原子荧光光度法测定工业炉气中的砷

采用原子荧光光度法测定炉气中砷的含量。方法探讨了盐酸酸度对测定结果的影响 ,确定本方法的检测限为2 .1 3ng/ml,样品回收率为 95.2 %～ 97.6%。     

Seasonal perspective of dietary arsenic consumption and urine arsenic in an endemic population

Exposure to arsenic in arsenic endemic areas is most remarkable environmental health challenges. Although effects of arsenic contamination are well established, reports are unavailable on probable seasonal variation due to changes of food habit depending on winter and summer seasons, especially for endemic regions of Nadia district, West Bengal. Complete 24-h diets, drinking–cooking water, first morning voided urine samples, and diet history were analyzed on 25 volunteers in arsenic endemic Chakdah block of Nadia district, once in summer followed by once in winter from the same participants. Results depicted no seasonal variation of body weight and body mass index. Arsenic concentration of source drinking and cooking water decreased (p?=?0.04) from 26 μg L^?1 in summer to 6 μg L^?1 in winter season. We recorded a seasonal decrease of water intake in male (3.8 and 2.5 L day ^?1) and female (2.6 and 1.2 L day^?1) participants from summer to winter. Arsenic intake through drinking water decreased (p?=?0.04) in winter (29 μg day^?1) than in summer (100 μg day^?1), and urinary arsenic concentration decreased (p?=?0.018) in winter (41 μg L^?1) than in summer (69 μg L^?1). Dietary arsenic intake remained unchanged (p?=?0.24) over the seasons. Hence, we can infer that human health risk assessment from arsenic needs an insight over temporal scale.     

Development of a sampling train for arsenic in pyrolysis vapours resulting from pyrolysis of arsenic containing wood waste

In the present study a sampling and analysis method for arsenic emissions during pyrolysis of arsenic containing wood, such as chromated copper arsenate (CCA) treated wood, has been developed. The procedure is based on the NIOSH (National Institute for Occupational Safety and Health) standard for arsenic trioxide sampling. Validation for this specific application is needed since pyrolysis of arsenic containing wood leads to a gas stream containing sticky tar compounds and aerosols. Validation was carried out through tube furnace experiments using both CCA treated wood and arsenic trioxide powder as input. The outlet of the tube furnace was coupled to a cooling section and sampling train. The sampling train consisted of one or more filter sections and impingers. Different combinations of filters (untreated or impregnated) and impingers, as well as different combinations of washing solutions were tested. The different units of the sampling train were analysed by inductively coupled plasma mass spectrometry (ICP-MS) in order to determine the distribution of arsenic over the different units. For the working conditions considered (pyrolysis at 350 degrees C for 20 minutes with a nitrogen flow rate of 100 Nl h(-1)) the combination of a quartz cooling tube and a cellulose ester membrane filter impregnated with a Na2CO3-glycerol solution was sufficient to capture the arsenic. Two extra impingers (the first one containing 50 ml HNO3 1 M in the case of CCA treated wood and 50 ml NaOH 0.1 M in the case of As2O3 and the second one containing 50 ml NaOH 0.1 M) were added downstream of the filter section as backup either in case of filter failure or to check whether all the arsenic released is captured by the cooling tube and filter.     

Desorption of arsenic from drinking water distribution system solids

Previous work has shown that arsenic can accumulate in drinking water distribution system (DWDS) solids (Lytle et~al., 2004) when arsenic is present in the water. The release of arsenic back into the water through particulate transport and/or chemical release (e.g. desorption, dissolution) could result in elevated arsenic levels at the consumers' tap. The primary objective of this work was to examine the impact of pH and orthophosphate on the chemical release (i.e. desorption) of arsenic from nine DWDS solids collected from utilities located in the Midwest. Arsenic release comparisons were based on the examination of arsenic and other water quality parameters in leach water after contact with the solids over the course of 168~hours. Results showed that arsenic was released from solids and suggested that arsenic release was a result of desorption rather than dissolution. Arsenic release generally increased with increasing initial arsenic concentration in the solid and increasing pH levels (in the test range of 7 to 9). Finally, orthophosphate (3 and 5 mg PO₄/L) increased arsenic release at all pH values examined. Based on the study results, utilities with measurable levels of arsenic present in their water should be aware that some water quality changes can cause arsenic release in the DWDS potentially resulting in elevated levels at the consumer's tap.     

