Impact of chromated copper arsenate (CCA) in wood mulch

The production of landscape mulch is a major market for the recycling of yard trash and waste wood. When wood recovered from construction and demolition (C&D) debris is used as mulch, it sometimes contains chromated copper arsenate (CCA)-treated wood. The presence of CCA-treated wood may cause some potential environmental problems as a result of the chromium, copper, and arsenic present. Research was performed to examine the leachability of the three metals from a variety of processed wood mixtures in Florida. The mixtures tested included mixed wood from C&D debris recycling facilities and mulch purchased from retail outlets. The synthetic precipitation leaching procedure (SPLP) was performed to examine the leaching of chromium, copper and arsenic. Results were compared to Florida's groundwater cleanup target levels (GWCTLs). Eighteen of the 22 samples collected from C&D debris processing facilities leached arsenic at concentrations greater than Florida's GWCTL of 50 microg/l. The mean leachable arsenic concentration for the C&D debris samples was 153 microg/l with a maximum of 558 microg/l. One of the colored mulch samples purchased from a retail outlet leached arsenic above 50 microg/l, while purchased mulch samples derived from virgin materials did not leach detectable arsenic (<5 microg/l). A mass balance approach was used to compute the potential metal concentrations (mg/kg) that would result from CCA-treated wood being present in wood mulch. Less than 0.1% CCA-treated wood would cause a mulch to exceed Florida's residential clean soil guideline for arsenic (0.8 mg/kg).     

A mass balance approach for evaluating leachable arsenic and chromium from an in-service CCA-treated wood structure

Many existing residential wood structures, such as playsets and decks, have been treated with chromated copper arsenate (CCA). This preservative chemical can be released from these structures incrementally over time through contact with rainfall. The objective of this study was to evaluate the levels of arsenic and chromium leached from an in-service CCA-treated deck exposed to rainfall, as well as their possible impacts on soils and shallow groundwater. Two monitoring stations, one containing a CCA-treated deck and the other containing an untreated deck as a control, were constructed outside for this study. Rainfall, runoff water from the decks, soils below the decks, and infiltrated water through 0.7-m depth of soil were monitored for arsenic and chromium over a period of 3 years. The concentration of the CCA-treated deck runoff for arsenic (0.114-4.66 mg/L) and chromium (0.008-0.470 mg/L) were significantly (p<0.001) higher than the untreated deck runoff (< or =0.002 mg/L for both). During the 3-year monitoring period, 13% of the arsenic and 1.4% of the chromium were leached from the amount initially present in the CCA-treated wood. Arsenic levels (<0.1-46 mg/kg) in soils under the CCA-treated deck were significantly (p<0.001) higher than under the untreated deck (<0.1-2.7 mg/kg), while chromium levels were statistically the same below the two decks (2.4-9.6 mg/kg). Approximately 94% of the arsenic from the runoff was absorbed in the soils below the CCA-treated deck; the upper 2.5 cm of the soils captured 42% of the total. The infiltrated water concentrations for arsenic (<0.001-0.085 mg/L) and chromium (<0.001-0.010 mg/L) below the CCA-treated deck were both significantly (p<0.001) higher than below the untreated deck (< or =0.006 mg/L). The amounts of arsenic found in the infiltrated water below the CCA-treated deck represented 6% of total arsenic leached and less than 0.7% of the initial mass in the wood. The study demonstrated that exposure of a CCA-treated deck to rainfall resulted in elevated arsenic concentrations in both runoff and soil. Although only a relatively small fraction of the initial arsenic from the wood was found to infiltrate through the soil, these impacts were significant and caused the infiltrated water to exceed drinking water standards. The study suggests that potential exposures to arsenic exist indirectly through an environment that is contaminated with arsenic leached from in-service CCA-treated wood.     

