A pH-based biosensor for detection of arsenic in drinking water

Arsenic contaminated groundwater is estimated to affect over 100 million people worldwide, with Bangladesh and West Bengal being among the worst affected regions. A simple, cheap, accurate and disposable device is required for arsenic field testing. We have previously described a novel biosensor for arsenic in which the output is a change in pH, which can be detected visually as a colour change by the use of a pH indicator. Here, we present an improved formulation allowing sensitive and accurate detection of less than 10 ppb arsenate with static overnight incubation. Furthermore, we describe a cheap and simple high-throughput system for simultaneous monitoring of pH in multiple assays over time. Up to 50 samples can be monitored continuously over the desired time period. Cells can be stored and distributed in either air-dried or freeze-dried form. This system was successfully tested on arsenic-contaminated groundwater samples from the South East region of Hungary. We hope to continue to develop this sensor to produce a device suitable for field trials.     

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.     

Effect of gamma-radiation on the Sn(II) content,radiochemical purity,in-vitro stability and biological distribution of some99mTc-labelled freeze dried kits

Gamma-irradiation can be used for the sterilization of some^99mTc-labelled freeze dried kits. In connection with this the effect of -radiation on Sn(II) content, radiochemical purity,in-vitro stability and biological distribution of some currently used^99mTc-labelled kits has been investigated. For irradiation the certain radiation sterilization doses (25 and 50 kGy) were used. A variable decrease of Sn(II) content was observed in all -irradiated kits. The losses are in the order of 10–25% compared with the Sn(II) content of original ones. The colour of the irradiated kits did not changed except DTPA which developed yellow colour after irradiation. For the irradiated and original kits nearly the same pH were found. The irradiated kits seemed to undergo partial decomposition or chemical alteration which led to some deviation of the biological distribution of them.     

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.     

Normalisation of data from allergens proficiency tests

The problem of allergen analysis using ELISA kits from different commercial products giving significantly different results is widely acknowledged. The effect on proficiency testing results is that different assigned values have to be generated for the different kits used. Some experimental Food Analysis Performance Assessment Scheme (FAPAS) proficiency tests aimed to establish whether the use of a standardised calibrant could be used to normalise the complete data set without recourse to differentiation. Three recent FAPAS proficiency tests (2776 peanut, 2778 soya and 2781 gluten) sent out a second spiked sample, in addition to the usual spiked and unspiked samples. Further analysis of the data was undertaken after the completion of the tests. The ratio of the submitted results for the two spiked samples yielded complete data sets which could be tested for normality of the distribution. Where the raw data for each individual test sample was clearly non-normal and multi-modal, the ratio data yielded a much more normal and symmetrical distribution. The use of one of the test samples as a single-point calibrant has some limitations but the principle of applying a standardisation clearly works. The development of internationally recognised sets of certified reference calibration standards for use by allergens testing laboratories would greatly benefit the analysis.     

Design and model of calibration for chemical measurements

The international standard ISO 11843 specifies basic methods to design experiments for estimation of critical values referring to the capability of detection. The detection capability depends on the experimental design, the calibration model used, and the errors of the measurement process. This study reports how the specification of the calibration points within the calibration range can be used as a-priori information for evaluation of calibration uncertainty without any consideration of the response variables of the calibration. As result of investigation of the experimental designs, calibration points within the calibration range can be omitted without significant changes of calibration uncertainty. The approach is demonstrated at a practical example, the determination of arsenic in surface water samples taken from a river in Germany.     

Speciation analysis of arsenic in groundwater from Inner Mongolia with an emphasis on acid-leachable particulate arsenic

Arsenic in drinking water affects millions of people around the world. While soluble arsenic is commonly measured, the amount of particulate arsenic in drinking water has often been overlooked. We report here determination of the acid-leachable particulate arsenic and soluble arsenicals in well water from an arsenic-poisoning endemic area in Inner Mongolia, China. Water samples (583) were collected from 120 wells in Ba Men, Inner Mongolia, where well water was the primary drinking water source. Two methods were demonstrated for the determination of soluble arsenic species (primarily inorganic arsenate and arsenite) and total particulate arsenic. The first method used solid phase extraction cartridges and membrane filters to separate arsenic species on-site, followed by analysis of the individual arsenic species eluted from the cartridges and filters. The other method uses liquid chromatography separation with hydride generation atomic fluorescence detection to determine soluble arsenic species. Analysis of acidified water samples using inductively coupled plasma mass spectrometry provided the total arsenic concentration. Arsenic concentrations in water samples from the 120 wells ranged from <1 to ∼1000 μg L⁻¹. On average, particulate arsenic accounted for 39 ± 38% (median 36%) of the total arsenic. In some wells, particulate arsenic was six times higher than the soluble arsenic concentration. Particulate arsenic can be effectively removed using membrane filtration. The information on particulate and soluble arsenic in water is useful for optimizing treatment options and for understanding the geochemical behavior of arsenic in groundwater.     

