Journal of Chromatography A, 1335 (2014) 214

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Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Review

Beyond dispersive liquidliquid microextraction

Mei-I. Leong a , Ming-Ren Fuh b,1 , Shang-Da Huang c,
a

Centro de Seguranca Alimentar, Instituto para os Assuntos Cvicos e Municipais (IACM), Macau, China Department of Chemistry, Soochow University, Taipei 11102, Taiwan c Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan
b

a r t i c l e

i n f o

a b s t r a c t
Dispersive liquidliquid microextraction (DLLME) and other dispersion liquid-phase microextraction (LPME) methods have been developed since the rst DLLME method was reported in 2006. DLLME is simple, rapid, and affords high enrichment factor, this is due to the large contact surface area of the extraction solvent. DLLME is a method suitable for the extraction in many different water samples, but it requires using chlorinated solvents. In recent years, interest in DLLME or dispersion LPME has been focused on the use of low-toxicity solvents and more conveniently practical procedures. This review examines some of the most interesting developments in the past few years. In the rst section, DLLME methods are separated in two categories: DLLME with low-density extraction solvent and DLLME with high-density extraction solvent. Besides these methods, many novel special devices for collecting low-density extraction solvent are also mentioned. In addition, various dispersion techniques with LPME, including manual shaking, air-assisted LPME (aspirating and injecting the extraction mixture by syringe), ultrasound-assisted emulsication, vortex-assisted emulsication, surfactant-assisted emulsication, and microwave-assisted emulsication are described. Besides the above methods, combinations of DLLME with other extraction techniques (solid-phase extraction, stir bar sorptive extraction, molecularly imprinted matrix solid-phase dispersion and supercritical uid extraction) are introduced. The combination of nanotechnique with DLLME is also introduced. Furthermore, this review illustrates the application of DLLME or dispersion LPME methods to separate and preconcentrate various organic analytes, inorganic analytes, and samples. 2014 Elsevier B.V. All rights reserved.

Article history: Received 24 October 2013 Received in revised form 9 February 2014 Accepted 10 February 2014 Available online 15 February 2014 Keywords: Dispersive liquidliquid microextraction Dispersion liquid-phase microextraction Preconcentration Sample preparation

Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. DLLME with lower-density extraction solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.1. DLLME based on solidication of oating organic droplet (DLLME-SFO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.2. DLLME with special extraction devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.3. Low-density-solvent based solvent demulsication DLLME (LDS-SD-DLLME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. DLLME with higher-density extraction solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1. DLLME with low-toxicity solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.2. Auxiliary solvent to adjust the density of DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.3. DLLME with automated online sequential injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Development of DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Various techniques for assisting dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Manual shaking for assisting dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2. Air-assisted liquidliquid microextraction (AALLME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.3. Ultrasound-assisted emulsication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 3 3 5 7 7 7 7 7 8 8 8 8 8

2.

Corresponding author. Tel.: +886 3 572 1194; fax: +886 3 573 6979. E-mail addresses: msfuh@mail.scu.edu.tw (M.-R. Fuh), sdhuang@mx.nthu.edu.tw (S.-D. Huang). 1 Tel.: +886 2 2881 9471x6821; fax: +886 2 2881 1053. http://dx.doi.org/10.1016/j.chroma.2014.02.021 0021-9673/ 2014 Elsevier B.V. All rights reserved.

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3.

4.

Surfactant-assisted emulsication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.4. 2.1.5. Vortex-assisted emulsication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.6. Microwave-assisted emulsication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Combination of techniques for extraction and analysis with DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Solid-phase extraction combined with DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Stir bar sorptive extraction (SBSE) combined with DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Molecularly imprinted matrix solid-phase dispersion combined with DLLME (MIMMSPDDLLME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Supercritical uid extraction (SFE) combined with DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5. Nanotechniques combined with DLLME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Other methods using low-toxicity solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . DLLME applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Application of DLLME for various analytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1. Organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.2. Inorganic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Application of DLLME to various eld samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

8 9 10 10 10 11 11 11 11 11 12 12 12 12 12 12 13 13 13

1. Introduction Liquidliquid microextraction (LPME) is usually applied in the extraction of environmental samples. LPME has several different operational modes, such as those that use a drop of solvent [1,2], porous hollow ber-protected solvent [35], and disperser solvent. The rst two methods are simple and use lower volumes of organic solvent. However, they are limited by the small contact surface area of the drop or ber, which necessitates long extraction times. In 2006, Rezaee et al. developed dispersive liquidliquid microextraction (DLLME) for preconcentration of polycyclic aromatic hydrocarbons (PAHs) in water samples [6]. The rst DLLME methods employ a mixture of a high-density extraction solvent, a water-miscible solvent, and a polar disperser solvent. The extraction solvent must be able to extract analytes, is soluble in the disperser solvent, insoluble in aqueous samples, and have density higher than that of water. The disperser solvent has to be soluble in both water and extraction solvent. In this method (Fig. 1(a)) [6], 5 mL of the aqueous solution is placed in a screw-cap glass test tube with a conical bottom. A solution of 1 mL of acetone (disperser solvent) and 8 L of tetrachloroethylene (TCE, the extraction solvent) is injected into the sample solution. A cloudy dispersion consisting of water, disperser solvent, and extraction solvent is formed in the test tube and is centrifuged. The dispersed ne droplets of the extraction phase settle at the bottom of the conical test tube and could be injected into a gas chromatograph for further analysis. Many conventional DLLME typically use 20100 L of chlorinated solvents as extraction solvent, 0.52 mL of disperser solvent, and 510 mL of aqueous sample. The total extraction time including the centrifugation time is generally 510 min. Advantages of this technique include simplicity of operation, rapid extraction, and high enrichment factors (EFs) [7,8]. However, the high-density extraction solvent used, which is typically chlorobenzene, chloroform, or carbon tetrachloride, is highly toxic. There are many excellent recent reviews on DLLME or dispersion LPME methods (methods that disperse extraction solvent for extraction) [913]. Kocrov et al. summarized a lot of details about DLLME using organic solvents lighter than water methods, and concludes the uses of special devices, the low-density solvent used (based on solidication and solvent demulsication) in DLLME procedures, the adjustment of extraction solvents mixture density and procedures based on automation of DLLME by sequential injection analysis [9]. Zgoa-Grze skowiak and Grze skowiak described the application of DLLME to pre-concentration of metal ions, pharmaceuticals, other organic compounds and many more modications