Distribution and mobility of chromium, copper, and arsenic in soils collected near CCA-treated wood structures in Korea

Chromated copper arsenate (CCA) is currently the most commonly used wood preservative in Korea. Questions, however, have been raised regarding the potential environmental impacts of metal leaching from CCA-treated wood to soil. Although a number of researchers from other countries have reported that chromium, copper, and arsenic do leach from CCA-treated wood over time, to date few field studies have been performed on those metals in soils adjacent to CCA-treated wood structures in Korea. The present study was conducted to determine the lateral and vertical distributions and accumulation of chromium, copper, and arsenic in soils collected from CCA-treated wood structures. A total of fifty-five composite soil samples were collected from four CCA-treated wood structures of approximately one year in age. The samples were analyzed for physicochemical properties as well as for the total chromium, copper, and arsenic concentrations. The chromium, copper, and arsenic concentrations in soil samples adjacent to the structures were as high as 79.0, 98.9, and 128 mg/kg, respectively, compared to background soil samples (48.2, 26.9, and 6.27 mg/kg, respectively). Arsenic was more mobile in soil than chromium and copper. The concentration gradient of arsenic in soil was observed only to the depth of approximately 5 cm in one year of outdoor exposure, whereas chromium and copper apparently remained near the surface (approximately less than 1 cm) after their release. Future efforts should be made to observe seasonal impacts on the release of metals and incorporate metal speciation into determining more detailed mobility and distribution.     

Arsenic levels in wipe samples collected from play structures constructed with CCA-treated wood: Impact on exposure estimates

Lumber treated with chromated copper arsenate (CCA) has been used in residential outdoor wood structures and playgrounds. The U.S. EPA has conducted a probabilistic assessment of children's exposure to arsenic from CCA-treated structures using the Stochastic Human Exposure and Dose Simulation model for the wood preservative scenario (SHEDS-Wood). The EPA assessment relied on data from an experimental study using adult volunteers and designed to measure arsenic in maximum hand and wipe loadings. Analyses using arsenic handloading data from a study of children playing on CCA-treated play structures in Edmonton, Canada, indicate that the maximum handloading values significantly overestimate the exposure that occurs during actual play. The objective of our paper is to assess whether the dislodgeable arsenic residues from structures in the Edmonton study are comparable to those observed in other studies and whether they support the conclusion that the values derived by EPA using modeled maximum loading values overestimate hand exposures. We compared dislodgeable arsenic residue data from structures in the playgrounds in the Edmonton study to levels observed in studies used in EPA's assessment. Our analysis showed that the dislodgeable arsenic levels in the Edmonton playground structures are similar to those in the studies used by EPA. Hence, the exposure estimates derived using the handloading data from children playing on CCA-treated structures are more representative of children's actual exposures than the overestimates derived by EPA using modeled maximum values. Handloading data from children playing on CCA-treated structures should be used to reduce the uncertainty of modeled estimates derived using the SHEDS-Wood model.     

Dislodgeable copper,chromium and arsenic from CCA-treated wood surfaces

Chromated copper arsenate (CCA) is commonly used to preserve wood, but its use poses risk of arsenic exposure. In order to evaluate the extent of exposure to As from physical contact with CCA-treated wood, dislodgeable As from treated wood surfaces (as well as Cu and Cr) was determined as a function of weathering time using dampened polyester wipe materials. Six sets of 2.5-m-long CCA-treated boards, three-four boards per set, were purchased from lumber yards and cut into 30- or 60-cm coupons. A total of 44 such coupons were placed outdoors and the dislodgeable CCA components from the surfaces of the wooden coupons were periodically determined over a 1- or 2-year period by a systematic wipe method followed by nitric acid extraction of the CCA components from the cloth. In all 316 samples, appreciable amounts of the three elements, Cu, Cr and As, were detected. The amounts of surface-dislodgeable As, the most potentially hazardous element and the one of major concern in this study, varied from 5 to 122 microg/100 cm(2) with an average value of 37+/-22 microg/100 cm(2). There was considerable variation in As dislodged among coupons, boards, sets and time. Test coupons that tended to release relatively higher (or lower amounts) over time initially, continued to do so over time. However, the amounts of arsenic dislodged over time did not follow a simple pattern. While the As dislodged tended to decrease with time during the first year, it approached the initial value or increased somewhat during the second year, presumably due to surface rejuvenation effects caused by erosion and weathering. When all the data were normalized to the initial values, no trend emerged, as indicated by the average normalized value of 1.0+/-0.4 for As dislodged over time. Apparently, on installations constructed with CCA-treated wood, arsenic may remain available for a number of years.     

