Articles

Environmental Chemistry
March 2010 Vol.55 No.9: 802808 doi: 10.1007/s11434-010-0058-x

SPECIAL TOPICS:

Oxidation of estrone by permanganate: Reaction kinetics and estrogenicity removal

SHAO XiaoLing*, MA Jun, WEN Gang & YANG JingJing
School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China Received January 23, 2009; accepted August 11, 2009

Permanganate was used as an oxidant to control estrone in the present study. Kinetics was determined at pH 2.59.4 and temperature 1540C for the reaction of estrone with potassium permanganate. It was found that the reaction is second-order overall and first-order with respect to both estrone and permanganate. The second-order rate constant for the reaction at pH 5.8 and 25C is 44.45 L mol1 s1. The reaction rate first decreased with the increase of pH in the range of 2.56.6 and then increased greatly with the increase of pH in the range of 6.69.4. In addition, the rate constant exponentially increased with the increase of reaction temperature. Removal of estrogenicity was also investigated during the degradation of estrone using yeast estrogen screen (YES). Results show that the estrogenicity increased in the initial 15 min of reaction and then decreased fast, with a removal rate of 73.8% within the 30 min of reaction. Results also demonstrate that the reaction rate between estrone and permanganate is faster in natural water background than in the ultra-pure water system. Permanganate oxidation is therefore a feasible option for removal of estrone in drinking water treatment processes. However, the contact time must be enough in order to remove estrone without causing the increase of estrogenicity. estrone, permanganate, rate constants, estrogenicity
Citation: Shao X L, Ma J, Wen G, et al. Oxidation of estrone by permanganate: Reaction kinetics and estrogenicity removal. Chinese Sci Bull, 2010, 55: 802808, doi: 10.1007/s11434-010-0058-x

Endocrine disrupting chemicals (EDCs) are a kind of micropollutants that will elicit adverse effects on endocrine systems of humans and wildlife. They have been implicated in a number of reproductive and sexual abnormalities observed in wildlife [13] and reduced sperm counts in human males [4]. These compounds may travel along the water path from wastewater treatment plants to the raw water used for drinking water production [1,57]. Studies indicate that mixtures of various EDCs are prevalent in most of natural waters [7]. Some of them are very refractory to be removed by conventional physicochemical water treatments (e.g., coagulation/sedimentation, filtration, and chlorination) and may enter into drinking water distribution systems [810]. Phenolic EDCs including natural steroid estrogens have been verified as the dominant form of estrogenic activity in
*Corresponding author (email: pooshao@gmail.com)

surface waters [11]. Studies indicate that these chemicals, even at extremely low concentrations, will cause significant health problems for wildlife and/or humans when they experience a long-term exposure to mixtures of them [1,1214]. Therefore, effective treatment approaches are very desirable for the destruction of these EDCs from source water. Chemical oxidation can convert hazardous contaminants to nonhazardous or less toxic compounds, and may be a good choice to eliminate EDCs in natural waters. Among those commonly used oxidants in waterworks (e.g., chlorine, ozone, UV photolysis, monochloramine, and chlorine dioxide), permanganate has been verified as an inexpensive, easy and effective oxidant for control or decomposition of many kinds of contaminants, also including phenolic EDCs [1520]. Abe et al. [20] found that permanganate can completely degrade bisphenol A and 4-t-butylphenol into organic acids and inorganic carbon. They found that the percsb.scichina.com www.springerlink.com

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manganate oxidation rates are comparable to that of hydroxyl radicals. Moreover, previous studies indicate that the formation of disinfection by-products (DBPs) is greatly reduced in the process of permanganate oxidation [21]. Therefore, permanganate oxidation has already been used in drinking water treatment processes in the waterworks of many Chinese cities, such as Beijing, Shanghai, Nanjing and Wuxi. However, most of these studies mainly concentrated on several kinds of compounds, such as cyanotoxins, trichloroethylene, tetrachloroethylene, and methyl-tert-butyl ether, or the changes of regular water quality parameters during permanganate oxidation. Few studies have centered on the oxidation of representative EDCs. In addition, the main concern of these studies was the concentration change of target chemicals. Little attention was paid to the toxicities of degradation products. Moreover, some of the previous results were obtained from experiments conducted in synthetic water samples. Thus, it is difficult to predict the actual situation in real water treatment processes. Therefore, the primary objectives of this study are (1) to determine the rate constant for the reaction of permanganate with estrone, one of the representative EDCs in surface waters, (2) to evaluate the effect of operating variables such as pH and temperature on permanganate oxidation rate constants, (3) to assess the estrogenicity variation during estrone oxidation by permanganate, and (4) to assess the validity of the determined rate constants when permanganate oxidation is applied to natural waters.

