 mg/L P. The system removes As from a 16-L batch of water in a bucket by filtration through a sand bed following the addition of about 1.5 g of ferric sulfate and 0.5 g of calcium hypochlorite. Arsenic concentrations in all but 1 of 72 samples of treated water were below the Bangladesh drinking water standard of 50 microg/L for As. Approximately half of the samples also met the World Health Organization (WHO) guideline of 10 microg/L. At the two wells that did not meet the WHO guideline, observations were confirmed by additional experiments in one case ([P] = 1.9 mg/L) but not in the other, suggesting that the latter household was probably not following the instructions. Observed residual As levels are consistent with predictions from a surface complexation model only if the site density is increased to 2 mol/mol of Fe. With the exception of Mn, the average concentrations of other inorganic constituents of health concern (Cr, Ni, Cu, Se, Mo, Cd, Sb, Ba, Hg, Pb, and U) in treated water were below their respective WHO guideline for drinking water.     

Arsenic accumulation and metabolism in rice (Oryza sativa L.)

The use of arsenic (As) contaminated groundwater for irrigation of crops has resulted in elevated concentrations of arsenic in agricultural soils in Bangladesh, West Bengal (India), and elsewhere. Paddy rice (Oryza sativa L.) is the main agricultural crop grown in the arsenic-affected areas of Bangladesh. There is, therefore, concern regarding accumulation of arsenic in rice grown those soils. A greenhouse study was conducted to examine the effects of arsenic-contaminated irrigation water on the growth of rice and uptake and speciation of arsenic. Treatments of the greenhouse experiment consisted of two phosphate doses and seven different arsenate concentrations ranging from 0 to 8 mg of As L(-1) applied regularly throughout the 170-day post-transplantation growing period until plants were ready for harvesting. Increasing the concentration of arsenate in irrigation water significantly decreased plant height, grain yield, the number of filled grains, grain weight, and root biomass, while the arsenic concentrations in root, straw, and rice husk increased significantly. Concentrations of arsenic in rice grain did not exceed the food hygiene concentration limit (1.0 mg of As kg(-1) dry weight). The concentrations of arsenic in rice straw (up to 91.8 mg kg(-1) for the highest As treatment) were of the same order of magnitude as root arsenic concentrations (up to 107.5 mg kg(-1)), suggesting that arsenic can be readily translocated to the shoot. While not covered by food hygiene regulations, rice straw is used as cattle feed in many countries including Bangladesh. The high arsenic concentrations may have the potential for adverse health effects on the cattle and an increase of arsenic exposure in humans via the plant-animal-human pathway. Arsenic concentrations in rice plant parts except husk were not affected by application of phosphate. As the concentration of arsenic in the rice grain was low, arsenic speciation was performed only on rice straw to predict the risk associated with feeding contaminated straw to the cattle. Speciation of arsenic in tissues (using HPLC-ICP-MS) revealed that the predominant species present in straw was arsenate followed by arsenite and dimethylarsinic acid (DMAA). As DMAA is only present at low concentrations, it is unlikely this will greatly alter the toxicity of arsenic present in rice.     

Solid-solution speciation and phytoavailability of copper and zinc in soils

The soil solution speciation and solid-phase fractionation of copper (Cu) and zinc (Zn) in 11 typical uncontaminated soils of South Australia were assessed in relation to heavy metal phytoavailability. The soils were analyzed for pH (4.9-8.4), soil organic matter content (3.5 to 23.8 g of C kg(-1)), total soil solution metal concentrations, Cu8 (49-358 microg kg(-1)) and Zn8 (121-582 microg kg(-1)), and dissolved organic matter (DOM) (69-827 mg of C L(-1)). The solid-liquid partition coefficient (Kd) ranged from between 13.9 and 152.4 L kg(-1) for Cu and 22.6 to 266.3 L kg(-1) for Zn. The phytoavailability of Cu and Zn could be predicted significantly using an empirical model with the solid-phase fractions of Cu and Zn, as obtained from selective sequential extraction scheme, as components. Phytoavailable Cu and Zn were found to significantly correlate with fulvic complex Cu (r= 0.944, P < 0.0001) and exchangeable Zn (r = 0.832, P = 0.002), respectively. The fulvic complex Cu was found to explain 89.2% of the variation in phytoavailable Cu, where as, the exchangeable Zn together with fulvic complex Zn could explain 78.9% of the variation in phytoavailable Zn. The data presented demonstrate the role of solid-phase metal fractions in understanding the heavy metal phytoavailability. The assessment of the role of solid-phase fractions in heavy metal phytoavailability is a neglected area of study and deserves close attention.     

