Sediment geochemistry and arsenic mobilization in shallow aquifers of the Datong basin,northern China

Understanding the mechanism of arsenic (As) mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Datong basin in northern China. The bulk geochemistry analysis of sediment samples from three 50-m boreholes drilled specifically for this study at As-contaminated aquifers, the groundwaters of which have an As concentration up to 1060 μg/l, revealed that the average bulk concentrations of major and trace elements of the samples are similar to those of the average upper continental crust. The average As content of the sediment samples (18.7 mg/kg) is higher than that of modern unconsolidated sediments (5–10 mg/kg). Moreover, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments, such as silt and clay. The concentration of NH₂OH–HCl-extracted iron (Fe) strongly correlated with that of extracted As, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. The results of microcosm experiments showed that As mobilization from sediments to groundwater is probably mainly related to changes in the redox conditions, with moderately reducing conditions being favorable for As release from sediments into groundwater.     

The arsenic content of bottled mineral waters

The arsenic levels of 23 mineral waters on sale to the public in the United Kingdom were measured. The arsenic content of most waters was below 1 g L^–1 but the statutory limits of 50 ug L^–1 for natural mineral waters and 100 g L^–1 for non-alcoholic beverages were exceeded by the French mineral water, Vichy Célestins (220 ug L^–1). Regular consumption of mineral water of such elevated concentration could make a significant contribution to the intake of the more toxic inorganic species of arsenic, with possible adverse long-term effects on the health of some individuals. The general need for analytical speciation studies of dietary arsenic is emphasised.     

The influence of arsenic speciation (AsIII & AsV) and concentration on the growth, uptake and translocation of arsenic in vegetable crops (silverbeet and amaranth): greenhouse study

We examined arsenic (As) uptake by vegetable crops (amaranth, Amaranthus gangeticus, and silverbeet, Beta vulgaris) as affected by As speciation (As^III and As^V) and their concentrations in nutrient solution. Amaranth and silverbeet were grown in a nutrient solution containing four levels of arsenate (As^V): 0, 1, 5, and 25 mg As/l and three levels of arsenite (As^III): 0, 5, 10 mg As/l. Both As^V and As^III are phytotoxic to these crops with the latter being five times more toxic. Amaranth treated with As^III exhibited As toxicity symptoms within 48 h of exposure and was close to death within 1 week. However, As^V treatment did not show clear toxicity symptoms other than wilting and yield reduction at the highest dose rate of 25 mg As^V/l. The main mechanism used by vegetable crops to tolerate As^V is probably avoidance—limiting As transport to shoots and increasing As accumulation in the root system. When As^V was added to the nutrient solution, the uptake of As in shoots increased and, at the highest dose (25 mg As^V/l), 60 μg As/g DW (3.6 mg/kg FW) accumulated in the edible portion, which exceeds the WHO recommended limit for food stuffs (2 mg/kg FW) as the water contents of the crops were 94%. It is therefore important to determine the nature of the As species and their bio-accessibility. Iron treatment with 0.5 mg NaFe(III)EDTA/l dose decreased silverbeet As uptake by 45% given its affinity to bind As at the root surface or root rhizosphere and so restrict As translocation to the shoots.     

Lung function decrement with arsenic exposure to drinking groundwater along River Indus: a comparative cross-sectional study

This study was designed to determine the association between chronic arsenic exposure through drinking groundwater and decrement in lung function, particularly among individuals who do not have signs of arsenic lesions, among an adult population. This was a comparative cross-sectional study conducted during the months of January to March 2009. One hundred participants ≥15 years of age in each group, i.e. exposed (≥100 μg/l) and unexposed (≤10 μg/l) to arsenic, determined by testing drinking water samples (using portable kits), were compared for effects on lung function using spirometry. A structured and validated questionnaire was administered. Examination for arsenic skin lesions was also done. There was a decline in the mean adjusted FEV1 of 154.3 ml (95% CI: −324.7, 16.0; p = 0.076), in mean adjusted FVC of 221.9 ml (95% CI: −419.5, −24.3; p = 0.028), and in FEV1/FVC ratio of 2.0 (95% CI: −25.3, 29.4; p = 0.884) among participants who were exposed to arsenic compared to those unexposed. A separate model comprising a total of 160 participants, 60 exposed to arsenic concentrations ≥250 μg/l and 100 unexposed at arsenic concentrations of ≤10 μg/l, showed a decrement in mean adjusted FEV1 of 226.4 ml (95% CI: −430.4, −22.4; p = 0.030), in mean adjusted FVC of 354.8 ml (95% CI: −583.6, −126.0; p = 0.003), and in FEV1/FVC ratio of 9.9 (95% CI: −21.8, 41.6; p = 0.539) among participants who were exposed to arsenic in drinking groundwater. This study demonstrated that decrement in lung function is associated with chronic exposure to arsenic in drinking groundwater, occurring independently, and even before any manifestation, of arsenic skin lesions or respiratory symptoms. The study also demonstrated a dose-response effect of arsenic exposure and lung function decrement.     

