Chemical transformation and flux of different forms of arsenic in the carb Carcinusmaenas

The amount of ingested arsenic assimilated and eliminated by the crab appeared to depend on chemical form of arsenic present in the food. Arsenic-74 was translocated rapidly with a high percentage located in hepatopancreas and exoskeleton. The speciation of radioarsenic determined by sequential extraction of experimental food, feces, muscle and hepatopancreas showed that there is no efficient mechanism within the crab which can covert lipid and water soluble arsenic to arsenite and residual arsenic or vice-versa. The biological mechanism in crab selectively and effectively excretes soluble form of arsenite and residual arsenic much more readily than organic arsenic.     

The formation of trimethylarsine oxide from arsenobetaine by biodegradation with marine microorganisms

Bottom sediments collected from coastal waters were aerobically incubated in inorganic medium containing arsenobetaine as a carbon source. An arsenic compound converted from arsenobetaine during incubation was purified from the medium by ion exchange chromatography. The purified compound was identified to be trimethylarsine oxide by TLC, HPLC, FAB-MS and NMR.     

Trace metal residues in shellfish from Maryland waters, 1976-1980

Levels of seven heavy metal residues, arsenic, cadmium, chromium, copper, lead, mercury and zinc were monitored in samples of the American oyster (Crassostrea virginica), the soft shell clam (Mya arenaria), the hard shell clam (Mercinaria mercinaria) and the blue crab (Callinectes sapidus). Samples were taken from the Maryland section of the Chesapeake Bay and its tributaries over a five year period (1976-80). This study was undertaken to provide an estimate of a baseline for values of trace heavy metals. Also, the oyster, being a non-mobile filter feeder, provides information regarding the level of metal residues in its environment (water and sediment), because heavy metal uptake is related to the surrounding metal concentrations. Additionally, this type of monitoring program is essential to ensure that shellfish sold for human consumption are within safe limits established for toxic substances by the United States Food and Drug Administration. Results of the study are consistent with data from previous years and no statistically significant year-to-year trends were observed over the period of the investigation.     

Studies on the accumulation and transformation of arsenic in freshwater organisms I. Accumulation, transformation and toxicity of arsenic compounds on the Japanese medaka, Oryzias latipes

Accumulation, transformation and toxicity of arsenic compounds to Japanese Medaka, Oryzias latipes were investigated. For sodium arsenite [As(II)] and disodium arsenate [As(V)], the mean value for 7-day lethal concentration LC50 for O. latipes were 14.6 and 30.3 mg As/l, respectively. Direct accumulation of arsenic in O. latipes increased as a function of As(III) concentration in water. A small proportion of accumulated arsenic was transformed to methylated arsenic. As much as 70% of the total arsenic accumulated in tissue was depurated. Accumulation and transformation of As(III) by O. latipes in a simple freshwater food chain were also investigated. The transformation of As(III) to As(V) by organisms was more prevalent than biomethylation of accumulated arsenic in organisms of the three steps of the food chain.     

Bacteria, hypertolerant to arsenic in the rocks of an ancient gold mine, and their potential role in dissemination of arsenic pollution

The aim of the present study was to find out if bacteria present in ancient gold mine could transform immobilized arsenic into its mobile form and increase its dissemination in the environment. Twenty-two arsenic-hypertolerant cultivable bacterial strains were isolated. No chemolithoautotrophs, which could use arsenite as an electron donor as well as arsenate as an electron acceptor, were identified. Five isolates exhibited hypertolerance to arsenic: up to 500 mM of arsenate. A correlation between the presence of siderophores and high resistance to arsenic was found. The results of this study show that detoxification processes based on arsenate reductase activity might be significant in dissemination of arsenic pollution. It was concluded that the activity of the described heterotrophic bacteria contributes to the mobilization of arsenic in the more toxic As(III) form and a new mechanism of arsenic mobilization from a scorodite was proposed.     

