Journal of Chromatography A, 1335 (2014) 2–14

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

Review

Beyond dispersive liquid–liquid microextraction
Mei-I. Leong a , Ming-Ren Fuh b,1 , Shang-Da Huang c,∗
a

Centro de Seguranca Alimentar, Instituto para os Assuntos Cívicos 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 liquid–liquid microextraction (DLLME) and other dispersion liquid-phase microextraction (LPME) methods have been developed since the first 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 first 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 emulsification, vortex-assisted emulsification, surfactant-assisted emulsification, and microwave-assisted emulsification 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 fluid 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 liquid–liquid 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 solidification of floating organic droplet (DLLME-SFO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.2. DLLME with special extraction devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.3. Low-density-solvent based solvent demulsification 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 liquid–liquid microextraction (AALLME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.3. Ultrasound-assisted emulsification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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.

. DLLME with lower-density extraction solvent 1. . . . 2. . . . .3. . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . .2. . . .5. . . . . . . . . . . . . . . . 4. . it does not use chlorinated solvents and conical bottom glass tubes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . chloroform. . . . . the high-density extraction solvent used. . . . . the adjustment of extraction solvents mixture density and procedures based on automation of DLLME by sequential injection analysis [9]. . . . . . . . . . . . . 2. . . . . . . . . . pharmaceuticals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8]. . . . . Depending on the extraction solvent used. . . . . . . . . . the low-density solvent used (based on solidification and solvent demulsification) in DLLME procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. . . . . . . . . . . . . . Unlike LLME-SFO. . . . . and disperser solvent. . . . . . . .2. . . . . . . . . . . Advantages of this technique include simplicity of operation. . . . . . . . . . . . . . . . . . . . . . . . . . . The disperser solvent has to be soluble in both water and extraction solvent. . . . . . However. . . . . . . . . . . . . . .4. . . . . . . . . . Introduction Liquid–liquid microextraction (LPME) is usually applied in the extraction of environmental samples. . . . . . . . . . . . . . . . . . . . . .1. . . . . Application of DLLME to various field samples . . . . . . . . . . . . . Zgoła-Grze´ skowiak and Grze´ skowiak described the application of DLLME to pre-concentration of metal ions. . . . . . . . . . . . . . . . .2. . . . . . . . . . . . . . . . In 2006. . . . . . . . . . . they are limited by the small contact surface area of the drop or fiber. . . . . . . . . which normally acts in a second step as the disperser solvent [12]. . . . a mixture of low-toxicity extraction solvent . . . . .5. . . which necessitates long extraction times. . . . . . . . . . . . . . . . . . . . . . . and a polar disperser solvent. . . . . . . Other novel online and automated procedures with DLLME that have a promising future in analytical methodology are also mentioned in this section. . . . . . Kocúrová et al. . . . 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Organic compounds . . . .2. . . . . . . . .4. . . . . . . . There are many excellent recent reviews on DLLME or dispersion LPME methods (methods that disperse extraction solvent for extraction) [9–13]. . . . . . . . . . . . . . and unlike traditional DLLME. . . . . . . . . . . . . . . . . . . . . . . . . . Application of DLLME for various analytes . . . . . . . . . . . . . . . . . . . . . . . A solution of 1 mL of acetone (disperser solvent) and 8 ␮L of tetrachloroethylene (TCE. . . . . . . .2. .1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kokosa reviewed the development of DLLME and summarized the techniques in three categories: DLLME using extraction solvents with density greater than water. [14. . . . . . . . . . . . Asensio-Ramos et al. . . . . . . . Nanotechniques combined with DLLME . . . . LPME has several different operational modes. . . . . . . . . . . . . . . . . . . . However. . . . . . . . . The first two methods are simple and use lower volumes of organic solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Stir bar sorptive extraction (SBSE) combined with DLLME . . .3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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. 2. . . . . 2. . . . . . . . . . . . . . . . . . .1. . . 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]. . . . . . . . A cloudy dispersion consisting of water. . . . . . . these methods enable easy separation of extraction solvent and samples solution by centrifugation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2. . . . . . . Many new techniques in the former category have been introduced to separate and collect the extraction solvent from sample solution. . . . . . . . . Conclusion . . . . . . . disperser solvent. . .15]. . . . . . . . . . . . . . . . . . . . 