Sampling technologies and air pollution control devices for gaseous and particulate arsenic: a review

Direct measurement of arsenic release requires a good sampling and analysis procedure in order to capture and detect the total amount of metals emitted. The literature is extensively reviewed in order to evaluate the efficiency of full field-scale and laboratory scale techniques for capturing particulate and gaseous emissions of arsenic from the thermo-chemical treatment of different sources of arsenic. Furthermore, trace arsenic concentrations in ambient air, national standard sampling methods and arsenic analysis methods are considered. Besides sampling techniques, the use of sorbents is also reviewed with respect to both approaches (1) to prevent the metals from exiting with the flue gas and (2) to react or combine with the metals in order to be collected in air pollution control systems. The most important conclusion is that submicron arsenic fumes are difficult to control in conventional air pollution control devices. Complete capture of the arsenic species requires a combination of particle control and vapour control devices.     

Investigation of arsenic removal in batch wise water treatments by means of sequential hydride generation flow injection analysis

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH(3), which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.     

Distribution of inorganic arsenic species in mine tailings of abandoned mines from Korea

The main objective of the present study is to determine arsenic species in mine tailings by applying an ion exchange method. Three abandoned mines, Jingok, Cheonbo and Sino mines in Korea, which had produced mainly gold, were selected for the collection and analysis of the tailings. It was found that the arsenic speciation using an ion exchange method was effective to separate As(III) and As(V) in leachate of mine tailings. The concentration of As(V) was found to be 63-99% in the leachate, indicating that As(V) would be the major arsenic species in the mine tailings and the tailings were under oxic conditions. The total concentrations of arsenic and metal elements in the mine tailings were up to 62,350 mg/kg As, 40 wt.% Fe, 21,400 mg/kg Mn, and 7,850 mg/kg Al. Sulfate was the dominant anion throughout the leachate, reaching a maximum dissolved concentration of 734 mg/l. The results of XRD and SEM in the mine tailings showed that main arsenic-containing minerals were pyrite (FeS2) and arsenopyrite (FeAsS) which would be the source of arsenic contamination in the study area.     

Speciation of Arsenic in Ambient Aerosols Collected in Los Angeles

First-time measurements of the potentially toxic inorganic species of arsenic (arsenite arid arsenate) have been obtained in fine (<2.5 µm AD) and coarse (>2.5 µm AD) atmospheric particles in the Los Angeles area. A recently developed method that includes procedures for sample collection, preparation, and analysis was used in this study. Size-fractlonated aerosol samples were collected with a high-volume dichotomous virtual impactor that employed polytetrafluoroethylene filters. Results were obtained for the recovery of arsenic standards added to unexposed and collected filters. Data from this study, indicated that the recently developed speciation method can be used to determine concentrations of As(lll) and As(V) In atmospheric particulate matter samples.

Size-fractionated aerosol samples were collected in the city of Industry during January and February 1987. In most samples, As(lll) and As( V) were above the detection limit (approximately 1 ng m^-3 of either species) in both aerosol size fractions. A greater portion (about 75 percent) of the two species were observed in the fine particles. The As(lll)/As(V) ratio for both particle sizes was close to 1 (I.e., an equal mixture of both species). Comparison of total suspended particulate arsenic measured by the speciation method to that measured by a routine California Air Resources Board-approved procedure showed good agreement (r = 0.94), indicating both methods were approximately equivalent for the collection and analysis of aerosol arsenic.     

Inter-Laboratory Comparison of Air Particulate Monitoring Data

ABSTRACT

This paper compares three analytical methods that are often used to analyze composition of atmospheric aerosol: Ion Chromatography (IC), Proton Induced X-ray Emission (PIXE), and X-Ray Fluorescence (XRF). Three monitoring studies are discussed: (1) a comparison of air particulate data collected by several independent sampler/ analytical technique suites run by different laboratories; (2) a study involving two identical samplers and a single suite of analytical techniques; and (3) analysis of identical aerosol samples by two different techniques (XRF vs. PIXE). While the XRF versus PIXE project shows a very good agreement for most elements, the first interlaboratory study demonstrates the “real-life” noise introduced into the final data set by various sampling complications and different collection characteristics of the samplers used. The XRF versus PIXE study also revealed an unexplained deviation in measured sulphur concentrations for very lightly loaded samples. In the five-sampler comparison, two data sets provided by IC were approximately 20% lower than the three data sets obtained by PIXE and XRF. When two identical IMPROVE-compat-ible samplers were used and samples were subjected to similar procedures and the same analytical techniques, the variability between the two air concentration data sets significantly decreased.     