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 behavior in paddy fields during the cycle of flooded and non-flooded periods

The behavior of As in paddy fields is of great interest considering high As contents of groundwater in several Asian countries where rice is the main staple. We determined the concentrations of Fe, Mn, and As in soil, soil water, and groundwater samples collected at different depths down to 2 m in an experimental paddy field in Japan during the cycle of flooded and non-flooded periods. In addition, we measured the oxidation states of Fe, Mn, and As in situ in soil samples using X-ray absorption near-edge structure (XANES) and conducted sequential extraction of the soil samples. The results show that Fe (hydr)oxide hosts As in soil. Arsenic in irrigation waters is incorporated in Fe (hydr)oxide in soil during the non-flooded period, and the As is quickly released from soil to water during the flooded period because of reductive dissolution of the Fe (hydr)oxide phase and reduction of As from As(V) to As(III). The enhancement of As dissolution by the reduction of As is supported by high As/Fe ratios of soil water during the flooded period and our laboratory experiments where As(III) concentrations and As(III)/As(V) ratios in submerged soil were monitored. Our work, primarily based on data from an actual paddy field, suggests that rice plants are enriched in As because the rice grows in flooded paddy fields when mobile As(III) is released to soil water.     

Antimony (Sb) and arsenic (As) in Sb mining impacted paddy soil from Xikuangshan, China: differences in mechanisms controlling soil sequestration and uptake in rice

Foods produced on soils impacted by antimony (Sb) mining activities are a potential health risk due to plant uptake of the contaminant metalloids (Sb) and arsenic (As). Here we report for the first time the chemical speciation of Sb in soil and porewater of flooded paddy soil, impacted by active Sb mining, and its effect on uptake and speciation in rice plants (Oryza sativa L. cv Jiahua). Results are compared with behavior and uptake of As. Pot experiments were conducted under controlled conditions in a climate chamber over a period of 50 days. In pots without rice plants, flooding increased both the concentration of dissolved Sb (up to ca. 2000 μg L(-1)) and As (up to ca. 1500 μg L(-1)). When rice was present, Fe plaque developing on rice roots acted as a scavenger for both As and Sb, whereby the concentration of As, but not Sb, in porewater decreased substantially. Dissolved Sb in porewater, which occurred mainly as Sb(V), correlated with Ca, indicating a solubility governed by Ca antimonate. No significant differences in bioaccumulation factor and translocation factor between Sb and As were observed. Greater relative concentration of Sb(V) was found in rice shoots compared to rice root and porewater, indicating either a preferred uptake of Sb(V) or possibly an oxidation of Sb(III) to Sb(V) in shoots. Adding soil amendments (olivine, hematite) to the paddy soil had no effect on Sb and As concentrations in porewater.     

In vitro gastrointestinal bioavailability of arsenic in soils collected near CCA-treated utility poles