Determination of arsenic in crude petroleum and liquid hydrocarbons

Total arsenic was determined in crude petroleum and liquid hydrocarbons derived from crude petroleum by extraction with boiling water or boiling aqueous nitric acid (concentration 0.25 to 2.5 M), mineralization of the extracts with concentrated nitric/sulphuric acid, and reduction of the arsenate to arsine in a hydride generator. The arsine was flushed into a helium-DC plasma. The arsenic emission was monitored at 228.8 nm. The total arsenic concentration in 53 crude oil samples ranged from 0.04 to 514 mg L^–1 (median 0.84 mg L^–1). Arsenic was also determined in several refined liquid hydrocarbons and in a commercially available arsenic standard in an organic matrix (triphenylarsine in xylene). The method was checked with NIST 1634b Trace Elements in Residual Fuel Oil. The arsenic concentration found in this standard agreed with the certified value (0.12±0.2 g g^–1) within experimental error. Viscous hydrocarbons such as the fuel oil must be dissolved in xylene for the extraction to be successful. Hydride generation applied to an aqueous not-mineralized extract from an oil containing 1.67 g As mL^–1 revealed, that trimethylated arsenic (520 ng mL^–1) is the predominant arsenic species among the reducible and detectable arsenic compounds. Monomethylated arsenic (104 ng ml^–1), inorganic arsenic (23 ng mL^–1), and dimethylated arsenic (low ng mL^–1) were also detected. The sum of the concentrations of these arsenic species accounts for only 39% of the total arsenic in the sample.On leave from Department of Chemistry, Indian Institute of Technology, New Delhi, India     

Field based speciation of arsenic in UK and Argentinean water samples

A field method is reported for the speciation of arsenic in water samples that is simple, rapid, safe to use beyond laboratory environments, and cost effective. The method utilises solid-phase extraction cartridges (SPE) in series for selective retention of arsenic species, followed by elution and measurement of eluted fractions by inductively coupled plasma mass spectrometry (ICP-MS) for “total” arsenic. The method is suitable for on-site separation and preservation of arsenic species from water. Mean percentage accuracies (n = 25) for synthetic solutions of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA), and dimethylarsinic acid (DMA) containing 10 μg l⁻¹ As, were 98, 101, 94, and 105%, respectively. Data are presented to demonstrate the effect of pH and competing anions on the retention of the arsenic species. The cartridges were tested in the UK and Argentina at sites where arsenic was known to be present in surface and groundwaters, respectively, at elevated concentrations and under challenging matrix conditions. In Argentinean groundwater, 4–20% of speciated arsenic was present as MA and 20–73% as As^III. In UK surface waters, speciated arsenic was measured as 7–49% MA and 12–42% DMA. Comparative data from the field method using SPE cartridges and the laboratory method using liquid chromatography coupled to ICP-MS for all water samples provided a correlation of greater than 0.999 for As^III and DMA, 0.991 for MA, and 0.982 for As^V (P < 0.01).     

