Anal Bioanal Chem (2011) 400:205212 DOI 10.

1007/s00216-011-4788-7

PAPER IN FOREFRONT

Micro-solid phase equilibrium extraction with highly ordered TiO2 nanotube arrays: a new approach for the enrichment and measurement of organochlorine pesticides at trace level in environmental water samples
Qingxiang Zhou & Yunrui Huang & Junping Xiao & Guohong Xie

Received: 29 November 2010 / Revised: 4 February 2011 / Accepted: 7 February 2011 / Published online: 23 February 2011 # Springer-Verlag 2011

Abstract Ordered TiO2 nanotube arrays have been widely used in many fields such as photocatalysis, self-cleaning, solar cells, gas sensing, and catalysis. This present study exploited a new functional application of the ordered TiO2 nanotube arrays. A micro-solid phase equilibrium extraction using ordered TiO2 nanotube arrays was developed for the enrichment and measurement of organochlorine pesticides prior to gas chromatography-electron capture detection. Ordered TiO2 nanotube arrays exhibited excellent
Electronic supplementary material The online version of this article (doi:10.1007/s00216-011-4788-7) contains supplementary material, which is available to authorized users. Q. Zhou (*) : Y. Huang Henan Key Laboratory for Environmental Pollution Control, Key Laboratory for Yellow River and Huaihe River Water Environment and Pollution Control, Ministry of Education, School of Chemistry and Environmental Sciences, Henan Normal University, Xinxiang 453007, China e-mail: zhouqx@henannu.edu.cn e-mail: zhouqx@cup.edu.cn Q. Zhou State Laboratory of Petroleum Resource and Prospecting, Key Laboratory of Earth Prospecting and Information Technology, College of Geosciences, China University of Petroleum Beijing, Beijing 102249, China J. Xiao Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China G. Xie College of Resources and Environment, Henan Institute of Science and Technology, Xinxiang 453003, China

merits on the pre-concentration of organochlorine pesticides and lower detection limits of 0.10, 0.10, 0.10, 0.098, 0.0076, 0.0097, 0.016, and 0.023 g L1 for -HCH, HCH, -HCH, -HCH, p,p-DDE, p,p-DDD, o,p-DDT, and p,p-DDT, respectively, were achieved. Four real water samples were used for validation, and the spiked recoveries were in the range of 78102.8%. These results demonstrated that the developed micro-solid phase equilibrium extraction using ordered TiO2 nanotube arrays would be very constructive and have a great beginning with a brand new prospect in the analysis of environmental pollutants. Keywords Ordered TiO2 nanotube array . Organochlorine pesticides . Micro-solid phase equilibrium extraction . Gas chromatography-electron capture detection

Introduction TiO2 has been widely used in many applications ranging from anticorrosion, self-cleaning coatings, paints to solar cells, and photocatalysts due to its high photocatalytic activity, chemical stability, non-toxicity, and relatively low cost [14]. Recently, TiO2 nanotubes have received considerable attention because of their higher surface area, better adsorption ability, and higher photocatalytic activity in comparison with TiO2 powders [58]. However, it was difficult to separate and reuse the TiO2 nanotubes from the solution. Therefore, the aim became to align the TiO2 nanotubes on a substrate or template. Zwelling and coworkers [9] made a first attempt and successfully achieved ordered TiO2 nanotubes arrays through a simple anodization process. Grimes and coworkers firstly utilized the

