Documente Academic
Documente Profesional
Documente Cultură
DOI 10.1007/s10653-007-9091-3
ORIGINAL PAPER
Abstract This study was undertaken to ascertain the best resolution and lowest detection limits.
optimal methods of sampling, preserving, separating, However, the procedure using a solid phase extrac-
and analyzing arsenic species in potentially contam- tion (SPE) cartridge can be used economically and
inated waters. Arsenic species are readily trans- conveniently for analyzing samples containing only
formed in nature by slight changes in conditions. inorganic arsenic species, such as groundwater,
Each species has a different toxicity and mobility. especially that related to mine activity.
The conventional field sampling method using filters
of 0.45 mm in size could overestimate the dissolved Keywords Arsenic speciation Sampling
arsenic concentrations, as passing suspended particles Preservation Analytical methods Sample condition
that can act as a sink or source of arsenic depending
on the site condition. For arsenic species in neutral
pH and iron-poor waters, the precipitation can be Introduction
stable for up to 3 days without any treatment, but for
longer periods, a preservative, such as phosphoric Arsenic is a problematic toxic contaminant, which
acid, is required. Also, the analytical procedure must has many chemical species, each with a different
be selected carefully because the levels and hydride toxicity and mobility (Mandal and Suzuki 2002). In
generation efficiencies of arsenic in different species natural water, arsenite [As(III)] and arsenate [As(V)]
can vary, even for the same amount of arsenic. For predominate (Plant et al. 2005). Organic arsenic
arsenic speciation in samples that also include species, such as monomethyl arsonate (MMA) and
organic species, a hybrid high-performance liquid dimethyl arsinate (DMA), are only present at low
chromatography (HPLC) column and inductively levels (Bednar et al. 2004). Inorganic arsenic species
coupled plasma mass spectrometry (ICP-MS) gave include known carcinogens (USEPA, accessed in
June 2006). Of these, As(III) is more toxic than
As(V), while the toxicities of the organic arsenic
Y.-T. Kim N.-C. Woo
species have not been fully evaluated (Thomas et al.
Department of Earth System Sciences, Yonsei University,
Seoul, Korea 2001; Hughes 2002; Aposhian et al. 2003). As with
their toxicities, the behaviors of arsenic species differ
Y.-T. Kim H. Yoon (&) C. Yoon markedly. The ionic charges of inorganic arsenic
Korea Basic Science Institute, Seoul Center, 136-600
species vary from 0 to 3, depending on the pH and
Seongbuk P.O. Box, 12, 88-3, Hawolgok 1-dong,
Seongbuk-gu, Seoul, Korea redox conditions (Raposo et al. 2006). For accurate
e-mail: dunee@kbsi.re.kr risk assessment of arsenic in the environment, the
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electro-chemical state of dissolved arsenic must be distinguishing the different organic species is gener-
retained during sample handling. ally difficult due to their low concentrations.
The stability of aqueous arsenic species is also In this study, our primary objective is to identify
dependent on the presence of other dissolved metal an optimal procedure for arsenic speciation in natural
ions. For example, iron is a common element in water samples without deforming chemical species.
arsenic-contaminated waters, which can precipitate if Sampling and preservation methods commonly used
oxidation occurs during sampling. Arsenic can co- for arsenic-bearing waters were thoroughly tested
precipitate with any Fe-oxyhydroxides or even under various conditions. Then, laboratory separation
change its oxidation state (Daus et al. 2002; Bednar procedures were compared with those employed in
et al. 2002). Pre-treatment of water samples involving the field and the limitations of the ICP-AES and ICP-
the complexation of metal ions or acidification of MS analytical methods for the determination of
samples has been proposed to prevent any precipita- arsenic species in natural samples under various
tion of metal oxyhydroxides. Daus et al. (2002) used conditions were discussed.
