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Water Research 39 (2005) 19461953 www.elsevier.com/locate/watres

Spectrophotometric determination of ferrate (Fe(VI)) in water by ABTS

Yunho Leea,b, Jeyong Yoona, Urs von Guntenb,
a

School of Chemical and Biological Engineering, College of Engineering, Seoul National University, San 56-1, Sillim-dong, Gwanak-gu, Seoul 151-742, Korea b Swiss Federal Institute for Environmental Science and Technology (EAWAG), Ueberlandstrasse 133, CH-8600, Du bendorf, Switzerland Received 1 November 2004; received in revised form 16 February 2005 Available online 3 May 2005

Abstract A new method for the determination of low concentrations (0.0335 mM) of the aqueous ferrate (Fe(VI)) was developed. The method is based on the reaction of Fe(VI) with 2,20 -azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) which forms a green radical cation (ABTSd+) that can be measured spectrophotometrically at 415 nm (ABTS method). The reaction of Fe(VI) with ABTS has a stoichiometry of 1 : 1 in excess of ABTS (73 mM). The increase in absorbance at 415 nm for ABTSd+ generation was linear with respect to Fe(VI) added (0.0335 mM) in buffered solutions (acetate/phosphate buffer at pH 4:3) and was (3.4070.05) 104 M1 cm1. The reaction of Fe(VI) with ABTS was very rapid with a half-life time below 0.01 s at pH 4.3 and 73 mM of ABTS. This enables the ABTS method to measure Fe(VI) selectively. The residual absorbance of ABTSd+ was found to be stable in several water matrices (synthetic buffer solution and natural waters) and concentrations of Fe(VI) spiked in natural waters could be determined with high accuracy. The ABTS method can also be used as a tool to determine rate constants of reactions of Fe(VI). The second-order rate constant for the reaction of phenol with Fe(VI) was determined to be 90 M1 s1 at pH 7. r 2005 Elsevier Ltd. All rights reserved.
Keywords: Ferrate; 2,20 -azino-bis(3-ethylbenzothiazoline-6-sulfonate); ABTS; Analysis; Oxidation; Kinetics

1. Introduction In recent years, ferrate (Fe(VI), iron in +6 oxidation state) has gained increasing attention as a novel water treatment chemical for oxidation/disinfection and coagulation processes due to its strong oxidizing properties and its yield of ferric ion (Fe(III)) as a non-toxic decomposition product (Sharma, 2002a; Jiang and Lloyd, 2002; Lee et al., 2004). Previous studies showed that Fe(VI) not only oxidizes rapidly sulfur- and nitrogen-containing pollutants (e.g. thiol compounds
Corresponding author. Tel.: +41448235270; fax: +41448235210. E-mail address: vongunten@eawag.ch (U. von Gunten).

and hydrazines) into non-hazardous products (Sharma, 2002a), but also effectively inactivates several types of bacteria and viruses (Schink and Waite, 1980). Fe(VI) was also proven as an efcient coagulant for removing various toxic metals and non-metals after oxidation (Bartzatt et al., 1992). In addition, several studies showed that Fe(VI) could play the multiple roles of oxidant, disinfectant, and coagulant simultaneously for the treatment of drinking waters and wastewaters (De Luca et al., 1992; Yuan et al., 2002; Lee et al., 2003). Despite the high potential of Fe(VI) as a versatile water treatment chemical, only a few analytical methods have been developed for measuring Fe(VI) concentrations in aqueous solutions. Schreyer et al. reported a method of Fe(VI) analysis based on the reaction of

