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Green Analyzer for the Measurement of Total Arsenic in Drinking Water: Electrochemical Reduction of Arsenate to Arsine and Gas Phase Chemiluminescence with Ozone
Mrinal K. Sengupta, Maather F. Sawalha, Shin-Ichi Ohira, Ademola D. Idowu, and Purnendu K. Dasgupta* Department of Chemistry and Biochemistry, University of Texas at Arlington, Planetarium Place, Arlington, Texas 76019-0065 We describe matrix-isolated, reaction chemistry based measurement of arsenic in water down to submicrograms per liter levels in a system that requires only air, water, electricity, and dilute sulfuric acid, the bulk of the latter being recycled. Gas phase chemiluminescence (GPCL) measurement of arsenic is made in an automated batch system with arsenic in situ electroreduced to arsine that is reacted with ozone to emit light. The ozone is generated from oxygen that is simultaneously anodically produced. Of 22 different electrode materials studied, graphite was chosen as the cathode. As(V) is reduced much less efciently to AsH3 than As(III). Prereducing all As to As(III) is difcult in the eld and tedious. Oxidizing all As to As(V) is simple (e.g., with NaOCl) but greatly reduces subsequent conversion to AsH3 and hence sensitivity. The rate of the AsH3-O3 GPCL reaction and hence signal intensity increases with [O3]. Using oxygen to feed the ozonizer produces higher [O3] and substantial signal enhancement. This makes it practical to measure all arsenic as As(V). The system exhibits an LOD (S/N ) 3) for total arsenic as As(V) of 0.36 g/L (5 mL sample). Comparison of total As results in native and spiked water samples with those from inductively coupled plasma mass spectrometry (ICPMS) and other techniques show high correlation (r2 ) 0.9999) and near unity slopes.
Exposure to elevated levels of arsenic, a class I human carcinogen,1 has become a global concern, affecting millions worldwide.2 The currently recommended upper limit of arsenic in drinking water is 10 g/L.3 Temporal and seasonal changes in arsenic in South Asian well water are well documented,4,5 necessitating frequent measurement. It is desirable that such
* Corresponding author. E-mail: Dasgupta@uta.edu. Phone: (817) 272-3171. Present address: Department of Chemistry, Palestine Technical University, Palestine. Present address: Department of Chemistry, Kumamoto University, Kumamoto, Japan 860-8555. Present address: Dow Chemical, Freeport, TX 77541. (1) IARC. Some Drinking-Water Disinfectants and Contaminants, Including Arsenic. IARC Press: Lyon, France, 2004. (2) Mukherjee, A.; Sengupta, M. K.; Ahamed, S.; Hossain, M. A.; Das, B.; Nayak, B.; Rahman, M. M.; Chakraborti, D. J. Health, Popul. Nutr. 2006, 24, 142 163. 10.1021/ac100604y 2010 American Chemical Society Published on Web 04/09/2010