1.2

Analytical methods

High performance liquid chromatography (HPLC) was used to determine the concentrations of estrone in water samples. The analytical system employs a Waters 1500 series binary pump, a Waters Symmetry C18 column (I.D=4.6 mm, length=150 mm, 5 m particle, made in Ireland), a Waters 717 plus auto-injector and a Waters 2487 dual UV detector. The mobile phase was run in an isocratic mode, with Milli-Q water used as mobile phase A and methanol (Dikma, USA) as mobile phase B. The proportion of A/B was 25/75 for the detection of estrone. The total flow rate of mobile phase A and B was 1.0 mL/min. The injection volume was 100 L for each sample. The wavelengths selected for the quantification were 224 and 280 nm. The analytes were quantified by external standard quantification procedure. The system was calibrated using standard solutions prepared in methanol at six concentration levels by serial dilutions from stock solution (0.370 mmol/L). The peak area vs. injected amount chart was obtained as standard curve with a correlation coefficient (R2) over 0.99. The detection limit is 5 g/L. 1.3 Permanganate oxidation experiment 100 mL of estrone working solution (0.5431.593 mol/L) was placed in cylindrical glass reactor, which was immersed in a thermostatic water bath to perform batch oxidation experiment. Magnetic stirrer was used under the water bath. The temperature of reaction systems was maintained at 25C except for the experiment conducted in natural water background. All pH values were measured by a pHs-3C pH meter with glass electrode that was pre-calibrated with standard buffer solutions (Leici, Shanghai, China). Compared with initial pH values, the changes of pH for all reaction systems did not exceed 0.3. Therefore, pH values were considered constant in the course of permanganate oxidation. The reaction was initiated by injection of 100800 L of KMnO4 working solution. Samples were collected at several time intervals, and quenched immediately with ascorbic acid working solution. The residual estrone concentrations were analyzed directly by HPLC. Each experiment was performed in duplicate. 1.4 Estrogenicity measurement

1 Materials and methods

1.1 Chemicals

Estrone (E1) is Sigma-Aldrich reagent. Other chemicals including potassium permanganate (KMnO4), hydrochloric acid (HCl), sodium hydroxide (NaOH) and ascorbic acid are of analytical grade and used without further purification. Ultra-pure water used in the experiment was Milli-Q water, 18.2 M cm. The natural water used was taken from Songhua River that is situated in the northern part of Harbin, China. Natural water sample was filtered through a glass fibre filter with pore size of 1 m (Whatman, GF/B) to remove suspended solids and then stored at 4C. The main water quality parameters of the filtered natural water are as follows: dissolved organic carbon (DOC), 4.5 mg/L; conductivity, 190 S/cm; pH 8.2; turbidity, 1.0 NTU. Estrone working solution was prepared daily in Milli-Q water or natural water using a magnetic stirrer and stored in amber glass bottle at ambient temperature. Potassium permanganate working solution (6.328 mmol/L), ascorbic acid working solution (5.678 mmol/L) and other reagents were also freshly prepared in Milli-Q water every four to seven days and stored in dark bottles to avoid light exposure.