A survey of arsenic in foodstuffs on sale in the United Kingdom and imported from Bangladesh

Arsenic is a highly toxic element and its presence in food composites is a matter of concern to the well being of both humans and animals. Arsenic-contaminated groundwater is often used in Bangladesh and West Bengal (India) to irrigate crops used for food and animal consumption, which could potentially lead to arsenic entering the human food chain. In this study, we used graphite furnace atomic absorption spectroscopy to determine the total arsenic concentrations in a range of foodstuffs, including vegetables, rice and fish, imported into the United Kingdom from Bangladesh. The mean and range of the total arsenic concentration in all the vegetables imported from Bangladesh were 54.5 and 5-540 microg/kg, respectively. The highest arsenic values found were for the skin of Arum tuber, 540 microg/kg, followed by Arum Stem, 168 microg/kg, and Amaranthus, 160 microg/kg. Among the other samples, freshwater fish contained total arsenic levels between 97 and 1318 microg/kg. The arsenic content of the vegetables from the UK was approximately 2- to 3-fold lower than those observed for the vegetables imported from Bangladesh. The levels of arsenic found in vegetables imported from Bangladesh in this study, in some cases, are similar to those previously recorded for vegetables grown in arsenic-affected areas of West Bengal, India, although lower than the levels reported in studies from Bangladesh. While the total arsenic content detected in our study in vegetables, imported from Bangladesh, is far less than the recommended maximum permitted level of arsenic, it does provide an additional source of arsenic in the diet. This raises the possibility that the level of arsenic intake by certain sectors of the UK population may be significantly higher then the general population and requires further investigations.     

Arsenic speciation and uranium concentrations in drinking water supply wells in Northern Greece: correlations with redox indicative parameters and implications for groundwater treatment

The cities in the Aksios and Kalikratia areas in Northern Greece rely on arsenic contaminated groundwater for their municipal water supply. As remedial action strongly depends on arsenic speciation, the presence of other possible contaminants, and on the general water composition, a detailed study with samples from 21 representative locations was undertaken. Arsenic concentrations were typically 10-70 microg/L. In the groundwaters of the Aksios area with lower Eh values (87-172 mV), pH 7.5-8.2 and 4-6 mM HCO(3) alkalinity, As(III) predominated. Manganese concentrations were mostly above the EC standard of 0.05 mg/L (0.1-0.7 mg/L). In groundwaters of the Kalikratia area with higher Eh values (272-352 mV), pH 6.7-7.5 and 6-12 mM HCO(3) alkalinity, As(V) was the main species. Uranium in the groundwaters was also investigated and correlations with total arsenic concentrations and speciation were examined to understand more of the redox chemistry of the examined groundwaters. Uranium concentrations were in the range 0.01-10 microg/L, with the higher concentrations to occur in the oxidizing groundwaters of the Kalikratia area. Uranium and total arsenic concentrations showed no correlation, whereas uranium concentrations correlated strongly with As(III)/As(tot) ratios, depicting their use as a possible indicator of groundwater redox conditions. Finally, boron was found to exceed the EC drinking water standard of 1 mg/L in some wells in the Kalikratia area and its removal should also be considered in the design of a remedial action.     

Arsenic concentrations in Chinese coals

The arsenic concentrations in 297 coal samples were collected from the main coal-mines of 26 provinces in China were determined by molybdenum blue coloration method. These samples were collected from coals that vary widely in coal rank and coal-forming periods from the five main coal-bearing regions in China. Arsenic content in Chinese coals range between 0.24 to 71 mg/kg. The mean of the concentration of Arsenic is 6.4+/-0.5 mg/kg and the geometric mean is 4.0+/-8.5 mg/kg. The level of arsenic in China is higher in northeastern and southern provinces, but lower in northwestern provinces. The relationship between arsenic content and coal-forming period, coal rank is studied. It was observed that the arsenic contents decreases with coal rank in the order: Tertiary>Early Jurassic>Late Triassic>Late Jurassic>Middle Jurassic>Late Permian>Early Carboniferous>Middle Carboniferous>Late Carboniferous>Early Permian; It was also noted that the arsenic contents decrease in the order: Subbituminous>Anthracite>Bituminous. However, compared with the geological characteristics of coal forming region, coal rank and coal-forming period have little effect on the concentration of arsenic in Chinese coal. The average arsenic concentration of Chinese coal is lower than that of the whole world. The health problems in China derived from in coal (arsenism) are due largely to poor local life-style practices in cooking and home heating with coal rather than to high arsenic contents in the coal.     