The determination of traces of arsenic in water by arsine generation and radiometric analysis

A tracer method based on the concentration-dependent distribution principle has been developed for trace arsenic determination. Standard and sample arsenic solutions labelled with a fixed amount of radioactive arsenic-74 are isolated by arsine generation with sodium borohydride followed by absorption in potassium iodide—iodine solution. The separated arsenic(III) is then extracted with equal but limited amounts of zinc diethyldithiocarbamate in chloroform and determined radiometrically by the concentration-dependent distribution principle. The method is practically free from interferences, and arsenic in aqueous solution as low as 0.5 ng ml^-1 can be determined. Results for natural and environmental water samples are compared with results obtained by the arsine generation-atomic absorption technique.     

Evaluation of a Renewable Resource-based Carbon-Iron Oxide Nanocomposite for Removal of Arsenic from Contaminated Water

High arsenic concentration in groundwater is found in many countries, including Bangladesh, India, Vietnam, Thailand and United States. In these countries, the arsenic concentrations have reached dangerous levels for human consumption, especially where the main source of drinking water is from groundwater. Many techniques have been developed for arsenic removal, one being the use of iron oxide or magnetite nanoparticles for heavy metal removal. In this study, a novel tannin-based carbon-iron oxide composite has been developed by us for arsenic removal and results show that a concentration of 100 ppb As in water could be brought down to <10 ppb with the maximum capacity of the arsenic removal calculated to be 1.5 mg As/g Fe in the nanocomposite. The characterization of the nanocomposite and the advantages of using this renewable resource-based nanocomposite are also discussed.     

Arsenic content of hair and bones in the case of the suspected poisoning of R. Brun,first mayor of the city of Zurich

On the occasion of the 1970 opening of the grave of R. Brun, which is suspected to have been poisoned in 1360, samples of hair, bones and soil were taken and analysed for arsenic by neutron activation. Whereas the arsenic content of the hair was normal (0.2 to 0.3 ppm), the bones gave results of approximately 2 ppm, which is far above the value expected for healthy people (approximately 0.1 ppm). However, bones from the same grave (but not belonging to the suspected victim showed similar high values. These high values are thought to be due to an arsenic uptake from the soil and the evidence for an arsenic poisoning is under these circumstances rejected.     

Blank values, adsorption, pre-concentration, and sample preservation for arsenic speciation of environmental water samples

Arsenic is the focus of public attention because of its toxicity. Arsenic analysis, its toxicity, and its fate in the environment have been broadly studied, still its blank values, adsorption to sampling materials and pre-concentration of water samples as well as stabilization of arsenic compounds in water samples under field conditions have been very little investigated. In this study, we investigate the blank values and adsorption of arsenic compounds for different laboratory materials. We focused our work onto pre-concentration of water samples and how to stabilize arsenic compounds under field conditions. When using glassware for arsenic analysis, we suggest testing arsenic blank values due to the potential release of arsenic from the glass. Adsorption of arsenic compounds on different laboratory materials (<10%) showed little influence on the arsenic speciation. Pre-concentration of methanol-water solutions could result in potential overestimation of arsenic compounds concentrations. Successful pre-concentration of water samples by nitrogen-purge provides an analytical possibility for arsenic compounds with high recoveries (>80%) and low transformation of arsenic compounds. Thus, concentrations as low as 1 ng As l⁻¹ can be determined. Addition of ethylenediaminetetraacetic acid (EDTA) and storage in the dark can decrease the transformation among arsenic compounds in rainwater and soil-pore water for at least a week under field conditions.     