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highly ordered TiO2 nanotube array film to fabricate the solar cell [10]. Afterwards, many related preparation methods and applications of TiO2 nanotubes arrays were reported, which made it easy to obtain needed TiO2 nanotubes arrays for many important engineering applications. Nowadays, TiO2 nanotubes arrays have been employed in many fields including photoelectrochemical hydrogen generation [1115], solar cells [1618], hydrogen storage [19], gas sensing [2022], templates for growth of compound semiconductor nanowires for radiation sensing [23], substrate for high interfacial bond strength hydroxyl apatite coating in implants [24, 25], biomedical applications [26], and catalyst supports [27]. In environmental field, TiO2 nanotubes arrays have also been reported for organic contaminant degradation based on its photoelectrocatalytic activity [2832]. However, to the best of our knowledge, there has been no report using TiO2 nanotube array for the goal of enrichment of environmental pollutants. Organochlorine pesticides (OCPs) have been widely used for the control of pests in agriculture and cities because of its low cost and effectiveness all over the world. A huge amount of organochlorinated compounds is continuously being released into the environment with the extensive use of OCPs and herbicides, and discharge of wastewater from bleaching of pulp and municipal wastewater treatment. Environmental contamination by OCPs has been a major concern over the past several decades in the world because of their persistence, long-distance transport, biological effects, and bioaccumulation along the food webs. Nowadays, OCPs are known as one of the most persistent organic pollutants in the environment and have absorbed much attention from most of the governments all over the world. To date, most of the developed and developing countries have already banned or restricted the production and usage of OCPs, such as dichlorodi-phenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), hexachlorobenzene, polychlorinated biphenyls, etc. The US Environmental Protection Agency (EPA) has identified 12 priority persistent bioaccumulative and toxic compounds of special interest [33], which includes DDT and its breakdown products, DDE and DDD. Some of them were listed in the Stockholm Convention on Persistent Organic Pollutants. However, recent studies have reported the presence of organochlorine pesticides in different sites [3436]. Therefore, it is necessary to monitor the amounts and distribution of OCPs and evaluate their effects on the environment. Thus, simple and highly sensitive analytical techniques are required to detect and quantify OCPs at trace levels. Usually, to achieve the necessary level of sensitivity, an enrichment step is needed before analysis. A variety of enrichment steps had been established for separation and preconcentration of OCPs such as solvent cooling-assisted dynamic hollow-fiber-supported headspace liquid-phase

microextraction [37], dispersive liquidliquid microextraction [38, 39], solid phase extraction [40], solid phase microextraction [41, 42], etc. Solid phase extraction has distinguished from many extraction techniques because of its advantages of lower cost, higher enrichment factor, and less consumption of organic solvents. The aim of present work was to establish a novel, effective, reusable, simple, and sensitive determination method for OCPs with TiO2 nanotube arrays. Used as adsorbents, TiO2 nanotube arrays would avoid the low flow rate of the conventional solid phase extraction with TiO2 nanotubes cartridge and the difficulty in separation from dispersion in solution and make it easy to reuse. This new protocol is to establish a convenient micro-solid phase equilibrium extraction (SPEE) with TiO2 nanotube arrays for the enrichment of OCPs and to enlarge the application field of TiO2 nanotube arrays.

Experimental Reagents and materials A working stock solution (10.00 mg L1) of OCPs was prepared in HPLC-grade methanol with mixed standards containing -hexachlorocyclohexane ( -HCH), hexachlorocyclohexane (-HCH), -hexachlorocyclohexane (-HCH), -hexachlorocyclohexane (-HCH), dichlorodiphenyltrichloroethane (o,p-DDT, p,p-DDT), dichlorodiphenyldichloroethylene (p,p-DDE), and dichlorodiphenyldichloroethane (p,p-DDD) from Beijing Yingtianyi Chemical Science and Technology Co., Ltd. (Beijing, China). All the standard solutions were stored at 4 C in the refrigerator and protected from light. The aqueous solutions were prepared daily by diluting the standard mixture with ultrapure water. HPLC-grade methanol and acetonitrile were obtained from Jiangsu Guoda Chemical Reagent Co., Ltd. (Huaian, China). Ultrapure water was prepared in the laboratory using a Millipore (Billerica, MA, USA) water generator system, and all the other solvents were of analytical reagent grade unless stated. One percent sodium hydroxide and 1 mol L1 hydrochloric acid were used for adjusting the pH value of the water samples. Titanium sheets (99.6% purity) from Beijing Hengli Taiye Co., Ltd. (Beijing, China), Pt electrode was obtained from Shanghai Ruosull Technology Co., Ltd., 30 V potentiostat (JWY-30 G, Shijiazhuang, China) Preparation and identification of TiO2 nanotube array Titanium sheets (0.2 mm thick, 1020 mm size) with 99.6% purity (Beijing, China) were polished with metallo-