Organic compounds in indoor air—their relevance for perceived indoor air quality?

It is generally believed that indoor air pollution, one way or another may cause indoor air complaints. However, any association between volatile organic compounds (VOCs) concentrations and increase of indoor climate complaints, like the sick-building syndrome symptoms, is not straightforward. The reported symptom rates of, in particular, eye and upper airway irritation cannot generally be explained by our present knowledge of common chemically non-reactive VOCs measured indoors. Recently, experimental evidence has shown those chemical reactions between ozone (either with or without nitrogen dioxide) and unsaturated organic compounds (e.g. from citrus and pine oils) produce strong eye and airway irritating species. These have not yet been well characterised by conventional sampling and analytical techniques. The chemical reactions can occur indoors, and there is indirect evidence that they are associated with eye and airway irritation. However, many other volatile and non-volatile organic compounds have not generally been measured which could equally well have potent biological effects and cause an increase of complaint rates, and posses a health/comfort risk. As a consequence, it is recommended to use a broader analytical window of organic compounds than the classic VOC window as defined by the World Health Organisation. It may include hitherto not yet sampled or identified intermediary species (e.g., radicals, hydroperoxides and ionic compounds like detergents) as well as species deposited onto particles. Additionally, sampling strategies including emission testing of building products should carefully be linked to the measurement of organic compounds that are expected, based on the best available toxicological knowledge, to have biological effects at indoor concentrations.     

Bioaccumulation of arsenic compounds in aquacultural clams (Meretrix lusoria) and assessment of potential carcinogenic risks to human health by ingestion

This study surveyed the total arsenic (As) and As species contents in clams (Meretrix lusoria) farmed in areas of hyperendemic blackfoot disease (BFD) in southwestern Taiwan. Total As and As species in sediment and pond water were also analyzed to examine the bioaccumulation of As in clams in their exposure environment. Moreover, potential carcinogenic risks associated with the ingestion of As in aquacultural clams were evaluated probabilistically. The average total As contents in medium-sized and small clams were 7.62 and 10.71 microg/g (dry wt), respectively. The content of the As species in this study was approximately 61% of the total As content. The other unquantified As species are possibly arsenocholine, arsenosugar and arsenolipid. The average ratios of inorganic As contents to total As contents in clams ranged from 12.3% to 14.0% which are much higher than that found in the farmed oyster (Crassostrea gigas), indicating that humans may expose to larger quantities of inorganic As by ingesting the same amount of clam as oyster. Using different ingestion rates derived by the average consumption method and the questionnaire method, the estimated risks to human health associated with consuming clams from the BFD area ranging from slightly to largely exceed the standard target risk. Based on the estimation of the TR model, a 0.18g/day-person of the safe ingestion rate of clams in the BFD region is recommended.     

The Analysis of Airborne Sulfate

This report reviews the current state of analytical methodology for sulfate in airborne particles. Methods for determination of total aerosol sulfate and total soluble sulfate are assessed. A more detailed review of the relatively new techniques for quantitative speciation of airborne sulfate then follows. Size distribution methodology and filter sampling difficulties relating to the collection of airborne sulfate-containing particles are enumerated. Experiments are suggested which use new, improved, and potentially applicable sulfate speciation techniques to obtain a better understanding of the generation, transport, transformation and removal processes that, in turn, determine the identity and concentrations of sulfate species in ambient air.     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.     

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

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

Relationship between arsenic accumulation in tissues and hematological parameters in mullet caught in Faro Lake: a preliminary study

The authors investigated the arsenic (As) accumulation in different tissues (muscle, gill, liver, stomach, and intestine) and the possible correlation between tissue concentration and hematological parameters in mullet (Mugil cephalus Linnaeus, 1758) caught in Faro Lake (Messina, Sicily, Italy). On all fish, hematological analyses of blood samples, measurement of biometric indices, and the removal of the muscles, gills, liver, stomach, and intestine for the determination of arsenic concentration were performed. A hemogram was performed to find effects of arsenic concentration in tissues on hematological variables. One-way analysis of variance showed significant differences of arsenic concentration in different tissues, with higher values in the gill. The correlation between hematological parameters and tissue arsenic concentration showed a statistical significance for red blood cell (RBC), hemoglobin concentration (Hb), and hematocrit (Hct) with the liver As concentration. Biometric indices (weight, length, and fork length) showed a significant correlation with As concentration of the muscle and liver also. Our results indicate the role of some hematological parameters as biomarkers useful to monitoring anthropogenic load of arsenic in water and sediment, because variations of these parameters represent one of the effects that arsenic exposure can have on fish.

     

Unusual arsenic speciation in sea anemones

Nine species of sea anemones (Anthopleura asiatica, Actinia equina, Actinodendron arboreum, Phymanthus loligo, Entacmaea actinostoloides, Stichodactyla gigantea, S. haddoni, S. mertensii and Metridium senile) contained arsenic in the range of 1.6-7.0microg As g(-1) (wet mass basis). Irrespective of the species, water-soluble arsenic compounds accounted for more than 80% of the total arsenic. Analysis of water-soluble arsenic compounds by LC/ESI-MS revealed that four arsenicals, arsenobetaine (AB), trimethylarsoniopropionate, arsenocholine (AC) and tetramethylarsonium ion (TEMA), are contained in most species but arsenate, methylarsonic acid, dimethylarsinic acid and trimethylarsine oxide are absent in all species. Interestingly, compositional patterns of the four arsenicals greatly differed from species to species. Only three species (S. gigantea, S. haddoni and M. senile) contained AB at the highest proportions, similar to the majority of marine animals. However, the remaining six species showed unusual compositional patterns of arsenic compounds; AC was most predominant in A. arboreum and P. loligo and TEMA in A. asiatica, A. equina, E. actinostoloides and S. mertensii. On the whole, high proportions (24.6-87.1% of the water-soluble arsenic) of TEMA appear to be a peculiar characteristic of many species of sea anemones. Thus, sea anemones are an important animal group in the arsenic cycling, especially in that they may be donors of TEMA to predators.     

Arsenic speciation in plants growing in arsenic-contaminated sites

Concentrations of total arsenic and of arsenic species were determined by ICPMS and HPLC-ICPMS in terrestrial plant samples. The arsenic concentration in plant samples from the contaminated sites ranged from 1.14 to 98.5 mg kg(-1) (dry mass). However, a very high value, exceeding largely this range was found in a moss sample growing in the contaminated area (1750 mg kg(-1)). Plants growing in a non-contaminated area with similar geological characteristics contained 0.06-0.58 mg As kg(-1). Plant samples from different species were selected and extracted with water, water/methanol (9+1, v/v), and water/methanol (1+1, v/v). Water/methanol (9+1, v/v) was selected as extractant for the speciation analysis for all the plant samples. The extraction efficiencies ranged from 3.0% to 41.4%, with good agreement between samples from the same plant species. Arsenite and/or arsenate were found in all the plant samples. Additionally, methylarsonate (MA), dimethylarsinate (DMA), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TETRA) were also identified in several plants, and in some cases MA and DMA were the main species found. TMAO, which is usually found as a trace constituent in organisms, was also a significant arsenical in one of the studied samples, where it constituted 24% of the extracted arsenic. In the present study, the patterns of arsenic species varied with the plant species and much higher proportion of organoarsenicals was found in plants from the more contaminated sites.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Non-Methane Hydrocarbon Air Quality Measurements

It is important in the implementation of the air quality standard for ozone/oxidants and non-methane hydrocarbons to develop quantitative relationships between these pollutants in air quality regions. Analyses for ambient air non-methane hydrocarbon give a direct measure of the progress in control of hydrocarbon emissions and in the reduction of oxidant/ozone concentration levels. Total hydrocarbon concentrations are much more available than non-hydrocarbon levels. An empirical relationship between total hydrocarbons and non-methane hydrocarbons has been obtained from measurements at both west and east coast sites in the U. S. The comparability of measurements from flame ionization analyzers and gas chromatography has been demonstrated. Either analytical technique can be applied to samples collected at monitoring sites to provide the 6-9 A.M. non-methane hydrocarbon aerometric results specified in the air quality standards.     

Influence of redox potential (Eh) on the availability of arsenic species in soils and soils amended with biosolid

A study was done on the influence of redox potential on the mobility and availability of the various arsenic chemical forms in a Mollisol soil from central Chile amended with biosolid. Arsenic availability was strongly dependent on the applied redox potential. As expected, under reducing conditions (-200 mV vs Hg/Hg(2)Cl(2)) arsenic availability increased significantly, and arsenic was found mainly as arsenite. On the contrary under oxidizing conditions (200 mV vs Hg/Hg(2)Cl(2)) arsenic solubility decreased markedly and was governed by the presence of arsenate. The greatest concentration of organic arsenic species was found under reducing conditions, which would indicate that methylated species may participate in the transformation of arsenate to arsenite. In biosolid-amended soils the concentrations of methylated species increased as a function of time under reducing conditions, which can be attributed to the greater microbial activity resulting from the organic matter supply from the biosolid to soil. In all the systems, a high concentration of As(V) was found under reducing conditions, indicating that the chemical kinetics for the conversion of arsenate to arsenite is slow. Along time, the content of As(V) increased in the control soils, which may be attributed to the possible dissolution of iron oxides and hydroxides under reducing conditions.     

