Analytica Chimica Acta 593 (2007) 16

Cathodic stripping voltammetric determination of As(III) with in situ plated bismuth-lm electrode using the catalytic hydrogen wave
Long Jiajie, Yukio Nagaosa
Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, University of Fukui, Bunkyo Fukui 910-8507, Japan Received 6 February 2007; received in revised form 22 April 2007; accepted 26 April 2007 Available online 1 May 2007

Abstract A highly sensitive method has been developed for the determination of trace As(III) by a square wave cathodic stripping voltammetry employing in situ plated bismuth-lm on edge-plane graphite substrate as working electrode. The presence of As(III) enhanced a cathodic peak corresponding to the catalytic hydrogen wave due to Se(IV) at about 1150 mV. Linear calibration curves for As(III) determination were obtained over the concentration ranges of 0.011.0 g L1 and 1.012.0 g L1 at deposition times of 30 s and 10 s, respectively. The detection limit (3) was estimated to be as low as 0.7 ng L1 As(III) at 30 s deposition time. The optimum experimental parameters and probable interference from foreign ions and organic compounds were investigated. This proposed method could be applied to analyses of certied reference material, synthetic and natural water samples. 2007 Elsevier B.V. All rights reserved.
Keywords: As(III); Speciation; Catalytic hydrogen wave; Bismuth-lm electrode; Edge-plane graphite; Square wave cathodic stripping voltammetry

1. Introduction Arsenic and its compounds have their own properties in toxicity and cancerogenic effect on human beings [15]. The accumulation of arsenic in all aquatic matrices of environment and in a variety of biological materials has been reported [68]. Arsenic(III) and its compounds are more toxic than arsenic(V) compounds, and inorganic arsenic is much more toxic than its organic compounds which are present at trace levels as certain co-enzymes in biological tissues [4,5,7]. Therefore, the determination of trace levels of arsenic and the arsenic speciation are required. For this purpose, a variety of methods have been developed and well established for the determination of arsenic species [912]. They include Hydride Generation Atomic Spectrometry (HGAAS), Graphite Furnace Atomic Absorption Spectrometry (GFAAS), an Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Atomic Fluorescence Spectrometry (AFS), X-ray Fluorescence, Neutron Activation Analysis, permitting accurate determination of trace levels of arsenic but mostly not for arsenic speciation. Pretreatment proce-

Corresponding author. Tel.: +81 776 27 8642; fax: +81 776 27 8747. E-mail address: Nagaosa@acbio2.acbio.fukui-u.ac.jp (Y. Nagaosa).

dures prior to arsenic determination, however, are so complicate and time-consuming that unreliable results are often produced in the on-site and eld analysis [312]. Electroanalytical methods such as stripping voltammetry, potentiometry and differential-pulse polarography have been reported for determining very low concentrations of arsenic in natural water samples. They have advantages over spectrometric methods in sensitivity, selectivity and capability for arsenic speciation analysis [12,13]. Most of the electrochemical methods include use of a hanging mercury dropping electrode (HMDE), a mercury-lm electrode or an in situ deposited mercury-lm electrode [11,14]. A glassy carbon and graphite carbons are very useful electrodes for anodic and cathodic stripping voltammetric methods [9,12]. Use of a catalytic hydrogen wave seems to be promising due to high sensitivity [13,15], in which cases As(III) can be electrochemically reduced to As(0) and arsine in acidic media onto the solid electrodes followed by cathodic stripping measurement. Interestingly, arsenic speciation was carried out in real matrices such as ground water, surface water and biological tissues by cathodic stripping voltammetry and constant-current potentiometry [16,17]. Being very toxic, mercury electrodes should be restricted for their use in electrochemical analysis. Recently, in situ bismuthlm electrodes as an alternative to mercury have been used