Arsenic groundwater contamination and its health effects in the state of Uttar Pradesh (UP) in upper and middle Ganga plain, India: a severe danger

This communication presents results of our 2-year survey on groundwater arsenic contamination in three districts Ballia, Varanasi and Gazipur of Uttar Pradesh (UP) in the upper and middle Ganga plain, India. Analyses of 4,780 tubewell water samples revealed that arsenic concentrations in 46.5% exceeded 10 microg/L, in 26.7%, 50 microg/L and in 10% 300 microg/L limits. Arsenic concentrations up to 3,192 microg//L were observed. The age of tubewells (n=1,881) ranged from less than a year to 32 years, with an average of 6.5 years. Our study shows that older tubewells had a greater chance of contamination. Depth of tubewells (n=3,810) varied from 6 to 60.5 m with a mean of 25.75 m. A detailed study in three administrative units within Ballia district, i.e. block, Gram Panchayet, and village was carried out to assess the magnitude of the contamination. Before our survey the affected villagers were not aware that they were suffering from arsenical toxicity through contaminated drinking water. A preliminary clinical examination in 11 affected villages (10 from Ballia and 1 from Gazipur district) revealed typical arsenical skin lesions ranging from melanosis, keratosis to Bowens (suspected). Out of 989 villagers (691 adults, and 298 children) screened, 137 (19.8%) of the adults and 17 (5.7%) of the children were diagnosed to have typical arsenical skin lesions. Arsenical neuropathy and adverse obstetric outcome were also observed, indicating severity of exposure. The range of arsenic concentrations in hair, nail and urine was 137-10,900, 764-19,700 microg/kg, and 23-4,030 microg/L, respectively. The urine, hair and nail concentrations of arsenic correlated significantly (r=0.76, 0.61, and 0.55, respectively) with drinking water arsenic concentrations. The similarity to previous studies on arsenic contamination in West Bengal, Bihar and Bangladesh indicates that people from a significant part of the surveyed areas in UP are suffering and this will spread unless drives to raise awareness of arsenic toxicity are undertaken and an arsenic safe water supply is immediately introduced.     

Survey of arsenic and other heavy metals in food composites and drinking water and estimation of dietary intake by the villagers from an arsenic-affected area of West Bengal,India

An investigation of arsenic, copper, nickel, manganese, zinc and selenium concentration in foodstuffs and drinking water, collected from 34 families and estimation of the average daily dietary intake were carried out in the arsenic-affected areas of the Jalangi and Domkal blocks, Murshidabad district, West Bengal where arsenic-contaminated groundwater (mean: 0.11 mg/l, n=34) is the main source for drinking. The shallow large diameter tubewells, installed for agricultural irrigation contain an appreciable amount of arsenic (mean: 0.094 mg/l, n=10). So some arsenic can be expected in the food chain and food cultivated in this area. Most of the individual food composites contain a considerable amount of arsenic. The mean arsenic levels in food categories are vegetables (20.9 and 21.2 microg/kg), cereals and bakery goods (130 and 179 microg/kg) and spices (133 and 202 microg/kg) for the Jalangi and Domkal blocks, respectively. For all other heavy metals, the observed mean concentration values are mostly in good agreement with the reported values around the world (except higher zinc in cereals). The provisional tolerable daily intake value of inorganic arsenic microg/kg body wt./day) is: for adult males (11.8 and 9.4); adult females (13.9 and 11); and children (15.3 and 12) in the Jalangi and Domkal blocks, respectively (according to FAO/WHO report, the value is 2.1 microg/kg body wt./day). According to WHO, intake of 1.0 mg of inorganic arsenic per day may give rise to skin lesions within a few years. The average daily dietary intake of copper, nickel and manganese is high, whereas for zinc, the value is low (for adult males: 8.34 and 10.2 mg/day; adult females: 8.26 and 10.3 mg/day; and children: 4.59 and 5.66 mg/day) in the Jalangi and Domkal blocks, respectively, compared to the recommended dietary allowance of zinc for adult males, adult females and children (15, 12 and 10 mg/day, respectively). The average daily dietary intake of selenium microg/kg body wt./day) is on the lower side for the children (1.07 and 1.22), comparable for the adult males (0.81 and 0.95) and slightly on the higher side for the adult females (1.08 and 1.26), compared to the recommended value (1.7 and 0.9 microg/kg body wt./day for infants and adults, respectively).     