Because of the potentially high arsenic concentrations found in soils immediately adjacent to chromated copper arsenate (CCA)-treated wood structures and utility poles, CCA-contaminated soil ingestion may be a significant exposure route to arsenic for children. Therefore, a strong need exists to provide accurate data on oral relative bioavailability (RBA) of arsenic (in vivo or in vitro) in field-collected CCA-contaminated soils. The objectives of this study were (1) to assess arsenic bioaccessibility in contaminated soils collected near in-service CCA-treated utility poles, (2) to determine the influence of soil properties and arsenic fractionation on arsenic bioaccessibility, and (3) to estimate an average daily arsenic intake from incidental soil ingestion. Arsenic bioaccessibility (in vitro gastrointestinal (IVG) method) was determined on surface soil samples collected immediately adjacent to 12 CCA-treated utility poles after 18 months of service. Bioaccessible arsenic was also determined in 3 certified reference materials. Total arsenic concentrations in soils (<300 microm) varied from 37 +/- 2 to 251 +/- 12 mg/kg, irrespective of soil organic matter contentwith the major soil-bound arsenic species being As(V). Arsenic bioaccessibility ranged between 25.0 +/- 2.7 and 66.3 +/- 2.3% (mean value 40.7 +/- 14.9%). The mean value was in agreement with the in vivo arsenic RBA reported by Casteel et al. (2003) in soil near CCA-treated utility poles. Bioaccessible arsenic was positively correlated with total organic carbon content (r2 = 0.36, p < 0.05) and with water-soluble arsenic (2 = 0.51, p < 0.01), and was negatively correlated with clay content (r2 = 0.43, p < 0.05). Using conservative exposure parameters, the mean daily arsenic intake from incidental ingestion of contaminated soil near CCA-treated utility poles was 0.18 +/- 0.09 microg As kg(-1) d(-1). This arsenic intake appeared negligible compared to the daily intake of inorganic arsenic from water and food ingestion for children.     

Environmental fate of roxarsone in poultry litter. Part II. Mobility of arsenic in soils amended with poultry litter

Poultry litter often contains arsenic as a result of organo-arsenical feed additives. When the poultry litter is applied to agricultural fields, the arsenic is released to the environment and may result in increased arsenic in surface and groundwater and increased uptake by plants. The release of arsenic from poultry litter, litter-amended soils, and soils without litter amendment was examined by extraction with water and strong acids (HCI and HNO3). The extracts were analyzed for As, C, P, Cu, Zn, and Fe. Copper, zinc, and iron are also poultry feed additives. Soils with a known history of litter application and controlled application rate of arsenic-containing poultry litter were obtained from the University of Maryland Agricultural Experiment Station. Soils from fields with long-term application of poultry litter were obtained from a tilled field on the Delmarva Peninsula (MD) and an untilled Oklahoma pasture. Samples from an adjacent forest or nearby pasture that had no history of litter application were used as controls. Depth profiles were sampled for the Oklahoma pasture soils. Analysis of the poultry litter showed that 75% of the arsenic was readily soluble in water. Extraction of soils shows that weakly bound arsenic mobilized by water correlates positively with C, P, Cu, and Zn in amended fields and appears to come primarily from the litter. Strongly bound arsenic correlates positively with Fe in amended fields and suggests sorption or coprecipitation of As and Fe in the soil column.     

Arsenic removal from Bangladesh tube well water with filter columns containing zerovalent iron filings and sand

Arsenic removal is often challenging due to high As(III), phosphate, and silicate concentrations and low natural iron concentrations. Application of zerovalent iron is promising, as metallic iron is widely available. However, removal mechanisms remained unclear and currently used removal units with iron have not been tested systematically, partly due to their large size and long operation time. This study investigated smaller filter columns with 3-4 filters, each containing 2.5 g of iron filings and 100-150 g of sand. At a flow rate of 1 L/h, these columns were able to treat 75-90 L of well water with 440 microg/L As, 1.8 mg/L P, 4.7 mg/L Fe, 19 mg/L Si, and 6 mg/L dissolved organic carbon (DOC) to below 50 microg/L As(tot), without addition of an oxidant. As(III) was oxidized in parallel to oxidation of corrosion-released Fe(II) by dissolved oxygen and sorbed on the forming hydrous ferric oxides (HFO). The open filter columns prevented anoxic conditions. DOC did not appear to interfere with arsenic removal. Manganese was reduced after a slight initial increase from 0.3 mg/L to below 0.1 mg/L. About 100 mg of Fe(0)/L of water was required, 3-5 times less than that for larger units with sand and iron turnings.     

