Arsenic in drinking water and in scalp hair by EDXRF: A major recent health hazard in Bangladesh

Arsenic content in drinking water and in scalp hair of the arsenic affected areas in Bangladesh were measured using energy dispersive X-ray fluorescence (EDXRF) to determine the contribution of drinking water to body burden and health risks. Around 61% of the water analyzed from tube-wells has arsenic content above 0.05 mg/l and about 13% have arsenic content above 0.01 mg/l. The mean concentration of arsenic in contaminated water is about 0.26 mg/l with the maximum level of 0.83 mg/l. The contaminated water thus contributes a significant amount to the arsenic budget in humans in Bangladesh and consequently, to their health hazards. The average concentration of arsenic in hair of a patient group drinking contaminated water is 14.1 mg/kg where the normal levels are <3.0 mg/kg. The distribution of arsenic in water and in hair is compared and discussed with the data reported in the literature. The daily dietary intake value of arsenic by the adult population in Bangladesh is estimated and assessed signifying health effects.     

Biomethylation of Arsenic in an Arsenic-rich Freshwater Environment

Arsenic circulation in an arsenic-rich freshwater ecosystem was elucidated to detect arsenic species in the river water and in biological samples living in the freshwater environment. Water-soluble arsenic compounds in biological samples were extracted with 70% methanol. Samples containing arsenic compounds in the extracts were treated with 2 mol dm³ of sodium hydroxide and reduced with sodium borohydride. The detection of arsenic species was accomplished using a hydride generation/cold trap/cryofocus/gas chromatography-mass spectrometry (HG/CT/CF/GC-MS) system. The major arsenic species in the river water, freshwater algae and fish are inorganic arsenic, dimethylarsenic and trimethylarsenic compounds, respectively. Trimethylarsenic compounds are also detected in aquatic macro-invertebrates. The freshwater unicellular alga Chlorella vulgaris, in a growth medium containing arsenate, accumulated arsenic and converted it to a dimethylarsenic compound. The water flea Daphnia magna, which was fed on arsenic-containing algae, converted it to a trimethylarsenic species. © 1997 by John Wiley & Sons, Ltd.     

Arsenic determination in soils and hair from schools in past mining activity areas in Ron Phibun district,Nakhon Si Thammarat province,Thailand and relationship between soil and hair arsenic

Arsenic (As) in soils and hair collected from schools in Ron Phibun district, Nakhon Si Thammarat province, Thailand, where former tin mining operation were located, was determined by hydride generation atomic absorption spectrophotometry. The relationship between As content in soils and hair with distance from secured landfill was also investigated. Soil and hair samples were collected from 6 schools in summer (February) and rainy season (July). For soils, silt+clay (<45 µm) fraction and sand (45 µm–2 mm) fraction were analyzed. The average concentrations of arsenic in soils during summer (21.70 ± 16.79 mg/kg) and rainy season (22.45 ± 14.17 mg/kg) were at the same concentration level. The average arsenic content in hair samples was 2.24 ± 0.05 mg/kg in rainy season which was higher than 1.05 ± 0.04 mg/kg in summer. It was found that arsenic contents in hair and soils are correlated with the distance from the secured landfill. Most importantly, a positive relationship between arsenic content in hair and soil was obtained for rainy season, which indicated that arsenic in soil corresponded to arsenic in hair. The cancer risk from soils ranged from 4.48 × 10^?7 to 2.06 × 10^?6 indicating low carcinogenic risk to school children.     