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graphic abrasive paper and were then degreased by sonicating in acetone, isopropanol, and methanol, respectively. The sheets were air-dried after rinsing with ultrapure water. The anodic oxidation was accomplished by using titanium sheet as anode and platinum as cathode. The distance between two electrodes was 3 cm in all experiments. The electrolyte was composed of 0.14 M NaF and 0.5 M H3PO4 [43]. The anodic oxidation was carried out at 20 V for 1 h. After electrolysis, a titanium sheet was rinsed with ultrapure water and then air-dried. The TiO2 nanotube arrays prepared were then analyzed with a field emission scanning electron microscope (S-4800 FESEM, Hitachi, Japan; see Fig. 1). SPEE procedure The TiO2 nanotube array sheet was directly immersed in 10 mL solution with a constant depth and then sealed in the sample vial. The extraction conditions were the same as that of the optimized conditions. The stirring rate of the magnetic stirrer was set at 500 rpm. After the

equilibrium between adsorption and desorption was basically reached, the TiO2 nanotube array sheet was taken out and rinsed with distilled water in order to remove co-adsorbed matrix substances, then air-dried and eluted for the desorption of analytes. TiO2 nanotube array sheet was directly immersed in a small amount of dichloromethane for complete desorption in an interval of 7 min. After that, the TiO2 nanotube array sheet was removed, and the dichloromethane was dried with mild stream of nitrogen gas. Then, the residue was dissolved in 100 L methanol. Finally, 1 L of the solution was injected for gas chromatography (GC) analysis. GC analysis GC analyses were performed on an Agilent 7890A gaschromatographic system, equipped with an electron capture detector (ECD). Separations were carried out using a HP-5 column (30 m0.32 mm0.25 m). Nitrogen (99.999%) was employed as the carrier gas (0.6 mL min1). The 1.0 L of a standard solution or sample solution was injected in the splitless mode at 250 C using the following program of 80 C (held 1 min), then 25 C min1 ramp to 200 C held for 2 min, and then 10 C min1 ramp to 300 C held for 5 min. Total run time was 22.8 min. The ECD was maintained at 300 C. Water samples In this work, four environmental water samples such as tap water, melted snow water, lake water, and reservoir water were collected for validating the proposed method. Tap water sample was collected from our own laboratory after it was flowing for 10 min at a very fast rate. A snow sample was collected from Henan Normal University, Xinxiang, Henan Province, 12 Nov 2009. Lake water sample was collected from Shouxihu Lake, Yangzhou, Jiangsu Province, China. Reservoir water sample was taken from Xiaoshangzhuang reservoir, Xinxiang, Henan Province, China. All the collected water samples were filtered through 0.45-m micropore membranes after sampling and were maintained in glass containers, and then stored at 4 C.

Results and discussion The effect of equilibrium between sample solution and TiO2 nanotube array In this SPEE procedure, the extraction is affected by several factors. The analytes, which exist as molecular form in the solution, would be enriched, and the enriched amount of analytes was related to the amount of analytes existing as

Fig. 1 FESEM images of TiO2 nanotube arrays. a Top view; b cross-view

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molecular form in the solution. However, two procedures will occur in the extraction process and influence the amount of molecular analytes in the solution, further influencing the enrichment performance. First, the analytes would migrate between gas and liquid phases due to the vapor pressure for the volatile or half volatile compounds. This procedure will reach equilibrium. This equilibrium obeys Henrys law when the concentrations of analytes are very low, pB kHxB 1

In general, these three steps will reach equilibrium, and the best enrichment will be achieved (see Fig. 2). On the other hand, if the concentrations of analytes are larger, which does not make them obey Henrys law, suppose the amount of volatile part as Cv, so: lg Q lg KF 1=n lgC0 Cv 6

where pB is the partial pressure of the (analytes) in the gas above the solution; xB is the concentration of the (analytes), and kH is known as the Henry's law constant, which depends on the solute (analytes), the solvent, and the temperature. The second procedure is the adsorption of analytes onto the adsorbents, and it is also a reversible procedure. Some of the HCHs and DDTs may adsorb on the surface of the adsorbents, and some of them will be desorbed at the same time. Finally, they will reach equilibrium. This equilibrium obeys the Freundlich equation (Freundlich adsorption isotherm): lg Q lg KF 1=n lg xB 4