0003-2670/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.aca.2007.04.052

L. Jiajie, Y. Nagaosa / Analytica Chimica Acta 593 (2007) 16

in anodic stripping [1820], and adsorptive stripping [21,22] voltammetry. The purpose of this work is to develop a catalytic cathodic stripping method for the determination of As(III) by employing the in situ plated bismuth-lm electrode in the presence of Se(IV) in non-deaerated solution. The electrochemical role of selenium and bismuth, the optimum experimental parameters and the applications of this proposed method are described. 2. Experimental 2.1. Reagent and chemicals All chemicals used were of analytical reagent grade, and all solutions were prepared with deionized and distilled water. The stock Bi(III) solution was prepared by dissolving BiCl3 (Wako Pure Chemical Industries, Tokyo, Japan) in 0.5 mol L1 hydrochloric acid. The other metal ion solutions were prepared by diluting their standard solutions (1000 mg L1 , Wako Pure Chemical Industries, Tokyo, Japan) with 0.2 mol L1 hydrochloric acid solution. All stock solutions were stored in a refrigerator at 2 C. 2.2. Apparatus A BAS Model CV-50 W Voltammetric Analyzer (Bioanalytical systems, USA) was employed for measurements of linear sweep voltammetry (LSV) and Osteryang square wave voltammetry (OSWV). Unless otherwise stated, the settings for OSWV measurements were as follows: 4 mV step potential; 25 mV square wave amplitude; 15 Hz frequency; 10 s quiet time. An edge-plane pyrolytic graphite disk (3.0 mm diameter, BAS) as working electrode substrate, a platinum wire counter electrode and an Ag/AgCl (sat. KCl) reference electrode were used. 2.3. Procedures Prior to electrochemical measurement, the edge-plane graphite electrode was cleaned daily by polishing with aluminum oxide slurry and lter paper. The treated electrode was then immersed in 1.0 mol L1 hydrochloric acid for 1 min, and rinsed with water. After voltammetric measurements, the working electrode was treated as described above, and was reactivated by keeping the electrode potential at 800 mV for 30 s. The recommended procedures for the determination of As(III) by OSWCSV were carried out as follows: an aliquot (3.5 mL) of sample solution was placed into a 10-mL electrochemical glass cell. The equilibrium concentrations of added reagents except As(III) were adjusted to 0.2 mol L1 hydrochloric acid, 100 g L1 Bi(III), 10.0 g L1 Se(IV) and 5.0 g L1 potassium chloride solution. The As(III) was initially reduced at a potential of 400 mV for 30 s in a stirred and non-deaerated solution. After 10 s quiet time, the electrode potential was scanned from 500 to 1400 mV to the negative direction. Synthetic water samples (Model samples) were prepared from the standard As(III) solutions at different concentrations. After a coastal seawater (Mikuni, Fukui, Japan) and river water

(Kuzuryu, Fukui, Japan) were taken up, the samples were ltered with a 0.45- m Nuclepore lter paper and then acidied to 0.2 mol L1 hydrochloric acid. The resultant sample solution was treated according to the procedures described above. For total arsenic analysis, the samples were treated with 2.5 g L1 l-cysteine, 1.0 mol L1 hydrochloric acid at 80 C for 10 min to reduce As(V) to As(III). The NBS standard reference material, Oyster Tissue (5.00 g), was heated with concentrated nitric acid and hydrochloric acid, and evaporated to almost dryness. The residue was diluted with water to get appropriate concentrations. All samples were analyzed by standard addition and background subtraction method. 3. Results and discussion 3.1. Electrochemical behavior of arsenic on the bismuth-lm graphite electrode The electrochemical nature of a catalytic hydrogen wave due to As(III) was investigated by linear sweep voltammetry (LSV). Fig. 1(1) shows a typical LSV curve for blank solution containing 100 g L1 Bi(III) and 10.0 g L1 Se(IV) in 0.2 mol L1 hydrochloric acid. When the potential was scanned from 500 to 1400 mV to a cathodic direction, a small response triggered by Se(IV) was observed at about 1150 mV before nal rise of hydrogen reduction wave. The addition of 1.0 g L1 As(III) to the blank solution showed an increase of the hydrogen catalytic peak, as shown in Fig. 1(2). The peak current further increased considerably when a cathodic stripping LSV was performed following pre-concentration with a deposition time of 10 s and at 400 mV (see Fig. 1(3)). Our preliminary studies showed that there was no selenium cathodic response observed at about 1150 mV in the absence of Bi(III), and no arsenic response at the potential unless both Se(IV) and Bi(III) exist. It seems that there are some intermingling effects and/or new mixed com-

Fig. 1. Linear sweep voltammograms. (1) 0.2 mol L1 HCl + 100.0 g L1 bismuth + 10.0 g L1 Se(IV); (2) (1) + 1.0 g L1 As(III); (3) stripping voltammogram for (2) after 10 s deposition time; deposition potential:400 mV; scan rate: 100 mV s1 .