A seasonal study of arsenic in groundwater,Snohomish County,Washington, USA

A series of arsenic poisonings near Granite Falls in Snohomish County, Washington, were identified during 1985–87. An initial investigation revealed the source of arsenic exposure to be high levels of arsenic in well water. A large number of wells in eastern Snohomish County were tested, residents were interviewed and sources of contamination, both natural and man-made, were investigated. More than 70 private drinking-water wells were found to contain elevated levels of arsenic . One well contained 33 mg As L^–1. The finding of elevated arsenic levels in a previously approved drinking-water well for a restaurant, plus suggestions of symptoms consistent with arsenic poisoning among people with wells with no detectable arsenic, raised concern over possible temporal variation in arsenic levels. To evaluate this temporal variation, a 12-month study of arsenic in groundwater was conducted in selected wells near Granite Falls. The 12-month study of 26 wells, conducted between February 1988 and January 1989, found arsenic levels for individual wells to vary from one to 19 fold over time. Because of this variability, four out of the eight wells with arsenic levels close to the Maximum Contamination Level (MCL) of 0.050 mg As L^–1 would have been considered safe on the basis of a single sample, but would have exceeded the MCL at another time of the year.In areas with a high occurrence of arsenic contaminated drinking water, approval of well water prior to the sale of a house or issuance of a building permit which is based on a single arsenic test may result in later findings of unacceptable drinking water. When the arsenic is near the MCL, it may be prudent to follow well-water arsenic concentrations over time to assure that the arsenic level remains within acceptable bounds. If lower arsenic standards are adopted for drinking water, the issue of temporal variation around the standard will become a matter of more widespread concern.To whom correspondence should be addressed. The contents of this paper do not necessarily reflect the views and policies of the US Environmental Protection Agency.     

Arsenic contamination in water,soil, sediment and rice of central India

Arsenic contamination in the environment (i.e. surface, well and tube-well water, soil, sediment and rice samples) of central India (i.e. Ambagarh Chauki, Chhattisgarh) is reported. The concentration of the total arsenic in the samples i.e. water (n=64), soil (n=30), sediment (n=27) and rice grain (n=10) were ranged from 15 to 825 μg L⁻¹, 9 to 390 mg kg⁻¹, 19 to 489 mg kg⁻¹ and 0.018 to 0.446 mg kg⁻¹, respectively. In all type of waters, the arsenic levels exceeded the permissible limit, 10 μg L⁻¹. The most toxic and mobile inorganic species i.e. As(III) and As(V) are predominantly present in water of this region. The soils have relatively higher contents of arsenic and other elements i.e. Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Ga, Zr, Sn, Sb, Pb and U. The mean arsenic contents in soil of this region are much higher than in arsenic soil of West Bengal and Bangladesh. The lowest level of arsenic in the soil of this region is 3.7 mg kg⁻¹ with median value of 9.5 mg kg⁻¹. The arsenic contents in the sediments are at least 2-folds higher than in the soil. The sources of arsenic contamination in the soil of this region are expected from the rock weathering as well as the atmospheric deposition. The environmental samples i.e. water, soil dust, food, etc. are expected the major exposure for the arsenic contamination. The most of people living in this region are suffering with arsenic borne diseases (i.e. melanosis, keratosis, skin cancer, etc.).     

Fractionation and speciation of arsenic in fresh and combusted coal wastes from Yangquan, northern China

In this study, the content and speciation of arsenic in coal waste and gas condensates from coal waste fires were investigated, respectively, using the digestion and sequential extraction methods. The fresh and fired-coal waste samples were collected from Yangquan, which is one of the major coal production regions in northern China. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to determine the concentrations of four major arsenic species [As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA)] in the extracts, while ICP-MS was used to measure total As content. Arsenic content in the investigated coal wastes and the condensate ranges between 23.3 and 69.3 mg/kg, which are higher than its reported average content in soils. Arsenic in coal waste exists primarily in the residual fraction; this is followed in decreasing order by the organic matter-bound, Fe–Mn oxides-bound, exchangeable, carbonates-bound, and water-soluble fractions. The high content of arsenic in the condensates indicates that combustion or spontaneous combustion is one of the major ways for arsenic release into the environment from coal waste. About 15% of the arsenic in the condensate sample is labile and can release into the environment under leaching processes. The water extractable arsenic (WEA) in the fresh coal waste, fired coal wastes, and the condensate varied between 14.6 and 341 μg/kg, with As(V) as the major species. Furthermore, both MMA and DMA were found in fresh coal wastes, fired coal wastes, and the condensate.     