of these newly developed techniques [10]. Kokosa reviewed the development of DLLME and summarized the techniques in three categories: DLLME using extraction solvents with density greater than water, DLLME using extraction solvents with density lower than water and automated DLLME [11]. Asensio-Ramos et al. summarized several DLLME applications in food analysis. Analytes can be initially extracted from the food matrix with an organic solvent, which normally acts in a second step as the disperser solvent [12]. Dadfarnia and Shabani summarized and discussed the application of DLLME in combination with different analytical techniques for preconcentration and determination of ultra trace amounts of metals and organometal ions in various matrices [13]. This review summarized and discussed the recent developments of DLLME and dispersion LPME including the utilization of various less toxic solvents, development various techniques to increase rate of mass transfer between two extracting solvent and sample solution, combination of other extraction with DLLME and design of special device for DLLME. Abbreviations of the DLLME and dispersion LPME methods in this review are shown in Table 1. Depending on the extraction solvent used, DLLME method may belong to one of two broad categories: those that use a lowerdensity extraction solvent and those that use a higher-density extraction solvent. Many new techniques in the former category have been introduced to separate and collect the extraction solvent from sample solution. Brominated or iodinated solvents and an auxiliary solvent in the latter category have been introduced; these methods enable easy separation of extraction solvent and samples solution by centrifugation. Other novel online and automated procedures with DLLME that have a promising future in analytical methodology are also mentioned in this section.

1.1. DLLME with lower-density extraction solvent 1.1.1. DLLME based on solidication of oating organic droplet (DLLME-SFO) Liquidliquid microextraction based on solidication of oating organic droplet (LLME-SFO) was introduced by Khalili-Zanjani et al. [14,15]. It is simple, inexpensive, and it involves minimal consumption of organic solvent. However, its extraction rate is lower than that of DLLME. DLLME-SFO [16,17] was developed to combine the benets of DLLME and LLME-SFO. Unlike LLME-SFO, DLLME-SFO does not involve stirring during extraction, and unlike traditional DLLME, it does not use chlorinated solvents and conical bottom glass tubes. Instead, a mixture of low-toxicity extraction solvent

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Fig. 1. Diagram of the extraction process of (a) DLLME and (b) DLLME-SFO.

Table 1 The abbreviations of the DLLME and dispersion LPME methods in this review. Method Dispersive liquidliquid microextraction DLLME with lower density extraction solvent DLLME based on the solidication of a oating organic drop Ionic liquid-based up-and-down shaker-assisted DLLME Low-density solvent-based solvent demulsication DLLME DLLME with higher density extraction solvent Low toxic DLLME Adjust the density of DLLME Injection dispersive liquidliquid microextraction Various techniques for assisting dispersion DLLME with a very low solvent consumption Air-assisted liquidliquid microextraction Ultrasound-assisted emulsication microextraction Surfactant assisted DLLME Coacervative microextraction ultrasound-assisted back-extraction technique Water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquidliquid microextraction Low-density solvent-based vortex-assisted surfactant-enhanced-emulsication liquidliquid microextraction Vortex-assisted supramolecular solvent microextraction Vortex-assisted liquidliquid microextraction Homogeneous ionic liquid microextraction Combination of techniques for extraction and analysis with DLLME Solid-phase extraction combined with DLLME Stir bar sorptive extraction combined with DLLME Matrix solid-phase dispersion combining with DLLME Supercritical uid extraction followed by DLLME Dispersive microsolid-phase extraction combined with DLLME Vortex-assisted micro-solid-phase extraction followed by low-density solvent based DLLME Other methods using low-toxicity solvent Flotation-assisted homogeneous liquidliquid microextraction Abbreviation of the method DLLME Ref. [6]

DLLME-SFO UDSA-IL-DLLME LDS-SD-DLLME

[16,17] [25] [26]

LT-DLLME AS-DLLME SI-DLLME

[28] [29] [3033]

DLLMELSC AALLME USAEME SA-DLLME CME-UABE WLSEME LDSVSLLME VASUSME VALLME HILME

[34] [35] [3645] [22,23] [39] [46] [48] [49] [38,4749] [50]

SPE + DLLME SBSE + DLLME MSPDDLLME SFE + DLLME D--SPE + DLLME VA--SPE + LDS-DLLME

[51] [52] [53] [54,55] [56,57] [58]

FA-HLLME

[76]