Effect of fasting on the pattern of urinary arsenic excretion

Millions of people in some of the poorest regions of the world are exposed to high levels of arsenic through drinking contaminated water. It has been reported that development of cancer caused by arsenic exposure in such populations is dependent on dietary and nutritional factors which can modulate arsenic metabolism. Many people in arsenic exposed regions of Bangladesh and India practice fasting for at least one month every year when they refrain from consumption of food and fluid during daylight hours. How such practices may modulate arsenic metabolism has not been previously investigated. This study investigated this issue by determining total arsenic and its species in urine samples from a group of 29 unexposed volunteers at the beginning of the fasting and at the end of approximately 12 h of fasting period. Inductively coupled plasma mass spectrometry (ICP-MS) and high performance liquid chromatography (HPLC) coupled with ICP-MS was used to measure the total arsenic and arsenic speciation in the urine samples, respectively. The mean total levels of arsenic at the beginning of fasting (18.3 microg g(-1) creatinine) and at the end of approximately 12 h of fasting (17.7 microg g(-1) creatinine) did not differ significantly (p > 0.05). However, the percentages of urinary arsenic as the methylated arsenic species methylarsonate (MA) were found to be significantly different (p < 0.05) and this species was observed more frequently at the end of fasting, although its overall concentration was similar. There were no significant differences (p > 0.05) in both the concentrations and percentages of other urinary arsenic species detected, namely arsenobetaine (AB) and dimethylarsinate (DMA). Arsenite (As(III)) and arsenate (As(V)) were also analyzed, but were not detected. We conclude that fasting for a period of 12 h results in a significant increase in the percentage of urinary arsenic as MA, and its frequency of detection in the volunteers at the end of the fasting period is almost nine fold higher. This suggests that metabolism of arsenic is altered by fasting.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.     

Determination of arsenic content of some Romanian natural mineral groundwaters

Romania is one of the countries that have natural arsenic groundwater problems. This paper presents the results of a study of arsenic concentration monitoring in natural mineral waters collected from 23 sampling sites located in the northern, central, and western regions of Romania. The sampling sites are both natural springs and drilled wells. The graphite furnace atomic absorption spectrometry was used for arsenic content determination. The Piper??s classification principle was applied in order to find out the hydrochemical type of the analyzed waters. Depending on the concentration of arsenic, the water analyzed can be classified into three main categories: (1) mineral natural waters containing less than 10???g/L arsenic, (2) mineral natural waters containing arsenic at concentrations several times higher than the limit of 10???g/L but less than 100???g/L, and (3) mineral natural waters containing arsenic at concentrations of ten to a hundred times higher than the allowed limit of 10???g/L. The last-mentioned waters are of bicarbonatate sodium type and were sampled from seven sources only, being prohibited for human and animal use.     

Simulation of arsenic partitioning in tributaries to drinking water resevoirs

Arsenic released by bottom sediments was determined by experiments in which the sediments were artificially re-suspended using a particle entrainment simulator (PES) to simulate river conditions. Sediment cores were collected from various tributaries to drinking water reservoirs in Connecticut spiked with arsenic, and run in the PES at simulated bed-flow shear stresses from 0.0 to 0.6 N/m². Under equilibrium conditions, the dissolved fraction of arsenic was found to range from 8.3 to 22.1 μg/l, which in most cases exceeded EPA Maximum Contaminant Level (MCL) of 10 μg/l. Experimental results from these simulations have shown that bed-flow shear stress causes an increased concentration of dissolved arsenic, most notably at shear stresses of 0.4, 0.5, and 0.6 N/m². For the solid phase under equilibrium, the concentrations of arsenic ranged between 71 and 275 mg/kg. The average concentration of arsenic on the solid phase as well as partitioning coefficient values (K _p) were highest at initial shear stress. This was attributed to the higher fraction of colloidal material and finer organic particles in the suspended solid mixture. Particles of such nature proved to have higher affinity to arsenic. K _p values were determined from PES data and were found to range from 4,687 to 24,090 l/kg. However, on a mass load basis, the amount of arsenic found in suspended sediment increased with the increase of shear stress. Similarly, the amount of arsenic in the solid phase increased significantly for sites with high Volatile Organic Carbon (VOC) content. Because of the influence of Total Suspended Solids (TSS) and VOC concentrations on K _p, the use of the PES is more appropriate in obtaining K _p values that would be found under real stream conditions when compared to the traditional way of measuring K _p using a jar study technique.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