Transfer of Listeria innocua from contaminated compost and irrigation water to lettuce leaves

Many foodborne outbreaks of some pathogens such as Escherichia coli O157:H7, Salmonella or Listeria have been associated with the consumption of contaminated vegetables. Contaminated manure and polluted irrigation water are probable vehicles for the pathogens. The aim of this study was to determine the potential transfer of Listeria innocua from soil fertilized with contaminated compost or irrigated with contaminated water to the edible parts of lettuce grown on these soils together with its survival in lettuce and in soil under field conditions during two different seasons. Moreover, its survival on lettuce sprinkled with contaminated irrigation water was evaluated. L. innocua survived in soil samples for 9 weeks at high concentrations, 10⁵ cfu gdw⁻¹ in fall and 10³ cfu gdw⁻¹ in spring. Pathogen survived better in fall, indicating an important influence of temperature and humidity. L. innocua population in lettuce leaves was very high on lettuce leaves after sprinkling, but decreased to undetectable levels at field conditions. There was also transfer of L. innocua from soil contaminated with compost or irrigated with contaminated water to lettuce leaves, mainly to the outer ones. Survival profiles of L. innocua on lettuce and soil samples contaminated either by application of contaminated compost or surface irrigation water was similar. Our results indicated that contaminated compost and contaminated irrigation water can play an important role in the presence of foodborne pathogens on vegetables.     

Limited temporal variability of arsenic concentrations in 20 wells monitored for 3 years in Araihazar, Bangladesh

Millions of people in Bangladesh have probably switched their water consumption to wells that meet the local standard for As in drinking water of 50 microg/L as a result of blanket field testing throughout the country. It is therefore important to know if As concentrations in those wells could change over time. To address this issue, we report here precise groundwater As analyses for time-series samples collected from a suite of 20 tube wells containing < or =50 microg/L As and ranging from 8 to 142 m in depth. For 17 out of 20 wells, the standard deviation of groundwater As concentrations was <10 microg/L over the 3-year monitoring period (n = 24-44 per well). Six of the 17 wells are community wells, each of which serves the needs of several hundred people in particularly affected villages. Of the three wells showing larger fluctuations in chemical composition including As, two are very shallow (8 and 10 m). Variations in As concentrations for one of these wells (50 +/- 32 microg/L, n = 36), as well as another shallow well showing smaller variations (48 +/- 5 microg/L, n = 36), appear to be coupled to seasonal precipitation and recharge linked to the monsoon. The other shallow well showing larger variations in composition indicates a worrisome and steady increase in As concentrations from 50 to 70 microg/L (n = 36) over 3 years. The time series of As (30 +/- 11 microg/L, n = 24) and other constituents in one deep community well (59 m) show large fluctuations that suggest entrainment of shallow groundwater through a broken PVC pipe. Even though the majority of wells that were initially safe remained so for 3 years, our results indicate that tube wells should be tested periodically.     

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.     

Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling

The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation plays an important role in relation to uptake of metals by plants. We investigated the influence of EDDS on speciation of dissolved metals in batch extraction experiments using fourfield-contaminated soils with pH varying between 4.7 and 7.2. Free metal concentrations were determined with the Donnan membrane technique, and compared with results obtained with the chemical speciation program ECOSAT and the NICA-Donnan model using a multicomponent approach. Addition of EDDS increased total metal concentrations in our soil extracts by a factor between 1.1 and 32 (Al), 2.1-48 (Cu), 1.1-109 (Fe), 1.1-5.5 (Ni), and 1.3-17 (Zn). In general, Al, Cu, Fe, and Zn had the largest total concentrations in the EDDS-treated extracts, but the contribution of these metals to the sum of total metal concentrations varied significantly between our soils. Free metal concentrations varied between 7.0 and 8.9 (pCd2+), 3.9-9.9 (pCu2+), 6.3-10.2 (pNi2+), and 5.2-7.0 (pZn2+). Addition of EDDS decreased free metal concentrations by a factor between 1.4 and 1.9 (Cd), 3.4-216 (Cu), 1.3-186 (Ni), and 1.3-3.3 (Zn). Model predictions of free metal concentrations were very good, and predicted values were mostly within 1 order of magnitude difference from the measured concentrations. A multicomponent approach had to be used in our model calculations, because competition between Fe and other metals for binding with EDDS was important. This was done by including the solubility of metal oxides in our model calculations. Multicomponent models can be used in chelant-assisted phytoextraction experiments to predict the speciation of dissolved metals and to increase the understanding of metal uptake by plants.