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(which is also less dense than water) and disperser solvent are rapidly injected into the sample solution to form a cloudy dispersion in the glass test tube. In this method [16] (Fig. 1(b)), a mixture of 0.5 mL of acetone and 10 L of 2-dodecanol is rapidly injected by syringe into a 5 mL water sample. After centrifugation, the test tube is transferred to a beaker containing crushed ice, and the solidied solvent is easily collected for analysis. To meet recent concerns about the costs and environmental hazards of waste solvent disposal, this method uses an extraction solvent of low toxicity and low volatility. The large contact surface area between the sample and the droplets of extractants facilitate mass transfer, resulting in extraction times similar to those of DLLME and shorter than that of LLME-SFO [14,15,18]. The drawbacks of this method are limited to the solvent chosen (low melting point) which is suitable for use in warm climates, if the laboratory is not air conditioned. 1.1.2. DLLME with special extraction devices Recently, many researchers have attempted to use lowertoxicity solvents with density lower than that of water in DLLME. One possible way of enabling the application of such solvents in DLLME is the use of special extraction devices, such as specially designed centrifugation tubes and pipette collection tubes. In 2009, Farajzadeh et al. designed a special vessel [19] for use in DLLME to extract organophosphorus pesticides (OPPs) (Fig. 2(a)). In this extraction method, a mixture of cyclohexane (extraction solvent) and acetone (disperser solvent) is rapidly injected by syringe into an aqueous sample in a special vessel. After centrifugation, ne droplets of cyclohexane accumulate in the upper layer of aqueous solution. The upper phase is injected into a gas chromatograph for separation. This method is rapid and easily recovers the extractant; however, it is not suitable for extracting volatile compounds. Hashemi et al. developed a DLLME method that uses a special device to enrich glycyrrhizic acid from aqueous extracts of licorice (Fig. 2(b)) [20]. The device consists of a narrow-necked glass tube (NNGT) inserted into a centrifuge tube. Hexanol and acetone are used as the extraction solvent and disperser solvent, respectively. A uniformly distributed cloudy suspension is produced by further aspiration and expulsion of about 2 mL of the cloudy sample by syringe. The mixture is then centrifuged for phase separation. Since hexanol is lighter than water, the extraction phase accumulates on the surface of the aqueous solution. Additional water is added from the opening of NNGT; then, the extraction phase is raised and lls the narrow neck of NNGT. As a result, the extraction phase can easily be withdrawn by microsyringe. Saleh et al. reported a centrifuge glass vial fabricated in-house for ultrasound-assisted emulsication microextraction (USAEME) (Fig. 2(c)) for the determination of PAHs in water samples [21]. In this method, the extraction solvent toluene is injected slowly into aqueous sample in a centrifuge glass vial in an ultrasonic water bath. After centrifugation, the separated toluene is injected into a gas chromatograph for analysis. This method affords very rapid extraction and recovery of the extractant. The only drawback of this and the aforementioned method by Hashemi et al. [20] is the difculty of cleaning the centrifuge glass vial. In 2011, Zhang et al. designed a special ask equipped with two narrow open ports, one of which has a capillary tip [22] to extract ultraviolet (UV) lters in environmental water samples (Fig. 2(d)). The ask is employed to facilitate the DLLME process. 1-Octanol, a low-density solvent, is used as the extraction solvent for DLLME and no disperser solvent is used. The extraction is accelerated by magnetic agitation. After extraction, no centrifugation step is necessary, and phase separation of the extraction solvent from the aqueous sample is easily achieved by allowing the extraction mixture to stand several minutes. The organic phase rises to the top of the mixture and concentrates in the narrow open tip of the ask upon addition of pure water into the extraction mixture through the other port. It

is thereafter withdrawn by microsyringe for HPLC analysis. This method is faster than many DLLME methods because it does not require centrifugation. It can be applied in the extraction of samples that are non-volatile and have large volumes. Hu et al. developed [23] a DLLME method based on a molecular complex for analysis of polar compounds in aqueous solution (Fig. 2(e)). The principle of this method is the hydrogen bonding between the extractant and the analytes. In this approach, the Lewis base tri-n-butylphosphate (TBP) instead of conventional water-immiscible organic solvents is directly used as extractant for DLLME. The sample containing the analytes is placed in a disposable polyethylene pipette. A mixture of the extractant TBP and the disperser solvent methanol is rapidly injected into the sample solution by syringe. Subsequently, the pipette is placed in a 10 mL Eppendorf tube and is agitated by a vortex mixer. After centrifugation, the organic phase oating on the aqueous solution is concentrated in the narrow neck of the pipette, and is easily withdrawn by a 10.0 L microsyringe. This technique expands the application of classical DLLME for various organic analytes, and enables extraction in a disposable polyethylene pipette. Su and Jen developed an in-syringe USAEME for the extraction of OPPs from water samples by using GC with micro electron capture detection [24] (Fig. 2(f)). Ultrasound radiation is applied to accelerate the emulsication of microliter volumes of low-density organic solvent in aqueous solutions to enhance the efciency of OPPs microextraction from the sample. Initially, the sample solution is drawn into a 5 mL syringe. After removal of the plunger and sealing of the syringe with a silicone-plug, the barrel is held upside down and the needle is removed. The extraction solvent (toluene) is then injected into the sample solution by using a 100 L glass syringe. After ultrasonication and centrifugation, the plunger of the 5 mL syringe is slowly pushed to transfer the recovered extractant into a graduated capillary tube. Finally, the extracting phase containing the target OPPs is easily recovered by syringe. One microliter of the separated extractant is injected into GC for analysis. This method uses a 5 mL syringe as the sample vial instead of a centrifuge tube, and a 100 L glass syringe is used to inject the extraction solvent and to recover the extractant. This device is easy to operate, and the extractant volume is easily read from the scale on the capillary tube. This method does not require a narrow-necked port to collect the extractants and the device is very easy to clean. To save time and effort, Ku et al. performed an up-and-down shaker assisted DLLME that uses an ionic liquid (IL) to preconcentrate three UV lters from eld water samples [25]. The up-and-down shaker model FS-6 was used to shake the mixture of extraction solvent and aqueous sample. In this method, a holder fabricated in-house is used to hold the sealed conical-bottom glass tubes. The extraction solvent 1-octyl-3-methylimidazolium hexauorophosphate ([C8 MIM][PF6 ]) (40 L) and the disperser solvent methanol (200 L) are used to extract the UV lters. After up-anddown shaking for 3 min, the aqueous mixture is centrifuged, and then a microtube is used to collect the extraction solvent for further analysis by ultra-performance liquid chromatography (UPLC). The apparatus for this method is simple and the extraction time is less than 4 min. This method also addresses the variation of the shaking process due to different operators. In addition, an IL of low toxicity such as [C8 MIM][PF6 ] is used instead of the highly toxic solvent normally used in DLLME. Dispersions in various special extraction devices are described in Table 2. The use of the narrow parts (neck, port, or nozzle) of devices can assist the collection of the low-density extraction solvent from the samples. Most of the devices use narrow necks or ports to gather the extractant drops [1922]. Before removal of the extractant, water must be injected to allow the extracted organic drop to reach the level of the neck or port of the tube or ask. Other methods that use the nozzle of a pipette [23] or syringe [24] to gather the extractant do not require injection of water and the

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Fig. 2. Diagram of the special device used in dispersion LPME with low-density extraction solvent: (a) special extraction vessel (DLLME), (b) glass tube with narrow neck (DLLME), (c) centrifuge glass vial designed in-house (USAEME), (d) special ask equipped with two narrow open ports (DLLME), (e) 5 mL polyethylene Pasteur pipette (DLLME), (f) 5 mL syringe as sample vial (DLLME) and (g) disposable polyethylene pipette (LDS-SD-DLLME).