Potential of the hybrid marigolds for arsenic phytoremediation and income generation of remediators in Ron Phibun District, Thailand

Nugget marigold, a triploid hybrid between American (Tagetes erecta L.) and French (Tagetes patula) marigolds, is a marketed flowering plant with a good ability in arsenic phytoremediation. During field trial in an arsenic-polluted area in Thailand, arsenic was found mostly in leaves (46.2%) while flowers contained the lowest arsenic content (5.8%). Arsenic species in aqueous extracts of nugget marigolds were determined by HPLC-UV-HG-QF-AAS. Inorganic arsenics, arsenite and arsenate, were the main arsenic chemical species found in roots, stems, and leaves of marigolds with accumulated arsenic. Nugget marigolds from experimental plots not only accumulated high levels of arsenic but also grew well in arsenic-contaminated areas. Phosphate fertilizer enhanced arsenic uptake when the plants were in the flowering stage. Arsenic remediation using nugget marigolds could also provide economic benefits to the remediators through marketing flowers. Therefore, marigolds should be considered as a potential economic crop for phytoremediation.     

Metal contents in the groundwater of Sahebgunj district, Jharkhand, India, with special reference to arsenic

A detailed study has been presented on groundwater metal contents of Sahebgunj district in the state of Jharkhand, India with special reference to arsenic. Both tubewell and well waters have been studied separately with greater emphasis on tubewell waters. Groundwaters of all the nine blocks of Sahebgunj district have been surveyed for iron, manganese, calcium, magnesium, copper and zinc in addition to arsenic. Normal distribution statistic, exploratory data analysis and robust Z-score analysis have been employed to find out the distribution pattern, localisation of data, outliers and other related information. Groundwaters of three blocks of Sahebgunj, namely, Sahebgunj, Rajmahal and Udhawa have been found to be alarmingly contaminated with arsenic present at or above 10 ppb. Arsenic distribution patterns in these blocks are highly asymmetric in nature with the common feature of increasing width from first to fourth quartile. A very broad fourth quartile in each case represents a long asymmetric tail on the right of the median. Tubewell waters of at least two more blocks require regular monitoring to identify the outbreak of arsenic at the onset. Groundwaters of Sahebgunj district in general contain high iron and manganese. It is by and large soft in nature. Well waters have been found to be better with regard to arsenic but iron and manganese contents do not vary significantly. Normal distribution analysis (NDA), box and whisker (BW) plot and Z-score analysis together can provide a reasonably complete statistical picture of metal contents in Sahebgunj district groundwaters.     

Uptake, distribution and elimination of monosodium methanearsonate following long term oral administration of the herbicide to sheep and goats

The rate and extent of accumulation and washout of arsenic, during daily oral administration of the herbicide monosodium methanearsonate (MSMA) were evaluated in Iranian dairy sheep and goats. Subjects received a dose of 10 mg of MSMA as arsenic per kg of body weight daily for 28 consecutive days. The total arsenic concentration in blood and milk was measured during and after the period of MSMA administration while arsenic in urine and feces was measured for 10 days following administration of last dosage of MSMA. Arsenic was accumulated slowly during 28 days of MSMA administration and steady states were essentially complete in sheep after 20 days and in goats following 25 days of MSMA administration. Blood arsenic concentration decreased rapidly after termination of MSMA administration. In both test animals, the half-lives of washout were smaller than accumulation. The concentration of arsenic in the urine and feces of both species did not increase significantly over controls and animals were free of arsenic relatively shortly after administration stopped. These data indicate that arsenic from MSMA is mainly absorbed from gastrointestinal tract and is not significantly accumulated in the body. Arsenic is eliminated from body by way of urine and feces with urinary excretion being the most important route.     

Effects of fenoxycarb exposure on complete larval development of the xanthid crab,Rhithropanopeus harrisii

Pest control agents, such as juvenile hormone analogues (JHA), have been developed to limit effects on non-target organisms that co-inhabit insect pest habitats. Rhithropanopeus harrisii, an estuarine xanthid crab, was used to observe the impacts of the JHA, fenoxycarb, on the pattern of complete larval development as well as survival of larvae and successful metamorphosis to first crab stage. Significant mortality occurred in the first of four zoeal stages (after 2-3 days of exposure) at the highest treatment of 240 microg fenoxycarb/l and in megalopae exposed to 48 microg fenoxycarb/l. The time required to metamorphose to the first crab stage was significantly increased for megalopae in all treatments 48 microg/l. This delay in development was sufficient to significantly prolong the entire developmental period from zoea to crabs. Unexposed larvae developed to crabs in an average of 16 days; larvae exposed to >/=48 microg/l required 19-20 days. Reduced survival and extended duration of developing larval stages in the life history of a benthic invertebrate may alter the population dynamics of these organisms in the estuary.     