The primary experiments have proved that it was right that the peak areas of HCHs were very small due to the relatively high vapor pressure or lower competitive adsorption. As the nonvolatile compounds are concerned, the adsorption obeys the Eq. 4. Beside these, the parameters including the kind of organic solvents, sample pH, extraction time, and desorption time would give rise to influence the enrichment efficiency. In order to obtain appropriate extraction efficiency, a procedure for optimization was necessary. Hence, we performed a series of experiments for obtaining optimal enrichment conditions. The effect of other factors on SPEE Effect of the kind organic solvents In a SPEE procedure, different desorption efficiency would be obtained when different solvents are used due to the different physical and chemical properties of the organic solvents and characteristics of the target analytes. In this experiment, there are five types of solvents such as methanol, acetonitrile, acetone, hexane, and dichlorome-

Where Q is the weight adsorbed per unit area of TiO2 nanotubes array sheet, kF and (1/n) are constants for a given adsorbate and adsorbent at a particular temperature, and pB is the partial pressure of the (analytes) in the gas above the solution. We substituted Eq. 1 into Eq. 4: lgQ lg KF 1=n lg kH 1=n lg pB 5

Fig. 2 Adsorption equilibrium of TiO2 nanotube arrays as adsorbents for analytes

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thane which were used for desorption of OCP pesticides. It was found that dichloromethane was the most effective solvent of the eight analytes, so it was used as the solvent for desorption. Effect of sample pH Sample pH plays an important role in the extraction procedure because pH value determines the existing form of the analytes, and then the pH of the sample solution affects the extraction efficiency. In this experiment, the effect of sample pH on the enrichment of OCPs was evaluated in a range of pH 3.0~8.0 (see Fig. 3). As can be seen, the peak area of four HCHs decreased with the increase of pH value, and the peak area of DDTs, DDD, and DDE reached the maximum at the pH 6.0. The extent of peak area decrease of HCHs was very small. Hence, pH 6 was used in the following experiments. Effect of salting-out effect Salting-out effect is often an important factor in the extraction procedure. In these experiments, it was optimized in the range of 0~30% (w/v). The peak areas of the HCHs increased a little with the increase of NaCl concentration and the peak areas of DDTs, DDD, and DDE decrease significantly when the NaCl concentration is in the range of 0~30%. The reason may be that addition of salt suppresses the thickness of electrical adsorption layer at the TiO2 solution interface, which leads to the decrease of mixed hemimicelles formed on the TiO2 surface. Based on these results, NaCl was not added. Effect of equilibrium time Equilibrium time is an important parameter in the SPEE procedure, which determines the enrichment performance better or not. In order to achieve a reasonable extraction

time, a series of experiments were designed for investigation of the effects of extraction time in the range of 20~ 90 min. The results were shown in Fig. 4. From the figure, we can see that the adsorption of HCHs reached the equilibrium rapidly and DDT, DDD, and DDE needed more time. So, the peak areas of DDT, DDD, and DDE increased straightly in the time interval. However, the extraction efficiency improved significantly with increasing equilibrium time up to 40 min; after that, the extraction efficiency increased slightly. Hence, for time saving in subsequent experiments, 40 min was used as the equilibrium time. Effect of desorption time In the SPEE procedure, two steps are very important; one is the adsorption of analytes on the surface of adsorbents, and the other is desorption of analytes from the adsorbents. Ideally, these two procedures are very rapid. In fact, the procedure may be various due to different conditions. Desorption of OCPs from the TiO2 nanotube array sheet with the dichloromethane is controlled by the time. In order to achieve complete desorption of OCPs, the desorption time was investigated in the range of 1~9 min. The results indicated that the desorption of HCHs was rapid and had no significant differences in the time interval, but the DDT and DDD reached the best desorption level in 7 min; DDE needed longer time for desorption. However, there were very limited peak area increases with the time over 7 min. So, 7 min was optioned in subsequent experiments. Analytical performance In this experiment, some important quantitative parameters of the proposed method such as linear range, correlation coefficients, limits of detection (LODs), and relative standard deviation (RSD) were evaluated by enriching 10 mL standard solutions, and the results were listed in