systems should be reliable, eld usable, inexpensive, sensitive and green, not involve unsafe, noxious, or expensive chemicals. A recent review covers the measurement of environmental arsenic.6 Electrochemistry may have the most promise to meet the desired goals but despite innovations,7,8 electrochemistry generally works only well with As(III). Reducing all As to As(III) is not practical in the eld and typically involves expensive reagents and/or heating. The reliability of Field Kit-results9 near the regulation limits have been questioned,10,11 aside from concerns with arsine leakage and lead/mercury waste generation.12 We have worked on practical eld-usable analytical methods for the gas phase chemiluminescence (GPCL)-based determination of arsenic that relies on CL produced by the arsine-ozone reaction.13 This has been used for chromatographic detection,14 validated for soil/dust samples,15 and adapted for manual lowcost use.16 Recently Xue et al.17 have also reported GPCL-based chromatographic measurement of As following photoxidation
(3) United States Environmental Protection Agency (U.S. EPA). Federal Register: January 22, 2001, Vol. 66, No. 14, pp 6975-7066. http:// www.epa.gov/fedrgstr/EPA-WATER/2001/January/Day-22/w1668.htm. (4) Chakraborti, D.; Basu, G. K.; Biswas, B. K.; Chowdhury, U. K.; Rahman, M. M.; Paul, K.; Chowdhury, T. R.; Chanda, C. R.; Lodh, D. Arsenic Exposure and Health Effects; Chappell, W. R., Abernathy, C. O., Calderon, R. L., Eds.; Elsevier Science: New York, 2001; pp 27-52. (5) Thundiyil, J. G.; Yuan, Y.; Smith, A. H.; Steinmaus, C. Environ. Res. 2007, 104, 367373. (6) Luong, J. H. T.; Majid, E; Male, K. B. Open Anal. Chem. J. 2007, 1, 714. (7) Male, K. H.; Hrapovic, S.; Santini, J. M.; Luong, J. H. T. Anal. Chem. 2007, 79, 78317837. (8) Hrapovic, S.; Liu, Y.; Luong, J. H. T. Anal. Chem. 2007, 79, 500507. (9) van Geen, A.; Cheng, Z.; Seddique, A. A.; Hoque, M. A.; Gelman, A.; Graziano, J. H.; Ahsan, H.; Parvez, F.; Ahmed, K. M. Environ. Sci. Technol. 2005, 39, 299303. (10) Rahman, M. M.; Mukherjee, D.; Sengupta, M. K.; Chowdhury, U. K.; Lodh, D.; Chanda, C. R.; Roy, S.; Selim, M.; Quamruzzaman, Q.; Milton, A. H.; Shahidullah, S. M.; Rahman, M. T.; Chakraborti, D. Environ. Sci. Technol. 2002, 36, 53855394. (11) Khandaker, N. R. Environ. Sci. Technol. 2004, 38, 479A. (12) Hussam, A.; Alauddin, M.; Khan, A. H.; Rasul, S. B.; Munir, A. K. M. Environ. Sci. Technol. 1999, 33, 36863688. (13) Idowu, A. D.; Dasgupta, P. K.; Genfa, Z.; Toda, K.; Garbarino, J. R. Anal. Chem. 2006, 78, 70887097. (14) Idowu, A.; Dasgupta, P. K. Anal. Chem. 2007, 79, 91979204. (15) Sawalha, M. F.; Sengupta, M. K.; Ohira, S.-I.; Idowu, A. D.; Gill, T. E.; Rojo, L.; Barnes, M.; Dasgupta, P. K. Talanta 2008, 77, 372379. (16) Sengupta, M. K.; Hossain, Z. A.; Ohira, S. I.; Dasgupta, P. K. Environ. Pollut. 2010, 158. 252257. (17) Xue, J. H.; Zhu, Z. L.; Zhang, S. C.; Zhang, X. R. Luminescence 2009, 24, 290294.

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Figure 1. System schematic: (a) liquid handling module, consisting of syringe pump and multiport distribution valve (SP) and various sample/ reagents. (b) Electrochemical arsine generation module: The electrochemical reactor (ECR) consists of a disposable syringe barrel (SB) with a neoprene stopper (NS) housing a Teon tape (TT) wrapped graphite rod (GR), ceramic tube (CT) that houses a Pt foil anode connected via a Pt wire exiting through the sealed end of tee T2. The power supply (PS) is connected to GR and the Pt anode. Tees, T1 providing waste/wash port WWP and T2 providing anode liquid outlet AO, connects to a three-way isolation valve IV with tee T3 placed in-between. The solid line of solenoid valve IV is the common port, normally connected to the reservoir vessel (RV) that acts as the anolyte and oxygen storage; when turned on, IV is connected to the container TC. One port of SP can access TC and deliver liquid back to RV via T3. The RV liquid is recirculated by pump PP through the anode liquid inlet AI connected to CT. Oxygen from RV exits through glass wool lled liquid trap GT and feeds the ozonizer OZG. (c) Gas phase chemiluminescence detection module. Ozone generated by OZG ows into the chemiluminescence chamber CC while arsine coming from SB via exit tube E enters CC via solenoid valve SV and liquid trap LT, the exit gas ows out through activated Mn oxide catalyst MC. The emitted light is detected by the photomultiplier tube (PMT).