Application of Physicochemical Treatment Allows Reutilization of <Emphasis Type="Italic">Arthrospira platensis</Emphasis> Exhausted Medium

Since cultivations of Arthrospira platensis have a high water demand, it is necessary to develop treatment methods for reusing the exhausted medium that may prevent environmental problems and obtaining useful biomass. The exhausted Schlösser medium obtained from A. platensis batch cultivation in bench-scale mini-tanks was treated by varying concentrations of different coagulants, ferric chloride (6, 10, and 14 mg L^?1) or ferric sulfate (15, 25, and 35 mg L^?1) and powdered activated carbon (PAC, 30 and 50 mg L^?1). Such treated effluent was restored with NaNO₃ and reused in new cultivations of A. platensis performed in Erlenmeyer flasks. Reusing media through the cultivation of A. platensis showed satisfactory results, particularly in the medium treated with ferric chloride and PAC. The maximum cell concentration obtained in the flasks was 1093 mg L^?1, which corresponded to the medium treated with ferric chloride (6 mg L^?1) and PAC (30 mg L^?1). This cellular growth was higher than in the medium treated with ferric sulfate and PAC, in which values of maximum cell concentration did not exceed 796 mg L^?1. The cultures in the media after treatment did not modify the biomass composition. Thus, combined coagulation/adsorption processes, commonly used in water treatment processes, can be efficient and viable for treating exhausted medium of A. platensis, allowing the production of such biomass with the reduction of production cost and saving water.     

Extraction of Arsenic(V) from Water Using Emulsion Liquid Membrane

In this article, the extraction of arsenic(V) from water by means of emulsion liquid membrane is investigated. The influence of operating factors such as stirring speed, concentration of sulfuric acid in the external aqueous phase, concentration of sodium sulfate in internal stripping phase, and concentration of carrier in the membrane phase on the extraction efficiency are investigated and their optimum values, which provide the maximum recovery of arsenic, are determined. Taguchi experimental design is used in order to reduce the number of experiments. The optimum amounts for the extraction of arsenic from water, based on the results, are: stirring speed, 500 rpm; concentration of sulfuric acid in the feed, 1.5 g mol/lit; concentration of reagent in internal phase, 1.5 g mol/lit; and concentration of carrier in 3 ml kerosene which is added to the membrane phase, 0.1 g mol/lit.     

Determination of arsenic in the presence of high copper concentrations using flow-injection analysis-hydride atomic absorption spectrometry

Summary Arsenic is determined in environmental samples containing metal ions up to 10,000 mg/l copper, 200 mg/l lead, 200 mg/l iron and 200 mg/l nickel by using the FIA-hydride-AAS technique. In the presented sample preparation method arsenic is prereduced and the interfering metal ions are precipitated. As signal depressions from metal ions are excluded, a detection limit of 1 g/l arsenic is achieved.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Selective extraction and preconcentration of ultra-trace amounts of arsenic(V) ions using carbon nanotubes as a novel sorbent

In the present study, multiwalled carbon nanotubes (MWCNTs) as solid phase extraction sorbent were developed for preconcentration of arsenic(V) species prior to graphite furnace atomic absorption spectrometry (GFAAS) determination. Arsenic(V) was selectively sorbed on the packed column with MWCNTs within a pH 9.5 in the presence of 2-(5-bromo-2-pyridylazo)-5-diethyl amino phenol (5-Br-PADAP). The adsorbed species was then desorbed with 1 mL of 2.0 M HNO₃. Experimental parameters including pH, sample volume and flow rate, type, volume and concentration of eluent that influence the recovery of the arsenic(V) species were optimised. Under the optimised conditions, the calibration curve was linear in the range of 0.2–10.0 µg L^?1 with detection limit of 0.016 µg L^?1. The relative standard deviations (RSD) for seven replicate determinations at 1.0 µg L^?1 level of arsenic was 6.69%. The proposed method was successfully applied to the determination of arsenic in water samples and certified reference material (NIST RSM 1643e).     