nitrilotriacetic acid (NTA), hydrochloric acid (HCl),
phosphoric acid (H3PO4), and acetic acid for this
procedure, and found the best results with Materials and methods
0.01 mol l1 H3PO4. Bednar et al. (2002) used
ethylenedinitrilotetraacetic acid (EDTA), sulfuric Water sampling and the application
acid (H2SO4), nitric acid (HNO3), and HCl to of the preservation method
preserve inorganic arsenic species in groundwater
and acid mine drainage samples. EDTA has been Groundwater samples were collected from the aban-
found to minimize precipitate formation and redox doned mines at Guryong and Ulsan, Korea. The
reactions. However, both of the above studies focused Guryong mine was an Au-Ag-Cu mine. The tailings
on iron-rich waters. Preferred pre-treatment proce- from this mine have been found to contain 7.04–
dures for iron-poor waters remain to be determined. 27.27 wt% Fe2O3, with As2O3 < 0.020 wt% (Kim
Various analytical techniques have been devel- 2004). Groundwater samples were taken from both
oped to distinguish and reduce the detection limits of monitoring wells (NX size, 3.500 inside diameter) and
different arsenic species. Different ion-exchange piezometers (100 inside diameter), and surface waters
resins have also been tried (Yu et al. 2003), and from a pond in the mine tailings. The Ulsan Fe-W
hydride generation procedures have been employed, mine was dug into a skarn that contains a consider-
in conjunction with atomic absorption spectrometry able amount of arsenopyrite (Choi and Youm 2000).
(AAS), atomic fluorescence spectrometry (AFS), Groundwater samples were collected from monitor-
inductively coupled plasma-atomic emission spectro- ing wells in the tailings and from domestic wells
photometry (ICP-AES) or ICP mass spectrometry around the mine. Surface waters were sampled from
(ICP-MS), not only to reduce the detection limits, but creeks and ponds near the Ulsan mine. All water
also to overcome interferences (Hung et al. 2004). samples showed high arsenic concentrations, which
Among these methods, a hybrid high-performance were generally in excess of the World Health
liquid chromatography (HPLC)/ICP-MS method has Organization (WHO) arsenic guideline of 10 mg l1
been most widely applied (B’Hymer and Caruso (WHO 1993) for drinking water, with the pH ranging
2004). In the majority of water analyses, most from neutral to weakly alkaline (pH 6.2–8.6).
attention has been paid to the predominant inorganic Along with groundwater sampling for a total
arsenic species, which are also recognized carcino- analysis of metal ions, various preservation methods
gens (Thirunavukkarasu et al. 2002). Analytical were applied to the separate samples to investigate
methods for the separation and detection of organic the changes in stability of dissolved ionic species,
arsenic species have been tested in the laboratory, but especially ‘‘arsenic,’’ by the duration of time after
these have only recently been applied to natural sampling has been done. Selective filter pore size
waters (Hung et al. 2004; Bednar et al. 2004; Akter and preserving chemicals have been applied to
et al. 2005; Sánchez-Rodas et al. 2005), where different samples for these purposes. Groundwater
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was not detected in water if it had not been acidified. of arsenic species are the same. However, different
In this case, precipitation can act as a sink for arsenic. behavior was observed when with the use of ICP-
H3PO4 can prevent the As co-precipitation with iron AES as the analytical method, the organic arsenic
oxides or hydroxides, and can also extract arsenic species in de-ionized water showed only half the
bound to these species (Ko et al. 2005). Therefore, intensities of the inorganic species. This problem can
the test changing the order of the H3PO4 addition, be resolved by acidifying the samples with nitric acid
before or after filtration, can inform us with regard to (Table 2).
the role of suspended particles. Groundwater samples Similarly, different intensities were obtained with
from the Ulsan mine contained some suspended different species during the HG procedure, even
particles; only one sample showed a difference in though the same concentrations of each arsenic
arsenic concentrations by changing the order of species were measured (Maity et al. 2004). The on-
H3PO4 addition: 4.15 mg l1 in the sub-sample of line HG method was tested for both inorganic and
H3PO4 addition before filtration, and 0.09 mg l1 in organic arsenic species by applying ICP-AES in order
the sub-sample of the H3PO4 addition after filtration. to achieve the lower detection limit. Figure 2 shows
This means that these suspended particles containing the hydride generation efficiencies of various arsenic
absorbed arsenic prior to sample collection can act as species in the same arsenic concentrations analyzed
a source of arsenic by condition change. by the on-line HG-ICP-AES. The efficiency of the
on-line HG procedure was best with the reduced
Analytical methods form, As(III), confirming the result of Hung et al.