similar to ref 14, while the photoxidation step is much faster, the limits of detection (LODs) obtained do not compare favorably. We have used borohydride reduction throughout to reduce arsenic; the kinetics of this reduction for As(III) and As(V) are very different.18 Electrochemical arsine generation (EAG) has been reproducibly achieved in ow systems with diverse detectors.19-26 In eld analysis, discrete batch measurement is more practical (better liquid economy) than ow methods. Except for an early attempt to couple EAG to GPCL in which both sensitivity and reproducibility were poor, described by us in a patent application,27 there are no reports of batch mode EAG. Here we describe a graphite cathode EAG-GPCL system that (a) oxidizes all As to As(V) in situ with NaOCl, (b) uses anodically generated O2 produced during EAG to make ozone, and (c)
(18) (19) (20) (21) (22) (23) (24) (25) (26) (27) Sengupta, M. K.; Dasgupta, P. K. Anal. Chem. 2009, 81, 97379743. Arbab-Zavar, M. H.; Hashemi, M. Talanta 2000, 52, 10071014. Ding, W.-W.; Sturgeon, R. E. J. Anal. At. Spectrom. 1996, 11, 225230. Shen-Tu, C.; Fan, Y.; Hou, Y.; Wang, K.; Zhu, Y. J. Chromatogr., A 2008, 1213, 5661. Li, X.; Jia, J.; Wang, Z. Anal. Chim. Acta 2006, 560, 153158. Ozmen, B.; Matysik, F. M.; Bings, N. H.; Broekaert, J. A. C. Spectrochim. Acta B 2004, 59, 941950. Pohl, P.; Zapata, I. J.; Bings, N. H. Anal. Chim. Acta 2008, 606, 918. Machado, L. F. R.; Jacintho, A. O.; Menegario, A. A.; Zagatto, E. A. G.; Gine, M. F. J. Anal. At. Spectrom. 1998, 13, 13431346. Hueber, D. M.; Winefordner, J. D. Anal. Chim. Acta 1995, 316, 129144. Dasgupta, P. K.; Idowu, A.; Li, J. Method and Apparatus for Analyzing Arsenic Concentrations Using Gas Phase Ozone Chemiluminescence. International Patent Publication No. WO 2007/081635 A2, July 19, 2007, http://www.wipo.int/pctdb/en/wo.jsp?WO)2007081635 (Accessed March 8, 2010).

utilizes the elevated O3 levels to enhance sensitivity and measures total As as As(V). EXPERIMENTAL SECTION Standards and Reagents. All reagents are commonly available and were obtained from standard suppliers; see Table S1 in the Supporting Information for details of cathode materials. Except as stated, graphite rods used were EDM graphite rods, type EC16, www.graphitestore.com). Instrumentation. The system (Figure 1) has three modules: The sample and reagent handling module a consists of a 48Kstep syringe pump SP with a 10 mL syringe and a multiport distribution valve (used previously, discussed therein13,15,18 and briey in the Supporting Information). The pump delivers sample and reagents to the electrochemical reactor (ECR), removes waste therefrom, and also supplies deionized wash water. Module b consists of the ECR, a 30 mL plastic syringe barrel SB (P/N 309650, Becton-Dickinson, http://www.bd.com), with a no. 4 neoprene stopper (NS) on the inverted end. Three components enter through the NS, from left: (1) the arsine generation electrode (except as stated, a graphite rod GR, 6.0 mm diameter 150 mm long, wrapped with PTFE tape TT to control the exposed area, only the bottom 2.5 mm was exposed during operation; sufcient length of the electrode protruded through the stopper to be connected to the negative terminal of the power supply PS (Hewlett-Packard 6266B)), (2) a 12 gauge PTFE anolyte inlet line AI (2.1 mm i.d., 3 mm o.d.), push t into a porous ceramic tube CT (3 mm i.d., 5 mm o.d., 0.2 m pores). At the bottom of the