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Fig. 2. Effect of scan rates on |Ip |/v1/2 . Conditions: 0.2 mol L1 HCl; 100.0 g L1 Bi(III); 10.0 g L1 Se(IV); 1.0 g L1 As(III); deposition potential, 400 mV; deposition time, 10 s.

plexes are formed with arsenic, selenium and bismuth, although the mechanism is still not clear. In order to clarify the electrode process of the cathodic stripping LSV, the effect of scan rate (v) on the cathodic stripping LSV peak current (Ip ) was investigated. The results show that there was a linear relationship between |Ip | and v1/2 and no zero intercept (|Ip | = 2.3932v1/2 + 11.981, R2 = 0.9891) demonstrated a typical irreversible and catalytic behavior of arsenic triggered by selenium on the bismuth-lm graphite electrode [23]. The stripping peak potential shifted gradually to negative directions from 1100 to 1300 mV, also indicating an irreversible electrode process. As can be seen from Fig. 2, the dependence of |Ip |/v1/2 on scan rate showed gradual decrease with increased scan rate in the range of 20200 mV s1 . The enhanced cathodic peak due to As(III) at 1150 mV, therefore, is considered to have a nature of catalytic electrode process [23,24]. Osteryoung square wave cathodic stripping voltammetry (OSWCSV) at varying concentrations of As(III), as depicted in Fig. 3, produced well-dened and characteristic catalytic stripping peaks at about 1150 mV even at ppt-level of As(III). This method utilizing the catalytic stripping response enables traces As(III) determination in natural water samples, having advantages over other stripping methods with mercury electrodes at a short deposition time. The proposed OSWCSV method was found to be more sensitive than the corresponding stripping ones obtained by both LSV and DPV modes. Therefore, OSWCSV mode was employed in the subsequent work. 3.2. Effect of hydrochloric acid and potassium chloride concentration A mixture of potassium chloride and hydrochloric acid was chosen as the best supporting electrolyte because it can provide the highest catalytic peak current for arsenic on the OSWCSV curve. The catalytic peak current due to As(III) was also found to be dependent upon the acid concentration. The effect of hydrochloric acid and potassium chloride concentration on the catalytic peak current was therefore investigated, as shown in

Fig. 3. OSWCSV curves. (1) 0.2 mol L1 HCl + 100.0 g L1 Bi(III) + 5.0 g L1 KCl; (2) (1) + 10.0 g L1 Se(IV); (3) (2) + 10.0 ng L1 As(III); (4) (2) + 50.0 ng L1 As(III); (5) (2) + 0.1 g L1 As(III); (6) (2) + 0.2 g L1 As(III); (7) (2) + 0.4 g L1 As(III); deposition potential:400 mV; deposition time: 30 s.

Fig. 4(a and b), respectively. The catalytic peak current increased with the acid concentration ranging from 0.05 to 0.10 mol L1 ; then it decreased from 0.10 to 0.70 mol L1 . This result is in good agreement with the ones obtained with mercury electrodes [5,24]. The addition of potassium chloride showed an increased response ranging from 1.0 to 5.0 g L1 and a constant from 5.0 to 20.0 g L1 . In order to avoid the hydrolysis of Bi(III) during the in situ plating and stripping procedures, 0.20 mol L1 hydrochloric acid and 5.0 g L1 potassium chloride were chosen as the most suitable ones. 3.3. Effect of Bi(III) and Se(IV) concentration The effect of Bi(III) concentration on the OSWCSV peak current of 1.0 g L1 As(III) was investigated in the presence of 0.2 mol L1 hydrochloric acid and 50.0 g L1 Se(IV). As seen from Fig. 5, the peak current was found to decrease exponentially as Bi(III) concentration increased from 50.0 to 100 g L1 , above which concentrations a gradual decrease was observed up to 500 g L1 . The addition of Bi(III) at higher concentrations decreased the reduction and adsorption of the arsenic species onto the electrode surface, which resulted in decrease of the OSWCSV response due to As(III). Furthermore, our preliminary studies showed that in the absence of Bi(III) no OSWCSV response was observed at about 1150 mV. At higher concentration of Bi(III), the linear dynamic range for As(III) determination expanded although the sensitivity decreased. In the following experiments, 100 g L1 Bi(III) was added to test solutions. The effect of Se(IV) concentration on the OSWCSV response due to As(III) was investigated in the concentration range from 10.0 to 110 g L1 . The peak current (Ip , A) was directly proportional to Se(IV) concentrations (CSe , g L1 ) (Ip = 0.5111CSe + 2.5542, R2 = 0.9866), which suggested that the presence of As(III) enhanced the catalytic hydrogen evolution due to Se(IV) by the cathodic scan. This catalytic electrode reac-