0043-1354/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2005.03.005

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Fe(VI) with arsenite or chromite and subsequent backtitration of liberated arsenate or dichromate (Schreyer et al., 1950a, b). However, this method is time consuming due to the titration steps and uses toxic heavy metals, which are not amenable to routine analysis. Direct monitoring of absorbance at 510 nm has been widely used to measure aqueous Fe(VI) concentrations, especially for kinetic studies of Fe(VI) (Sharma, 2002a; Lee et al., 2004). This direct spectrophotometric method is simple and convenient; however, the molar absorption coefcient of aqueous Fe(VI) at 510 nm (eFe(VI), 510 nm) is not only low but also varies signicantly depending on the pH (i.e. eFe(VI), 510 nm is 520 M1 cm1 at pH 6.2 and 1150 M1 cm1 at pH 9.1) (Rush et al., 1996). In addition, the ferric ion generated from Fe(VI) decomposition precipitates rapidly in absence of strong chelating agents (i.e. EDTA or phosphate), which can also produce signicant errors in optical monitoring of the solution (Carr et al., 1985). Information on the reactivity of Fe(VI) with various compounds relevant to water treatment is relatively limited, although several reaction rate constants of Fe(VI) with sulfur- and nitrogen-containing compounds have been reported (Sharma, 2002a). Moreover, the reported rate constants of Fe(VI) are usually available only in the basic pH region due to the fast disproportionation of Fe(VI) at neutral and acidic pH regions (Lee et al., 2004). A sensitive analytical method for Fe(VI) (below mM range) can solve this problem since it allows the use of lower Fe(VI) and substrate concentrations, which can permit measurements of higher observed rate constants. In addition, the self-decomposition of Fe(VI) can be minimized at lower Fe(VI) concentrations, since its mechanism is characterized by a second-order decay kinetic with respect to Fe(VI) (Rush et al., 1996). In this study, we have developed a new method for the determination of aqueous Fe(VI) concentration which is simple, highly sensitive, and exhibits fewer interferences than prior analytical protocols. The new method is based on the reaction between Fe(VI) and 2,20 -azinobis(3-ethylbenzothiazoline-6-sulfonate (ABTS), a commercial reagent which has been used for analysis of percarboxylic acids (Pinkernell et al., 1997) and selective determination of reactive bromine and chlorine species (Pinkernell et al., 2000). As shown in Fig. 1, the colorless ABTS reacts with oxidants via single-electron transfer to yield ABTSd+, a stable and intense green colored radical (Scott et al., 1993).

O3S

S N N C2 H 5 ABTS N

S N C2 H 5

SO3

One-electron Oxidation
-

O3S

S N+ C 2 H5 ABTS . +
.

S N N N C2 H5

SO3-

Fig. 1. ABTS and its one-electron oxidation product, ABTSd+.

2. Experimental 2.1. Materials All water used was from a Barnstead B-Pure system. All chemicals used were of analytical grade if not stated

otherwise. The stock solutions of ABTS reagent were prepared by dissolving 1 g diammonium-ABTS salt (Aldrich) in 1 L distilled water (1.82 mM) and stored at 4 1C. When the ABTS stock solution had a slightly higher blank absorption (0.02 at 415 nm and in a 10 cm path length), it was replaced. A pH 4.1 buffer solution was prepared by dissolving 34.3 mL of CH3CO2H, 6.9 g of NaH2PO4 H2O, and 26.7 g of Na2HPO4 2H2O in 1 L distilled water to yield 0.6 M acetate and 0.2 M phosphate. The phosphate was used in the buffer reagent for stabilization of iron(III), which otherwise precipitates as a hydroxide that interferes with the optical monitoring of the solution. Dilution of this buffer (5 mL) with the sample (19 mL) and the ABTS reagent (1 mL) resulted in a nal solution pH of 4.3. Potassium ferrate (K2FeO4) of high purity 495% was prepared by the method of Thompson et al., 1951. Primary stock solutions of Fe(VI) (100300 mM) were prepared by dissolving solid samples of K2FeO4 in 5 mM Na2HPO4/1 mM borate buffer pH % 9:1 where aqueous Fe(VI) is known to be most stable (Sharma and Bielski, 1991). Working Fe(VI) stock solutions (below 40 mM) were made by dilution of the primary stock solution with 5 mM Na2HPO4/1 mM borate buffer solution. Fe(VI) concentrations in primary stock solutions decreased by less than 1% within 10 min after preparation. Diluted Fe(VI) stock solutions were more stable than primary Fe(VI) stock solutions. In experiments involving spiking of Fe(VI) into natural waters, working stock solutions of Fe(VI) were prepared in distilled water. More than 200 mM of Fe(VI) was prepared in distilled water with a pH close to 9.1 and was also quite stable at least within 10 min (less than 1% concentration decrease). One should be cautious if a