Uptake,distribution and elimination of monosodium methanearsonate following long term oral administration of the herbicide to sheep and goats

Abstract

The rate and extent of accumulation and washout of arsenic, during daily oral administration of the herbicide monosodium methanearsonate (MSMA) were evaluated in Iranian dairy sheep and goats. Subjects received a dose of 10 mg of MSMA as arsenic per kg of body weight daily for 28 consecutive days. The total arsenic concentration in blood and milk was measured during and after the period of MSMA administration while arsenic in urine and feces was measured for 10 days following administration of last dosage of MSMA.

Arsenic was accumulated slowly during 28 days of MSMA administration and steady states were essentially complete in sheep after 20 days and in goats following 25 days of MSMA administration. Blood arsenic concentration decreased rapidly after termination of MSMA administration. In both test animals, the half‐lives of washout were smaller than accumulation. The concentration of arsenic in the urine and feces of both species did not increase significantly over controls and animals were free of arsenic relatively shortly after administration stopped.

These data indicate that arsenic from MSMA is mainly absorbed from gastrointestinal tract and is not significantly accumulated in the body. Arsenic is eliminated from body by way of urine and feces with urinary excretion being the most important route.     

A study of ground water contamination by arsenic in the residential area of Behala, Calcutta due to industrial pollution

Due to the discharge of industrial effluent after production of the insecticide Paris-Green [Copper acetoarsenite Cu(CH(3)COO)(2).3Cu(AsO(2))(2)] by a local factory at the P. N. Mitra Lane, Behala, ground water has become contaminated with arsenic. More than seven thousand people were using this arsenic contaminated tube-well water for drinking and house-hold purposes. Many people of the area were hospitalised and symptoms of arsenic toxicity were visible amongst a large number of the population. Analytical study reveals that soil around the area of effluent dumping point, which is at the middle of the locality, contains a very high concentration of arsenic and copper. For the last 20 years this factory had been producing 20 tons of Paris-Green per year and had been dumping its effluent in that area. It seems, the effluent treatment for arsenic removal was not adequate and finally arsenic percolated to the underground aquifers. Consequently, arsenic concentration in the ground water is very high. Both arsenite and arsenate are present in ground water. An alternate source of water other than the ground water is immediately necessary for the people of P. N. Mitra Lane.     

Spatial distribution and vertical variation of arsenic in Guangdong soil profiles, China

Total of 260 soil profiles were reported to investigate the arsenic spatial distribution and vertical variation in Guangdong province. The arsenic concentration followed an approximately lognormal distribution. The arsenic geometric mean concentration of 10.4 mg/kg is higher than that of China. An upper baseline concentration of 23.4 mg/kg was estimated for surface soils. The influence of soil properties on arsenic concentration was not important. Arsenic spatial distributions presented similar patterns that high arsenic concentration mainly located in limestone, and sandshale areas, indicating that soil arsenic distribution was dependent on bedrock properties than anthropogenic inputs. Moreover, from A- to C-horizon arsenic geometric mean concentrations had an increasing tendency of 10.4, 10.7 to 11.3 mg/kg. This vertical variation may be related to the lower soil organic matter and soil degradation and erosion. Consequently, the soil arsenic export into surface and groundwaters would reach 1040 t year-1 in the study area.     

Arsenic methylation, GSTO1 polymorphisms, and metabolic syndrome in an arseniasis endemic area of southwestern Taiwan

Previous studies have shown that hair arsenic (As) levels are associated with an increased prevalence of metabolic syndrome (MetS), which is a strong predictor for type 2 diabetes. The objective of this study was to evaluate whether urinary arsenic methylation is related to MetS in an arseniasis endemic area of southwestern Taiwan, taking genetic factors into account. Subjects were from a community-based cohort recruited in 1990 from three villages in Putai Township. In 2002-2003, we successfully followed 247 subjects and measured their urinary arsenic species including inorganic arsenic, monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), as well as the coding region polymorphisms of three genes known to involve in arsenic methylation. Results showed that subjects of MetS had a history of consuming well water of higher arsenic concentration as compared to those without MetS. We also found a significant association between urinary arsenic species and risk for MetS, where the odds ratio of MetS was increased with decreasing proportion of MMA and low rate of primary methylation (defined as MMA/inorganic As). The increased risk associated with low primary methylation rate was further modified by the GSTO1 A140D polymorphism, with the D allele carriers showing a slightly higher risk for MetS. Our results suggest that a low MMA% is associated with increased risk for MetS among As-exposed subjects and the genetic polymorphism of GSTO1, an enzyme responsible for the reduction of pentavalent arsenic species, may also play a modest modification role.     