M.-I. Leong et al. / J. Chromatogr. A 1335 (2014) 214 Table 2 Dispersion in different special extraction devices. Fig. 2 (a) (b) (c) (d) (e) (f) (g) Special sample vessel/tube/vial A special extraction vessel A glass tube with a narrow neck A home-designed centrifuge glass vial A special ask equipped with two narrow open ports A 5-mL soft polyethylene Pasteur pipette A 5 mL syringe as the sample vial A disposable polyethylene pipette Method DLLME DLLME USAEME DLLME DLLME DLLME LDS-SD-DLLME Instrumentation GC-FID HPLC GC-FID HPLC GC-ECD HPLC GCMS Analytes OPPs Glycyrrhizic acid PAHs UV lters OPPs Phenols PAHs Extraction solvent Cyclohexane n-Hexanol Toluene 1-Octanol Toluene TBP n-Hexane Ref. [19] [20] [21] [22] [23] [24] [26]

extraction apparatus is easy to clean. Except for the methods that use a special ask [22] for magnetic agitation or use an up-anddown shaker [25] to disperse the extraction solvent, there are many extraction methods use disperser solvent or surfactant to assist the dispersion of the extraction solvent. 1.1.3. Low-density-solvent based solvent demulsication DLLME (LDS-SD-DLLME) All of the aforementioned extraction devices possess advantages and drawbacks in terms of ease of operation and manifold complexity. Guo and Lee [26] reported a LDS-SD-DLLME method for the determination of 16 priority PAHs in environmental samples (Fig. 2(g)). No centrifugation is required in this procedure. A 5 mL sample solution is placed in a 5 mL polyethylene Pasteur pipette by using a 5 mL syringe. A mixture of the extraction solvent n-hexane (50 L) and the dispersive solvent acetone (500 L) is injected rapidly into the sample solution by a 1.0 mL syringe to form an emulsion. The demulsication solvent acetone (500 L) is then injected into the aqueous solution to break up the emulsion and separate it into two layers. The upper layer (about 35 L n-hexane) is collected and analyzed by gas chromatographymass spectrometry (GCMS). Notably, the extraction requires only 23 min, and is therefore faster than conventional DLLME or similar techniques. This method permits a solvent that is less dense than water to be used as extraction solvent, and expands the applicability of DLLME to a wider range of solvents. Chang et al. used DLLME combined with an improved solvent collection system to separate water and organic solvent in the collected extractant drop [27]. This method uses very small volumes of low-toxicity solvents (11 L of 1-nonanol and 400 L of methanol) to extract organochlorine pesticides (OCPs) from 10 mL water samples prior to analysis by GC. After centrifugation, a liquid organic drop accumulates between the water surface and the glass wall of the centrifuge tube. The liquid organic drop is transferred along with some of the water into a microtube (3 mm 15 mm) by syringe. The organic and aqueous phases then immediately separate in the microtube. The organic solvent is easily collected by syringe and then injected into the GC instrument for analysis. Moreover, it is better to centrifuge the collected phases in the microtube for about 1 min before injection, because it further removes water; in this manner, two clear phases are obtained. This improved solvent collection system can protect the instrument from damage by the injected water and increase the reproducibility of the results. 1.2. DLLME with higher-density extraction solvent 1.2.1. DLLME with low-toxicity solvent In addition to the many DLLME methods that have been developed to use low-density organic solvents, other methods using higher-density extraction solvent have been introduced to overcome the drawbacks of normal DLLME. In 2010, LT-DLLME was developed by Leong et al. [28]. This method uses lowertoxicity brominated, iodinated and other halogenated solvents such as 1-bromo-3-methylbutane (1-bromo-3-methylbutane, the median lethal dose (LD50 ) 6150 mg kg1 ) instead of the

highly toxic solvents normally used in DLLME. This method also demonstrates that propionic acid is suitable as a disperser solvent; as little as 50 L of the acid is sufcient for extraction. A 7 mL sample of water is spiked with PAHs. The disperser solvent propionic acid and the extraction solvent 1-bromo-3-methylbutane (10.0 L) are rapidly injected into the sample solution and the resulting mixture is shaken by hand for a few seconds. Potassium hydroxide (88 L, 40% (w/v)) is added to the sample to minimize emulsion formation by the extraction solvent before centrifugation. After centrifugation, the organic solvent is sedimented at the bottom of the conical test tube, and then a microsyringe is used to collect and inject it into a gas chromatograph for further analysis. The selected extraction solvent is less toxic than chlorinated solvents in normal DLLME. In particular, some brominated solvents are less toxic than the conventional low-density solvents in DLLME or dispersion LPME. 1.2.2. Auxiliary solvent to adjust the density of DLLME Kocrov et al. [29] developed an adjusting-density DLLME (ASDLLME) technique. A quaternary system consisting of an aqueous sample, an extraction solvent, an auxiliary solvent, and a disperser solvent is employed in this method. The auxiliary solvent (a chlorinated solvent), which is denser than water, is used to adjust the density of the extraction solventauxiliary solvent mixture to facilitate its separation from the aqueous sample by centrifugation. This method does not require the use of special devices. A 5 mL sample solution containing Au (III) is prepared in conical microcentrifuge tubes. A 0.5 mL mixture of the disperser solvent methanol, the extraction solvent toluene (145 L), and the auxiliary solvent carbon tetrachloride (CCl4 ; 145 L) is vigorously injected by using a 0.5 mL glass syringe. The mixture is gently shaken and centrifuged. A layer of sediment containing a mixture of toluene and CCl4 accumulates at the bottom of the tube. The extractant is removed by syringe and then analyzed by UVvisible spectrometer. Alternatively, the extractant may be transferred to a graphite atomizer for atomic absorption spectroscopy. This novel method combines the advantages of conventional DLLME and the use of lower-density solvent and lower volumes of toxic solvents. 1.2.3. DLLME with automated online sequential injection Anthemidis and Ioannou developed an automated on-line sequential injection dispersive liquidliquid microextraction SIDLLME system for metal preconcentration [3032] (Fig. 3(a)). The mixture of disperser solvent, extraction solvent, and chelating agent is mixed with a stream of aqueous sample through an online system. After extraction, droplets of the organic phase are retained in a microcolumn. The eluent is then transferred by a nebulizer for analysis by ame atomic absorption spectrometry (FAAS) analysis [30,31], or injected into a graphite tube for electrothermal atomic absorption spectrometry (ETAAS) measurement [32]. This method does not require centrifugation and an extraction solvent that is denser than water, and the process is fully automated. However, this method requires a microcolumn for retention of the analytes and several hundred microliters of solvents for elution of the analytes. Andruch et al. [33] reported a novel SI-DLLME (Fig. 3(b)). In