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syringe, rst a larger tee (T1, 3/8 in., polypropylene) is afxed and into it is push t a second, smaller tee (T2, 3/16 in., both tees: www.arkplas.com). The reactor is washed/drained through the T1 side arm by SP. The bottom of tube CT seals into T2, and the T2 side arm provides the anolyte outlet (AO). A Pt foil electrode (45 mm long, 2.5 mm wide) is connected to a 0.25 mm diameter Pt wire. This electrode assembly is inserted into CT through T2 bottom; the protruding wire is sealed in with hotmelt adhesive and connected to PS(+). The micropores in CT provide bulk ow resistance and prevent catholyte-anolyte mixing but ionic passage under applied voltage (and hence current) is easily established. To minimize effective anode area continuously changing from gas bubbles in a narrow tube, the anolyte (0.1 M H2SO4) was recirculated at 6 mL/min by a peristaltic pump PP (Dynamax RP-1, www.Rainin.com). (3) The third component entering the NS is a PTFE tube E that carries the liberated AsH3 to the GPCL detection module (Figure 1c). After electroreduction proceeds for a preset period, the normally closed solenoid valve (SV) opens to let liberated AsH3/H2 enter the chemiluminescence chamber CC (externally silvered inverted test tube) sitting atop a photomultiplier tube (PMT) via a glass wool lled liquid trap LT. The GPCL module has been described;13-16 some details are in the Supporting Information. Ozone is generated with air (5-10 standard cubic centimeters/ min (sccm) pumped by a small miniature air pump) or with electrogenerated oxygen (vide infra). The reactant gases exit CC through a MnOOH catalyst bed MC (Carulite 200, www. caruscorporation.com) to destroy unreacted ozone. Electrogenerated Oxygen-Based Ozone Generation. While oxygen can be independently generated and supplied, oxygen anodically generated during EAG was already available. We used simple gravity-based gas-liquid partitioning (Figure 1b). The reservoir vessel, RV (1-2 L capacity, 75% lled with 0.1 M H2SO4) supplies the anolyte to pump PP that recirculates it through the ECR anode chamber. During electrolysis, the T2 side arm brings out both the anolyte and O2. Through another 3/32 in. tee T3, the stream enters RV where oxygen accumulates in the headspace and passes into the ozonizer (OZG, Figure 1c) through a glass wool trap (GT) that removes any liquid droplets; the ow rate at steady state is 4 sccm, the same as that produced electrolytically, enough to supply sufcient ozone ow for the CL reaction. In order to maintain a constant liquid level in RV and constant O2 ow to the OZG, a three-way solenoid valve IV (both SV and IV from www.Nresearch.com) interfaces the ECR via T3 to either RV or SP. During ECR wash, the owing anolyte goes to a temporary container TC and is later resupplied (as a 3 mL aliquot) to RV by SP through T3. Note that water is lost through both electrolysis and by evaporation from the electrically heated liquid via the evolved gases. The acid concentration in RV thus gradually increases. With 1 L capacity RV 75% lled in the beginning and an EAG current of 1 A and operating at an ambient temperature of 23 C, we nd that the acid level can be maintained constant if instead of the acid, 3 mL of water is supplied after every 19 samples. For an anolyte concentration around 0.1 M H2SO4, minor increases in concentration does not greatly inuence the analyte response. The reason for slow concentration increase of the anolyte is discussed in more detail in the Supporting Information.

Operational Sequence. Initially, anolyte ow from RV to the ECR anode chamber is started by pump PP. SP then introduces 5.0 mL of sample, followed by 2.0 mL of 0.5 M H2SO4 as the outer catholyte. Electrolysis begins immediately; a constant current of 1 A is maintained, requiring 15-18 V. Electrolysis gases are allowed to accumulate for 60 s before SV opens for the next 5 min and electrogenerated AsH3 proceeds completely to CC. After measurement of the CL signal, IV connects to SP; SP withdraws the catholyte and sends it to waste. Depending on the desired degree of sample carryover, up to 10 mL of water is pumped into the ECR and kept for 30 s before aspirating off. IV closes, followed by a 3 mL addition of 0.1 M H2SO4 from TC to RV. The entire cycle is 8 min/sample. RESULTS AND DISCUSSION System Optimization. Initial optimization of gas ow rates, electrolyte concentration/ow rates was performed using the platinum anode and cathode. Platinum as the anode provides the needed inertness;28 it was also initially selected as the cathode based on its reported use in EAG systems,20,25,26,29,30 albeit some report low efciency. Key EAG literature ndings are summarized in Table S2 in the Supporting Information. After the nal cathode choice, electrolyte concentration/ow rates were reoptimized. Glass and polypropylene ECR bodies performed equally well; we retained the plastic disposable syringe. The cathode and anode compartments require a bulk ow barrier; initial comparison of the ceramic tube used with Naon tubing (4.5/6.6 mm i.d./o.d.) in 1.0/0.2 M H2SO4 catholyte/anolyte showed 30% less resistance for the ceramic tube based cell; it was henceforth used. Ozone and Analyte Flow. The GPCL signal depends in a complex fashion on the ozonizer ow rate. At high ow rates, generated [O3] is reciprocally related to the air/O2 feed rate (constant mass of ozone produced). At very low ow rates, a maximum plateau concentration is seen (this equilibrium concentration is 5 higher for O2 than for air). The ASH3-O3 reaction is not instantaneous, higher [O3] leads to a faster reaction and a sharper signal. However, a high ow of O3 reduces the cell residence time and the reactants escape the PMT view before reaction completion. The relevant [O3] value here is that in the cell, after dilution with the AsH3/H2 ow. Consider that electrolytic H2 produced with 1 A current is 7 sccm; accordingly, we found that 4-9 sccm ozonizer ow produces the maximum CL intensity. A further ow increase decreases the signal (details can be seen in Figure S1 in the Supporting Information). Thus, we selected 4 sccm oxygen or 7 sccm air feed ow into the ozonizer. Choice of Cathode. The cathode is critical for EAG and affects hydride generation efciency and reproducibility; acidic sample compatibility is also important.30 Carbon in different forms and lead have been most commonly used in electrochemical hydride generation (EHG) systems.21,23,28,29 They tolerate acidic media, and proponents report better EHG efciency than other cathodes. However, carbon electrodes also reportedly show so much lower response for As(V) compared to As(III)20,31 that prereduction is
(28) Laborda, F.; Bolea, E.; Castillo, J. R. Anal. Bioanal. Chem. 2007, 388, 743 751. (29) Ding, W. W.; Sturgeon, R. E. Spectrochim. Acta B 1996, 51B, 13251334. (30) Denkhaus, E.; Golloch, A.; Guo, X. M.; Huang, B. J. Anal. At. Spectrom. 2001, 16, 870878.