Arsenic speciation in saliva of acute promyelocytic leukemia patients undergoing arsenic trioxide treatment

Arsenic trioxide has been successfully used as a therapeutic in the treatment of acute promyelocytic leukemia (APL). Detailed monitoring of the therapeutic arsenic and its metabolites in various accessible specimens of APL patients can contribute to improving treatment efficacy and minimizing arsenic-induced side effects. This article focuses on the determination of arsenic species in saliva samples from APL patients undergoing arsenic treatment. Saliva samples were collected from nine APL patients over three consecutive days. The patients received 10 mg arsenic trioxide each day via intravenous infusion. The saliva samples were analyzed using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Monomethylarsonous acid and monomethylmonothioarsonic acid were identified along with arsenite, dimethylarsinic acid, monomethylarsonic acid, and arsenate. Arsenite was the predominant arsenic species, accounting for 71.8 % of total arsenic in the saliva. Following the arsenic infusion each day, the percentage of methylated arsenicals significantly decreased, possibly suggesting that the arsenic methylation process was saturated by the high doses immediately after the arsenic infusion. The temporal profiles of arsenic species in saliva following each arsenic infusion over 3 days have provided information on arsenic exposure, metabolism, and excretion. These results suggest that saliva can be used as an appropriate clinical biomarker for monitoring arsenic species in APL patients.

铁基水处理材料除砷技术的研究进展

自然环境中的砷污染问题被认为是全球最严重的环境威胁之一,人类长期暴露于含砷饮用水环境中会引起各种疾病的发生,因此,开发经济有效的除砷技术一直是砷污染治理领域的研究热点。铁基水处理材料由于其对砷的良好亲和力、表面反应活性强、价廉易制、便于回收等特点,一直备受关注。本文综述了近年来不同铁基水处理材料如铁(氢)氧化物、纳米零价铁、铁基多金属氧化物复合材料除砷技术的研究进展,论述了铁基水处理材料对水相中砷去除的影响因素及机理;同时,对影响铁基水处理材料砷解吸的因素和毒性评估研究进行了总结;指出了目前铁基水处理材料砷污染去除技术研究中存在的主要问题,并对水相砷污染去除技术研究中值得关注的重要发展方向进行了展望。     

Arsenic calamity in the Indian subcontinent What lessons have been learned?

Groundwater arsenic (As) contamination in West Bengal (WB, India) was first reported in December 1983, when 63 people from three villages of two districts were identified by health officials as suffering from As toxicity. As of October 2001, the authors from the School of Environmental Studies (SOES) have analyzed >105 000 water samples, >25 000 urine/hair/nail/skin-scale samples, screened approximately 86 000 people in WB. The results show that more than 6 million people in 2700 villages from nine affected districts (total population approximately 42 million) of 18 total districts are drinking water containing >/=50 mug l(-1) As and >300 000 people may have visible arsenical skin lesions. The As content of the physiological samples indicates that many more may be sub-clinically affected. Children in As-affected villages may be in special danger. In 1995, we had found three villages in two districts of Bangladesh where groundwater contained >/=50 mug l(-1) As. The present situation is that in 2000 villages in 50 out of total 64 districts of Bangladesh, groundwater contains As above 50 mug l(-1) and more than 25 million people are drinking water above >/=50 mug l(-1) As. After years of research in WB and Bangladesh, additional affected villages are being identified on virtually every new survey. The present research may still reflect only the tip of iceberg in identifying the extent of As contamination. Although the WB As problem became public almost 20 years ago, there are still few concrete plans, much less achievements, to solve the problem. Villagers are probably in worse condition than 20 years ago. Even now, many who are drinking As-contaminated water are not even aware of that fact and its consequences. 20 years ago when the WB government was first informed, it was a casual matter, without the realization of the magnitude this problem was to assume. At least up to 1994, one committee after another was formed but no solution was forthcoming. None of the expert reports has suggested solutions that involve awareness campaigns, education of the villagers and participation of the people. Initially, international aid agencies working in the subcontinent simply did not consider that As could be present in groundwater. Even now, while As in drinking water is being highlighted, there have been almost no studies on how additional As is introduced through the food chain, as large amounts of As are present in the agricultural irrigation water. Past mistakes, notably the ceaseless exploitation of groundwater for irrigation, continue unabated today; at this time, more groundwater is being withdrawn than ever before. No efforts have been made to adopt effective watershed management to harness the extensive surface water and rainwater resources of this region. Proper watershed management and participation by villagers are needed for the proper utilization of water resources and to combat the As calamity. As in groundwater may just be nature's initial warning about more dangerous toxins yet to come. What lessons have we really learned?     