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solvent diethyl ether at a ratio of 6:4 is added to the tube, and then the tube is shaken vigorously for 90 s. Fine organic droplets are subsequently formed in the sample solution by manually shaking the test tube containing the mixture of sample solution and extraction solvent. The large surface area of the organic solvent droplets increases the rate of mass transfer from the water sample to the extractant, and allows efcient extraction in a short period. This method is a rapid and convenient procedure for qualitative and quantitative analyses of OCPs. Manual shaking may be done for dispersion and extraction, or as a premixing step before extraction. 2.1.2. Air-assisted liquidliquid microextraction (AALLME) Farajzadeh and Mogaddam developed an AALLME method for extraction and preconcentration of phthalate esters from aqueous samples prior to GC analysis [35]. In this method, ne organic droplets are formed by aspirating and expelling the mixture of aqueous sample solution and extraction solvent by syringe for several times in a conical test tube. After extraction, phase separation is performed by centrifugation, and the enriched analytes are determined by GCFID. This method requires less volume of organic solvent and does not use a disperser solvent. The extraction solvent is dispersed by aspiration and expulsion of the sample mixture by syringe instead of using disperser solvent. It is simple, requires little organic solvent, and is suitable for extraction of various organic compounds in aqueous samples. 2.1.3. Ultrasound-assisted emulsication Ultrasound-assisted [36,37] and vortex-assisted emulsication [24,38] reduce the consumption of solvent. Regueiro et al. [36] and Fontana et al. [37] developed USAEME for concentration of analytes. Ultrasound-assisted emulsication has been found to improve efciency by increasing the rate of mass transfer between the two immiscible phases. In 2008, Regueiro et al. developed a novel method based on USAEME and GCMS for the analysis of synthetic musk fragrances (Fig. 4(a)) [36]. In their method, a 10 mL sample is placed in a 15 mL conical-bottom glass centrifuge tube, and 5 ng of the surrogate standard PCB-166 in acetone is added to the sample. A 100 L solution of 5 ng of PCB-195 (internal standard) in chloroform is added as extractant. The tube is then immersed in an ultrasonic water bath (40 kHz ultrasound frequency and 100 W power for 10 min at 25 3 C). The resulting emulsion is then disrupted by centrifugation and the organic phase is sedimented at the bottom of the conical tube. Chloroform is removed by using a syringe and the remaining extract is transferred to a 100 L glass insert in a 1.8 mL GC vial. Extracts are stored at 20 C until analysis by GCMS. USAEME is an efcient, simple, rapid, and inexpensive alternative to other extraction techniques such as solid-phase extraction (SPE), solid phase microextraction (SPME), and LPME. A similar approach of extraction reported by Fontana et al. uses ultrasound and surfactant [39]. It is environmentally friendly because of the low consumption of organic solvent. However, ultrasound-assisted emulsication for extended periods may lead to decomposition of analytes. A number of reports indicated that the use of manual shaking in USAEME improves the extraction efciency and lowers the ultrasonic extraction time, which minimizes decomposition of analytes [40,41]. Lin and Fuh used ultrasound with occasional manual shaking to form a cloudy suspension, and obtained good results [42]. Other fast and novel USAEME methods that use low-density solvent were developed by Lees group [4345]. 2.1.4. Surfactant-assisted emulsication Surfactant-assisted DLLME (SA-DLLME) [22,23] followed by HPLC has been developed for the extraction and determination of chlorophenols in environmental water samples (Fig. 4(b)). In this approach, the cationic surfactant cetyltrimethylammonium

Fig. 3. Diagram of (a) SI-DLLME with retention microcolumn and (b) SI-DLLME with conical tube.

the method, sample and all reagents are drawn into the holding coil of the sequential injection analysis (SIA) manifold, and the resulting mixture is delivered into a conical tube. A mixture of the extraction solvent is then added at a high ow rate to form a cloudy suspension and to extract the analytes. The extraction phase consequently separates rapidly at the bottom of the conical tube. Afterward, the extraction phase is transferred to a microvolume Z-ow cell for spectrophotometric detection. The online DLLME methods achieved a major breakthrough in DLLME and overcame the difculties of rapidly extracting analytes and collecting the organic solvent in online analysis. 2. Development of DLLME Recent trends in DLLME include the use of lower volumes of less toxic solvents and techniques for dispersing extraction solvents and aqueous samples rapidly. Table 3 shows the extraction solvents and extraction times for various techniques. 2.1. Various techniques for assisting dispersion 2.1.1. Manual shaking for assisting dispersion Tsai and Huang reported DLLME with very low consumption of solvent (DLLMELSC) method [34]. In DLLME-LSC, much less volume of organic solvent is used as compared with DLLME. A 10 mL aqueous sample spiked with each targeted OCP is transferred to a glass centrifuge tube with conical bottom. Sodium chloride (300 mg) is added to the glass tube and dissolved completely. A 13 L mixture of the extraction solvent TCE and the disperser

M.-I. Leong et al. / J. Chromatogr. A 1335 (2014) 214 Table 3 Extraction solvent and extraction time of different dispersion techniques. Dispersion techniques Manual shaking Air-assisted emulsication Ultrasound-assisted emulsication Surfactant assisted emulsication Vortex-assisted emulsication Low-density solvent-based vortex-assisted surfactant-enhanced-emulsication Vortex-assisted supramolecular solvent microextraction Homogeneous ionic liquid microextraction Method DLLME-LSC AALLME USAEME SA-DLLME VALLME LDSVSLLME VASUSME HILME Extraction solvent TCE Chloroform Chloroform 1-Octanol Octanol Toluene Octyl alcohol and THF [C4 MIM][PF4 ] Extraction time (min) 1.5 <0.5 10 3 2 1 2 6 Ref [34] [35] [36] [22] [38] [48] [49] [50]

bromide (CTAB) is used as a dispersing agent. An extraction solvent is injected rapidly into the aqueous sample containing CTAB, and the resulting mixture is shaken for 13 min to disperse the organic phase. After extraction, the mixture is centrifuged and the