Removal copper,chromium and arsenic from CCA-treated yellow pine by oleic acid

Removal of Cu, Cr and As metals from chromated copper arsenate (CCA) treated yellow pine wood samples with three different dimensions were investigated by extraction with oleic acid at four different pH levels. The concentrations of Cu, Cr and As were determined by XRF. The effects of pH, dimension and duration on remediation of CCA-treated wood samples were determined. Oleic acid was found to be very effective to remove copper, chromium and arsenic from CCA-treated wood samples especially at lower pH levels (pH=2.00 and 2.50). In addition, the best models estimate copper, chromium and arsenic leaching from CCA-treated wood samples by oleic acid remediation were determined by step-wise regression analysis.     

Influence of cooking method on arsenic retention in cooked rice related to dietary exposure

Arsenic concentration in raw rice is not only the determinant in actual dietary exposure. Though there have been many reports on arsenic content in raw rice and different tissues of rice plant, little is known about arsenic content retained in cooked rice after being cooked following the traditional cooking methods employed by the people of arsenic epidemic areas. A field level experiment was conducted in Bangladesh to investigate the influence of cooking methods on arsenic retention in cooked rice. Rice samples were collected directly from a severely arsenic affected area and also from an unaffected area, to compare the results. Rice was cooked according to the traditional methods employed by the population of subjected areas. Arsenic concentrations were 0.40+/-0.03 and 0.58+/-0.12 mg/kg in parboiled rice of arsenic affected area, cooked with excess water and 1.35+/-0.04 and 1.59+/-0.07 mg/kg in gruel for BRRI dhan28 and BRRI hybrid dhan1, respectively. In non-parboiled rice, arsenic concentrations were 0.39+/-0.04 and 0.44+/-0.03 mg/kg in rice cooked with excess water and 1.62+/-0.07 and 1.74+/-0.05 mg/kg in gruel for BRRI dhan28 and BRRI hybrid dhan1, respectively. Total arsenic content in rice, cooked with limited water (therefore gruel was absorbed completely by rice) were 0.89+/-0.07 and 1.08+/-0.06 mg/kg (parboiled) and 0.75+/-0.04 and 1.09+/-0.06 mg/kg (non-parboiled) for BRRI dhan28 and BRRI hybrid dhan1, respectively. Water used for cooking rice contained 0.13 and 0.01 mg of As/l for contaminated and non-contaminated areas, respectively. Arsenic concentrations in cooked parboiled and non-parboiled rice and gruel of non-contaminated area were significantly lower (p<0.01) than that of contaminated area. The results imply that cooking of arsenic contaminated rice with arsenic contaminated water increases its concentration in cooked rice.     

Arsenic speciation in moso bamboo shoot--a terrestrial plant that contains organoarsenic species

Arsenic is predominantly found as an inorganic species in most terrestrial plants. However, we found that a significant proportion of organic arsenic was present in moso bamboo (Phyllostachys pubescens Mazel) shoot in a market survey of arsenic species in edible terrestrial plants. Moso bamboo shoots from different producing areas in China were collected for analysis to confirm the ubiquity of methylated arsenic species. The total arsenic concentrations of bamboo shoots were determined by hydride generation coupled atomic fluorescence spectrometry (HG-AFS), ranging from 27.7 to 94.0 microg/kg. Information about arsenic species was acquired from cold trap-hydride generation-atomic absorption spectrometry (CT-HG-AAS). Dimethylarsinic acid (DMA) was present in the amount of 13.9% to 44.9% of sum of the arsenic species in all these samples. Monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) were also detected in certain samples in the range of 4.2-16.5% and 11.8-18.4%, respectively. In addition, bamboo shoots collected in winter were found to have more total arsenic and organic arsenic than those collected in spring. To investigate the source of the organic arsenic in moso bamboo shoots, arsenic species in the rhizosphere soils of the plants were examined. The absence of organic arsenic in soils would suggest the possibility of formation of methylated arsenic in the plants. In addition, studies of arsenic speciation in the peel and core of winter bamboo shoots showed that all the cores contained organic arsenic while no organic arsenic was detected in the peels. The study provides useful information for better understanding of the distribution of arsenic species in terrestrial plants.     