The speciation of arsenic(V) and arsenic(III), by ion-exclusion chromatography, in solutions containing iron and sulphuric acid

Arsenic(V) and arsenic(III) can be separated, by ion-exclusion chromatography, in solutions containing iron and sulphuric acid. Iron is removed by ion-exchange before the speciation of arsenic, with phosphoric acid as the eluent. The separated arsenic(V) and arsenic(III) are measured spectrophotometrically in the ultraviolet region at a wavelength of 195 mn. Arsenic(V) and arsenic(III) can be determined at concentrations > or = 3 mg/1. The relative standard deviations are 1.3% for arsenic(V) and 0.9% for arsenic(III), at the 10 mg/1. level. The time required for the separation of the inorganic arsenic species is 11 min.     

Phytoremediation of arsenic by two hyperaccumulators in a hydroponic environment

Phytofiltration involves the use of plants to remove toxic compounds from water. Arsenic is an element of considerable environmental and toxicological interest because of its potential deleterious effects upon human health. In this research, a laboratory-constructed hydroponic system was employed to characterize phytofiltration for the uptake of arsenic and macronutrients by two arsenic hyperaccumulators, Pteris cretica cv Mayii (Moonlight fern) and Pteris vittata (Chinese brake fern). Arsenic was shown to preferentially accumulate in the leaves and stems of P. cretica cv Mayii compared to roots. The amounts of the macronutrients calcium and phosphorous absorbed were compared for control plants (growth solution) and plants exposed to arsenic(III) (growth solution and arsenic(III)). Significant differences in the concentration levels of the macronutrients were observed in roots, stems, and leaves between the control and arsenic-exposed plants. The arsenic contents of entire P. vittata plants exposed to hydroponic solutions containing arsenic(III) and arsenic(V) were compared, and no significant difference was observed.     

Arsenic concentration and speciation in infant formulas and first foods

Arsenic exposure to humans is pervasive, and, increasingly, studies are revealing adverse health effects at ever lower doses. Drinking water is the main route of exposure for many individuals; however, food can be a significant source of arsenic to an individual, especially if their diet is rice-based. Infants are particularly susceptible to dietary exposure, since many first foods contain rice and they have a low body mass. Here we report on arsenic concentration and speciation in infant formulas and first foods. Speciation is essential for food analysis because of the much greater toxicity of inorganic arsenic species and the possibility that arsenic in food (unlike water) may be present in either inorganic or organic forms. Infant milk formulas were low in total arsenic (2.2-12.6 ng g(-1), n=15). Non-dairy formulas were significantly higher in arsenic than dairy-based formulas. Arsenic in formula was almost exclusively inorganic and predominantly arsenic(V). Arsenic concentration in purees (n=41) and stage 3 foods (n=18) ranged from 0.3-22 ng g(-1). Rice-fortified foods had significantly higher total arsenic concentrations than non rice-based foods. Again arsenic speciation was predominantly inorganic; arsenic(III) was the main species with lower concentrations of DMA and arsenic(V) also present. These data confirm that infants are exposed to arsenic via diet, and suggest that careful attention to diet choices may limit this.     