organic phase is subjected to HPLC analysis. In addition, coacervative ultrasound-assisted back-extraction was developed to extract and preconcentrate OPPs from honey samples prior to GCMS [39]. In this method, an aliquot of 10 mL 50 g L1 honey blend solution is conditioned by addition of 100 L of 0.1 mol L1 hydrochloric acid (pH 2) and 100 L of 100 g L1 Triton X-114 and manual shaking of the mixture. After several steps, ultrasound-assisted back-extraction is done by addition of extraction solvent. One of the major drawbacks of SA-DLLME is that some of the surfactant is also extracted from the aqueous sample into the extraction solvent; as a result, it may limit the selection of detection methods for analytes. Li et al. developed a SA-DLLME method that uses water with low concentration of surfactant in dispersed solvent-assisted emulsion to decrease the volume of surfactant used in extraction; consequently, surfactant in the nal extractant is greatly reduced [46]. 2.1.5. Vortex-assisted emulsication In 2010, Yiantzi et al. described vortex-assisted liquidliquid microextraction (VALLME) for the analysis of alkylphenols [38]. The analytes were agitated with a vortex mixer, which accelerated mass transfer to the organic phase. The extractant octanol (50 L) was mixed with 20 mL of aqueous sample without adjusting the ionic strength or pH. The vortex agitator was set at 2500 rpm for 2 min extraction time. After centrifugation, the oating octanol phase was easily collected with a microsyringe. Ultrasoundassisted and vortex-assisted emulsication reduced the volume of organic solvent required. Compared with ultrasound-assisted emulsication, homogenization or emulsication with ultrasound was faster because formation of submicron droplets greatly increased the contact surface between the two liquids, resulting in fast and efcient analyte transfer. However, ultrasound-assisted emulsication for extended periods may cause analytes to decompose. Zhang and Lee developed VALLME [47] and vortex-assisted surfactant-enhanced-emulsication liquidliquid microextraction based on low-density solvent (LDS-VSLLME) [48]. In this method, the sample solution is injected into a mixture of the extraction solvent toluene and the surfactant CTAB. The resulting mixture is transferred to a glass tube with conical bottom and then vortexed to form an emulsion. After extraction and phase separation by centrifugation, the spent sample is removed and the toluene extract is collected and analyzed by GCMS. Addition of surfactant enhances dispersion of the extraction solvent in the aqueous sample and favors the mass transfer of analytes from the aqueous sample to the extraction solvent. This method has a total extraction time of less than 1 min, and uses minimal surfactant as emulsier instead of traditional organic dispersive solvents. In 2013, Li et al. compared the extraction droplets produced in manual-assisted emulsication, vortex-assisted emulsication, and ultrasound-assisted extraction (USE) [49]. Micrographs of droplets show that vortex-assisted emulsication dispersed analytes well in the emulsion, and that ultrasound-assisted

Fig. 4. Diagram of the extraction process of (a) USAEME, (b) VALLME, and (c) HLLE.

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Fig. 5. Diagram of extraction by (a) MSPDDLLME and (b) D--SPE.

emulsication over-emulsied the mixture and resulted in incomplete phase separation.

suitable for the extraction of active constituents in natural products.

2.1.6. Microwave-assisted emulsication In 2012, homogeneous ionic liquid microextraction with microwave-assisted emulsication was developed for the extraction of active constituents from fruits of Schisandra chinensis and Schisandra sphenanthera [50]. In this method, 10 mg of sample powder, 150 L of 1-butyl-3-methylimidazolium tetrauoroborate ([C4 MIM][BF4 ]), and 10 mL of deionized water were combined in a microwave extraction vessel. After the sealed vessel was shaken, it was exposed to microwave radiation at 200 W for 6 min. After the vessel is cooled to ambient temperature, 0.8 g of ammonium hexauorophosphate ([NH4 ][PF6 ]), which is used as an ion-pairing agent, is added. A cloudy mixture is formed because of formation of ne droplets of [C4 MIM][PF6 ] homogeneously dispersed in an emulsion. Upon formation of [C4 MIM][PF6 ], the analytes are extracted into the IL phase. After centrifugation, the IL phase deposits at the bottom of the centrifuge tube. This method is

2.2. Combination of techniques for extraction and analysis with DLLME 2.2.1. Solid-phase extraction combined with DLLME SPE and DLLME coupled with GC were used for determination of 13 OPPs in aqueous samples [51]. The analytes were collected from large volumes of aqueous solutions (100 mL) into the sorbent SPE C18 (100 mg). The C18 SPE cartridge was used in separation of the desired compounds by elution with 1 mL of acetone. Eluates were collected into a 10 mL screw-cap glass test tube. Chlorobenzene (12 L) was added to the test tube and the resulting mixture was drawn into a syringe and rapidly injected into double distilled water in a screw-cap glass test tube with conical bottom. The mixture was then centrifuged and the extractant was injected into the GC for analysis. This method is fast and simple, and affords very high EFs and short analysis time.