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solution with Fe(VI) less than 200 mM is prepared in distilled water. This is relatively unstable since the pH of the resulting solution is lower than 9. All prepared stock solutions of Fe(VI) were usually used within 30 min after preparation in which no signicant decomposition of Fe(VI) occurred (less than 5% concentration decrease). Standardization of all Fe(VI) stock solutions was performed by measuring Fe(VI) absorbance at 510 nm and using a molar absorptivity of Fe(VI), e510 nm 1150 M1 cm1, for pH above 9.0 (Rush et al., 1996). Free chlorine solutions were prepared from a sodium hypochorite stock (5% in water, Fluka). Free chlorine concentrations were determined by UV-spectrophotometric measurement of triiodide (I 3 ) formed by oxidation of iodide (Bichsel and von Gunten, 1999). 2.2. Experiments in natural waters Two different natural waters were used to evaluate ABTS for measurement of Fe(VI) in natural waters: (i) raw water from Lake Zurich, Switzerland (DOC1.6 mg L1 and alkalinity 130 mg L1 as CaCO3), (ii) raw water from Lake Greifensee, Switzerland (DOC3.6 mg L1 and alkalinity 190 mg L1 as CaCO3). All natural water samples were ltered (0.45 mm cellulose nitrate) upon delivery to the laboratory and stored at 4 1C until use. 2.3. Apparatus Absorption measurements for the ABTS method were performed at 415 nm on a UVIKON 940 spectrophotometer (Kontron Instrument) using 1, 5, or 10 cm quartz UV cells. pH measurements were carried out with a Metrohm 632 pH-meter (Herisau, Switzerland) which was calibrated with standard buffer solutions (Merck). 2.4. Procedures General procedure for Fe(VI) determination with the ABTS method was as follows: 5 mL of the buffer reagent (pH 4:2; 0.6 M acetate/0.2 M phosphate) and 1 mL of ABTS reagent (1.82 mM) were added to a 25 mL volumetric ask. Then, a sample containing Fe(VI) was added under stirring and the ask was lled with deionized water. A sample volume between 1 and 19 mL was selected to ensure that the nal concentrations of Fe(VI) were below 35 mM. After the completion of green color formation (less than 1 sec), the solution was transferred into suitable photometric cells (1, 5 or 10 cm depending on absorbance ranges) to read the absorbance at 415 nm. A blank solution was prepared by using the sample without Fe(VI). In most cases, the blank absorbance at 415 nm was from the ABTS reagent itself and close to 1 103 cm1. The concentration of

Fe(VI) in a sample was calculated from the measured absorbance at 415 nm by considering the following relationship: FeVIsample DA415 l V final , lV sample (1)

where DA415 is the absorbance at 415 nm after correcting l for blank in cell of path length l ;  34; 000 (7500) M1 cm1, l the path length of optical cell, Vnal the nal volume after addition of all reagents and buffer (25 mL), and Vsample the volume of original sample (119 mL). Standard curves were determined from a series of 25 mL volumetric asks containing the buffer and ABTS reagent. To obtain responses at 415 nm absorbance as a function of Fe(VI) concentration, the following two different modes were used. Firstly, 19 mL of solutions containing various concentrations of Fe(VI) (040 mM prepared in 5 mM Na2HPO4/1 mM borate buffer) were added into each ask of the series. Secondly, different amounts (e.g. 0, 2, 4, 6, 10, 14, and 19 mL) of diluted Fe(VI) stock solutions (e.g. 5 mM, prepared in 5 mM Na2HPO4/1 mM borate buffer) were dosed. Then, the asks were lled with distilled water or a 5 mM Na2HPO4/1 mM borate buffer solution. Standardization of Fe(VI) concentrations (140 mM) was performed by measuring the absorbance of the solutions at 510 nm using a 10 cm cell. The concentrations of Fe(VI) less than 1 mM could not be measured properly by the 510 nm absorbance method and were therefore estimated from corresponding dilution factors. Estimation of Fe(VI) concentration by the latter approach was suitable because Fe(VI) is quite stable at low levels (o5 mM, decreased less than 1% within 1 h). The molar absorptivity of ABTSd+ at 415 nm was determined as a function of pH (2.06.1) by using the reaction of chlorine with ABTS to produce ABTSd+ in the presence of iodide (5 mM) as a catalyst. Prior investigators reported a stoichiometry of one mole of chlorine to two moles of ABTS yielding two moles of ABTSd+ (Pinkernell et al., 2000). 2.5. Kinetic experiments The reaction rates between Fe(VI) and ABTS were measured with an Applied Photophysics SX-17MV stopped-ow spectrophotometer system. The extent of the reaction was monitored by the increase of the absorbance at 415 nm for ABTSd+ under various experimental conditions. Detailed experimental procedures for study of the reaction kinetics will be described elsewhere (Lee et al., in preparation). The rate constant of the reaction between Fe(VI) (0.53 mM) and phenol was determined under pseudo rst-order conditions in excess of phenol (150 mM) by