2. . . . . . . . . . . . . . Abbreviations of the DLLME and dispersion LPME methods in this review are shown in Table 1. . . . . . . . . which is typically chlorobenzene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . DLLME-SFO [16. . This review summarized and discussed the recent developments of DLLME and dispersion LPME including the utilization of various less toxic solvents. . . . . . . . . .6. . . . . . . . summarized a lot of details about DLLME using organic solvents lighter than water methods. . 1(a)) [6]. . . . . . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . . . . . . Inorganic compounds . Conflict of interest . . . . 3. . . . . . . . . . . . . . . . . . The total extraction time including the centrifugation time is generally 5–10 min. . . . . . . . . . . and concludes the uses of special devices. . . . . . . and extraction solvent is formed in the test tube and is centrifuged. . . . . . . . . . . . . . . . . . . . . . . . . . . . Leong et al. . . . . . . . . 5 mL of the aqueous solution is placed in a screw-cap glass test tube with a conical bottom. . . .1. . . . . . . . . . The first DLLME methods employ a mixture of a high-density extraction solvent. . . . . . . . . . . 2. . . . . . . . . Surfactant-assisted emulsification . . . . . . . . . . . .17] was developed to combine the benefits of DLLME and LLME-SFO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other methods using low-toxicity solvent . rapid extraction. . . . . . . . . . . . . . . . . . . . . . . . . However. It is simple. . . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . . . . . . . . . . . is soluble in the disperser solvent. . . . . . . . . . . . . . . . . . . . . . . . . 8 9 10 10 10 11 11 11 11 11 12 12 12 12 12 12 13 13 13 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . such as those that use a drop of solvent [1. . . . . . . . . . The extraction solvent must be able to extract analytes. . . . . . . . . . . . . . . . . . . . . . . . . . inexpensive. . . . developed dispersive liquid–liquid microextraction (DLLME) for preconcentration of polycyclic aromatic hydrocarbons (PAHs) in water samples [6]. . . development various techniques to increase rate of mass transfer between two extracting solvent and sample solution. . . . . . . . . . . . . Combination of techniques for extraction and analysis with DLLME . . . . . . . . . . . . . 0. . . . . . . . . insoluble in aqueous samples. . . . . . . . . . . . . . . . . . . 3. . . . . . . . . . . . . . . . the extraction solvent) is injected into the sample solution. . . . . . . . . .1. . . . . . . . . . . . . A 1335 (2014) 2–14 3 3. . . .1. . . . Instead. . . . . . . . . . . . . . . . / J. . . . . . . . . . . . . . . other organic compounds and many more modifications of these newly developed techniques [10]. . . . . . . . . . . . . . . . Chromatogr. . . . . . . . . Supercritical fluid extraction (SFE) combined with DLLME . . . . . . . . . . . . . . . . . . . . . . combination of other extraction with DLLME and design of special device for DLLME. . . . . . . . . . . . . . . . is highly toxic. . . . DLLME applications . . . . . . . . . . . . . . . . . . . Many conventional DLLME typically use 20–100 ␮L of chlorinated solvents as extraction solvent. . . . . . . . . . .2. . . and have density higher than that of water. . . The dispersed fine 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. . . . . . . . summarized several DLLME applications in food analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . porous hollow fiber-protected solvent [3–5]. . . . . . . . . . DLLME-SFO does not involve stirring during extraction. . . . . . and 5–10 mL of aqueous sample. . . . . In this method (Fig. . . . . . . . . . . . . . . . . . . . . DLLME based on solidification of floating organic droplet (DLLME-SFO) Liquid–liquid microextraction based on solidification of floating organic droplet (LLME-SFO) was introduced by Khalili-Zanjani et al. . . . . . .-I. . . . . . . . . . . . . . . . . . . .1. . . . . . . . .M. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . . . Solid-phase extraction combined with DLLME . . . . . Rezaee et al. . . . . . . . . . . . . . . . . . . a water-miscible solvent. . Molecularly imprinted matrix solid-phase dispersion combined with DLLME (MIM–MSPD–DLLME) . . . Brominated or iodinated solvents and an auxiliary solvent in the latter category have been introduced. . . . . . . . . . . .2. . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . DLLME using extraction solvents with density lower than water and automated DLLME [11]. . . . . . . Analytes can be initially extracted from the food matrix with an organic solvent. . . . and it involves minimal consumption of organic solvent. . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . 2. . . its extraction rate is lower than that of DLLME. . . . . . . . . .2]. . . . . . . . . . .5–2 mL of disperser solvent. . . . . or carbon tetrachloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Microwave-assisted emulsification . . . . Vortex-assisted emulsification . . . . . . . . and high enrichment factors (EFs) [7. . . . . . .2. . .