Environmental assessment of arsenic released from potential pollution sources

An assessment study of the environmental pathways of arsenic released from a coal-fired power plant (CFPP) or introduced into soil as a contaminant by phosphatic fertilizers has been carried out using a time-dependent forecasting model.The long-term predictions indicate that arsenic can be taken up by plants and that it can migrate into the groundwater system through soil layers. However, arsenic exhibits such a high degree of mobility that its retention and accumulation in biota should remain low. This fact may explain the relatively low concentrations of arsenic in environmental media as well as in groundwater systems.     

Removing arsenic from groundwater in Cambodia using high performance iron adsorbent

In Cambodia, groundwater has been contaminated with arsenic, and purification of the water is an urgent issue. From 2010 to 2012, an international collaborative project between Japan and Cambodia for developing arsenic-removing technology from well water was conducted and supported by the foundation of New Energy and Industrial Technology Development Organization, Japan. Quality of well water was surveyed in Kandal, Prey Veng, and Kampong Cham Provinces, and a monitoring trial of the arsenic removal equipment using our patented amorphous iron (hydr)oxide adsorbent was performed. Of the 37 wells surveyed, arsenic concentration of 24 exceeded the Cambodian guideline value (50 μg L^?1), and those of 27 exceeded the WHO guideline for drinking water (10 μg L^?1). Levels of arsenic were extremely high in some wells (>1,000–6,000 μg L^?1), suggesting that arsenic pollution of groundwater is serious in these areas. Based on the survey results, 16 arsenic removal equipments were installed in six schools, three temples, two health centers, four private houses, and one commune office. Over 10 months of monitoring, the average arsenic concentrations of the treated water were between 0 and 10 μg L^?1 at four locations, 10–50 μg L^?1 at eight locations, and >50 μg L^?1 at four locations. The arsenic removal rate ranged in 83.1–99.7 %, with an average of 93.8 %, indicating that the arsenic removal equipment greatly lower the risk of arsenic exposure to the residents. Results of the field trial showed that As concentration of the treated water could be reduced to <10 µg L^?1 by managing the As removal equipment properly, suggesting that the amorphous iron (hydr)oxide adsorbent has high adsorbing capacity for As not only in the laboratory environment but also in the field condition. This is one of the succeeding As removal techniques that could reduce As concentration of water below the WHO guideline value for As in situ.     

Assessment of metals in down feathers of female common eiders and their eggs from the Aleutians: arsenic, cadmium, chromium, lead, manganese, mercury, and selenium

Concentrations of arsenic, cadmium, chromium, lead, manganese, mercury and selenium were examined in the down feathers and eggs of female common eiders (Somateria mollissima) from Amchitka and Kiska Islands in the Aleutian Chain of Alaska to determine whether there were (1) differences between levels in feathers and eggs, (2) differences between the two islands, (3) positive correlations between metal levels in females and their eggs, and (4) whether there was more variation within or among clutches. Mean levels in eggs (dry weight) were as follows: arsenic (769 ppb, ng/g), cadmium (1.49 ppb), chromium (414 ppb), lead (306 ppb), manganese (1,470 ppb), mercury (431 ppb) and selenium (1,730 ppb). Levels of arsenic were higher in eggs, while chromium, lead, manganese, and mercury were higher in feathers; there were no differences for selenium. There were no significant interisland differences in female feather levels, except for manganese (eider feathers from Amchitka were four times higher than feathers from Kiska). Levels of manganese in eggs were also higher from Amchitka than Kiska, and eider eggs from Kiska had significantly higher levels of arsenic, but lower levels of selenium. There were no significant correlations between the levels of any metals in down feathers of females and in their eggs. The levels of mercury in eggs were below ecological benchmark levels, and were below human health risk levels. However, Aleuts can seasonally consume several meals of bird eggs a week, suggesting cause for concern for sensitive (pregnant) women.     