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and Bader, 1994). using a dispenser system (Hoigne Samples were withdrawn with a dispenser at timed intervals into a solution containing the ABTS reagent where the remaining Fe(VI) leads to a coloration of the solution.

3. Results and discussion 3.1. Absorption spectra of ABTSd+ Fig. 2 shows the absorption spectrum of the ABTS reagent solution after its reaction with different doses of Fe(VI) (0.73.3 mM). The generated ABTSd+ had a
1.50 Absorbance, (10-cm cell) 1.25 1.00 0.75 0.50 0.25 0.00 300 400 no Fe(VI)
2.0 M Fe(VI) 1.3 M Fe(VI) 0.7 M Fe(VI) 3.3 M Fe(VI)

broad and intense absorption spectrum containing several maxima at 415, 650, 732, and 820 nm, which was found to be identical to the absorption spectra reported in previous studies (Scott et al., 1993; Pinkernell et al., 1997). Since the absorbance at 415 nm was the highest lmax ; it was used throughout this study. The shape of the absorption curve and lmax did not change with Fe(VI) dose. 3.2. Sensitivity and precision Fig. 3 shows the standard curves measured for Fe(VI) concentration ranges between 035 mM as representative data. All standard curves were linear (R2 40:99 for 28 standard curves) and their slopes were nearly the same (less than 1.5% deviation) even though the Fe(VI) concentration was varied by three orders of magnitude. Due to the intrinsic self-absorbance of the ABTS reagent at 415 nm (E1 103 cm1), the standard curves pass through the zero intercept only when they are corrected by the blank absorbance. The absorbance change for the ABTS method at 415 nm was determined to be (3.4070.05) 104 M1 cm1 per mole L1 of added Fe(VI) present in the nal solution. This sensitivity is quite high and a limit of detection of about 0.03 mM of Fe(VI) (4 mg L1 as FeO4) can be achieved with a 10 cm path length. Fig. 4 shows the standard curves of the ABTS method measured in two different types of natural waters (waters from Lake Zurich and Lake Greifensee) and distilled water for comparison. The slopes in the two natural waters were nearly the same as that in distilled

500

600

700

800

900

Wavelength, nm

Fig. 2. Absorption spectra of the ABTS reagent after reaction with Fe(VI).

0.150 0.125 Absorbance, 415 nm 0.100 0.075 0.050 0.025 0.000 10-cm cell

1.50 1.25 1.00 0.75 0.50 0.25 0.00

1.50 1.25 1.00 A = 3.4 x 104 M-1 cm-1 0.75 0.50 0.25 0.00 5 0.5 0.05 10 1.0 0.10 15 1.5 20 2.0 25 2.5 30 3.0 0.30 35 3.5 0.35 40 4.0 0.40

10-cm 1-cm 0 cell cell 0.0 0.00

0.15 0.20 0.25 [Fe(VI)], M

Fig. 3. Standard curves for the ABTS method. Fe(VI) was prepared in buffered solution of pH 9.1 (5 mM Na2HPO4/1 mM borate). Concentration ranges of Fe(VI): (00.35 mM), m (03.5 mM),  (035 mM).