Occurrence of arsenic contamination in Canada: sources, behavior and distribution

Recently there has been increasing anxieties concerning arsenic related problems. Occurrence of arsenic contamination has been reported worldwide. In Canada, the main natural arsenic sources are weathering and erosion of arsenic-containing rocks and soil, while tailings from historic and recent gold mine operations and wood preservative facilities are the principal anthropogenic sources. Across Canada, the 24-h average concentration of arsenic in the atmosphere is generally less than 0.3 microg/m3. Arsenic concentrations in natural uncontaminated soil and sediments range from 4 to 150 mg/kg. In uncontaminated surface and ground waters, the arsenic concentration ranges from 0.001 to 0.005 mg/L. As a result of anthropogenic inputs, elevated arsenic levels, above ten to thousand times the Interim Maximum Acceptable Concentration (IMAC), have been reported in air, soil and sediment, surface water and groundwater, and biota in several regions. Most arsenic is of toxic inorganic forms. It is critical to recognize that such contamination imposes serious harmful effects on various aquatic and terrestrial organisms and human health ultimately. Serious incidences of acute and chronic arsenic poisonings have been revealed. Through examination of the available literature, screening and selecting existing data, this paper provides an analysis of the currently available information on recognized problem areas, and an overview of current knowledge of the principal hydrogeochemical processes of arsenic transportation and transformation. However, a more detailed understanding of local sources of arsenic and mechanisms of arsenic release is required. More extensive studies will be required for building practical guidance on avoiding and reducing arsenic contamination. Bioremediation and hyperaccumulation are emerging innovative technologies for the remediation of arsenic contaminated sites. Natural attenuation may be utilized as a potential in situ remedial option. Further investigations are needed to evaluate its applicability.     

Arsenic, cadmium, lead, copper and zinc in cattle from Galicia, NW Spain

Knowledge of trace and toxic metal concentrations in livestock is important for assessing the effects of pollutants on domestic animals and contaminant intakes by humans. Metal levels in cattle have been measured in various countries but not in Spain. In this study, the (wet wt.) concentrations of three toxic elements (arsenic, cadmium, lead) and two trace elements (copper, zinc) were quantified in the liver (Li), kidney (Ki), muscle (M) and blood (Bl) of calves (males and females between 6 and 10 months old) and cows (2-16 years old) from Galicia, NW Spain. For the toxic elements, geometric mean concentrations of arsenic in calves (sexes combined) and cows were 10.8 and 10.2 microg/kg (Li), 11.3 and 15.2 microg/kg (Ki), 3.75 and 4.25 microg/kg (M), 3.23 and 2.92 microg/l (Bl). The corresponding cadmium concentrations were 7.78 and 83.3 microg/kg (Li), 54.3 and 388 microg/kg (Ki), 0.839 and 0.944 microg/kg (M), 0.373 and 0.449 microg/l (Bl). Geometric mean concentrations of lead in calves and cows were similarly low and were 33.0 and 47.5 microg/kg (Li), 38.9 and 58.3 microg/kg (Ki), 6.37 and 12.5 microg/kg (M), 5.47 and 12.2 microg/l (Bl). Sex had almost no effect on the amount of toxic metal accumulated except that kidney cadmium concentrations were significantly higher in females than males. Age did influence accumulation; cadmium and lead (but not arsenic) concentrations in most tissues were significantly greater in cows than female calves. For the trace elements, geometric mean copper levels in calf and cow tissues were 49.9 and 36.6 mg/kg (Li), 4.27 and 3.63 mg/kg (Ki), 0.649 and 1.68 mg/kg (M) and 0.878 and 0.890 mg/l (Bl). The corresponding zinc concentrations were 46.3 and 52.5 mg/kg (Li), 14.2 and 20.7 mg/kg (Ki), 47.3 and 52.5 mg/kg (M) and 2.80 and 2.22 mg/l (Bl). Female calves had significantly higher levels than males of muscle zinc and blood copper and zinc. Female calves accumulated more copper but less zinc in the liver and kidneys compared with cows; this may have been associated with the chronic, low-level cadmium accumulation observed in cows. Overall, the levels of arsenic, cadmium, lead and zinc in cattle in Galicia do not constitute a risk for animal health. However, up to 20% of cattle in some regions in Galicia had levels of copper in the liver that exceeded 150 mg/kg wet wt. These animals may be at risk from copper poisoning.     