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Fig. 6. Effect of deposition potential on OSWCSV peak current. Conditions: 0.2 mol L1 HCl + 100.0 g L1 Bi(III) + 10.0 g L1 Se(IV) + 5.0 g L1 KCl + 1.0 g L1 As(III); deposition time, 60 s.

split. In the recommended procedure, 10.0 g L1 Se(IV) was chosen. 3.4. Effect of deposition potential and time The effect of deposition potential on OSWCSV peak current due to arsenic was investigated in the range of 100 to 650 mV versus Ag/AgCl. The results shown in Fig. 6 indicate that the peak current started a rise at 200 mV, below which potentials Bi(III) was reduced to Bi and As(III) deposited to As together. At an applied potential of 400 mV, the peak current reached to a maximum, and gradually decreased with decreasing potentials; this is probably because the current efciency of arsenic reduction directly to AsH3 was decreased by the presence of dissolved oxygen. Another reason is unfavorable arsenic species (AsSe) formed on the electrode at the deposition step. The effect of deposition time on the peak current was also investigated in the range of 10180 s. The arsenic peak current (Ip , A) increased linearly as the deposition time (t, s) increased (Ip = 0.4033t 5.0679, R2 = 0.9961). Longer deposition times result in much more adsorption of arsenic species on the working electrode, improving the analytical sensitivity and therefore enabling ultra-traces of As(III) determination. One or 2 min as the deposition time should be chosen for As(III) analysis at ng L1 (ppt) concentration levels. In this study, 400 mV deposition potential and 30 s deposition time were employed. 3.5. Calibration curves and detection limit Under the chosen experimental conditions, the calibration curves for As(III) determination were constructed by OSWCSV employing the catalytic peak at different deposition time. As shown in Fig. 7(a), with 30 s deposition time, a linear relationship (r2 = 0.9898) was obtained between peak current and As(III) concentration. The linear dynamic range for trace As(III) determination was 0.011.0 g L1 with high sensitivity (slop = 17.50 A g1 L). The relative standard deviation was 5% (n = 4) at 1.0 g L1 As(III). The detection limit calculated as 3 from a calibration point at 10.0 ng L1 of As(III)

Fig. 4. Effect of HCl and KCl concentration on OSWCSV peak current. Conditions: (a) 100.0 g L1 Bi(III) + 30.0 g L1 Se(IV) + 1.0 g L1 As(III); (b) 0.2 mol L1 HCl + 100.0 g L1 Bi(III) + 10.0 g L1 Se(IV) + 1.0 g L1 As(III); deposition potential, 400 mV; deposition time, 60 s.

tion is so sensitive that the determination of trace levels of As(III) in natural waters is considered possible. Our preliminary studies also demonstrated that no peak was observed at 1150 mV without Se(IV) ions in the test solution. However, higher concentration of Se(IV) produced wider peak, and was easy to

Fig. 5. Effect of Bi(III) concentration on OSWCSV peak current. Conditions: 0.2 mol L1 HCl + 50.0 g L1 Se(IV) + 1.0 g L1 As(III); other conditions are the same as those in Fig. 4.

L. Jiajie, Y. Nagaosa / Analytica Chimica Acta 593 (2007) 16 Table 1 Interferences of foreign ions Foreign inorganic ions Sb(III), Zn(II) Fe(III), Pb(II), Cd(II) Cu(II), Hg(II), Ca(II) Mn(II) V(V) Na(I), Mg(II), Al(III), Co(II), Ni(II), Sn(II), W(VI), Mo(VI) NO3 , SO4 2 H2 PO4 NH4 +
a b

Tolerance level ( g L1 )a,b 0.5 0.8 1.0 10.0 50.0 103 103 2 103 7.0 102 160.0

1.0 g L1 As(III) taken. Within 8% error.