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Absorbance (415 nm,10-cm cell)

0.6
Stoichiometric factor

1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 1 2 3 4 pH 5 6 7

0.5 0.4 0.3 0.2 0.1

Distilled water Lake Zurich water Lake Greifensee water A = 3.4 x 104 M-1 cm-1

0.0 0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 [Fe (VI)], M

Fig. 4. Standard curves for the ABTS method to determine Fe(VI) present in different types of waters to which Fe(IV) was added. The pH of all three waters was adjusted to 8.0 by 10 mM borate. DOCLake Zurich waterE1.6 mg L1 and DOCLake Greifensee water % 3:6 mg L1 : The baseline absorbance was taken from distilled water.

Fig. 5. Stoichiometric factor for Fe(VI)-ABTS reaction as a function of pH (2.06.1).

between Fe(VI) and ABTS FeVI ABTS ! FeV ABTSd rate limiting step;

(2) (3)

water, although a slightly higher blank absorbance at 415 nm was found in the two natural waters. This result indicates that components in natural waters do not affect signicantly the calibration factor of the ABTS method. The effect of mixing rate on the sensitivity of the ABTS method was examined and found to be negligible between vigorous and very slow stirring. 3.3. Stoichiometric factor of ABTSd+ generation The stoichiometric factor of ABTSd+ generation in the ABTS method DABTSd =DFeVI can be obtained by dividing the measured sensitivity of the ABTS method DA415 nm =DFeVI 3:40 by the molar absorptivity of ABTSd+ 104 M1 cm1 at 415 nm DA415 nm =DABTSd ABTSd;415 nm : Since the eABTSd+,415 nm under conditions of the method is not known, it was measured by using the reaction of a standardized chlorine solution with ABTS to produce a known concentration of ABTSd+ (Pinkernell et al., 2000). The eABTSd+,415 nm was determined to be (3.3070.1) 104 M1 cm1 and was comparable to the value reported by Scott et al., 3.47 104 M1 cm1, measured at pH 0 and wavelength of 417 nm (Scott et al., 1993). The determined stoichiometric factor is therefore nearly 1 (1.03), indicating that one mole of Fe(VI) produces one mole of ABTSd+ from its reaction with ABTS. The stoichiometric factor was measured at different pH conditions and also found to be 1 regardless of pH from 2.0 to 6.1 as shown in Fig. 5. A stoichiometric factor of 1 can be rationalized by considering the following proposed reaction scheme

FeV ABTS !! FeIII ABTSoxidized ; Net : FeVI 2ABTS ! FeIII ABTSd ABTSoxidized :

(4)

Fe(VI) oxidizes ABTS via an one-electron transfer step generating Fe(V) and ABTSd+ (reaction (2)) (Scott et al., 1993). The generated Fe(V) rapidly oxidizes additional ABTS, however, this reaction may produce another form of oxidized ABTS (ABTSoxidized) rather than ABTSd+ (reaction (3)). This assumption is plausible since Fe(V) is a much more powerful oxidant than Fe(VI) (103105 faster reaction kinetics) (Sharma, 2002b). It can react non-selectively at various active sites of the ABTS molecule which does not produce ABTSd+. Overall, the net reaction of this reaction scheme (reaction (4)) shows that one Fe(VI) oxidizes two ABTS producing one ABTSd+. 3.4. Reaction rates between Fe(VI) and ABTS Stopped-ow experiments were conducted to obtain the reaction rate between Fe(VI) and ABTS. The reaction was found to be rst order with respect to both reactants and occurred on the millisecond time scale. The color formation of ABTSd+ was found to be completed within no more than 0.1 s under the applied experimental condition ([ABTS] 73 mM). This high rate of reaction is desirable since it allows selective determination of Fe(VI). More detailed kinetic data for this reaction will be published elsewhere (Lee et al., in preparation).