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Figure 2. Chemiluminescence signal from 50 g/L As(III) and 50 g/L As(V) on different cathodes relative to the response of 50 g/L As(III) on a Pt cathode taken as unity. Metals Nd-Pt are listed in order of their standard reduction potential; carbon, nichrome, and stainless steel are listed thereafter.

essentially mandatory. A Pb cathode reportedly suffers from interferences by high concentrations of other elements.20 It is difcult to compare different literature reports as no two use the same conditions. We compared the performance of 20 metals (Pb, Sn, Zn, Ni, Nb, Cd, Co, C (graphite), Mo, Ti, W, In, Zr, Ta, Pd, V, Nd, Pt, Cu, and Al) and two alloys (Ni-Cr and type 316 stainless steel) as cathodes. Most electrodes were initially tested as 1 cm 1 cm foils, with a 0.25 mm Pt-wire providing electrical connection; Ni-Cr was tested as a 40-mesh gauze of equivalent electrode area. All cathode materials were tested using 50 g/L As(III) and As(V) each, with a Pt anode, 0.1/0.5 M H2SO4 as the catholyte/ anolyte (latter recirculated at 6 mL/min), and a constant current of 1.0 A. (These are default conditions for all experiments unless otherwise stated.) A recent review by Laborda et al.28 suggest that EHG takes place in four steps: (a) diffusion of the analyte to the cathode (it is thus essential to convert As(V) to an uncharged species by a strongly acidic medium); (b) reduction to the element on the cathode surface; (c) reduction of water to hydrogen, also on the cathode surface and formation of the hydride thereon; and (d) diffusion of the hydride away from the electrode. Hydride generation efciencies are the parameters of general interest. Interference by high levels of other metals, sometimes considered a performance parameter, is not relevant in drinking water analysis. In Figure 2, the response of different cathodes toward 50 g/L of As(III) and As(V) are shown with the As(III) response of a platinum cathode taken as unity. Hydrogen evolution overpotential (HEO) of a metal has often been regarded as an important parameter in governing EAG cathode behavior. With higher HEO values, more of the atomic hydrogen will still be on the electrode surface and thus take part in hydride formation. HEO is a function of the solution composition and current density. Denkhaus et al.30 measured HEO at various current densities for several electrode materials, and they reported that EAG efcien(31) Schaumloffel, D.; Neidhart, B. Fresenius J. Anal. Chem. 1996, 354, 866 869.