Water samples were first concentrated by solid phase extraction (SPE) using Waters C18 cartridges (3 mL, 500 mg), which were pre-conditioned with 5 mL methanol and 5 mL Milli-Q water. The cartridges were then eluted with 10 mL of methanol/dichloromethane (80/20, v/v) twice. Two aliquots were combined and concentrated under a gentle nitrogen stream to dryness and then the samples were solvent exchanged to dimethyl sulfoxide (DMSO, HPLC grade, Sigma Chemical Co.) and stored at 20C for bioassay. The

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recoveries of estrone are 81.7%7.4% in the procedure. The yeast two-hybrid assay was used to estimate the estrogenic activity in the process of estrone oxidation by permanganate. The yeast (Saccharomyces cerevisiae) cell was engineered with a human estrogen receptor gene and a coactivator gene, which binds to an estrogen response element regulated-expression plasmid (lac-Z) coded to express -galactosidase [12]. Upon binding an active ligand, the estrogen-occupied receptor interacts with transcription factors and other transcriptional components to modulate gene transcription. This causes expression of the reporter gene lac-Z and the production of -galactosidase. Then the enzyme metabolizes the colorless substrate, o-nitrophenyl -D-galactopyranoside (ONPG) into o-nitrophenol (ONP). ONP is normally yellow and can be quantified using a spectrometer by absorbance at 420 nm. The yeast cells were cultured and the bioassay procedure was carried out as described detailedly by Ma et al. [22]. The results of estrogenic activities of water samples were expressed as estradiol equivalents (EEQs). 1.5 Manganese ion measurement The concentration of manganese ion in water samples was determined by a PerkinElmer Optima 5300 DV ICP-AES instrument (made in USA) after the filtration of water samples with cellulose acetate membranes with a pore size of 0.45 m.

performed at pH 5.8 and 25C and different initial estrone and permanganate concentrations. The values of kobs in these experiments were calculated by linear regression analysis and are summarized in Table 1. From the similar kobs values in experiments performed with different initial estrone concentrations, it can be deduced that the rate of estrone degradation is independent on the initial estrone concentration while an increase in the initial permanganate dose leads to the faster estrone degradation. The plot of kobs values as a function of the initial concentrations of permanganate (eq. (3)) is presented in Figure 2. A straight line was obtained with a correlation coefficient higher than 0.99, confirming the rate of estrone degradation is also first-order with respect to permanganate concentration. After linear analysis of data in Figure 2, a second-order rate constant at pH 5.8 and 25C of 44.450.94 L mol1 s1 can be calculated. Therefore, the rate of estrone degradation is second-order overall and first-order with respect to permanganate and estrone, and can be expressed by eq. (4). (4) r = 44.45[E1][KMnO4].

Results and discussion

2.1 Kinetics of the reaction of permanganate with estrone The reactions between estrone and permanganate occurred in ultra-pure water background with natural pH 5.8. The reaction was considered as a second-order reaction overall and first-order with respect to estrone ([E1]) and permanganate ([KMnO4]) concentrations. The rate of estrone degradation could be expressed as: (1) r = d[E1]/dt = k2 [E1][KMnO4], where k2 is the second-order kinetic constant. In the present study, permanganate was in large excess and its decrease in concentration was smaller than 20% of its initial concentration. Hence, permanganate concentration could be considered constant during reaction and the rate of estrone degradation can be expressed as: (2) r = d[E1]/dt = kobs[E1], (3) kobs = k2[KMnO4], where kobs is the pseudo-first-order kinetic constant. Therefore, a plot of ln[E1] as a function of the reaction time leads to a straight line, the slope of which is kobs. The first-order reaction rate with respect to estrone is confirmed in Figure 1, where ln([E1]0/E1]) versus time is shown for experiments
Figure 1 Pseudo-first-order kinetic plot for the oxidation of estrone with permanganate at 25C and pH 5.8. The solid line is a linear least-squares regression of the data. Initial concentration: [KMnO4]0=6.328 mol/L, [E1]0=1.593 mol/L (); [KMnO4]0= 12.656 mol/L, [E1]0=1.593 mol/L (); [KMnO4]0=18.984 mol/L, [E1]0=1.593 mol/L (); [KMnO4]0 = 31.640 mol/L, [E1]0=1.593 mol/L (); [KMnO4]0=50.623 mol/L, [E1]0=1.215 mol/L (); [KMnO4]0=50.623 mol/L, [E1]0= 1.593 mol/L (); [KMnO4]0=50.623 mol/L, [E1]0=0.885 mol/L (); [KMnO4]0= 50.623 mol/L, [E1]0=0.581 mol/L ().