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% Change of 415 nm absorbance

0.6

0.04 0.03 0.02 0.01 0.00

10
[Fe(VI)], M

4 3 2 1

10 mM phosphate, distilled water

0.5 0.4 0.3 0.2 0.1 0.0

0 -10 -20
Lake Zurich water

(a) 0

-30 -40

Lake Greifensee water

Abs at 415 nm, 5-cm cell

0.6 4 [Fe(VI)], M

0.04 0.03 0.02 0.01 0.00

30

60 Time, min

90

120

10 mM borate, distilled water

0.5 0.4 0.3 0.2

3 2 1

Fig. 6. Stability of ABTSd+ generated from Fe(VI) present in natural waters and distilled water. Fe(VI) doses were 1.2 mM for Lake Zurich and Lake Greifensee waters, and 2.4 mM for distilled water.

0.1 0.0

(b) 0

Abs at 415 nm, 5-cm cell

The residual absorbance of ABTSd+ (l 415 nm) generated from the Fe(VI) present in distilled water (E2.4 mM) was quite stable and decreased less than 5% within 10 h. This stability is comparable to that reported by Pinkernell et al. (2000), who generated ABTSd+ by using chlorine or bromine species at pH 6.5. To test further the water matrix effects on the stability of ABTSd+, Fe(VI) was spiked in two different natural waters (waters from Lake Zurich and Lake Greifensee) and measured by the ABTS method. Fig. 6 shows that although the ABTSd+ (E 1.2 mM) generated in the presence of the components of the natural waters was slightly less stable than that in the absence of those, it decreased less than 5% within 1 h, which is still sufcient for accurate determination of Fe(VI). 3.6. Measurement of Fe(VI) decrease in various water matrices Fig. 7 shows the decrease of Fe(VI) ([Fe(VI)]0 E4.570.2 mM) in three water types (pH 7.5) measured by the ABTS method and the direct method at 510 nm. In a phosphate buffered distilled water (Fig. 7a), the decrease of Fe(VI) measured by both methods was nearly identical. However, in a borate buffered distilled water and a borate buffered natural water (Lake Greifensee), the results from both methods were signicantly different. As shown in Fig. 7b and c, the observed decrease in the 510 nm absorbance of these solutions became slower than that observed by the ABTS method as the reaction proceeded. This is presumably caused by the hydrolysis and polymerization of ferric ion produced from the Fe(VI) decay in the absence of phosphate. It should be noted that even a

[Fe(VI)], M

3 2 1 0

0.6 10 mM borate, 0.5 Lake Greifensee water 0.4 0.3 0.2 0.1 0 30 60 90 120 150 180 210 240 Time, min 0.0

0.04 0.03 0.02 0.01 0.00

(c)

Fig. 7. Determination of the Fe(VI) decrease in various water matrices with the ABTS method (open circles and 415 nm on right hand scale) and the direct 510 nm monitoring method (lines and 510 nm on right hand scale). The pH of all solutions was adjusted to 7.5 by 10 mM phosphate or borate. (a) phosphate buffered solution, (b) borate buffered solution, and (c) borate buffered Lake Greifensee water. A molar absorptivity of 910 M1 cm1 at pH 7.5 was used to calculate Fe(VI) concentrations from the 510 nm absorbance measurements (Rush et al., 1996).

small change in the optical properties of the solution can cause signicant errors in the absorbance at 510 nm at this low absorption range (00.05 even in a 10-cm cell). Therefore, Fig. 7 clearly shows the failure of the direct 510 nm monitoring method for measuring Fe(VI) in waters without proper chelating agents (e.g. phosphate) which can prevent the precipitation of ferric ion. Contrarily, the errors in the absorbance at 415 nm caused by the precipitation of ferric ion in the ABTS method can be considered negligible due to the relative much higher absorption range of the ABTS method (00.6 in a 5-cm cell). The rate of Fe(VI) decrease (as measured via the ABTS method) was found to be nearly the same in both