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2.2.2. Stir bar sorptive extraction (SBSE) combined with DLLME SBSE combined with DLLME [52] has been developed for the extraction of six triazole pesticides in aqueous samples. In this method, 100 mL of standard or sample solution is stirred with a stir bar coated with octadecyl silane for 30 min at 300 rpm. The stir bar is subsequently removed and placed in a 1.5 mL glass vial containing 1 mL of methanol for liquid desorption. After the stir bar is removed, 25 L of the extraction solvent 1,1,2,2-tetrachloroethane is added to the extracted analytes. The resulting solution is rapidly injected into 5 mL of sodium chloride solution by syringe and then centrifuged. The sedimented organic phase is removed and injected into GC for analysis. This method enables simple, selective, and sensitive determination of analytes in complex matrixes. 2.2.3. Molecularly imprinted matrix solid-phase dispersion combined with DLLME (MIMMSPDDLLME) A MIM synthesized by aqueous suspension polymerization was applied as a selective sorbent for the simultaneous determination of four Sudan dyes in egg yolk samples (Fig. 5(a)) [53]. The sorbent was a miniaturized matrix solid-phase dispersion used for MSPDDLLME. The miniaturized MSPD procedure was performed by using small amounts of sample, support, and solvent. An aliquot of the egg yolk sample and MIM sorbent were placed in a small glass beaker and blended together. The homogenized mixture was transferred to an empty cartridge (5 cm 8 mm i.d., prepacked with 50 mg of MIM), rinsed with 4.0 mL of methanolwater solution, and then eluted with 3.0 mL of acetoneacetic acid solution. The eluate was collected in a 10 mL conical tube and then evaporated to 1.0 mL. It was then mixed with 100 L of TCE and 5.0 mL of water for further purication and concentration of analytes by DLLME. This MIMMSPDDLLME method combined the advantages of MIM, MSPD, and DLLME. 2.2.4. Supercritical uid extraction (SFE) combined with DLLME SFE followed by DLLME [54,55] has been developed for extraction and determination of PAHs in marine sediments. SFE of PAHs was performed at 313 K and 253.2 bar, and the extracted PAHs were collected in 1 mL of acetonitrile. Subsequently, 16 L of the extraction solvent chlorobenzene was added to the collecting solvent (1.0 mL of acetonitrile). The resulting mixture was rapidly injected into 5.0 mL of aqueous solution. After centrifugation, the PAHs in the sedimented phase were analyzed by GC. This procedure extends the application of DLLME to solid samples. In particular, it holds great potential in the analysis of trace organic compounds in solid samples. 2.2.5. Nanotechniques combined with DLLME Dispersive micro-solid-phase extraction (D--SPE) (Fig. 5(b)) combined with DLLME [56,57] was developed for GCMS of PAHs in environmental samples. For the dispersion step, 1-octanol is injected rapidly into a vial containing sample solution and the vial is subsequently sealed and vortexed. For SPE step (absorption and elution), derivatized magnetic nanoparticles are then quickly added to the vial. In this approach, hydrophobic magnetic nanoparticles are used to recover the extractant 1-octanol in the DLLME step. A magnet is held next to the bottom of the vial to attract and isolate the nanoparticles, and the sample solution is discarded by decantation. The magnet is thereafter removed, and 100 L of acetonitrile is introduced to the vial to desorb the 1-octanol from the nanoparticles by sonication. Finally, the magnet is again placed next to the vial, and the supernatant is collected into an Eppendorf tube by an automatic pipettor for analysis. This procedure does not require special apparatus such as conical-bottom test tubes as well as tedious procedures of centrifugation and refrigeration of the solvent. It also potentially lends itself to possible automation.

Recently, a simple and efcient two-step method, vortexassisted micro-solid-phase extraction (VA--SPE) followed by dispersive liquidliquid microextraction based on low-density solvent (LDS-DLLME), was developed for the determination of trace-level phthalate esters in environmental water samples [58]. Each -SPE device was fabricated by packing 4 mg of multiwalled carbon nanotubes in a 1.0 cm 0.8 cm porous polypropylene membrane with heat-sealed edges. In the rst step of VA--SPE, the -SPE device is placed in a 20 mL sample solution, which is then vortexed for 6 min. After extraction, the -SPE device is removed and placed in a glass insert. Analytes are desorbed by sonication for 5 min and acetonitrile (350 L) is used as dispersing solvent in the next extraction (DLLME) step. In LDS-DLLME, a mixture of extraction solvent and acetonitrile extract is rapidly injected into a 5 mL 10% NaCl solution by plastic Pasteur pipette to form an emulsion. After extraction, the emulsion is separated into two phases by centrifugation. The organic extract is conveniently collected by using a 50 L microsyringe, and the extract is injected into the GCMS system for analysis. A novel and highly efcient microextraction methodology based on the use of palladium nanoparticles was developed for the preconcentration and determination of Hg and other inorganic analytes in water samples [59]. Analytes were selectively separated in LLME by application of clusters protected by a monolayer of dodecanethiolate-coated Pd (C12S Pd MPCs). A 20 L portion of the toluene phase containing C12S Pd MPCs was used for extraction, and the nal phase was injected into an electrothermal atomic absorption spectrometer for Hg detection. 2.3. Other methods using low-toxicity solvent At present, the development of extraction methods includes the use of room-temperature ILs and surfactants. ILs are generally composed of organic cations and inorganic anions [6063]. Compared with conventional organic extraction solvents, ILs have low vapor pressure, high viscosity, good thermal stability, tunable miscibility and polarity, and good extractability with various organic and inorganic compounds [63,64]. Therefore, application of ILs in DLLME to determine many various types of contaminants and pesticides in environmental water samples have been reported [5775]. Ku et al. used an up-and-down shaker and ILs to extract analytes while reducing levels of extracted ILs and the use of disperser solvent [25]. Last year, otation-assisted homogeneous liquidliquid microextraction (FA-HLLME) followed by GCFID analysis was developed for the extraction of four PAHs in soil samples [76]. In this method, PAHs are extracted from soil samples into methanol and water (1:1, v/v) by using ultrasound, and ltration is subsequent done as a cleanup step. The ltrate is added into an extraction cell, which contains a mixture of 1.0 mL of methanol (homogenous solvent) and 150.0 L of toluene (extraction solvent). Through N2 otation, the dispersed extraction solvent is transferred to the surface of the mixture and then collected by microsyringe. Subsequently, 2 L of the collected organic phase is injected into the GCFID system for subsequent analysis. This new procedure is different from the conventional homogeneous liquidliquid microextraction (HLLE) (Fig. 4(c)), as it does not need centrifugation to separate the organic phase. In this method, N2 otation is used to break up the emulsion of organic solvent in water and to nish the extraction process. Another new method, vortex-assisted supramolecular solvent microextraction, has been developed for determination of bisphenol-A, 2,4-dichlorophenol, bisphenol-AF, and tetrabromobisphenol-A in liquid foods and their packaging materials [49]. Here, a supramolecular solvent is prepared by mixing 2 mL of octylalcohol and 10 mL of tetrahydrofuran in 38 mL of

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distilled water and 10 L of HCl (2 M). After the sample preparation, 500 L of the supramolecular solvent as extraction solvent is added into the sample, the mixture is vortexed for 2 min. After centrifugation, the supramolecular solvent, which is less dense than water, forms the top layer of the mixture. It is then removed and diluted to 1.0 mL with acetonitrile, 10.0 L of the solution is analyzed by HPLC.