cies did track the HEO values. Further, on electrodes such as Pb, Cd, and amalgamated silver, they reported that As(V) could be reduced as easily as As(III). Our data are clearly not concordant. Neodymium was the only metal that produced no signal; the Nd electrode could not be kept from dissolving even with high negative voltages applied. Electrodes of graphite, Al, V, Zn, In, Sn, Pb, Pd, and stainless steel (316SS) were more effective than Pt for the reduction of As(III). Only Al produced statistically equivalent responses for As(III) and As(V). Appreciable As(V) response was also produced by Zn, In, Pb, 316SS, and to a smaller extent, the graphite electrodes. Al, Zn, and V slowly eroded even with cathodic potential applied; considering the low cost and ready availability of Al foil, it may nevertheless be possible to design a disposable Al electrode based device. In these initial experiments, graphite showed the highest As(III) response but the variability was high. The imprecision came from the fragile nature of the graphite foil and the difculty of reproducibly establishing electrical connections. Switching to a mechanically robust graphite rod solved reproducibility issues. Cathode Memory and Conditioning. All aspects of EAG cathode behavior are not revealed by Figure 2; these data represent stable signals that are nally obtained when 50 g/L As is repeatedly injected. Cathodes of Mo, W, In, Zn, Zr, Pd, V, and 316SS exhibited varying degrees of memory; i.e., starting from a blank when the rst standard was injected, the response was low. Only after a number of injections was a steady stable response observed. Similarly, returning to blanks did not immediately produce a zero response. This may be related to specic metals forming surface alloys/intermetallic composites with As. The extant literature indicates cathode preconditioning, whether by mechanical scrubbing/polishing, chemical oxidation by brief immersion in nitric/chromic acids, or electrochemical polarity reversal, is often necessary. In our experiments, the need for such conditioning varied considerably: electrodes of Cd, Ni-Cr, Sn, Co, In, and Ni required frequent conditioning. Otherwise after about an hour of operation, the response decreased. Cathode Response and Reproducibility. On the basis of these results, we selected 316SS, Pb, and two different types of carbon (graphite and high-purity spectroscopic grade carbon rods) for further investigation. Reproducibility was checked over 3-6 consecutive days on the same electrode; the 316SS and Pb electrodes were foils while both carbon electrodes were 3-6 mm diameter rods. Response to 50 g/L As(III) is shown in Figure 3; the response with a 316SS cathode was the lowest and typically exhibited the highest within-day variance. Lead showed great variability between the rst and subsequent days. Spectroscopic carbon response increased over days; it is possible with this and the Pb electrodes that deposition of impurity metals (including As) or surface alteration leads to better performance. By far the best performance, in terms of response, within-day and betweenday reproducibilities, was observed with the graphite cathodes. Intraday or interday precision were <5% in relative standard deviation (rsd); no memory effects were observed and no conditioning was required. EAG performance difference of different carbon types has been noted by others as well.23 Graphite rods were henceforth used.

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Figure 3. Reproducibility of selected cathode materials for EAG from 50 g/L As(III). Each bar represents a particular day and the number above the bar indicates the number of measurements made that day. Standard deviation of the measurements over each day is shown as an error bar.

Figure 5. Response of 50 g/L As(III) and As(V) at different anolyte (0.1 M H2SO4); oxygen-based ozone generation.

Figure 4. Response for catholyte and anolyte concentration at 50 g/L As(III) (solid line) and As(V) (dotted line) operated at a constant current 1.0 A and 1 cm2 cathode surface area. Anolyte recirculated at 6 mL/min; O2-based O3 generation. In this and subsequent gures, the lines simply connect successive data points.

Electrolyte Concentration and Flow Rate. As the acidic electrolyte for EAG, H2SO4 has been preferred over HCl, HClO4, HNO3, etc.30,32 and we chose the same. The CL intensity of 50 g/L of As(III) and As(V) as a function of varying anolyte H2SO4 concentrations (0.01-2.0 M) is shown in Figure 4. Both As(III) and As(V) showed qualitatively the same pattern although As(III) absolute signals were much higher. The CL signals increased dramatically from 0.01 to 0.1 M H2SO4 and decreased slowly thereafter (decreasing by <10% in going from 0.1 to 0.2 M H2SO4); hence 0.1 M H2SO4 was chosen as the anolyte.
(32) Zhang, W. B.; Gan, W.; Lin, X. Q. Talanta 2006, 68, 13161321.