Spectrophotometric determination of arsenic via arsine generation and in-situ colour bleaching of methylene blue (MB) in micellar medium

A new spectrophotometric method has been developed to determine arsenic in parts-per-million (ppm) level. It is based on the colour bleaching of methylene blue (MB) in anionic micellar medium. Arsine gas was formed by borohydride reduction of arsenite/arsenate. Arsine generation and colour bleaching (quantification of arsenic) could be done in one-pot. The presence of silver or gold nanoparticles makes the determination faster. Different calibration graphs at the three different ranges of arsenic concentration such as 0-8.63, 0-1.11 and 0-0.11 ppm were constructed and limit of detection (LODs) were found to be 1.3, 0.53 and 0.03 ppm, respectively. The method is simple, rapid, reproducible (relative standard deviations lies within +/-5%) and eco-friendly. It is free from phosphate and silicate interferences and applicable for real sample analysis.     

Arsenic speciation in hair extracts

Ingested arsenic is known to be not only excreted by urine, but to be stored in sulphydryl-rich tissue like hair, nail or skin. We developed an extraction method for arsenic species from these tissues and studied the stability of different arsenic species during the extraction process. Inorganic and pentavalent methylated arsenic was found to be stable under the extraction conditions, whereas trivalent methylated arsenicals and the thio-analogue of DMA^V (DMAS) showed reduced stability. The absorption ability of hair for these different species was studied as well. Inorganic arsenic is better absorbed by hair than monomethyl- or dimethyl-arsenicals, whereby the trivalent forms are taken up better than the pentavalent forms. Independent of which methylated arsenical was used for the incubation, the pentavalent form was always the dominant form after extraction. Hair and nail samples from humans suffering from chronic arsenic intoxication contained dominantly inorganic arsenic with small and strongly varying amounts of DMA^V and MA^V present. DMAS was only found in some nail sample extracts containing unusually high amounts of DMA^V and is believed to be formed during the extraction process.     

Displacement substoichiometric separations in radioanalytical chemistry

The principle of displacement substoichiometry and the possibilities of its practical use have been outlined. The substoichiometric separation of lead, arsenic, and zinc can be carried out by applying diethyldithiocarbamate complexes and solvent extraction.     

Isotope hydrology and its impact in the developing world

Ground water has increasingly taken its place in the provision of safe, potable supply in the developing world. Large investments have been made in infrastructural development for rural ground water supply schemes, but far too little attention has been given to assess the sustainability of these supplies. Overexploitation of aquifers, evident in failing boreholes and deteriorating water quality, has become a world-wide concern. Developments in physics half a century ago established the basis of isotope hydrology. Radioactive isotopes give information on ground water dynamics and recharge rates whilst non-radioactive - or stable - isotopes indicate origins of ground water and delineate ground water bodies. Environmental isotope hydrology is increasingly seen as a powerful discipline in assessing ground water systems. This is particularly important in developing environments, where historical data is rarely available. Brief examples are presented of isotope applications to collaborative ground water studies conducted at the University of the Witwatersrand. Recharge estimates based on isotope snapshot data conform well with results from subsequent long-term water level observations in the Kalahari of Botswana. The importance is demonstrated of irrigation return flow and pollution hazard to the Lomagundi dolomite of Zimbabwe. Isotopes suggest the source of high nitrate concentrations to an important ground water supply in Tanzania. Mechanisms of the release of arsenic into millions of tube wells in Bangladesh are put into perspective. Isotope hydrology as appropriate technology is highlighted in terms of its cost-effectiveness and the investigative empowerment of local investigators.     

Dealing with repetitions in sequencing by hybridization

DNA sequencing by hybridization (SBH) induces errors in the biochemical experiment. Some of them are random and disappear when the experiment is repeated. Others are systematic, involving repetitions in the probes of the target sequence. A good method for solving SBH problems must deal with both types of errors. In this work we propose a new hybrid genetic algorithm for isothermic and standard sequencing that incorporates the concept of structured combinations. The algorithm is then compared with other methods designed for handling errors that arise in standard and isothermic SBH approaches. DNA sequences used for testing are taken from GenBank. The set of instances for testing was divided into two groups. The first group consisted of sequences containing positive and negative errors in the spectrum, at a rate of up to 20%, excluding errors coming from repetitions. The second group consisted of sequences containing repeated oligonucleotides, and containing additional errors up to 5% added into the spectra. Our new method outperforms the best alternative procedures for both data sets. Moreover, the method produces solutions exhibiting extremely high degree of similarity to the target sequences in the cases without repetitions, which is an important outcome for biologists. The spectra prepared from the sequences taken from GenBank are available on our website http://bio.cs.put.poznan.pl/.     