Fig. 3 Effect of sample pH equilibrium time, 40 min; NaCl, 0%; desorption time, 5 min; spiked sample concentration, 1 g L1 for each compound. () -HCH ( ) -HCH ( ) -HCH ( ) -HCH ( ) p,p-DDE ( ) p,p-DDD ( ) o,p-DDT ( ) p,p-DDT

Fig. 4 Effect of equilibrium time. pH, 6; desorption time, 5 min; spiked sample concentration, 1 g L1 for each compound () -HCH ( )-HCH ( ) -HCH ( ) -HCH ( ) p,p-DDE ( ) p,p-DDD ( ) o,p-DDT ( ) p,p-DDT

210 Table 1 Linear range, correlation coefficient, precision, and detection limits (S/N=3) Compound -HCH -HCH -HCH -HCH p, p-DDE p, p-DDD o, p-DDT p, p-DDT Linear range (gL1) 0.140 0.140 0.140 0.140 0.1100 0.1100 0.1100 0.1100 R2 0.9947 0.9915 0.9973 0.9989 0.9950 0.9951 0.9966 0.9952 Precision (RSD%, n =6) 9.12 7.91 7.32 8.94 8.01 7.00 9.88 9.58

Q. Zhou et al. LOD (gL1) 0.10 0.10 0.10 0.098 0.0076 0.0097 0.016 0.023

Table 1. Calibration curves were performed using 10 mL ultrapure water spiked with 0.1~100 g L1 each of the OCPs. Each analyte exhibited good linearity with correlation coefficient (R2)>0.99 in the studied range. The limits of detection, calculated on the basis of signal-to-noise ratio of 3 (S/N=3) were in the range of 0.062~0.212 g L1. The precision of analytical method was investigated using six replicate experiments with 10 mL standard solution containing each of the OCPs at 1.0 g L1, and the RSD of below 10.0% was obtained. Analysis of real water samples To demonstrate the applicability of the TiO2 nanotube array sheet as SPEE adsorbents, the proposed procedure has been carried out on four real environmental water samples, and the results were shown in Table 2. The results indicated that no OCPs were found in water samples; maybe, it was due to the limited sample volume which the too-low concentration of OCPs could not provide enough amount

for detection. So, these samples were then spiked with OCPs at three different concentration levels to investigate the effect of sample matrices. The spiked recoveries were satisfied in the range of 78~102.8%. The typical chromatograms of real water sample were demonstrated (see Fig. S1, Electronic Supplementary Material). Comparison with SPE In order to validate the proposed method, comparisons with conventional solid-phase equilibrium (SPE) and dispersive liquid-liquid microextraction (DLLME) were performed. The four environmental water samples were preconcentrated with SPE using C18 and TiO2 nanotubes as the adsorbents, and their amounts were 200 and 100 mg, respectively. The enrichment conditions were as that reported in reference [44]. Sample volume is 50 mL. Dispersive liquidliquid microextraction was carried out under the conditions as reported in [45], and the sample volume is 10 mL. The results (see Table S1, Electronic Supplementary Material)

Table 2 Recoveries of real water samples spiked at three concentration levels with proposed method Water samples Blank Added levels (gL1) 0.2 1 5 0.2 1 5 0.2 1 5 0.2 1 5 -HCH -HCH -HCH -HCH p,p-DDE p,p-DDD o,p-DDT p,p-DDT

Tap water

Snow water

Shouxihu Lake water

Xiaoshangzhuang wastewater

ND ND ND ND ND ND ND ND ND ND ND ND

79.23.4 78.02.5 88.25.1 80.11.9 82.35.5 80.53.1 80.22.3 79.84.1 81.53.2 81.52.9 79.23.5 81.42.9

80.22.9 78.66.1 80.14.2 82.55.4 83.62.9 80.92.8 82.33.2 81.43.7 82.34.8 81.23.1 80.65.5 80.93.1

82.14.8 83.55.9 86.72.8 79.82.1 82.65.6 81.85.6 85.64.2 87.84.6 86.62.7 80.65.2 79.87.1 81.54.1

80.53.4 89.62.9 87.65.6 88.26.2 86.73.2 89.54.6 88.96.1 89.12.9 90.11.9 82.52.8 83.22.9 85.12.8

95.86.1 96.24.3 98.66.1 92.82.9 96.54.2 98.53.3 95.85.2 98.63.2 99.46.2 98.66.1 99.26.4 97.95.1