Electrochemical measurement and speciation of inorganic arsenic in groundwater of Bangladesh

The presence of arsenic in groundwater above the maximum permissible limit of 50 mug l(-1) has threatened the health of more than 50 million people in Bangladesh and neighboring India. We report here the development of an inexpensive anodic stripping voltammetric (ASV) technique for routine measurement and speciation of arsenic in groundwater. The measurements are validated by more expensive atomic absorption, atomic emission and other techniques. To understand the present situation in Bangladesh, we measured As(III) in 960 water samples collected from 18 districts. A random distribution of 238 samples was used to measure both As(III) and As(V). The results from the present study indicate that most toxic form of inorganic arsenic, As(III), has the broad range of 30-98%. It shows 60% of the samples have 10 mug l(-1) and 44% of the samples have 50 mug l(-1) or more As(III). The fractional distribution pattern shows significant skew towards high percent occurrence which may indicate a progressive reduction process with a single source or a single mechanism for the formation of As(III). For direct consumption, this is possibly one of the most toxic groundwater known today. Speciation distribution at groundwater pH value shows H(3)AsO(3) is the predominant species including H(2)AsO(4)(-) and H(2)AsO(4)(2-) whose distribution is significantly pH dependent. This is also supported by E(h)-pH measurements. The depth distribution for Kushtia shows most of the As(III) is located within 100-200 ft deep aquifers. Similar fractional distribution of As(III) is found in deeper aquifers and may indicate contamination by leakage from upper aquifer. This study clearly demonstrates the aquifer environment is reductive and conducive to the formation of As(III) species.     

Arsenic Compounds in Terrestrial Organisms II: Arsenocholine in the Mushroom Amanita muscaria

Arsenic compounds were identified and quantified in the mushroom Amanita muscaria, collected close to a facility that had roasted arsenic ores. The powdered dried mushrooms were extracted with methanol/water (9:1), the extracts were concentrated and the concentrates were dissolved in water. The resulting solutions were chromatographed on anion-exchange, cation-exchange and reversed- phase columns. Arsenic was detected on-line with an ICP–MS detector equipped with a hydraulic high-pressure nebulizer. Arsenite, arsenate, dimethylarsinic acid and the tetramethylarsonium cation were minor arsenic compounds (∼2% each of the total 22 mg kg⁻¹ dry mass), and arsenobetaine, arsenocholine (∼15% each) and several unidentified arsenic compounds (∼60%) were the major arsenic compounds in Amanita muscaria. The presence of arsenocholine (detected for the first time in a terrestrial sample) was ascertained by matching retention times in the anion-exchange, cation- exchange and reversed-phase chromatograms with the retention time of synthetic arsenocholine bromide and chromatographing extracts spiked with arsenocholine bromide. © 1997 John Wiley & Sons, Ltd.     

Uptake and excretion of total inorganic arsenic by the freshwater alga Chlorella vulgaris

Arsenic-tolerant freshwater alga Chlorella vulgaris which had been collected from an arsenicpolluted environment were tested for uptake and excretion of inorganic arsenic. Approximately half the quantity of arsenic taken up by C. vulgaris was estimated to be adhered to the extraneous coat (10 wt %) of the cell. The remainder was bioaccumulated by the cell. Both adhered and accumulated arsenic concentrations increased with an increase in arsenic(V) concentration of the aqueous phase. Arsenic(V) accumulation was affected by the growth phse: arsenic was most actively accumulated when the cell was exposed to arsenic during the early exponential phase and then accumulation decreased with an increase in culture time exposed to arsenic. The alga grew well in the modified Detmer (MD) medium containing 1 mg As(III) dm^?3 and the growth curve was approximated by a ‘logistic equation’. Arsenic(III) was accumulated up to the second day of the culture time and arsenic(III) accumulation decreased with an increase in the culture time after that. Arsenic accumulation was also largely affected by various nutrients, especially by managanese, iron and phosphorus compounds. A modified MD medium with the three nutrients was proposed for the purpose of effective removal of arsenic from the aqueous phase. Using radioactive arsenate (Na₂H⁷⁴AsO₄), the arsenic accumulated was found to be readily excreted under conditions which were unfavourable for the multiplication of C. vulgaris.     