Portable X-ray fluorescence in the characterisation of arsenic contamination associated with industrial buildings at a heritage arsenic works site near Redruth,Cornwall, UK

An investigation using in situ analysis by portable X-ray fluorescence (PXRF) has shown that contamination present on industrial buildings at a heritage arsenic works site near Redruth, Cornwall, UK results from the absorption of arsenic by porous and semi-porous building materials that were in contact with arsenic-rich flue gases. Results from a preliminary survey indicate that arsenic remains locked in these materials and is being gradually leached out by weathering processes. This weathering causes general contamination of the adjacent building surfaces averaging 1845 microg g(-1) arsenic, presumably caused by evaporation of leach solutions in contact with air at the surface of the building materials. More extensive crystalline deposits were found under arches protected from dissolution and further dispersion by rain water. These deposits appeared to comprise calcium sulfate (gypsum), associated with on average between 1.2 and 6.8% m/m As. In situ PXRF proved to be highly effective in locating sources of contamination at the site and in providing data that allowed a hypotheses for the origin of this contamination to be formulated and tested in the field.     

Population-based biomonitoring in the Czech Republic: urinary arsenic

The method of Guo et aL (AnaL Chim. Acta, 1997, 349, 313-318) for the determination of the toxicologically relevant arsenic in urine was verified and then used for the determination of arsenic in urine of the Czech population for monitoring purposes. Statistical evaluation at the level alpha = 0.05 did not prove any significant differences between industrial and agricultural regions, between males and females and smokers and nonsmokers. Likewise no differences were found among children in all the regions monitored. In the adult population small differences were found between some regions but these differences were not dependent on industrial pollution. The values of toxicologically relevant arsenic are low for all regions. The summarised value of the median for all groups together is 3.5 microg (g creatinine)(-1).     

Inorganic arsenic levels in rice milk exceed EU and US drinking water standards

Under EU legislation, total arsenic levels in drinking water should not exceed 10 microg l(-1), while in the US this figure is set at 10 microg l(-1) inorganic arsenic. All rice milk samples analysed in a supermarket survey (n = 19) would fail the EU limit with up to 3 times this concentration recorded, while out of the subset that had arsenic species determined (n = 15), 80% had inorganic arsenic levels above 10 microg l(-1), with the remaining 3 samples approaching this value. It is a point for discussion whether rice milk is seen as a water substitute or as a food, there are no EU or US food standards highlighting the disparity between water and food regulations in this respect.     

Comparison of arsenic uptake ability of barnyard grass and rice species for arsenic phytoremediation

In this research, the relative performance in arsenic (As) remediation was evaluated among some barnyard grass and rice species under hydroponic conditions. To this end, four barnyard grass varieties and two rice species were selected and tested for their remediation potential of arsenic. The plants were grown for 2 weeks in As-rich solutions up to 10 mg As L^?1 to measure their tolerance to As and their uptake capabilities. Among the varieties of plants tested in all treatment types, BR-29 rice absorbed the highest amount of As in the root, while Nipponbare translocated the maximum amount of As in the shoot. Himetainubie barnyard grass produced the highest biomass, irrespective of the quantity of As in the solution. In all As-treated solutions, the maximum uptake of As was found in BR-29 followed by Choto shama and Himetainubie. In contrast, while the bioaccumulation factor was found to be the highest in Nipponbare followed by BR-29 and Himetainubie. The results suggest that both Choto shama and Himetainubie barnyard grass varieties should exhibit a great potential for As removal, while BR-29 and Nipponbare rice species are the best option for arsenic phytoremediation.     