Abs at 510 nm, 10-cm cell

3.5. Stability of ABTSd+

Abs at 510 nm, 10-cm cell

Distilled water

Abs at 510 nm, 10-cm cell

20

5 Abs at 415 nm, 5-cm cell

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the phosphate (Fig. 7a) and borate buffered distilled waters (Fig. 7b). However, Fe(VI) decreased about two times faster in the Lake Greifensee water than in the distilled water as shown in Fig. 7c. Given that all three experiments were conducted at the same pH (7.5), the faster decrease observed in Lake Greifensee water can be attributed to the reaction of Fe(VI) with various components present in the natural water, plausibly with dissolved organic matter (DOCE3.6 mg L1). The results shown in Fig. 7c are the rst quantitative measurements of Fe(VI) decrease in a natural water. 3.7. Application of the ABTS method for kinetic studies with Fe(VI) Fig. 8 shows a representative example for the application of the ABTS method to measure Fe(VI) reaction rate constants at neutral pH conditions. To obtain the rate constant for reaction of Fe(VI) with phenol at pH 7.0 without interference from the selfdecay of Fe(VI), a very low initial Fe(VI) concentration (0.53 mM) was applied in the presence of excess phenol (150 mM). No signicant self-decay of Fe(VI) was observed in the absence of phenol at pH 7. This is shown in Fig. 8 (less than 10% decay within 10 min). A separate experiment showed that at the same pH, about 40% of initial Fe(VI) decayed within 1 min when 100 mM of Fe(VI) was applied (data not shown), which has been a typical initial Fe(VI) concentration used in prior stopped-ow kinetic investigations (Lee et al., 2003). In the presence of 150 mM phenol, Fe(VI) ([Fe(VI)]0 0.53 mM) followed a pseudo-rst-order decrease with a rate constant of 1.35 102 s1. Based on this, the resulting second-order reaction rate constant of Fe(VI) with phenol was calculated as 90 M1 s1 at pH 7. This is in agreement with previous measurements
0.6 0.4 [Fe(VI)], M 0.2 0.1 0.08 0.06 0.04 0 120 150 M phenol 240 360 Time, sec 480 600 Without phenol kobs = 1.35x10-2 sec-1

(100 M1 s1) by a stopped-ow system using the 510 nm monitoring method (Rush et al., 1995). The ABTS method therefore appears to be very useful for measurements of Fe(VI) reaction kinetics at neutral or even acidic pH. Further application of the ABTS method in reaction rate investigations could permit measurement of kinetic data necessary for applications of Fe(VI) in water treatment.

4. Conclusions A new method was developed to measure Fe(VI) in aqueous solution, based on the reaction of Fe(VI) with ABTS. This reaction produces a stable colored radical, ABTSd+, which can be measured by absorbance at 415 nm. The main features and advantages of the ABTS method are as follows:

 The method is highly sensitive (34,000 M1 cm1 per

mol L1 of added Fe(VI)) and covers three orders of magnitude of Fe(VI) concentrations from 0.03 to 35 mM (0.0044.2 mg L1 as FeO4). The sensitivity of the method does not vary with Fe(VI) concentration, or with the chemical composition of the water (e.g. natural waters). The method is simple and does not require any difcult or time-consuming operations. It can be performed by using standard laboratory instruments (spectrophotometer). The ABTS reagent is stable and can be stored for a month as a stock solution. The ABTSd+ is also stable in natural waters, which allows one to perform spectrophotometric measurements several hours after Fe(VI) has reacted with the ABTS reagent. The reaction of Fe(VI) with ABTS is very fast. Therefore, the ABTS method can measure Fe(VI) selectively or quench very fast reactions of Fe(VI) in its application to kinetic experiments.

 

Acknowledgement This work was supported by the Korea Science and Engineering Foundation (KOSEF). The authors thank Michael Dodd for his helpful comment and reviewing the manuscript, Professor V.K. Sharma for his kind gift of high purity Fe(VI) sample, and Elisabeth Salhi for her laboratory assistance.

Fig. 8. Reaction of Fe(VI) with phenol. Testing the ABTS method to measure the rate constant for the reaction of Fe(VI) with phenol at neutral pH conditions. [phenol]0 0 or 150 mM, [Fe(VI)]0 0.53 mM, pH 7:0 (25 mM phosphate buffer) and 25 1C.

References
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