95.81.8 99.83.8 102.52.1 98.58.1 92.66.1 96.22.8 98.24.6 97.84.1 101.27.1 98.22.6 97.84.1 98.65.2

95.62.8 96.98.1 99.22.8 99.82.9 100.25.2 99.81.8 99.85.2 98.64.6 102.82.5 99.85.1 101.25.2 100.13.7

100.25.2 98.92.1 99.84.9 99.66.4 98.55.3 101.58.1 99.85.6 98.66.8 102.32.2 99.83.8 98.93.7 101.24.2

ND not detected

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211 Acknowledgements This work was supported by the Natural Science Foundation of China (20877022), the Natural Science Foundation of Henan Province (082102350022), and the Personal Innovation Foundation of Universities in Henan Province ([2005]126).

showed that the enrichment performance was different for different target analytes, different sample matrices, and different initial concentrations of the analytes. In contrast, the spiked recoveries of the target analytes in wastewater and lake water were better than that in tap water and snow water; this was due to the high ionic strength in these two water matrices. The detection limits of these target analytes in real water samples (see Table S2, Electronic Supplementary Material) exhibited that the sensitivity of proposed method was the same as that of DLLME and was lower than that obtained with C18 and TiO2 nanotubes SPE. The results were predicted because of two reasons. One is the sample volume, which was five times higher than that of proposed method. This accounted for a part of the results. The other is the different amount of the adsorbents. The effective amount of TiO2 nanotube arrays for SPEE was far lower than that for SPE. Because the TiO2 nanotube array sheet was 400 mg, and the thickness was 200 m. The length of TiO2 nanotube was about 400500 nm, and there had one layer each side on the titanium sheet. Hence, the thickness of TiO2 nanotube arrays were about 1 m, and the amount of TiO2 nanotube arrays was about 0.5% of the amount of titanium sheet. Based on the LODs in Table S2 (see S2, Electronic Supplementary Material), we can predict that the practice sensitivity of proposed method will be much higher than that of SPE if the sample volume, and the amount of adsorbent were as the same. All these results indicated that the developed SPEE provided relative stable and excellent results and was a new, robust, and good mode for the determination of such compounds.

References
1. Linsebigle AL, Lu GQ, Yates JT (1995) Chem Rev 95:735758 2. Liaw WC, Chen KP (2007) Eur Polym J 43:22652278 3. Verma A, Kar M, Agnihotry SA (2007) Sol Energ Mat Sol C 91:13051312 4. Wang C, Deng ZX, Li YD (2001) Inorg Chem 40:52105214 5. Koenenkamp R, Henninger R, Hoyer P (1993) J Phys Chem 97:73287330 6. Wang YQ, Hu GQ, Duan XF, Sun HL, Xue QK (2002) Chem Phys Lett 365:427431 7. Lakshmi BB, Patrissi CJ, Martin CR (1997) Chem Mater 9:2544 2550 8. Miao Z, Xu D, Ouyang J, Guo G, Zhao X, Tang Y (2002) Nano Lett 2:717720 9. Zwilling V, Aucouturier M, Darque-Ceretti E (1999) Electrochim Acta 45:921929 10. Mor GK, Shankar K, Paulose M, Varghese OK, Grimes C (2006) Nano Lett 6:215218 11. Raja KS, Misra M, Mahajan VK, Gandhi T, Pillai P, Mohapatra SK (2006) J Power Sources 161:14501457 12. Raja KS, Mahajan VK, Misra M (2006) J Power Sources 159:12581265 13. Mor GK, Shankar K, Paulose M, Varghese OK, Grimes CA (2005) Nano Lett 5:191195 14. Paulose M, Mor GK, Varghese OK, Shankar K, Grimes CA (2006) J Photochem Photobiol A 178:815 15. Varghese OK, Paulose M, Shankar K, Mor GK, Grimes CA (2005) J Nanosci Nanotech 5:11581165 16. Macak JM, Tsuchiya H, Ghicov A, Schmuki P (2005) Electrochem Commun 7:11331137 17. Zhu K, Neale NR, Miedaner A, Frank A (2007) Nano Lett 7:69 74 18. Mor GK, Varghese OK, Paulose M, Shankar K, Grimes CA (2006) Sol Energy Mater Sol Cells 90:20112075 19. Pillai P, Raja KS, Misra M (2006) J Power Sources 161:524530 20. Grimes CA (2007) J Mater Chem 17:14511457 21. Mor GK, Varghese OK, Paulose M, Grimes CA (2003) Sens Lett 1:4246 22. Varghese OK, Gong D, Paulose M, Ong KG, Dickey EC, Grimes CA (2003) Adv Mater 15:624627 23. Gandhi T, Raja KS, Misra M (2006) Electrochim Acta 51:5932 5942 24. Raja KS, Misra M, Paramguru K (2005) Mater Lett 59:21372141 25. Kar A, Raja KS, Misra M (2006) Surf Coat Technol 201:3723 3731 26. Macak JM, Tsuchiya H, Taveria L, Ghicov A, Schmuki P (2005) J Biomed Mater Res A 75:928933 27. Macak JM, Tsuchiya H, Bauer S, Ghicov A, Schmuki P, Barczuk PJ, Nowakowska MZ, Chojak M, Kulesza PJ (2005) Electrochem Commun 7:14171422 28. Quan X, Yang S, Ruan X, Zhao H (2005) Environ Sci Technol 39:37703775 29. Quan X, Ruan X, Zhao H, Chen S, Zhao Y (2007) Environ Pollut 147:409414 30. Zhang Z, Yuan Y, Shi G, Fang Y, Liang L, Ding H, Jin L (2007) Environ Sci Technol 41:62596263 31. Lu N, Quan X, Li J, Chen S, Yu H, Chen G (2007) J Phys Chem C 111:1183611842