Microbial degradation of arsenobetaine, the major water soluble organoarsenic compound occurring in marine animals

The conversion of arsenobetaine into other arsenic compounds by microorganisms occurring in the bottom sediments from coastal waters was demonstrated for the first time. Three arsenic metabolites were observed on high performance liquid chromatogram during incubation at 25 °C for 80 days in 2 kinds of media, 1/5 ZoBell 2216E and a medium composed of inorganic salts. The time course pattern of arsenic metabolites during incubation was fairly different between these 2 media.     

Contributions of Pesticide use to Urban Background Concentrations of Arsenic in Denver,Colorado, U.S.A.

Soil investigations near a former smelter have revealed that historic use of arsenical pesticides has contributed significantly to anthropogenic background concentrations of arsenic on certain residential properties in Denver, Colorado, U.S.A. Remedial investigation data, based on samples collected in relatively undisturbed locations, had previously indicated that the "upper limit" of background arsenic concentrations was 28 mg/kg in the site vicinity. This value compares reasonably well with more regional data, which indicate increasing arsenic concentrations moving from rural to urban land use. Soil sampling during cleanup, however, revealed the presence of arsenic concentrations of a few hundred to more than 1000 mg/kg on a large number of residential lawns due to historic applications of a crabgrass killer, which was missed by the earlier investigation samples because of the sampling bias toward undisturbed land. Data from over 20,000 soil samples now show that several different populations comprise urban background levels of arsenic and that these populations may be stratified by land use and have spatial patterns that should be considered during any background study. A variety of forensic techniques, including spatial analysis, arsenic speciation, and calculation of metals ratios were necessary to separate the smelter impacts from pesticide impacts.     

The fate and transport of arsenic species in the aquatic ecosystem: a case study on Bestari Jaya,Peninsular Malaysia

The field of arsenic pollution research has grown rapidly in recent years. Arsenic constitutes a broad range of elements from the Earth’s crust and is released into the environment from both anthropogenic and natural sources due to its relative mobility under different redox conditions. The toxicity of arsenic is described in its inorganic form, as inorganic arsenic compounds can leach into different environments. Sampling was carried out in the Bestari Jaya catchment while using a land use map to locate the site, and experiments were conducted via sequential extraction and inductively coupled plasma optical emission spectroscopy to quantify proportions of arsenic in the sediment samples. The results show that metals in sediments of nonresidual fractions, which are more likely to be likely released into aquatic environments, are more plentiful than the residual sediment fractions. These findings support the mobility of heavy metals and especially arsenic through sediment layers, which can facilitate remediation in environments heavily polluted with heavy metals.     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 microg/L to 191 microg/L with a mean concentration of 33 microg/L. Groundwater is mainly Ca-HCO(3) type with high concentrations of dissolved As, Fe, and Mn, but low level of SO(4). The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 microg/L. Deeper aquifer (>100 m depth) has a mean arsenic concentration of 18 microg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

A methodological approach for the identification of arsenic bearing phases in polluted soils

A methodological approach is used to characterize arsenic pollution in three soils and to determine arsenic speciation and association with solid phases in three polluted soils. HPLC-ICP-MS was used for arsenic speciation analysis, SEM-EDS and XRD for physical characterization of arsenic pollution, and sequential chemical extractions to identify arsenic distribution. Arsenic was concentrated in the finest size fractions also enriched in iron and aluminium. Total arsenic concentrations in soils are close to 1%. Arsenic was mainly present as arsenate, representing more than 90% of total arsenic. No crystallised arsenic minerals were detected by XRD analysis. SEM-EDS observations indicated arsenic/iron associations. Modified Tessier's procedure showed that arsenic was mainly extracted from amorphous iron oxide phase. The results of this methodological approach lead to predict the formation of iron arsenates in the case of one of the studied soils while arsenic sorption on iron amorphous (hydr)oxides seemed to be the determinant in the two other soils.     

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators.