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Trends in Analytical Chemistry, Vol. 23, No.

1011, 2004

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Extraction and analysis of arsenic in soils and sediments


K.A. Hudson-Edwards , S.L. Houghton, A. Osborn
The ability to extract arsenic (As) from soils and sediments, and analyze it with accuracy and precision, is of paramount importance, given the high risk that As, even in relatively low concentrations, poses to pore waters and biota. A large number of methods exist for extracting and analyzing total As, and As associated with a variety of operationally dened phase associations, in soils and sediments. We give an overview of methods used at present, and consider potential problems. We strongly recommend adoption of universal standard techniques and certied reference materials, especially for sequential extraction schemes. 2004 Elsevier Ltd. All rights reserved.
Keywords: Analysis; Arsenic; Extraction; Sediment; Sequential extraction; Soil

1. Introduction
K.A. Hudson-Edwards* School of Earth Sciences, Birkbeck College, University of London, Malet Street, London WC1E 7HX, UK Wolfson Laboratory for Environmental Geochemistry, Research School of Earth Sciences at UCL-Birkbeck, University of London, Gower Street, London WC1E 6BT, UK S.L. Houghton, A. Osborn Department of Earth Sciences, UCL, Gower Street, London WC1E 6BT, UK Wolfson Laboratory for Environmental Geochemistry, Research School of Earth Sciences at UCL-Birkbeck, University of London, Gower Street, London WC1E 6BT, UK

*Corresponding author. Tel.: +44 207 679 7715; Fax: +44 207 383 0008; E-mail: k.hudson-edwards@ geology.bbk.ac.uk

Although arsenic (As) is only the 20th most abundant element in the continental crust, it occurs in detectable, but generally low, amounts in virtually all soils and sediments. Higher concentrations of As are recorded in soils and sediments that have been affected by anthropogenic activities, or where the soils and sediments overlie or are derived from As-rich mineralized rocks. Anthropogenic sources of arsenic include coal and metal mining, sewage, phosphate fertilizers, pesticides, wood preservatives and paints. Both high (up to 50010,000 ppm) and low concentrations of As in soils and sediments are potentially of concern, because they may contribute to high concentrations of As in pore or surface waters through desorption or dissolution, plants through growth and uptake, or animals (including humans) through ingestion (e.g., [1,2]). One of the most important examples of this that has been highlighted in recent years is the worldwide mass poisoning of tens of millions of people through drinking As-contaminated ground water (e.g., Bangladesh, Vietnam [3,4]). In these cases, the source of the

aqueous As is sediment that contains low concentrations of As (generally less than 25 ppm). The pathways of As from soil and sediment to water, plants and animals depend on the solid-phase partitioning of the As. Oxidation states of As in oxidized or weakly reduced soils and sediments are arsenite (III) and arsenate (V), while in strongly reduced soils, As(III) and As(0) may occur [5]. The major complexes formed by arsenite (As(OH)3 , As(OH)4 and AsO2 (OH)2 ) and arsenate (AsO43 ) are sorbed onto common soil minerals including clays [6] and hydrous Al, Fe and Mn oxides [7,8]. In order to be able to properly understand the global distribution of As in soils and sediments and its pathways to water, plants and animals, it is vitally important to be able to collect accurate and precise total and solid-phase partitioning data for As at high and low concentrations. To this end, we present in this article an overview of current methods used for the extraction and analysis of total As, and single and sequential extraction schemes for the solid-phase partitioning of As, in soils and sediments.

2. Methods for extracting and analyzing total As in soils and sediments A wide variety of methods exist for extracting and analyzing of total As in soils and sediments. Colorimetry has been recommended by the European Commission (EEC, Directive 90/515/EEC 1990) for the analysis of As in soils. X-ray uorescence spectrometry (XRF) is used by some workers [9] and government surveys [10]. Discs composed of homogenized, powdered 745

0165-9936/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2004.07.010

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Trends in Analytical Chemistry, Vol. 23, No. 1011, 2004

sediment or soil sample, and a sample binder, such as Molwiol, are subjected to high pressure (about 5 tonnes) and analyzed using an XRF instrument. The precision of XRF for samples with concentrations less than 500 ppm is very good, at 2 relative error [9]. The most common methods used to extract the total As from soils and sediments for later analysis involve wet ashing of the sample using one or a combination of the acids H2 SO4 , HNO3 , H2 O2 , HCl, H3 BO3 and HF. Some methods add a dry-ashing step prior to the wet ashing. The acids are used to achieve complete destruction of all As-bearing phases in the soil and sediment. Examples of these methods, which are used by governments and researchers, are summarized in Table 1. Recoveries for these methods, assessed through analysis of standard reference materials (SRMs) or certied reference materials (CRMs), are reported to be in the range 74110% (Table 1) (e.g., [1113]). These variations are ascribed to sample heterogeneity [14] and to loss of volatile As during extraction [13]. The latter can be limited by the use of H2 SO4 , which prohibits the formation of volatile species of As, and by the use of microwave-digestion instruments ([13], see below). The ashing methods can be carried out using a hotplate or microwave-digestion ovens [15,16]. Microwave methods are often recommended because there is little to no loss of volatile As during the extraction, analytical blanks are lower, and less time and less acid are needed to carry out the extraction. The extraction vessels used are typically made of uoropolymers (e.g., Teon, TFM or PFA), which can withstand high temperatures and high pressures (e.g., up to 260C for Teon [17]; or, 500 psi [18]) so that more efcient extraction of As is achieved. It is normally recommended that, following ashing and extraction, solutions be stored in polyethylene or polypropylene containers prior to analysis, since the As in glass can be leached and thus contaminate the sample. Extractant solutions are analyzed by a number

of analytical instruments, including graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). All of these methods may be combined with hydride generation (HG). Flame atomic absorption spectrometry (FAAS) is not commonly used for the analysis of As extracts, because of interferences and poorer detection limits (<1 mg/l As) than GF-AAS. HG-FAAS is used [16], as are GF-AAS and HG-GF-AAS [19]. Matrix modiers, such as nitrates of Ni, Pd or Mg, are added to each sample on injection to avoid losing As in the ashing stage (As sublimes at 613C), and to ensure that consistent signal intensities are achieved. With AAS techniques, background corrections can be made via the deuterium lamp as the wavelength (193.7 nm) for As is low and susceptible to interference from light scattering and matrix effects. HG is widely used because it can improve detection limits by up to 100 times. Many elements are difcult to analyze by FAAS as their primary atomic lines are below 200 nm, where the lines from the ame gases are also strong. HG is a powerful technique that utilizes chemical properties typical of the metalloid group of elements (e.g., As, Bi, Sb, Se, Te, Ge and Sn) to form volatile hydrides (arsine in the case of As). These hydrides are carried using a stream of inert gas to the atomizer and on into the ame. This method not only lowers the amount of matrix interference taken into the atomizer, but it also provides a longer residence time for atoms in the ame during their measurement, greatly improving sensitivity. ICP-AES is not used to a great extent for As analysis, because emission spectra suffer from interferences that give erroneous results. However, HG-ICP-AES is used to reduce or to eliminate these interferences and to improve detection limits [20]. ICP-MS is used extensively for the analysis of As-bearing extracts [12,13], but samples with high Cl concentrations lead to molecular interferences from

Table 1. Examples of extraction and analysis methods for total As in soils and sediments Reference United States Environmental Protection Agency (US-EPA) 2065, 1974 US-EPA 7060A, 1994 US-EPA 3050B, 1996 United States Geological Survey (USGS); [53] United States Department of Agriculture, 2001 (CLG-ARS.03) [14] [14] [24] Extraction method H2 SO4 HNO3 Analysis method AAS Recovery Not available Repeatability/ reproducibility Not available

H2 O2 HNO3 HNO3 HCl HNO3 H2 O2 , H2 SO4 HFHCl HNO3 HCl HNO3 H2 SO4 HClO4 HNO3 HCl H2 O2 HNO3

GF-AAS GF-AAS or ICP-MS HGFAAS AAS AAS AAS GF-AAS

Not available 100102% Not available 80110% (acceptable) 96 3% 74 1% Not available

Not available Not available Not available Repeatability (CV) 6 10 Reproducibility 6 20 Not available Not available RSD 1115%

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Trends in Analytical Chemistry, Vol. 23, No. 1011, 2004


40 Ar35 Cl in lower-resolution quadrupole instruments. It is therefore recommended that digests carried out with HCl should not be analyzed on such instruments. Techniques such as addition of nitrogen to the carrier gas [21] can be employed to reduce the interferences.

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3. Single and sequential extractions for As in soils and sediments Although it is undoubtedly important to know the total concentrations of As in soils and sediments, these concentrations do not give any information about the solid-phase partitioning and potential mobility of As within the soils. This is particularly important for As, which in many areas is in too low abundance or is associated with such ne-grained solid phases that characterization by standard mineralogical techniques is extremely difcult or time-consuming. Despite the well-known pitfalls of such sequential extractions (re-adsorption, poor reproducibility, lack of selectivity) [22,23], many workers have devoted time and effort to devising both single and sequential extraction chemical procedures for As in soils and sediments to estimate the operationally dened phase associations, solubility and availability of As, with a view to understanding the factors controlling As mobility. At present, there is no universally agreed standard method for single or sequential extractions of As in soils and sediments [2426]. Many sequential extraction schemes used for As are based on conventional schemes used to extract metals and other elements that form cations [22,2729]. However, other schemes recognize the anionic behavior of As in soils and sediments, and are based on extraction procedures for P [3035]. Schemes have also been developed for As specically [15,19], and are based on the knowledge that As is stable over a smaller range of Eh and pH than P, As has a greater propensity to form bonds with S and C than P, and organic As is less common than organic P in soils [19,30,36]. A summary of a selection of sequential extraction schemes used presently for As in soils and sediments is presented in Table 2. Attempts have been made in Table 2 to assign the reagents used by each author or group of authors to a standard descriptor (in the heading of the table); if the authors describe the extractant differently, the name that they use for the extraction step is indicated in parentheses. The most obvious feature of the schemes is the different numbers of steps involved, and different extractions used. Shaking times for each step are also vastly different, but are not shown in the table; readers are referred to the specic articles for more information. Virtually all of the schemes extract an easily sorbed phase, an Al-, Fe- and/or Mn-oxyhydroxide phase and a residual phase. Other operationally dened phases

extracted include water- or easily soluble, acid volatile sulphide, organic matter, acid-soluble, Ca-associated, As oxide and silicate, and As or Fe sulphide (Table 2). In general, most soil or sediment As is extracted by the Fe oxyhydroxide (reducible) phase, reecting the well-known association of As for Fe oxyhydroxides. The chemicals used for sequential extractions are introduced in increasing strengths and varying pHs, are chosen to minimize re-adsorption or precipitation between steps, and vary depending on the preference of the authors (Table 2) (e.g., ionically bound or exchangeable As is extracted using MgCl2 [22,24], (NH4 )2 SO4 [15], NaNO3 [37] and anion exchange membrane strips [19,35]). All of these extractants rely on the principle of ion exchange, whereby loosely bound As (indiscriminate with respect to mineral type) is exchanged with one of the components of the chemical extractants or membrane strips. Keon et al. [24], Wenzel et al. [15] and Cai et al. [37] have also extracted a specically adsorbed As fraction, using NaH2 PO4 , NH4 H2 PO4 and KH2 PO4 , respectively (Table 2). The basis of this fraction is the competitive exchange between phosphate (PO43 ) and arsenate (AsO43 ) in soils, where, because of the smaller size and higher charge density of phosphate, arsenate is preferentially desorbed over phosphate [38]. Acid volatile sulphides, carbonates, Mn oxides and amorphous Fe oxyhydroxides are extracted using a variety of chemicals (Table 2). By contrast, Al-associated As is almost always extracted by NH4 F [19,35], because of the stability of AlFe complexes [39]. Wenzel et al. [15] tested and subsequently questioned the ability of NH4 F to extract Al-bound As. They found no microscopic evidence for AsAl association, and suggested that the correlation between As and Al extracted by NH4 F was circumstantial for the soils that they were studying. Furthermore, they felt that signicant re-adsorption might occur between an NH4 F extraction and subsequent, often NaOH, extraction, and decided not to use it in their extraction scheme. However, they did suggest that NH4 F should probably be used in As-extraction schemes for soils rich in Al-clays. To extract As associated with amorphous and/or crystalline Fe oxyhydroxides, NaOH [19,35,40], oxalate/ oxalic acid [24], Ti(III)-citrateEDTA-bicarbonate [24], NH4 -oxalateascorbic acid [15] and Na citrate NaHCO3 HNO3 [19,35] are used as reagents (Table 2). Some of these reagents are oxidizing, promoting ligand dissolution (e.g., oxalate/oxalic acid of Keon et al. [24]), while others rely on reductive dissolution to release the As (e.g., Ti(III)-citrateEDTA-bicarbonate of Keon et al. [24]; Na citrateNaHCO3 HNO3 of Cappuyns et al. [35] and Van Herreweghe et al. [19]). Most of these reagents are regarded efcient in terms of removing Fe oxyhydroxide-associated As, but it should be noted that weaker chemicals, such as NaH2 PO4 and NH4 H2 PO4 , used for
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Table 2. Examples of sequential extraction schemes for arsenic


Reference (Water) Soluble Ionicallybound/ exchangeable Strongly adsorbed Acid volatile sulphides, carbonates, Mn oxides and amorphous Fe oxyhydroxides Al-associated Organic Amorphous matter/ and/or oxidisable crystalline Fe oxyhydroxides/ reducible Low (or acid) soluble Arsenic oxides and silicates / residual Pyrite and amorphous As2S Orpiment and other recalcitrant minerals

Chang and Jackson [42]

(1) 1 M NH4Cl

(2) 0.5 M NH4F

(3) 0.1 M NaOH

(4) 2 M H2SO4 (Caassociated) (5) CBD (reductantsoluble Feassociated) (5) HF/ HClO4

Tessier et al. [22]

(1) 1 M MgCl2

(2) 1 M NaOAc (carbonate)

(4) 8.8 M H2O2 / HNO3 + 0.8 M NH4OAc

(3) 0.04 M NH2OHHCl

Amacher and KotubyAmacher [44]

Ilyin and Konarbayeva [39]

(1) NH4Cl

(2) (NH4)2CO3 (sulphides & As bound to Al compounds) (3) Trilon B (enhanced dissolution of carbonates)

(2) (NH4)2CO3 (sulphides & As bound to Al compounds)

(4) NaOH (organic matter and Fe hydroxides)

(5) H2SO4

(1) 0.25 M HN2OHHC l/0.2 M HCl/0.025 M H3PO4 (metal oxides) (6) residual

(2) aqua regia + 8.8 M H2O2 (metal sulphides)

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Montperrus et al. [26]*

(1) Ultrapure water

(2) 0.1 M hydroxylamine hydrochloride (3) 0.2 M ammonium oxalate (2) 0.2 M oxalate/oxalic acid

(4) 0.3 M H3PO4

Gleyzes et al. [41]

(1) 0.1 M KH2PO4/ K2HPO4 (easily extractable) (1) 0.1 M (2) 0.1 M KH2PO4 NaNO3 (1) 1 M MgCl2 (2) 1 M NaH2PO4 (3) 1 M HCl

Cai et al. [37] Keon et al. [24]

Wenzel et al. [15]

(1) 0.05M (NH4)2SO4 (nonspecifically sorbed)

(2) 0.05 M NH4H2PO4 (specifically sorbed)

(3) 0.2 M + NH4 -oxalate buffer in the dark (amorphous and poorlycrystalline hydrous oxides of Fe and Al) (2) 0.5 M NH4F (pH 8.2) (NH4Fextractable)

(4) 0.2 M oxalate/oxalic acid (5) 0.05 M Ti(III)-citrateEDTAbicarbonate (4) 0.2 M + NH4 oxalate buffer + ascorbic acid (wellcrystallized hydrous oxides of Fe and Al) (3) 0.1 M NaOH (NaOH or Febound) (4) 0.5 M Na citrate & 1 M NaHCO3 while adding 0.5 g Na2S2O42H2O (4) 0.1 M NaOH (NaOH or Febound) (5) 0.5 M Na citrate + 1 M NaHCO3 0.02 MHNO3 (5) 0.25 M H2SO4

(6) 10 M HF

(7) 16 M HNO3

(8) 16 M HNO3 + 30% H2O2

(5) HNO3/H2O2 (microwave digestion) (residual)

Cappuyns et al. [35] and Van Herreweghe et al. [19] (based on Manful [34]) Scheme I

(1) 1 M NH4Cl (easily soluble)

(6) HCl / HNO3 / HF (residual)

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Cappuyns et al. [35] and Van Herreweghe et al. [19] (based on Manful [34]) Scheme II

(1) H2O

(2) 2 anionexchange membrane (AEM) strips

(3) 0.5 M NH4F (NH4Fextractable)

(6) 8.8 M H2O2 + HNO3 (0.02 M)

(7) HCl / HNO3 / HF (residual)

Where the descriptor of the operationally dened extraction for a given reference is different from that in the heading of the table, the difference name is given in parentheses after the chemical extractant used. * Carried out in a single extraction rather than in sequential extractions.

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strongly or specically adsorbed As, are also thought to remove As sorbed to Fe phases (e.g., ferrihydrite and goethite) [15]. Furthermore, even with the care taken with extraction schemes and quality-assurance measures, the extractions are not always selective. Van Herreweghe et al. [19] believed that they extracted Pb-arsenate during their NaOH extraction, which was designed to extract only Fe oxyhydroxide-associated As. H2 SO4 is used by some workers to extract Ca-associated, or acid-soluble, As [19,34,35,40]. Ca-arsenates are stable only in highly oxidizing and alkaline environments, and are more soluble than Al- and Fe-arsenates. Because of this, Van Herreweghe et al. [19] suggested that any Ca-arsenates would dissolve in weaker extractants (e.g., NH4 F) used earlier in sequential extraction schemes, so the H2 SO4 would not selectively extract Ca-arsenates but, rather, As bound to Fe oxyhydroxides. Van Herreweghe et al. [19] subsequently abandoned extraction of Ca-arsenates in favor of an operationally dened As oxide and silicate phase (Scheme II of Van Herreweghe et al. [19]; Table 2). Oxidizing, often concentrated, acids and reagents (e.g., H2 O2 , HF, HNO3 and aqua regia) are used to extract As bound to relatively insoluble phases and minerals, including sulphides, silicates, oxides and residual phases (Table 2). These are similar reagents to those used to extract total As from soils and sediments. Many of the sequential extraction methods and extractants used have been evaluated by Gleyzes et al. [41] and Van Herreweghe et al. [19], with conicting results. Gleyzes et al. [41] carried out careful comparisons of different extraction schemes on contaminated soils, and concluded that a cation-based scheme (slightly modied from [22]) was more convenient than the anionic, P-based scheme of Chang and Jackson [42] in evaluating the mobilization potential of As for their samples. Van Herreweghe et al. [19] compared the Community Bureau of Reference (BCR) cation-based scheme to an anion-based scheme specic to the properties of As, and recommended the latter (Table 2). Van Herreweghe et al. [19] also evaluated other sequential extraction schemes for As. Although they criticized the method of Keon et al. [24] as being circumstantial and using very hazardous reagents (HF and Ti(III) chloride), in fact, Keon et al. [24] did carry out rigorous quality assurance procedures. Moreover, the Keon et al. [24] method was used by Harvey et al. [43] to evaluate the solid-phase partitioning of As in sediments responsible for ground water As contamination. Harvey et al. [43] found that the sum of extractions was 120 39% of the total As determined by XRF, which was regarded as acceptable. The two-step method of Amacher and KotubyAmacher [44] that was developed to selectively extract As associated with metal oxides and metal sulphides (Table 2) was also criticized by Van Herreweghe et al. 750
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[19] because, during the reductive dissolution of amorphous Fe oxide by warm, acidied hydroxylamine hydrochloride in the rst step, As re-adsorbed to goethite. Van Herreweghe et al. [19] used the method of Jackson and Miller [45] and recommended that 0.1 M PO4 be added to step one to prevent this re-adsorption. A number of techniques are used to test the efciency of sequential extraction schemes for As in soils and sediments, including: intra-method reproducibility tests between different types of sample [24], adding known amounts of common As-bearing minerals and phases to sediment sub-samples [24], testing the extraction of As at different molar extractant strengths and times [15], and most commonly, comparing the sums of data for each extraction step with data for total elements [13,15, 19,24,43]. Coefcients of variation and relative standard deviations for replicates are reported by some researchers to vary from less than 5% to 10%, and accuracies from 88% to more than 90% [15,19,24]. Van Herreweghe et al. [19] found that the coefcient of variation was poorer for heavily contaminated natural samples (1120%), and attributed this to sample heterogeneity. Many researchers have strongly stressed the need for complementary mineralogical (X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, electron microprobe analysis), and spectroscopic methods (X-ray absorption near edge structure, [XANES] and X-ray absorption ne structure [EXAFS]) to validate sequential extraction data for As [13,19,24,26]. Two-step sequential extractions are used for bioavailability tests of As in humans, which in several cases are based on the fact that one of the major pathways of soils and sediments to humans (especially children) is ingestion through hand-to-mouth activity [46]. Rodriguez et al. [47] evaluated the bioavailability of As from mine- and smelter-contaminated soils by means of a sequential extraction scheme involving simulated gastric (0.15 M NaCl and 1% porcine pepsin) and intestinal solutions (NaHCO3 and porcine bile extract). Ruby et al. [48] devised a physiologically based extraction to simulate the conditions in the stomach (pH 2.5) and small intestine (pH 7). Simulated gastric solutions are prepared using HCl, pepsin, citrate, malate, lactic acid and acetic acid, and NaHCO3 is used to simulate intestinal conditions. Tests such as these are very useful bases for human risk-assessment studies. Single extractions are employed to determine the amounts of As that may be released from soils and sediments under particular environmental conditions. Some of these are based on portions of the sequential extraction schemes described above, while others have

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been developed for a specic purpose. Many workers have sought to assess the degree of afnity of As for Fe oxides in soils and sediments, because reduction of such As-bearing, amorphous Fe oxides may lead to release of As to water systems. Acid ammonium oxalate is used for this purpose [12], but it has been recognized that it may be too harsh an extractant and not selective enough, since it dissolves clay minerals and more crystalline Fe minerals (e.g., magnetite) [49]. Hydroxylamine hydrochloride is also used to extract Fe oxide-associated As [26,50]. The weakly acid-extractable concentrations of As in soils are determined using acetic acid [25,51]. Bhattacharya et al. [52] used sodium pyrophosphate (Na2 P4 O7 ) to extract organically associated As from alluvial sediments, and achieved accuracy and precision of 5%. Obviously, the choice of single or sequential extraction scheme for As will depend on the types of soils and sediments being analyzed. This was elegantly shown by Gleyzes et al. [41] and by Montperrus et al. [26], who found that orthophosphoric acid was the most efcient extractant for As in river sediment and sludge, and ammonium oxalate the most efcient for As in soil. A substantial amount of information about the soil or sediment should therefore be procured prior to undertaking the sequential extraction work. This should comprise analysis of the organic matter and nutrient (N, P) content, mineralogy, cation-exchange capacity, and the major and trace element geochemistry of the whole sediment or soil (e.g., soils with high concentrations of Fe oxides should employ a scheme that includes an extraction for As bound to Fe oxyhydroxides, and soils with high concentrations of Al and Al-clays, an extraction for As bound to Al-phases).

carried out to validate the operationally dened sequential extraction results for As. Moreover, efforts should be made to adopt universal standard methods for total and sequential extraction schemes of As in soils and sediments, because of its globally hazardous effects and scientic efforts to understand its biogeochemical cycling. There may be a need to adopt more than one sequential extraction scheme, because of the widely varying characteristics of As-bearing soils and sediments. Once the sequential extraction schemes are adopted, CRMs should be manufactured for each operationally dened phase of the scheme, and these should be made widely available. Acknowledgements We acknowledge support from the UK Natural Environment Research Council (NERC), The Royal Society, British Council, University of London Central Research Fund and Birkbeck College Faculty of Science that we have received over the years for our As-related research. References
[1] N. Belzile, A. Tessier, Geochim. Cosmochim. Acta 54 (1990) 103. , P. Tume, [2] J. Bech, C. Poschenrider, M. Llugany, J. Barcelo F.J. Tobias, J.L. Barranzuela, E.R. V asquez, Sci. Total Environ. 203 (1997) 83. [3] R.T. Nickson, J.M. McArthur, W.G. Burgess, K.M. Ahmed, P. Ravenscroft, M. Rahman, Nature (London) 395 (1998) 338. [4] M. Berg, H.C. Tran, T.C. Nguyen, H.V. Pham, R. Schertenleib, W. Giger, Environ. Sci. Technol. 35 (2001) 2621. [5] M.B. McBride, Environmental Chemistry of Soils, Oxford University Press, New York, USA, 1994. [6] M.A. Anderson, J.F. Ferguson, J. Gavis, J. Colloid, Interface Sci. 54 (1975) 391. [7] M.L. Peterson, T. Carpenter, Geochim. Cosmochim. Acta 50 (1986) 353. [8] A.L. Foster, G.E. Brown Jr., G.A. Parks, Geochim. Cosmochim. Acta 67 (2003) 1937. [9] A. Black, D. Craw, Int. J. Coal Geol. 45 (2001) 181. [10] British Geological Survey (BGS), Regional Geochemistry of NorthEast England, BGS, Keyworth, Nottingham, UK, 1996. [11] P.E. Kneebone, P.A. ODay, N. Jones, J.G. Hering, Environ. Sci. Technol. 36 (2002) 381. [12] K.A. Hudson-Edwards, M.G. Macklin, H.E. Jamieson, P.A. Brewer, T.J. Coulthard, A.J. Howard, J. Turner, Appl. Geochem. 18 (2003) 221. [13] A.G. Gault, D.A. Polya, J.M. Charnock, F.S. Islam, R.J. Lloyd, D. Chatterjee, Min. Mag. 67 (2003) 1183. lvez, C. Barbas, Anal. Chim. Acta 442 [14] A. Mar n, A. L opez-Gonza (2001) 305. [15] W.W. Wenzel, N. Kirchbaumer, T. Prohaska, G. Stingeder, E. Lombi, D.C. Adriano, Anal. Chim. Acta 436 (2001) 309. [16] A. Mucci, B. Boudreau, C. Guignard, Appl. Geochem. 18 (2003) 1011. [17] W. Goessler, D. Kuehnelt, in: W.T. Frankenberger Jr (Editor), Environmental Chemistry of Arsenic, Marcel Dekker, New York, USA, 2002, p. 27. [18] CEM Technologies, Microwave Digestion System, Promotional Literature, 2004.

4. Conclusions A wide variety of methods exists for extracting and analyzing total As and operationally dened solid fractions of As in soils and sediments. Extraction for total As is carried out by colorimetry, XRF, or wet ashing using acids on a hotplate or a microwave-digestion instrument. Analysis of acid extracts is carried out by FAAS, GF-AAS, ICP-AES or ICP-MS, with or without HG, which generally improves detection limits by up to 100-fold. Studies focusing on the determination of the solid-phase partitioning of As in soils and sediments employ sequential chemical extraction schemes, of which a wide variety exist. Schemes are based on those for extraction of cations or the anions P and As. Single extractions are also used to estimate bioavailable As or As associated with a particular, operationally dened phase, such as Fe oxides. We strongly recommend that complementary techniques (mineralogical and spectroscopic analysis, pore water analysis, and platinum-electrode potential [24]) be

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[19] S. Van Herreweghe, R. Swennen, C. Vandecasteele, V. Cappuyns, Environ. Pollut. 122 (2003) 323. [20] J. Dedina, D.L. Tsalev, Arsenic, in: J.D. Winefordner (Editor), Hydride Generation Atomic Absorption Spectrometry, Wiley, Chichester, West Sussex, UK, 1995, p. 182. [21] S. Branch, L. Ebdon, M. Ford, M. Foulkes, P. ONeill, J. Anal. Atom. Spectrom. 6 (1991) 151. [22] A. Tessier, P.G.C. Campbell, M. Bisson, Anal. Chem. 51 (1979) 844. [23] P.M.V. Nirel, F.M.M. Morel, Water Res. 24 (1990) 1055. [24] N.E. Keon, C.H. Swartz, D.J. Brabander, C. Harvey, H.F. Hemond, Environ. Sci. Technol. 35 (2001) 2778. [25] M.A. Taggart, M. Carlisle, D.J. Pain, R. Williams, D. Osborn, A. Joyson, A.A. Meharg, Sci. Total Environ. 323 (2004) 137. [26] M. Montperrus, Y. Bohari, M. Bueno, A. Astruc, M. Astruc, Appl. Organometall. Chem. 16 (2002) 347. [27] A. Ure, Ph. Quevauviller, H. Muntau, B. Griepink, Report EUR 14763 EN, European Commission, Brussels, Belgium, 1993. [28] Ph. Quevauviller, G. Rauret, H. Muntau, A.M. Ure, R. Rubio, J.F. Lopez-Sanchez, H.D. Fiedler, B. Griepink, Fresen. J. Anal. Chem. 349 (1994) 808. [29] D.E. Voigt, S.L. Brantley, R.J.-C. Hennet, Appl. Geochem. 11 (1996) 633. [30] L.R. Johnson, A.E. Hiltbold, Soil Sci. Soc. Am. J. 33 (1969) 279. [31] L.W. Jacobs, J.K. Seyers, D.R. Keeney, Soil Sci. Soc. Am. J. 34 (1970) 750. [32] E.A. Woolson, J.H. Exley, P.C. Kearney, Soil Sci. Soc. Am. J. 37 (1973) 254. [33] K.A. Gruebel, J.A. Davis, J.O. Leckie, Soil Sci. Soc. Am. J. 52 (1988) 390. [34] G.A. Manful, Occurrence and ecochemical behavior of arsenic in a goldsmelter impacted area in Ghana, Ph.D. Dissertation, Centrum voor Milieusanering, RUG, Ghent, Belgium, 1992. [35] V. Cappuyns, S. Van Herreweghe, R. Swennen, R. Ottenburgs, J. Deckers, Sci. Total Environ. 295 (2002) 217.

Trends in Analytical Chemistry, Vol. 23, No. 1011, 2004


[36] P. ONeill, Arsenic, in: B.J. Alloway (Editor), Heavy Metals in Soils, second ed., Blackie Academic & Professional, Glasgow, UK, 1995. [37] Y. Cai, J.C. Cabrera, M. Georgiadis, K. Jayachandran, Sci. Total Environ. 192 (2002) 123. [38] B.A. Manning, S. Goldberg, Soil Sci. Soc. Am. J. 60 (1996) 121. [39] W.L. Lindsay, Chemical Equilibria in Soils, Wiley, New York, USA, 1979. [40] B.V. Ilyin, G.A. Konarbayeva, Eurasian Soil Sci. 28 (1996) 144. [41] C. Gleyzes, S. Tellier, M. Astruc, in: Ph. Quevauviller (Editor), Methodologies for Soil and Sediment Fractionation Studies, Royal Society of Chemistry, Cambridge, UK, 2002 (Chapter 4). [42] S.C. Chang, M.L. Jackson, Soil Sci. 84 (1957) 133. [43] C.F. Harvey, C.H. Swartz, A.B.M. Badruzzaman, N. Keon-Blute, W. Yu, M. Ashraf Ali, J. Jay, R. Beckie, V. Niedan, D. Bradbander, P.M. Oates, K.N. Ashfaque, S. Islam, H.F. Hemond, M.F. Ahmed, Science (Washington, DC) 298 (2002) 1602. [44] M.C. Amacher, J. Kotuby-Amacher, Agron. Abstr. 86 (1994) 256. [45] B.P. Jackson, W.P. Miller, Soil Sci. Soc. Am. J. 54 (2000) 1616. [46] E. Calabrese, R. Barnes, E.J. Stanek, Reg. Toxicol. Pharmacol. 10 (1989) 123. [47] R.R. Rodriguez, N.T. Basta, S.W. Casteel, L.W. Pace, Environ. Sci. Technol. 33 (1999) 642. [48] M.V. Ruby, A. Davies, R. Schoof, S. Eberle, C.M. Sellstone, Environ. Sci. Technol. 30 (1996) 422. [49] P.L. Smedley, D.G. Kinniburgh, Appl. Geochem. 17 (2002) 517. mez-Ariza, D. Sanchez Rodas, I. Giraldez, J. Anal. Atom. [50] J.L. Go Spectrom. 13 (1998) 1375. [51] J. Kowalska, J. Golimowski, E. Kazimierska, Electroanalysis (NY) 13 (2001) 872. [52] P. Bhattacharya, G. Jacks, J. Jana, A. Sracek, J.P. Gustafsson, D. Chatterjee, KTH Special Publication, TRITA-AMI Report 3084 (2001) 21. [53] S.R. Jones, J.R. Garbarino, US Geological Survey Open-File Report 98639, 1999.

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