(2004). According to the results in Fig. 2, the relative
Various techniques have been used for the determi- intensity of As(III), As(V), and MMA showed about
nation of arsenic speciation. Widely used procedures 50% intensities, and DMA about 10% intensities
have employed exchange resins to separate arsenic compared with 100%, or even. AsB failed to generate
species, coupled with spectroscopic and ICP analyses hydride gas.
to measure the arsenic concentrations (Hung et al. Until now, a conventional HG method, without
2004). In our study, both the SPE cartridge and HPLC any pre-reduction, has been most frequently used to
column were used for both field and laboratory measure the total arsenic concentrations in most
separation of arsenic species to examine any prob- applications, largely because organic species and
lems that could arise during analysis. As(III) are normally rare in natural waters (Maity
et al. 2004). However, where these species are
Analytical implications for various arsenic species present at high levels, the use of conventional
methods for the determination of the total arsenic
The measured intensities of different inorganic concentrations of waters would lead to under- or
arsenic species yield almost the same values during over-estimations. Consequently, whenever the con-
ICP-MS analysis (Table 1) if the absolute concentrations ventional HG method is used to measure the total
Table 1 Calculated intensities of arsenic species containing the same amount of arsenic, as measured by inductively coupled plasma
mass spectrometry (ICP-MS). All intensities were corrected using an internal standard
Species Intensity for 10 mg l1 Calibration
of arsenic
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Table 2 Relative spectral intensities produced by the same Moreover, in natural waters, organic arsenic species,
amount of arsenic for different species within different matri- such as MMA and DMA, are present as anions.
ces, as measured by inductively coupled plasma-atomic emis-
Consequently, As(III) will not be trapped in an SPE
sion spectrophotometry (ICP-AES)
cartridge, while As(V), MMA and some of the
Species Intensity for 50 mg l1 of arsenic organic species present as anions will (Yu et al.
De-ionized water 2% HNO3 2003), and can be extracted in the laboratory prior to
analysis. In the results of Yu et al. (2003), the
As(V) 1,817.64 1,881.95 percentages of As(III), As(V), DMA, MMA, and AsB
As(III) 1,597.83 1,772.39 retained on 2 g of strong anion exchange sorbent are
MMA 700.67 1,835.86 0, 100 ± 3, 41 ± 5, 100 ± 2, and 6.5 ± 3%. By
DMA 550.98 1,689.41 application of this method, Bednar et al. (2004) found
AsB 777.77 2,173.96 a recovery of 99% for 25 mg l1 As(V) after 47 days.
However, this technique can only be applied to
separate inorganic species if there are, as two or more
arsenic species, present as anions, cannot be sepa-
rated within the SPE cartridge. Further, it is useful to
know the rough arsenic concentrations involved due
to the limited cartridge capacity. For the analysis of
extractants with elevated anion contents, it is better to
avoid ICP-MS analysis, as arsenic when measured at
m/z 75 suffers from 40Ar35Cl+ interference.
Laboratory separation
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Fig. 4 The stability of arsenic species with different preser- 23.7 mg l1 and Fe 0.03 mg l1). Dashed lines were
vatives over time compared using laboratory separation concentrations of As(III) (bottom) and As(V) (top) using field
methods for (a) groundwater (pH 7.8, AsT 73.3 mg l1 and separation methods
Fe < 0.01 mg l1), and (b) surface water (pH 7.1, AsT
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small amounts of AsB, As(III) (1.9 mg l1) and DMA amounts of organic arsenic species. Hence, the
(3.4 mg l1; Fig. 5c). AsB is the predominant species SPE cartridge, used as a short column, is
in marine organisms, but is rare in freshwater appropriate for arsenic speciation in groundwater
(Dembitsky and Rezanka 2003). A creek water samples, but an HPLC column is required to
sample from the Ulsan area (Fig. 5d) showed high speciate arsenic in surface water samples.
arsenic concentrations. Although the dominant ar-
In conclusion, researchers should select their field
senic species in most surface waters is As(V), the
and laboratory procedures with caution and pay
As(III) concentration in this sample was 25.6 mg l1,
attention to the procedures of sample collection,
notably higher than the 11.0 mg l1 for As(V).
preservation, and analysis as well as consideration of
Construction involving the disturbance of surface
site characteristics.
sediments was being undertaken at this creek during
sampling, and the suspended surface sediments could Acknowledgement This research is a part of the Ph.D.
have influenced the arsenic species. dissertation work of Youn-Tae Kim, Yonsei University.
Financial support was provided by the research fund from
the Korea Basic Science Institute (N26051) and the Korea
Research Foundation (KRF-2005-C00081).
Conclusion
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