Inorganic arsenic in cooked rice and vegetables from Bangladeshi households

Many Bangladeshi suffer from arsenic-related health concerns. Most mitigation activities focus on identifying contaminated wells and reducing the amount of arsenic ingested from well water. Food as a source of arsenic exposure has been recently documented. The objectives of this study were to measure the main types of arsenic in commonly consumed foods in Bangladesh and estimate the average daily intake (ADI) of arsenic from food and water. Total, organic and inorganic, arsenic were measured in drinking water and in cooked rice and vegetables from Bangladeshi households. The mean total arsenic level in 46 rice samples was 358 microg/kg (range: 46 to 1,110 microg/kg dry weight) and 333 microg/kg (range: 19 to 2,334 microg/kg dry weight) in 39 vegetable samples. Inorganic arsenic calculated as arsenite and arsenate made up 87% of the total arsenic measured in rice, and 96% of the total arsenic in vegetables. Total arsenic in water ranged from 200 to 500 microg/L. Using individual, self-reported data on daily consumption of rice and drinking water the total arsenic ADI was 1,176 microg (range: 419 to 2,053 microg), 14% attributable to inorganic arsenic in cooked rice. The ADI is a conservative estimate; vegetable arsenic was not included due to limitations in self-reported daily consumption amounts. Given the arsenic levels measured in food and water and consumption of these items, cooked rice and vegetables are a substantial exposure pathway for inorganic arsenic. Intervention strategies must consider all sources of dietary arsenic intake.     

Arsenic chemical species-dependent genotoxic potential in water extracts from two CCA-contaminated soils measured by DNA-repair deficient CHO-cells

Two soils with similar contamination levels from wood preservatives containing Chromium (Cr), Copper (Cu) and Arsenic (As) (CCA), were assessed for their general toxicity and genotoxicity. A set of water-based extraction methods, including pressurized liquid extraction (PLE), and batch leaching in milli-Q water and a weak CaCl₂-solution, was used to produce soil extracts containing available fractions of contaminants. In addition, to obtain indications of the contaminants' bioavailability and toxic potential the genotoxicity of the extracts was estimated by testing their ability to inhibit the growth of wildtype Chinese hamster ovary cells (CHO-cells) and three genetically modified pheno-types that are deficient in different DNA-repair mechanisms. Total extractable arsenic concentrations in the extracts were comparable between the sites. However, the genotoxic potential was clearly higher in soil R extracts. The differences in genotoxic responses were related to differences in inorganic arsenic speciation. The ratio of trivalent arsenic (As^III) to pentavalent arsenic (As^V) was higher in all soil extracts from soil R, regardless of the leaching method used. The results of the various combinations of soil extraction techniques and assays using the CHO-cell lines reflected important differences in arsenic speciation in the two soils and possible synergistic effects in CCA-related exposure. They also indicate that speciation and combinatory effects are factors that should be taken into account when assessing risks at former wood impregnation sites contaminated by CCA-agents.     

Arsenic bioaccessibility in CCA-contaminated soils: Influence of soil properties, arsenic fractionation, and particle-size fraction

Arsenic bioaccessibility in soils near chromated copper arsenate (CCA)-treated structures has recently been reported, and results have shown that soil properties and arsenic fractionation can influence bioaccessibility. Because of the limited data set of published results, additional soil samples and a wider range of soil properties are tested in the present work. The objectives are: (1) to confirm previous results regarding the influence of soil properties on arsenic bioaccessibility in CCA-contaminated soils, (2) to investigate additional soil properties influencing arsenic bioaccessibility, and to identify chemical extractants which can estimate in vitro gastrointestinal (IVG) bioaccessibility, (3) to determine arsenic speciation in the intestinal phase of the IVG method and, (4) to assess the influence of two particle-size fractions on arsenic bioaccessibility. Bioaccessible arsenic in eight soils collected near CCA-treated utility poles was assessed using the IVG method. Five out of the eight soils were selected for a detailed characterization. Moreover, these five soils and two certified reference materials were tested by three different metal oxide extraction methods (citrate dithionite (CD), ammonium oxalate (OX), and hydroxylamine hydrochloride (HH)). Additionally, VMINTEQ was used to determine arsenic speciation in the intestinal phase. Finally, two particle-size fractions (< 250 μm, < 90 μm) were tested to determine their influence on arsenic bioaccessibility. First, arsenic bioaccessibility in the eight study-soils ranged between 17.0 ± 0.4% and 46.9 ± 1.1% (mean value 30.5 ± 3.6%). Using data from 20 CCA-contaminated soil samples, total organic carbon (r = 0.50, p < 0.05), clay content (r = − 0.57, p < 0.01), sand content (r = 0.48, p < 0.05), and water-soluble arsenic (r = 0.66, p < 0.01) were correlated with arsenic bioaccessibility. The mean percentage of total arsenic extracted from five selected soils was: HH (71.9 ± 4.1%) > OX (58.0 ± 3.1%) > water-soluble arsenic (2.2 ± 0.5%), while the mean value for arsenic bioaccessibility was 27.3 ± 2.8% (n = 5). Arsenic extracted by HH (r = 0.85, p < 0.01, n = 8) and OX (r = 0.93, p < 0.05, n = 5), showed a strong correlation with arsenic bioaccessibility. Moreover, dissolved arsenic in the intestinal phase was exclusively under the form of arsenate As(V). Finally, arsenic bioaccessibility (in mg/kg) increased when soil particles < 90 μm were used.     