Table 1 Results normalized to plots of ln([E1]0/[E1])-t for degradation of estrone under varied permanganate and estrone initial concentrations [KMnO4]0 (mol/L) 6.328 12.656 18.984 31.640 50.623 50.623 50.623 50.623 [E1]0 (mol/L) 1.593 1.593 1.593 1.593 1.593 1.215 0.885 0.581 R2 0.9889 0.9906 0.9931 0.9915 0.9998 0.9988 0.9915 0.9948 kobs104 (s1) 2.35 5.25 9.32 14.45 22.08 21.63 23.55 24.58

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Figure 2 Pseudo-first-order rate constant as a function of initial KMnO4 concentration for use in calculating the second-order rate constant between estrone and KMnO4.

Figure 3 Influence of the pH on the pseudo-first-order rate constant at 25C. [E1]0=1.481 mol/L, [KMnO4]0=12.656 mol/L.

Due to the effects of pH and background composition, the rate constant will be further enhanced during the permanganate oxidation of estrone in natural water background, which will be discussed in following sections. In comparison with phenolic EDCs reactivity with other oxidants, permanganate is a moderate oxidant. The reaction between phenolic EDCs and hydroxyl radicals is fast with an overall rate constant of 9.81091.411010 L mol1 s1 [23,24]. In the case of ozone, the rate constants are 1.68104107 L mol1 s1 [23,25,26], while for ferrate (Fe(VI)), it was found to be 6.41027.7102 L mol1 s1 [27]. The rate constants between phenolic EDCs and chlorine are 12.6131.1 L mol1 s1, which is comparative to the case of permanganate [28]. It seems that ozone and chlorine together with permanganate are feasible options for the removal of estrone or other phenolic EDCs during water treatment processes. However, bromate formation must be controlled in the ozonation of natural waters with high bromide level. Similarly, the formation of DBPs in the treated water may be an issue that limits the chlorine dose. On the contrary, permanganate preoxidation may be useful in enhancing the following coagulation and filtration processes [29] and controlling the formation of trihalomethanes and other DBPs [21]. 2.2 Effect of pH

decreased with the increase of pH in the range of 2.56.6 and then increased greatly with the increase of pH in the range of 6.69.4. The minimum degradation rate of estrone takes place at pH 6.6. In addition, when the pH is vicinal to 9, estrone can be diminished to below the limit of detection in less than 1 min. Permanganate usually undergoes a three-electron exchange under pH 3.512 (eqs. (5) (6)) and a five-electron exchange under lower pH conditions (pH<3.5, eq. (7)). (5) MnO4 + 4H+ + 3e = MnO2 + 2H2O MnO4 + 2H2O + 3e = MnO2 + 4OH (6) MnO4 + 8H+ + 5e = Mn2+ + 4H2O (7) The redox potential of permanganate is higher in acidic conditions (E0=1.70 V) than that in alkaline conditions (E0=0.59 V) [17], which might induce the higher reaction rate in acidic conditions. However, as to the fast decay of estrone under alkaline conditions, it might be due to the deprotonation of estrone which facilitates the attack by permanganate [30]. Ladbury and Cullis [31] reported that the ionized organic compounds, especially phenoxy groups, were easily attacked by MnO4. Considering the pKa of estrone 10.310.8 [12], the pH adopted is more vicinal to the pKa, where higher percentage of estrone will be dissociated. As a result, the oxidation rate is fast under the alkaline conditions. The result agrees with that obtained by Bastos et al. [18] who found that brominated phenols with lower pKa values reacted faster with KMnO4 at pH 7.6. 2.3 Effect of temperature

Investigations on the effect of pH on the oxidation rate of estrone were conducted at pH 2.59.4. The pH of the tested aqueous solutions was adjusted with 0.1 mol/L of HCl solution for pH<5 and buffered with phosphate or carbonate salts (1 mmol/L) for pH=510, respectively. To compare the reaction rate constants at different pH values, we assumed that the same order of reaction is valid under alkaline and acidic conditions. Therefore, pseudo-first-order rate constants were calculated by applying eq. (2) (R2=0.9355 0.0903). As can be observed in Figure 3, the pH influence on the reaction rate is significant. The reaction rate first

The effect of temperature on the reaction between permanganate and estrone was determined in experiments performed at six different temperatures (15, 20, 25, 30, 35 and 40C) in ultra-pure water background. Pseudo-first-order constants of (2.6312.07)104 s1 were also calculated by linear regression analysis (R2 >0.99). The relationship between the rate constant and temperature is showed in Figure 4. It can be seen that the rate constant increased slowly with tem-

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Figure 5 Estrogenicity of estrone solution during the course of permanganate oxidation at 25C. [E1]0=0.543 mol/L, [KMnO4]0=12.656 mol/L, pH 5.8.