slop = 1.707 A g1 L), and the 3 detection limit was 0.2 g L1 . 3.6. Interference The effect of foreign ions on the OSWCSV determination of 1.0 g L1 As(III) by the proposal method was investigated at a range of concentrations. Table 1 summarizes the tolerance amounts that 1.0 g L1 As(III) could be determined within 8% error. The tolerance levels were 0.5 g L1 for Sb(III) and Zn(II), 0.8 g L1 for Fe(III), Pb(II) and Cd(II), 1.0 g L1 for Cu(II), Hg(II) and Ca(II), respectively. Especially, Cu(II), Hg(II) and Se(IV) are known to cause the formation of binary intermetallic compounds. The redox potentials of Sb(III) and Pb(II) are close to that of Bi(III). Such metal ions as Mn(II) and V(V) were tolerable at amounts up to 10 g L1 and 50 g L1 , respectively. There were no interference from Na(I), Mg(II), K(I), Al(III), Co(II), Ni(II), Sn(II), W(VI), Mo(VI) at 1000fold amounts relative to As(III). Such anions as NO3 and SO4 2 had no effect up to 2.0 mg L1 , and PO4 0.7 mg L1 , NH4 + 0.16 mg L1 , respectively. The presence of l-cysteine, sodium dodecylbenzene sulfonate, polyethyleneglycol mono-pnonylpheny ether were permissble at amounts less than 1.0, 0.1 and 0.1 g L1 , respectively. EDTA interfered seriously with the OSWCSV determination of As(III) at 0.1 g L1 .

Fig. 7. Calibration curves for As(III) determination by OSWCSV with deposition time (a) 30 s and (b) 10 s Conditions: 0.2 mol L1 HCl + 100.0 g L1 Bi(III) + 10.0 g L1 Se(IV) + 5.0 g L1 KCl; deposition potential, 400 mV.

was 0.7 ng L1 As(III) at 30 s deposition time. Considerably low detection limits lower than sub-ppt orders are expected to be obtained at longer deposition time. Evidently, the proposed methodology exhibited so high sensitivity, compared with the ones obtained by the stripping methods using mercury and other electrodes [14,2530]. Hopefully, the direct determination of trace or ultra-trace As(III) species in real samples is expected. Fig. 7(b) shows the calibration curve obtained with a shorter deposition time of 10 s; As(III) can be determined over the concentration range of 1.012.0 g L1 (r2 = 0.9924,

Table 2 Analytical results of As(III) determination in synthetic and real water samples Samples Model 1 Model 2 Model 3 Model 4a Seawater River water Seawater River water Experimental results ( g L1 ) 0.029 0.049 0.710 4.05 0.053 0.01 0.072 0.01 5.6 0.2 5.5 0.1 Reference values ( g L1 ) 0.030 0.050 0.700 4.00 0.045b 0.073b Relative errors (%) 3.3 2.0 1.4 1.3 Correlation coefcient (r2 ) 0.998 0.998 0.989 0.996 0.9967 0.9998 0.9895 0.9863

As(III)

AsTOT
a b

10 s deposition time. Determined by differential-pulse anodic stripping voltammetry.

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The proposed method is so sensitive and reliable that arsenic speciation of natural samples was possible with satisfactory results. 4. Conclusion The proposed OSWCSV method enables arsenic speciation at the trace levels by utilizing the co-deposition of Bi(III) and Se(IV) onto the edge-plane pyrolytic graphite substrate. The detection limit was estimated to be 0.7 ng L1 (ppt) As(III) with 30 s deposition time. The reference material (Oyster Tissue), coastal seawater and river water samples could be analyzed with good results. References
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Fig. 8. OSWCSV curves for arsenic determination of Oyster tissue. (1) 0.2 mol L1 HCl + 5.0 g L1 KCl; (2) (1) + 100.0 g L1 Bi(III); (3) (2) + 10.0 g L1 Se(IV); (4) (3) + real sample; (57) (4) + successive addition of 20 ng L1 As(III); deposition potential:400 mV; deposition time: 30 s.

3.7. Sample analyses At established experimental parameters, the proposed OSWCSV method was applied to synthetic and real sample analyses by standard addition and background subtraction method. In order to ensure the possibility of arsenic speciation, As(III) was rst determined followed by total arsenic determination after l-cysteine reduction. Synthetic samples (Models 14) spiked a known amount of As(III) were analyzed, and good recovery more than 97% was obtained (see Table 2). To validate the method, the standard reference material (Oyster tissue) was analyzed by standard addition method (see Fig. 8), and the analytical result (13.0 0.3 g g1 ) was consistent with the certied value (13.4 1.9 g g1 ). Table 2 also summarizes the results of arsenic speciation [As(III) and total arsenic] in coastal seawater (Mikuni, Fukui, Japan) and river water (Kuzuryu, Fukui, Japan) on four replicate analyses. The analytical results of As(III) determination were 0.053 0.010 and 0.072 0.013 for the seawater and river water samples, respectively (see Table 2).