Dietary intake of cadmium by children and adults from Germany using duplicate portion sampling

The dietary intake of cadmium was studied among children and adults from Germany. The study area comprised the highly industrialized Ruhr district as well as the North Sea island Amrum. A total of 229 duplicate samples were collected from 49 individuals between December 1994 and May 1995. The sampling period for each participant was either 3 or 7 days. Cadmium concentrations in duplicate samples were measured by atomic absorption spectrometry. The daily cadmium intakes (geometric mean) for 4 different groups of individuals distributed as follows: for small children (mean age: 1.8 years) from the Ruhr district 0.17 microg/(kg(bw) x day) [range: 0.02-1.62 microg/(kg(bw) x day)], for children (mean age: 3.8 years) from the Ruhr district 0.49 microg/(kg(bw) x day) [range: 0.11-2.06 microg/(kg(bw) x day)], for children (mean age: 3.9 years) living on the North Sea island Amrum 0.35 microg/(kg(bw)-day) [range: 0.09-1.13 microg/ (kg(bw) x day)] and for adults (mean age: 40.9 years) from the Ruhr district 0.37 microg/(kg(bw) x day) [range: 0.05-1.32 microg/(kg(bw) x day)]. Compared to the provisional tolerable weekly intake (PTWI) of 7 microg/(kg(bw) x week) proposed by the WHO the dietary intake of cadmium was rather high. The geometric mean and maximum intake values for the different groups ranged between 24.3-55.7% and 62.7-120.7 respectively of the PTWI. We therefore conclude, that the cadmium exposure of the population needs to be reduced in order to minimize the risk of adverse health effects related to this metal.     

Groundwater derived arsenic in high carbonate wetland soils: sources, sinks, and mobility

Wetlands and organic soils have been recognized as important sinks for arsenic in the environment, yet sources and immobilization mechanisms of As are often unclear. To begin rectifying this deficiency, we investigated As retention and binding mechanisms at a degraded, minerotrophic wetland site in contact with groundwater rich in As and Fe. Arsenic occurred in high dissolved concentrations of up to 467 microg L(-1) in the groundwater, but dropped to values below 10 microg L(-1) towards the surface. The solid phase As content instead was high in the topsoil with up to 3400 mg kg(-1) and decreased with depth to 15 mg kg(-1). A similar pattern was observed with respect to Fe. Amorphous and crystalline iron precipitates were the main sorbents for arsenic in the soil horizons according to results from wet chemical sequential extractions. Arsenic was apparently not associated with inorganic carbon phases, but a substantial portion of up to 31% of As(tot) could be mobilized by dispersion of soil organic matter. Ratios of dissolved As(III)/As(V) decreased from the deeper As(III) dominated groundwater to the As(V) dominated soil porewaters, where As was apparently immobilized in its oxidized form. Concentrations of the organic species DMA and MMA were negligible. According to the results of simple one-dimensional estimates the vertical arsenic transport from the source in the groundwater to the topsoil was slow given an extrapolation of current conditions. These results suggest that As accumulation started before the beginning of drainage in the now degraded peatland soils and the degradation and mass loss of organic matter under oxic conditions caused the very high As concentrations found in the topsoil horizon today.