3.2. Application of DLLME to various eld samples Before 2009, only a few papers describe the use of DLLME in the analysis of analytes in food samples. Most of these works focus on water samples or aqueous phases [127143]. Because of the increased regulation for food safety, the importance of analysis for contaminants or other harmful substances has been greatly acknowledged. Food matrixes are notoriously complex; they contain components such as carbohydrates, lipids, and proteins [144]. Bakar et al. used DLLME to extract vegetable oils containing phenolic acids into an aqueous solution [145]. Other complex analytes for which DLLME is used for extraction prior to analysis polychlorinated biphenyls in sh [102] and soil [146], polybrominated diphenyl ethers in animal tissue [147], Rh in leaves [124], Cd in beverage and cereal [119], and Al in fruit juice [148]. Sample preparation can affect the analyte concentration and the cleanliness of the sample prior to further analysis. The numbers of methods that use a two-step preparation have increased in the last few years. Solid samples generally require previous extraction with a suitable solvent to make the analytes available in a liquid matrix [149]. In these methods, analytes may be extracted from the food matrix with an organic solvent, by shaking or stirring [102,147,150154], USE [155,156], SPE [81,154,156], or microwave-assisted extraction [157]. A second step that uses a disperser solvent is typically performed [81,102,147,150157]. On the other hand, DLLME may be a cleanup step before extraction from the food matrix.

3. DLLME applications DLLME is simple, rapid, and inexpensive, requires low volumes of sample, and affords high EF. It can be applied in the analysis of organic compounds (pesticides, pharmaceuticals, and phenols) and inorganic analytes (Cu, Pb, and Cd). DLLME methods have been used in the analysis of various samples such water samples, food, urine, animal tissue or offal, soil, and leaves. DLLME is a popular sample pretreatment step in methods developed for analysis of food.

3.1. Application of DLLME for various analytes 3.1.1. Organic compounds After DLLME has been introduced by Rezaee et al. [6], it has often been used in the analysis of pesticides in water samples mainly because many highly toxic pesticides have low solubility in water and high solubility in non-polar extraction solvents. The extraction solvent must have ability to extract target analytes, low solubility in aqueous samples, and applicability to the analytical method. Pesticides that are commonly analyzed upon extraction by DLLME include OPPs [77], triazole pesticides [52], triazine herbicides [78], methomyl [79], heterocyclic insecticides [80], fungicides [81], carbamate pesticides [82], and n-methyl carbamate pesticides [83]. These pesticides are extracted with toxic chlorinated solvents. However, other pesticides have been analyzed by using less-toxic extraction solvents in water. For example, OPPs [84] and benzoylurea pesticides have been extracted with hexadecane and [C6 MIM][PF6 ] [85], respectively. DLLME has also been applied to the analysis of pharmaceuticals, and phenols such as chloramphenicol [86], clenbuterol [87], inammatory drugs [88], lovastatin [89], uoroquinolones [90], alkylphenol [91], bisphenol and bisphenol B [92], volatile phenols [93], chlorophenols [94,95], PAHs [54,56,96]. Besides the above compounds, other organic compounds such as ame retardants and plasticizers [97102], aromatic amines [103], anilines [104], fatty acids [105], glycyrrhizic acid [20], parabens [106], and antioxidants [107]. These above applications illustrate that DLLME is suitable for use in extraction of different types of organic compounds.

4. Conclusion Many DLLME methods have been developed in recent years. DLLME is a novel microextraction technique with great potential in sample pretreatment. This review introduces many novel DLLME techniques, disperser techniques, and new combinations with DLLME. Advantages of these techniques include simplicity of operation, low cost, rapid extraction, and great potential. In addition, this review illustrates the application of dispersion LPME methods to allow separation and preconcentration of various types of analytes and samples. The rst section discusses various less toxic solvents that are successfully used to develop new methods, and many devices that were developed for DLLME. Other novel online DLLME techniques were reported. Some of the aforementioned dispersion techniques use very low volumes of organic solvent or no dispersion solvent. Furthermore, these techniques may also be combined with DLLME with lowdensity solvent and high-density solvents to develop other new methods. Combining other extraction methods with DLLME for analysis of complex samples may be more effective and useful. Many combinations with DLLME have been reported, but not much is known about combinations of extraction methods with DLLME with low-toxicity solvent or dispersion LPME. This direction of the research may well repay investigation. The above DLLME or dispersion LPME methods have benets as cleanup and ltering steps to remove impurities of samples. By using the new nanotechnique to assist extraction, the surface of nanoparticles can be modied to extract various organic compounds and solvents. For example, specially coated nanoparticles and magnetic nanoparticles may be used to assist extraction and to retrieve the extraction solvent, respectively. Newly prepared functional nanoparticle will extend the usages DLLME in various applications. Apart from the combined methods, many traditional LPME methods with no dispersing solvent or DLLME have been reported.

3.1.2. Inorganic compounds DLLME has been applied to the extraction and concentration of a wide variety of organic compounds and metal ions [10], mainly from water samples. After pesticides, metals are the second most common analytes that are extracted by DLLME. DLLME has been used in the last few years in the extraction and preconcentration of metals for analysis [31,33,108126]. Zgoa-Grzes kowiak and Grze skowiak summarized the DLLME methods for the analyses of various metals [10]. In these methods, chelating agent is added to the sample to extract the metal ions. Ions from the liquid phase are then extracted to the extracting solvent as a complex. Finally, ions are analyzed through appropriate techniques such as graphite furnace atomic absorption spectrometry [112,120,121,124], inductively coupled plasma optical emission spectrometry [113], or FAAS [122,123]. The number of published studies on inorganic analysis assisted by DLLME may increase very rapidly in the near future.

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Among LPME methods, these have much potential for development. Some of the conventional DLLME methods were developed to obviate centrifugation and the use of disperser solvent or to lower the volume of the organic solvent used. Finally, the current trend is moving toward simplication and miniaturization of sample preparation as well as reduction of the cost, labor, time and quantities of organic solvents used. DLLME and dispersion LPME have great prospects for these approaches in the future. Conict of interest The authors declare no conict of interest. Acknowledgments This work was supported by the National Science Council of Taiwan (NSC 99-2113-M-007-004-MY3). We would like to express our sincere appreciation to Professor David J. Wilson for assisting our research work and for assisting in editing our manuscripts during the last 30 years. References
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