Total and inorganic arsenic in dietary supplement supplies in northern Mexico

The aim of this study was to evaluate the presence of total and inorganic arsenic in dietary supplements composed of herbal plants and seaweed, and to determine the potential toxicological risk. Total arsenic was determined by dry ashing and hydride generation atomic absorption spectrometry, and inorganic arsenic was determined by acid digestion, solvent extraction, and hydride generation atomic absorption spectrometry. Total and inorganic arsenic in the supplements ranged from 0.07 to 8.31 mg?kg^?1 dry weight and from 0.14 to 0.28 mg?kg^?1 dry weight, respectively. Daily intake of total arsenic ranged from 0.05 to 12.46 μg?day^?1. Inorganic arsenic intake ranged from 0.21 to 0.83 μg?day^?1, values that are below the Benchmark Dose Lower Confidence Limit recommended by the Word Health Organization. Therefore, there appears to be a low risk of adverse effects resulting from excess inorganic arsenic intake from these supplements. This is the first study conducted in Mexico that investigates total and inorganic arsenic in dietary supplements. Although the results do not suggest toxicological risk, it is nonetheless important considering the toxicity of inorganic arsenic and the increasing number consumer preferences for dietary supplements. Moreover, it is important to improve and ensure the safety of dietary supplements containing inorganic arsenic.     

Fractionation of sedimentary arsenic from Port Kembla Harbour, NSW, Australia

The binding of arsenic in sediments of the heavily industrialised Port Kembla Harbour, NSW, Australia, has been investigated. Both dredge and core samples have been used to develop a sieving/sequential extraction (SE) procedure. Dredge samples included oxic surficial and deeper anoxic sediment. The main core sample analysed was 18 cm deep, sliced at 2 cm intervals. Sediment was sieved to three size ranges (<63 microm, 63-250 microm, >250 microm) and each of these was then subjected to a four step SE, sequentially solubilizing arsenic as ion exchangeable, 1 M HCl soluble, NH(2)OH.HCl soluble, and strong oxidising acid soluble. Concentrations of 50-500 mg As kg(-1) were found, elevated well above local background values. The core sample showed elevated concentrations of arsenic within the top 6-8 cm (300-500 mg As kg(-1)), relative to the deeper sediment (100-200 mg As kg(-1)). Substantial portions of the total arsenic present in the 0-8 cm sediments of core and dredge samples, were found to be soluble in 1 M pH 5 phosphate buffer or 1 M HCl. Arsenic in the lower 8-18 cm of the core displayed different solubility, the fourth stage SE strong acid digestion being required to solubilize >90% of the deep sediment arsenic. It appears that diagenesis had resulted in remobilisation of weakly bound arsenic with subsequent diffusion and deposition in surficial layers. Strong acid soluble arsenic present in deeper sediments has two possible origins: sedimented as strongly bound remaining untouched by diagenetic events, or subjected to diagenetic reactions such as pyritization, which lead to more stable crystalline forms of minerals.     

Induction of sperm impairments in mice as a sensitive biomarker of arsenic toxicity

The ubiquitous presence of arsenic (a toxic metalloid) in our environment, particularly in our drinking water, is a serious health hazard of global concern. The present work deals with the assessment of arsenic toxicity through the analysis of induced sperm impairments in sperm head morphology and sperm count in mice at low exposures compared to the magnitude of response at high exposure levels. The animals were exposed to four doses of arsenic, ranging from lowest dose of 0.3 μg kg^?1 day^?1 (the human reference dose) to higher dose of 30 μg kg^?1 day^?1 for 15 consecutive days. The epididymal sperms were harvested after one spermatogenic cycle on the 36th day and were scored for the presence of any abnormality in their head morphology as well as changes in their count. Exposure to arsenic significantly induced, in a dose-dependent manner, increases in the frequency of sperms with abnormal head morphology from 5.12 % in control to 9.23 % in lowest dose group and 23.02 % in highest dose group. In contrast, the mean sperm counts in the epididymal wash were decreased from 6.05 million per milliliter in the control to 4.95 million per milliliter in the lowest dose group and 3.07 million in the highest dose group. The analysis of sperm impairments in mice was, therefore, found to be a highly sensitive assay to assess arsenic toxicity, exhibiting a marked male reprotoxic effect of arsenic even at its low exposure levels including the human reference dose.