Adsorption of arsenic(V) onto fly ash: a speciation-based approach

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.     

The oxidation states of arsenic in well-water from a chronic arsenicism area of northern Mexico

Aquifers in the Región Lagunera in northern Mexico are heavily contaminated with arsenic. The range of total arsenic concentrations in 128 water samples analyzed was 0.008 to 0.624 mg litre(-1), and concentrations greater than 0.05 mg litre(-1) were found in 50% of them. Approximately 400 000 people living in rural areas were exposed to high As concentrations. Most of the As was in inorganic form and pentavalent arsenic [As(V)] was the predominant species in 93% of the samples. In 36% of the samples, however, variable percentages (20-50) of trivalent As [As(III)] were found. Organic arsenicals were present in very small amounts. Since As(III) is several times more toxic than As(V), we suggest that periodic studies be performed on the As(III)/As(V) ratio in wells whose total As concentrations are above 0.05 mg litre(-1), in combination with epidemiological studies to evaluate possible differences in health effects produced by different As species.     

A preliminary risk assessment of trace elements accumulated in fish to the Indo-Pacific Humpback dolphin (Sousa chinensis) in the northwestern waters of Hong Kong

In order to assess the potential risks associated with consumption of contaminated prey items to the Indo-Pacific Humpback dolphin (Sousa chinensis), fish species (Collichthys lucida, Pseudosciaena crocea, Johnius sp., Thryssa sp., Mugil sp. and Trichiurus sp.) representing the main food items of the dolphin were collected from the northwestern waters of Hong Kong, including the Sha Chau and Lung Kwu Chau Marine Park, which form the main habitat of the dolphin in Hong Kong. Within these waters, there are several potential sources of pollution including significant inputs from the Pearl River catchment, several major sewage outfalls and a series of mud pits that receive contaminated dredged sediments. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V, and Zn) in the fish tissue were analyzed by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of the risks of adverse effects on the dolphin due to consumption of tainted fish was undertaken using two toxic reference benchmarks, namely the reference dose (RfD) and toxicity reference value (TRV). The risk quotient (RQ) calculated for each element showed that the risks from consumption of fish were generally low and within safe limits. The risks associated with arsenic, cadmium and mercury were, however, elevated. The highest calculated RQ was associated with total arsenic; however, the majority of arsenic in marine organisms tends to be in the non-toxic organic form, and the actual risk to the dolphin due to this metalloid is likely to be lower.     

Determination of total arsenic content in water by atomic absorption spectroscopy (AAS) using vapour generation assembly (VGA)

Analysis of arsenic in water is important in view of contamination of ground water with arsenic in some parts of the world including West Bengal in India and neighboring country Bangladesh. WHO has fixed the threshold for arsenic in drinking water to 10ppb (microg/l) level, hence the methodology for determination of arsenic is required to be sensitive at ppb level. Atomic absorption spectrophotometry with vapour generation assembly (AAS-VGA) is well known technique for the trace analysis of arsenic. However, total arsenic analysis [As(III)+As(V)] is very crucial and it requires reduction of As(V) to As(III) for correct analysis. As(III) is reduced to AsH3 vapours and finally to free As atoms, which are responsible for absorption signal in AAS. To accomplish this the vapour generation assembly attached to AAS has acid channel filled with 10 M HCl and the reduction channel with sodium borohydride. Further sample can be reduced either before aspiration for analysis, using potassium iodide (KI) or the sample can be introduced in the instrument directly and KI can be added in the reduction channel along with the sodium borohydride. The present work shows that samples prepared in 3 M HCl can be reduced with KI for 30 min before introduction in the instrument. Alternatively samples can be prepared in 6 M HCl and directly aspirated in AAS using KI in VGA reduction channel. The latter methodology is more useful when the sample size is large and time cycle is difficult to maintain. It is observed that the acid concentration of the sample in both the situations plays an important role. Further reduction in acid concentration and analysis time is achieved for the arsenic analysis by using modified method. Analysis in both the methods is sensitive at ppb level.