The anolyte is made to ow or else gas bubbles in the small anode compartment disrupt steady state operation. Bottom-up ow may seem to be better for gas removal, but the anodic gas can go through the ceramic tube to the outer headspace if driven above the outer liquid level. The efcacy of ow-driven gas bubble removal increases with the anode liquid ow velocity/rate. Although the electronics can be congured for constant current, at low anolyte ow rates with gas bubbles mostly covering the anode, applied voltage increases erratically and steeply, generating large amounts of heat. As(III) and As(V) responded somewhat differently to anolyte ow (Figure 5); the specic reason for this is not understood. However, in both cases, a recirculation rate of 6 mL/min gave the optimum combination of sensitivity and precision; therefore, this was adopted. For the catholyte, we studied 0.25-2.0 M H2SO4, with 0.1 M H2SO4 as the anolyte. As shown in Figure 4, for both As(III) and As (V), the CL signal decreased with increasing [H2SO4], at rst slowly and later more steeply. We are not presently certain why this occurs; the higher voltage and higher power dissipated at constant current with a more resistive catholyte may be leading to a higher catholyte temperature and, hence, greater arsine efux. Precision was much better for 0.5 M, rather than 0.25 M H2SO4 as the catholyte, and we therefore chose the former. What Roles Do Current and Current Density Play? For any given electrode, the HEO increases with increasing current density. Whether or not HEO is directly involved, it is reasonable that as more electrons are pumped in per unit electrode area and atomic hydrogen forms, more of it will be available for hydride formation reactions. In Figure 6 we show the CL response of As(III) as a function of current density. In one set of experiments (triangles) current density was varied by varying the current at a constant cathode area of 0.5 cm2, whereas in the other set (circles), the cathode area was varied at a constant current of 1.0 A. Both sets of data approach a plateau value at high current densities with an approximate rst order dependence. This plateau signal (area) is 95% of the signal obtained with NaBH4, indicating near-quantitative reduction. The two curves intersect where the conditions are the same (i ) 1.0 A, cathode area )
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Figure 6. Filled and open symbols As(III) and As(V), respectively. As(III): circles, operated at constant current, cathode area varied; triangles, constant electrode area, total current varied. As(V): diamonds and squares correspond to the circles and triangles, respectively. Note right ordinate scale magnied 1.25 relative to the left; 50 g/L As, 0.1/0.5 M H2SO4 catholyte/anolyte, O2 used for ozone generation.