Conclusions TiO2 nanotube array as a novel nanomaterial has gained much more attention in many fields. However, its merits have not been utilized completely. This work demonstrated for the first time that TiO2 nanotube array could be used as effective SPEE materials for the enrichment of OCPs in four different environmental water samples. The proposed method provided good linear range, reproducibility, and detection limits. Based on the experimental results, a simple and reliable determination method for OCPs was developed based on the SPEE. According to the physical and chemical properties of TiO2 nanotube array and the different preparation method, different TiO2 nanotube arrays with good structure would be achieved easily. It is expected that they would have better enrichment capacity for selected analytes. TiO2 nanotube array will give a much higher enrichment performance with the same effective amount of adsorbents than the established methods. TiO2 nanotube array can be potentially applied to the enrichment and determination of many other pollutants.

212 32. Liu Z, Zhang X, Nishimoto S, Jin M, Tryk DA, Murakami T, Fujishima A (2008) J Phys Chem C 112:253259 33. U. S. Environmental Protection Agency, http://www.epa.gov/ opptintr/pbt/cheminfo.htm 34. Qiu XH, Zhu T, Wang F, Hu JX (2008) Environ Sci Technol 42:19281932 35. Bustnes J, Yiccoz N, Bangjord G, Polder A, Skaare JU (2007) Environ Sci Technol 41:84918497 36. Zhang G, Chakraborty P, Li J, Sampathkumar P, Balasubramanian T, Kathiresan K, Takahashi S, Subramanian A, Tanabe S, Jones KC (2008) Environ Sci Technol 42:82188223 37. Huang SP, Huang SD (2007) J Chromatogr A 1176:1925

Q. Zhou et al. 38. Cortada C, Vidalb L, Pastora R, Santiagoa N, Canalsb A (2009) Anal Chim Acta 649:218221 39. Tsai W, Huang S (2009) J Chromatogr A 1216:51715175 40. Kima M, Kanga TW, Pyob H, Yoonc J, Choic K, Honga J (2008) J Chromatogr A 1208:2533 41. Fidalgo-Used N, Montes-Bayn M, Blanco-Gonzlez E, SanzMedel A (2008) Talanta 75:710716 42. Dong C, Zeng Z, Li X (2005) Talanta 66:721727 43. Liu H, Liu G, Zhou Q (2009) J Solid State Chem 182:32383242 44. Zhou QX, Ding YJ, Xiao JP, Liu GG, Guo XY (2007) J Chromatogr A 1147:1016 45. Zhou QX, Pang L, Xiao JP (2009) J Chromatogr A 1216:66806684