Figure 4 Pseudo-first-order kinetic plot for the oxidation of estrone by permanganate at different reaction temperatures (a), and the effect of reaction temperature on the pseudo-first-order rate constant (b). [E1]0=1.463 mol/L, [KMnO4]0=12.656 mol/L, pH 5.8.

perature ranging from 15C to 30C, whereas the rate constant increased significantly at higher temperature, which results in the exponential growth of the rate constant in the whole studied temperature range. The second-order rate constants (20.895.3 L mol1 s1) at these temperatures were calculated according to eq.(3) and were used to calculate activation energy (Ea) with the linearized Arrhenius equation (eq. (8)). (8) lnk2=lnAEa/RT. After linear regression analysis (R2=0.9550), a value of 43.07 kJ/mol (10.25 kcal/mol) was calculated for Ea. This activation energy value is a little higher than that measured for other organic compounds during permanganate oxidation, such as cyanotoxins MC-RR (28.8 kJ/mol) [17] and chloroethylene (24.3639.1 kJ/mol) [32,33]. 2.4 Estrogenicity removal

compared with the initial estrogenic activity of water sample (t = 0). It can only be explained by the formation of intermediates with higher estrogenicities in the initial stages of the reaction. Because compounds with higher estrogenicities always have similar molecular structures as natural estrogens [34]. Therefore, we supposed that these intermediates probably have similar molecular structures as estrone. However, Abe et al. [20] supposed that KMnO4 directly cleaves the aromatic rings of phenolic compounds to form organic acids and inorganic carbon, since few decomposition products with aromatic rings were observed in the permanganate oxidation of phenol, bisphenol A and 4-t-butylphenol. Thus, further study is needed to determine the by-products of estrone by GC/MS or GC/MS/MS. Then, the estrogenicity decreased after 15 min of reaction. Estrogenicity was removed by 73.8% within 30 min of reaction, which is higher than the removal of estrone (about 60%) within the same time. The phenomena might be induced by the anti-estrogen by-products produced in the later stages of the reaction. These anti-estrogens can interrupt the combination of estrone with the estrogen acceptors contained in the yeast strain, which might lead to the higher removal of estrogenicity in water samples. Through the above-mentioned study, it can be concluded that enough contact time must be ensured in order to remove estrone and its estrogenicity during permanganate oxidation. 2.5 Estrone removal by permanganate in natural water background The oxidation of estrone in the natural water background mentioned above was conducted with permanganate dose of 12.656 mol/L at pH 8.2. A comparison study was conducted in Milli-Q water background at natural pH 5.8. To emphasize the effect of pH, experiments were also performed in the natural water at pH 5.8 and Milli-Q water at pH 8.2. The former and the latter were adjusted by 0.1

The estrogenic activities of estrone solutions were measured after the reaction started for 0, 5, 10, 15, 20 and 30 min in ultra-pure water background. It can be seen from Figure 5 that the estrogenicities of water samples increased in the initial 15 min of reaction. The maximum estrogenicity takes place at 15 min of reaction, which increased by 41.8%