Plastic vs. Liquid Scintillation for C radiotracers determination in high salt matrices

The use of radiotracers is a common procedure for better understanding of the dynamics of oil reservoirs. Several molecules and radionuclides are implemented for this purpose; one of these is ¹⁴C labelled thiocyanate.Samples taken from fluids in production wells require a pre-treatment step in order to purify and concentrate the activity of the radiotracer before measurement. Pre-treatment is based on ionic exchange and the solution eluted includes a high concentration of salt that can be a serious drawback for the development of a stable emulsion when the liquid sample and the scintillation cocktail are mixed for Liquid Scintillation (LS).The objective of this study is to evaluate the capability of Plastic Scintillation (PS) to determine the activity of radiotracers in salt matrices.For this purpose, an initial comparative study of the influence of salt and coloured matrices on the detection efficiency for PS and LS was performed. Results indicate that in both techniques colour quenching produces the same effects: efficiency decrease and spectra shift, whereas salt quenching produces different effects for PS and LS, ionization quenching for PS and chemical quenching for LS. As a result of this divergence, the calibration required for each counting method is different: two steps for PS and a single step for LS.After system study and procedure optimization, radiotracer activities in real samples taken from oil reservoirs have been determined. The results indicated that PS shows similar capability to the classical LS to determine the activity in these salt matrix samples with the additional advantages that no separation of the phase can appear and no mixed waste is produced after measurement.     

Evaluation of extraction procedures for the ion chromatographic determination of arsenic species in plant materials

The determination of arsenic species in plants grown on contaminated sediments and soils is important in order to understand the uptake, transfer and accumulation processes of arsenic. For the separation and detection of arsenic species, hyphenated techniques can be applied successfully in many cases. A lack of investigations exists in the handling (e.g., sampling, pre-treatment and extraction) of redox- and chemically labile arsenic species prior to analysis. This paper presents an application of pressurized liquid extraction (PLE) using water as the solvent for the effective extraction of arsenic species from freshly harvested plants. The method was optimized with respect to extraction time, number of extraction steps and temperature. The thermal stability of the inorganic and organic arsenic species under PLE conditions (60-180 degrees C) was tested. The adaptation of the proposed extraction method to freeze-dried, fine-grained material was limited because of the insufficient reproducibility in some cases.     

Improved model for improving the inter-instrument agreement of spectrocolorimeters

A proposal by Robertson slightly modified by Berns and Petersen, to use spectral differences to predict systematic errors in spectrophotometers has found limited success in practical application. Porter suggested a way to improve the level of agreement between standardizing laboratories based on the Berns and Petersen method but suggested using derivatives calculated from piecewise polynomial splines. He did not know it at the time, but such a model was already in use. That model now has over five years of successful field testing and this paper discloses how the model was developed, the efficiency with which it can reduce systematic errors and the kinds of errors that cannot presently be corrected by computational comparison of reflectance or transmittance factor readings. For instruments of the same basic design, this model will produce a reduction of the systematic errors in colorimetric coordinates on the order of factors of 2–3. The magnitude of the initial color differences appears to be irrelevant. The corrective power of the model is limited by the numerical noise generated by the process of simulating analytical derivatives. We show that instruments with average color differences of 1.0 CIELAB unit can be reduced to a level of 0.5–0.3 units. Our testing has included a large variety of material samples including textiles, plastics, inks, paints and ceramics. Over 400 samples have been measured in proving this method. In addition, the model has been in place in industrial environments where multiple instruments of different manufacturer have been made to operate successfully from the same set of laboratory standards at reproducibility levels that rival those of national standards laboratories.     

Historical cohort studies in three arsenic poisoning areas in japan

The results of historical cohort studies of three arsenic poisoning incidents in Japan are presented. The first episode was in a small mountainous community near an arsenic mine and refinery, at Toroku, where patients with chronic arsenism were certified by application of the Pollution Health Damage Compensation Law. The second area was in a small town, Namiki-cho, near Nakajo-machi, where wells were poisoned by arsenic produced in an arsenic(III) sulfide factory. As to the third cohort, eight residents of Nishikawa-machi who ingested well-water suffered arsenic poisoning about 35 years ago. The standardized mortality ratios were used in analyzing these data. Excesses of cancer mortality, especially lung cancer, were observed among the subjects in these areas. In Japan, there are many arsenic poisoning episodes, involving for example soy-sauce poisoning, powdered-milk poisoning and other incidents associated with arsenic mines. Thus it is necessary to clarify the chronic effects of arsenic in these areas.