0.5 cm2). These data indicate that both current and current density must be important. The constant current-variable current density data (circles) underscores the importance of current density. Yet, the triangles always fall below the circles at low current densities (although a greater electrode area must help analyte capture); hence, the absolute value of the current must also be important. The As(V) data in Figure 6 are qualitatively similar to those for As(III) except the response is lower. The current density dependence at constant current shows two distinct regions of the slope, possibly suggesting that the ultimate reduction to AsH3 may be taking place in two steps. Experience also indicated that maintaining a high current density solely by reducing the cathode area leads to cathode erosion. We chose to operate with an electrode area of 1 cm2; at a constant current of 1.0 A, this gave statistically identical signal intensities as a 0.5 cm2 electrode and better precision. More extended rationale for choosing this electrode area is given in Figure S2a and S2b and attendant discussion in the Supporting Information. Dealing with the As(III) and As(V) Response Difference Problem. Minimally, one would like to measure total As in the samples of interest. It would be nice to separately measure As(III) and As(V). We hope to address the latter issue in a future publication. Despite Denkhaus et al.,30 our experience is that in practical EAG systems where the cathodes exhibit a minimum of memory effects and conditioning needs, a response difference between As(III) and As(V) is unavoidable. This is shared by others; at least there is no extant literature that performs EAG on real samples and can reliably determine total As without prior conversion of one species into the other. Under optimum anolyte/ catholyte conditions, in an air-based ozone generation system, we obtained linear responses (linear r2 values > 0.99) for both As(III)
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and As(V) with respective slopes of 132 and 29.5 mV/(g/L As). For the O2-based ozone generation system, slopes of 170.6 and 81.6 mV/(g/L As) were obtained, respectively, for As(III) and As(V), r2 > 0.99 (see Figures S3 and S4 in the Supporting Information). While the difference between As(III) and As(V) signal heights does decrease with oxygen-based ozone generation, the disparity is still too large. Because As(III) is more responsive, we rst explored reduction by KI-ascorbic acid23 (for procedure, see the Supporting Information). At 50 g/L As(V), 80% was converted to As(III) as judged by the response; this did not improve by increasing the reduction time from 3 to 5 min. In addition, (a) the blank signal increased, deteriorating LOD to 1 g/L As, suggesting the presence of As in the relatively concentrated reductant (or CL from some substance derived from the reductant) and (b) the linearity decreased signicantly (r2 ) 0.98); data in Figure S5 in the Supporting Information indicate that reduction is less complete at higher [As(V)], characteristic of an equilibrium-driven process. Pre-EAG oxidation of As(III) to As(V) is usually not attempted because of sensitivity loss. We reasoned that even an air-ozonizer GPCL approach may nevertheless provide sufcient sensitivity for drinking water analysis in South Asia and chose NaOCl, an inexpensive strong oxidizing agent. A small amount (0.1 mL of 0.6% w/v NaOCl) was added to the ECR after sample introduction. We observed identical response slopes (26.9 1.3 and 26.8 1.1 mV/(g/L) As(III) and As(V) originally taken) with intercepts indistinguishable from zero (details in Figures S6 and S7 in the Supporting Information). The reproducibility permitted a S/N ) 3 LOD of 0.65 g/L, better than that obtained with KI-ascorbate reduction. Oxygen-Based Ozone Generation. We had previously known that if O2 instead of air is used for ozone generation, the CL signal increases markedly.14 However, for a eld instrument, carrying an oxygen tank is a burden. Oxygen is, however, generated during EAG and is readily available for ozone generation. Under conditions described in the Experimental Section, we indeed observed 3 better sensitivity (details in Figure S8 in the Supporting Information) and 2 better LOD (0.36 g As/L) compared to the air-based ozone generation, more than sufcient to meet drinking water As analysis needs. Note that water vapor reduces the CL intensity. It has previously been shown that the use of small CaCl2 packed tubes prior to the CL reaction increases the signal 2.5 (ref 14). However, the LOD here was considered adequate, and the added complexity was not pursued. Analysis of Real Samples and Intercomparison/Validation. We analyzed six tap water samples from Western Texas/ Eastern New Mexico; these regional samples have very high total dissolved solids (TDS) and high total hardness and contain low levels of As (<10 g/L; a 2008 report33 of Lubbock, TX water reports these respective parameters at 830, 260, and 0.0021-0.0039 mg/L). High mineral and low arsenic content provides a challenging end of drinking water samples. We did not have access to naturally occurring higher arsenic content samples; to provide samples at the high end, we spiked with As(V) local tap water34 (200 mg/L TDS, 100 mg/L total hardness, <1 g/L Total As).
(33) Lubbock Water Quality Report, 2008. http://water.ci.tx.us/pdf/WQR/ 2008WQR.pdf (Accessed February 18, 2010).

The results showed excellent correlation between the present method and inductively coupled plasma mass spectrometry (ICPMS) (r2 ) 0.9999, slope 0.97, intercept statistically indistinguishable from zero, ICPMS conditions described in ref 17; a plot is shown in Figure S9 in the Supporting Information). In addition, we also compared the results on the same samples with chemical reduction hydride generation-GPCL methods, both the automated13 and manual16 versions. Comparison with these two methods also both exhibited linear r2 values g 0.9999, with a slope of 0.99 and 0.95 vs the automated and the manual methods (details appear in Figure S10 in the Supporting Information, and all the intercomparison data are summarized in Figure S11 in the Supporting Information). We have presented here a simple, inexpensive, highly sensitive eld portable analyzer for measuring arsenic in water that uses merely water, electricity, and some sulfuric acid (much of which is recycled) as consumables, capable of measuring submicrogram
(34) Arlington Water Quality Report, 2008. http://www.arlingtontx.gov/water/ studiesandreports_drinkingwaterquality.html (Accessed March 6, 2010).

per liter levels of arsenic. Beyond the performance parameters, this approach gets us ever closer to a totally green analyzer where reaction chemistry nevertheless remains the heart of the analytical chemistry. ACKNOWLEDGMENT This work was supported by the National Science Foundation through Grant CHE-0709994. We thank Dr. Andrea B. Kirk for the samples from West Texas and New Mexico, collected as part of a project sponsored by the Centers for Disease Control. We thank Kelsey D. Cook for his faith in this work. SUPPORTING INFORMATION AVAILABLE Additional information as noted in text. This material is available free of charge via the Internet at http://pubs.acs.org.

Received for review March 7, 2010. Accepted April 6, 2010.

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