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mol/L of HCl solution and 0.1 mol/L of NaOH solution, respectively. Since the background concentration of estrone in the natural water was in lower ng/L level, it was therefore negligible in calculation. As shown in Figure 6, the reaction rate in the filtered natural water background is significantly higher than that in ultra-pure water system under the same pH conditions within the studied reaction time. Moreover, the oxidation rate of estrone increased greatly with the pH increased from 5.8 to 8.2 both in natural water and in ultra-pure water background. However, the enhancement of removal rates is higher in natural water system than that in ultra-pure water system. The removal of estrone increased by 21%45% for the former, whereas it increased by 9%36% for the latter. Additionally, the reactivities between estrone and permanganate in natural water system at pH 5.8 and in ultra-pure water system at pH 8.2 are almost equal. It means that the effect of background components is comparative to that of pH in the fast removal of estrone in the natural water system. Thus, the effect of background components, including cations, anions, organics etc., enhanced the oxidation of estrone by permanganate, which will be presented in a separate paper in due course. Permanganate is always applied as a preoxidant in actual drinking water treatment processes and the contact time is often more than 30 min. This means that the removal of the produced MnO2 can be carried out easily in the following traditional treatment units, e.g., coagulation/sedimentation, filtration, etc. However, particular care must be taken to the residual manganese as metallic ions that can cause many problems in drinking water. It means that the permanganate dose has to be optimized during permanganate oxidation. The Chinese government has set a guideline value of 0.1 mg/L for manganese ion in Standards for Drinking Water Quality (GB5749-2006). Therefore, the concentrations of the residual manganese ion were measured by ICP-AES after 30 min of reaction mentioned above between estrone and permanganate in the natural water at pH 8.2. The back

ground concentration of manganese ion was 0.005 mg/L in the natural water. Results show that a level of 0.13 mg/L of manganese ion is left in the reaction system. The value can be easily decreased to below 0.1 mg/L by other traditional treatment processes. Thus, it can be assumed that the control of estrone by permanganate oxidation is feasible. It should also be mentioned that the concentrations of estrone and other phenolic EDCs are in ng/L or low g/L range in actual environmental samples [7]. Therefore, further work is needed to understand the real application of permanganate in potable water treatment and the possible formation of by-products associated with estrone or other phenolic compounds.

Conclusions

The reaction of the investigated typical EDCs, estrone with permanganate fits overall second-order kinetics, and firstorder with respect to both estrone and permanganate. The second-order rate constant for the oxidation of estrone by permanganate at 25C is 44.45 L mol1 s1. It was found that pH has an important effect on the oxidation rate of estrone. The reactivity between estrone and permanganate decreased with the increase of pH in the range of 2.56.6 and increased with the increase of pH in the range of 6.69.4. The minimum reaction rate takes place at pH 6.6. An activation energy of 43.07 kJ/mol was obtained from experiments conducted at temperatures of 1540C. From the comparison of the results obtained in previous reports with those obtained in the present research, it seems that permanganate is an optional oxidant for controlling estrone in natural waters. However, enough contact time must be carefully ensured in order to remove estrone to avoid the increase of estrogenicity during permanganate oxidation.
This work was supported by the Ministry of Education of China under the scheme of Key Project of Innovation (Grant No. 705013) and the National Natural Science Foundation of China under the Scheme of National Creative Research Groups (Grant No. 50821002). We are grateful to Prof. M Ma for kindly providing two-hybrid yeast strains. 1 2 Jobling S, Nolan M, Tyler C R, et al. Widespread sexual disruption in wild fish. Environ Sci Technol, 1998, 32: 24982506 Facemire C F, Gross T S, Guillette L J. Reproductive impairment in the Florida panther: Nature or nurture? Environ Health Perspect, 1995, 103: 7986 Guillette L J, Gross T S, Masson G R, et al. Developmental abnormalities of the gonad and abnormal sex hormone concentrations in juvenile alligators from contaminated and control lakes in Florida. Environ Health Perspect, 1994, 102: 680688 Carlsen E, Giwercman A, Keiding N, et al. Evidence for decreasing quality of semen during past 50 years. Br Med J, 1992, 305: 609613 Desbrow C, Routledge E J, Brighty G C, et al. Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation and in vitro biological screening. Environ Sci Technol, 1998, 32: 15491558 Routledge E J, Sheahan D, Desbrow C, et al. Identification of estrogenic chemicals in STW effluent. 2. In vivo responses in trout and

4 5 Figure 6 Oxidation of estrone by permanganate in a filtered natural water background at pH 8.2 () and pH 5.8 (). Comparison experiments were also conducted in the ultra-pure water system at pH 5.8 () and pH 8.2 (). [E1]0=1.248 mol/L, [KMnO4]0=12.656 mol/L, ambient temperature, 281C.

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