Mobilization of arsenic from technosols in a short-term dynamic column experiment

The release of arsenic from technosols was monitored using short-term dynamic leaching of homogeneous soil columns with native solution. Large amounts of readily available arsenic (16 mg kg^?1) were extracted from arsenic-rich ashy samples while representing less than 4 wt % of their total contents. In the first hour of leaching, the observed concentrations of water-soluble arsenic ranged from 650 to 830 μg L^?1, further increasing in the following leachates. The results showed that the concentrations of water-soluble arsenic were several times higher than the recommended limits for drinking water. Yet, most of arsenic is strongly bound to amorphous aluminosilicate phases. The contents of arsenic in the studied plant samples, including calculated transfer factors, confirmed that increased concentrations of arsenic in the soil of geological environment affected by dam failure of a coal ash pond may have a negative effect on crops since arsenic becomes part of the food chain.     

Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes.     

Tracing the factors responsible for arsenic enrichment in groundwater of the middle Gangetic Plain,India: a source identification perspective

Arsenic contamination in groundwater is of increasing concern because of its high toxicity and widespread occurrence. This study is an effort to trace the factors responsible for arsenic enrichment in groundwater of the middle Gangetic Plain of India through major ion chemistry, arsenic speciation, sediment grain-size analyses, and multivariate statistical techniques. The study focuses on the distinction between the contributions of natural weathering and anthropogenic inputs of arsenic with its spatial distribution and seasonal variations in the plain of the state Bihar of India. Thirty-six groundwater and one sediment core samples were collected in the pre-monsoon and post-monsoon seasons. Various graphical plots and statistical analysis were carried out using chemical data to enable hydrochemical evaluation of the aquifer system based on the ionic constituents, water types, hydrochemical facies, and factors controlling groundwater quality. Results suggest that the groundwater is characterized by slightly alkaline pH with moderate to strong reducing nature. The general trend of various ions was found to be Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ > NH₄ ⁺; and HCO₃ ⁻ > Cl⁻ > SO₄ ²⁻ > NO₃ ⁻ > PO₄ ³⁻ > F⁻ in both seasons. Spatial and temporal variations showed a slightly higher arsenic concentration in the pre-monsoon period (118 μg/L) than in the post-monsoon period (114 μg/L). Results of correlation analyses indicate that arsenic contamination is strongly associated with high concentrations of Fe, PO₄ ³⁻, and NH₄ ⁺ but relatively low Mn concentrations. Further, the enrichment of arsenic is more prevalent in the proximity of the Ganges River, indicating that fluvial input is the main source of arsenic. Grain size analyses of sediment core samples revealed clay (fine-grained) strata between 4.5 and 7.5 m deep that govern the vertical distribution of arsenic. The weathering of carbonate and silicate minerals along with surface-groundwater interactions, ion exchange, and anthropogenic activities seem to be the processes governing groundwater contamination, including with arsenic. Although the percentage of wells exceeding the permissible limit (50 μg/L) was less (47%) than that reported in Bangladesh and West Bengal, the percentage contribution of toxic As(III) to total arsenic concentration is quite high (66%). This study is vital considering that groundwater is the exclusive source of drinking water in the region and not only makes situation alarming but also calls for immediate attention.     

Bioaccessible arsenic in soil of thermal areas of Viterbo,Central Italy: implications for human health risk

Environmental Geochemistry and Health - Thermal waters near the city of Viterbo (Central Italy) are known to show high As contents (up to 600&nbsp;µg/l). Travertine is precipitated by...     

Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

Automated method for the determination of total arsenic and selenium in natural and drinking water by HG-AAS

A multicommutated flow system was designed and evaluated for the determination of total arsenic and selenium by Hydride Generation Atomic Absorption Spectrometry (HG-AAS). It was applied to the determination of arsenic and selenium in samples of natural and drinking water. Detection limits were 0.46 and 0.08 μg l⁻¹ for arsenic and selenium, respectively; sampling frequency was 120 samples h⁻¹ for arsenic and 160 samples h⁻¹ for selenium. Linear ranges found were 1.54–10 μg l⁻¹ (R = 0.999) for arsenic and 0.27–27 μg l⁻¹ (R = 0.999) for selenium. Accuracy was evaluated by spiking various water samples and using a reference material. Recoveries were in the range 95–116%. Analytical precision (s _r (%), n = 10) was 6% for both elements. Compared with the Standard Methods, APHA, 3114B manual method, the system consumes at least 10 times less sample per determination, and the quantities of acid and reducing agent used are significantly lower with a reduction in the generation of pollutants and waste. As an additional advantage, the system is very fast, efficient and environmentally friendly for monitoring total arsenic and selenium levels in waters.     