Hydride Generation Atomic Fluorescence Spectrometric Determination of Ultratrace Arsenic in High Purity Indium Oxide

A simple, sensitive, and interference free method was proposed for the determination of total arsenic in high purity indium oxide by hydride generation atomic fluorescence spectrometry (HG-AFS). Preconcentration was carried out by distillation of volatile arsenic trichloride. Hydrazine sulfate was used as a prereductant to reduce As (V) to As (III). The volatile arsenic trichloride generation was based on the reaction between As (III) and hydrochloric acid, and vapors were absorbed with water. The method provides a linear response range of 2 ng/mL–70 ng/mL, a detection limit of 0.1 ng/mL, a recovery of 96%–113%, and an average relative standard deviation of 2.42%. The method was validated by means of interlaboratory comparative analysis with the proposed method HG-AFS, and the comparison of data by using proposed method HG-AFS and reference methods of ICP-OES and spectrophotometry.     

Arsenic contamination in groundwater: some analytical considerations

For countries such as Bangladesh with a significant groundwater arsenic problem, there is an urgent need for the arsenic-contaminated wells to be identified as soon as possible and for appropriate action to be taken. This will involve the testing of a large number of wells, potentially up to 11 million in Bangladesh alone. Field-test kits offer the only practical way forward in the timescale required. The classic field method for detecting arsenic (the 'Gutzeit' method) is based on the reaction of arsine gas with mercuric bromide and remains the best practical approach. It can in principle achieve a detection limit of about 10 mug l(-1) by visual comparison of the coloured stain against a colour calibration chart. A more objective result can be achieved when the colour is measured by an electronic instrument. Attention has to be paid to interferences mainly from hydrogen sulfide. Due to analytical errors, both from the field-test kits and from laboratory analysis, some misclassification of wells is inevitable, even under ideal conditions. The extent of misclassification depends on the magnitude of the errors of analysis and the frequency distribution of arsenic observed, but is in principle predictable before an extensive survey is undertaken. For a country with an arsenic distribution similar to that of Bangladesh, providing care is taken to avoid sources of bias during testing, modern field-test kits should be able to reduce this misclassification to under 5% overall.     

Differential preconcentration of arsenic(III) and arsenic(V) with thionalide loaded on silica gel

2-Mercapto-N-2-naphtylacetamide (thionalide) on silica gel is used for differential preconcentration of μg l^?1 levels of arsenic(III) and arsenic(V) from aqueous solution. In batch experiments, arsenic(III) was quantitatively retained on the gel from solutions of pH 6.5–8.5, but arsenic(V) and organic arsenic compounds were not retained. The chelating capacity of the gel was 5.6 μmol g^?1 As(III) at pH 7.0. Arsenic retained on teh column was completely eluted with 25 ml of 0.01 M sodium borate in 0.01 M sodium hydroxide containing 10 mg l^?1 iodine (pH 10). The arsenic was determined by silver diethyldithiocarbamate spectrophotometry. Arsenic(V) was subsequently determined after reduction to arsenic(III) with sulphite and iodide. Arsenic(III) and arsenic(V) in sea water are shown to be < 0.12 and 1.6 μg l^?1, respectively.     

Blue light induces arsenate uptake in the protist Thraustochytrium

The effects of light on arsenic accumulation of Thraustochytrium CHN‐1 were investigated. Thraustochytrium CHN‐1, when exposed to blue light from light‐emitting diodes (LEDs), accumulated arsenate added to its growth medium to a much greater extent than Thraustochytrium cells exposed to fluorescent or red light, or when cultured in the dark. Arsenic compounds in Thraustochytrium CHN‐1 were analyzed by high‐performance liquid chromatography, with an inductively coupled plasma mass spectrometer serving as an arsenic‐specific detector. Arsenate, arsenite, monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA) and arsenosugar were identified. The order of arsenic species in Thraustochytrium CHN‐1 was arsenic(V)> arsenic(III)> MMAA > DMAA at an arsenic concentration of 10 mg dm^?3 in the medium in blue LED light. As it is known that blue light induces the synthesis of certain metabolites in plants and microorganisms, this indicates that the accumulation of arsenic is an active metabolic process. Copyright © 2005 John Wiley & Sons, Ltd.