Screening of Cucumis sativus as a new arsenic-accumulating plant and its arsenic accumulation in hydroponic culture

Phytoextraction is a remediation technology with a promising application for removing arsenic (As) from soils and waters. Several plant species were evaluated for their As accumulation capacity in hydroponic culture amended with As. Cucumis sativus (cucumber) displayed the highest tolerance against As among 4 plants tested in this study (corn, wheat, sorghum and cucumber). The germination ratio of Cucumis sativus was more than 50% at the high concentration of 5,000 mg-As/l. In Cucumis sativus grown in a solution contaminated with 25 mg-As/l, the accumulated As concentrations in the shoot and root were 675.5 ± 11.5 and 312.0 ± 163.4 mg/kg, respectively, and the corresponding values of the translocation and bioaccumulation factors for As were 1.9 ± 0.9 and 21.1 ± 8.4, respectively. These results indicate Cucumis sativus is to be a candidate plant for phytoextraction of As from soils and water.     

An assessment of sampling,preservation, and analytical procedures for arsenic speciation in potentially contaminated waters

This study was undertaken to ascertain optimal methods of sampling, preserving, separating, and analyzing arsenic species in potentially contaminated waters. Arsenic species are readily transformed in nature by slight changes in conditions. Each species has a different toxicity and mobility. The conventional field sampling method using filters of 0.45 μm in size could overestimate the dissolved arsenic concentrations, as passing suspended particles that can act as a sink or source of arsenic depending on the site condition. For arsenic species in neutral pH and iron-poor waters, the precipitation can be stable for up to 3 days without any treatment, but for longer periods, a preservative, such as phosphoric acid, is required. Also, the analytical procedure must be selected carefully because the levels and hydride generation efficiencies of arsenic in different species can vary, even for the same amount of arsenic. For arsenic speciation in samples that also include organic species, a hybrid high-performance liquid chromatography (HPLC) column and inductively coupled plasma mass spectrometry (ICP-MS) gave the best resolution and lowest detection limits. However, the procedure using a solid phase extraction (SPE) cartridge can be used economically and conveniently for analyzing samples containing only inorganic arsenic species, such as groundwater, especially that related to mine activity.     

黄土性土壤对砷的净化作用及迁移规律研究

通过土柱淋滤试验,从动态角度研究了黄土性土壤对砷的净化作用及迁移规律。研究结果表明,黄土性土壤对砷是一次性的吸附净化并达到饱和状态。土壤对砷净化吸附分为3个阶段:全吸附段、部分吸附段和吸附饱和段。受土壤粘粒和钙影响,黄土性土壤中砷运移的速度不同,其顺序为v(粘化层)相似文献   

Environmental geochemistry study of arsenic in Western Hunan mining area,P.R. China

The geochemical characteristics of arsenic in the soil of the Western Hunan mining area of P.R. China were systematically studied. The results show that the strata of Western Hunan are rich in arsenic and that Western Hunan is a geochemically abnormal region for arsenic. The experimental study on speciation in the strata also indicates that the speciation of arsenic in the Neoproterozoic-Cambrian strata are mainly easily transferred speciation (exchangeable, carbonate-bound, sulfides-bound), which are approaching or exceed 60%. Arsenic content in the main soil of Western Hunan is in the range of 8.8–22.8 μg g⁻¹, the mean value is 16.1 μg g⁻¹, which is larger than the arsenic background value of Hunan soil. The distribution of rock with high arsenic content or high easily transferred arsenic speciation is consistent with the distribution of high arsenic content soil. In the mining region, part soils and river/brook waters were polluted by mine tailings and mining/smelting waste water. The arsenic content in polluted paddy soils and river/brook water is 46.26–496.19 μg g⁻¹, 0.3–16.5 mgL⁻¹, respectively. The positive abnormality and pollution of arsenic in the soil and water affects the arsenic content of the crop and the inhabitants’ health.     

In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 μg/L.