Table 1 The abbreviations of the DLLME and dispersion LPME methods in this review.23] [39] [46] [48] [49] [38. Method Dispersive liquid–liquid microextraction DLLME with lower density extraction solvent DLLME based on the solidification of a floating organic drop Ionic liquid-based up-and-down shaker-assisted DLLME Low-density solvent-based solvent demulsification DLLME DLLME with higher density extraction solvent Low toxic DLLME Adjust the density of DLLME Injection dispersive liquid–liquid microextraction Various techniques for assisting dispersion DLLME with a very low solvent consumption Air-assisted liquid–liquid microextraction Ultrasound-assisted emulsification microextraction Surfactant assisted DLLME Coacervative microextraction ultrasound-assisted back-extraction technique Water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid–liquid microextraction Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid–liquid microextraction Vortex-assisted supramolecular solvent microextraction Vortex-assisted liquid–liquid 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 fluid 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 liquid–liquid microextraction Abbreviation of the method DLLME Ref. A 1335 (2014) 2–14 Fig.55] [56.-I. / J. 1. Chromatogr. Diagram of the extraction process of (a) DLLME and (b) DLLME-SFO.57] [58] FA-HLLME [76] .4 M. [6] DLLME-SFO UDSA-IL-DLLME LDS-SD-DLLME [16. Leong et al.47–49] [50] SPE + DLLME SBSE + DLLME MSPD–DLLME SFE + DLLME D-␮-SPE + DLLME VA-␮-SPE + LDS-DLLME [51] [52] [53] [54.17] [25] [26] LT-DLLME AS-DLLME SI-DLLME [28] [29] [30–33] DLLME–LSC AALLME USAEME SA-DLLME CME-UABE WLSEME LDS–VSLLME VASUSME VALLME HILME [34] [35] [36–45] [22.

the extraction phase can easily be withdrawn by microsyringe. Subsequently. designed a special vessel [19] for use in DLLME to extract organophosphorus pesticides (OPPs) (Fig.1. In this extraction method. The device consists of a narrow-necked glass tube (NNGT) inserted into a centrifuge tube. then. This method also addresses the variation of the shaking process due to different operators. Before removal of the extractant. and phase separation of the extraction solvent from the aqueous sample is easily achieved by allowing the extraction mixture to stand several minutes. This technique expands the application of classical DLLME for various organic analytes. and the solidified solvent is easily collected for analysis. Saleh et al. The use of the narrow parts (neck. After centrifugation. After up-anddown shaking for 3 min. a mixture of cyclohexane (extraction solvent) and acetone (disperser solvent) is rapidly injected by syringe into an aqueous sample in a special vessel. A 1335 (2014) 2–14 5 (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. 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 . In addition. The mixture is then centrifuged for phase separation. [20] is the difficulty of cleaning the centrifuge glass vial. respectively. the sample solution is drawn into a 5 mL syringe. and then a microtube is used to collect the extraction solvent for further analysis by ultra-performance liquid chromatography (UPLC). In 2011. After centrifugation. the Lewis base tri-n-butylphosphate (TBP) instead of conventional water-immiscible organic solvents is directly used as extractant for DLLME. 2(e)). The only drawback of this and the aforementioned method by Hashemi et al. Hashemi et al.M. Initially. The large contact surface area between the sample and the droplets of extractants facilitate mass transfer. The sample containing the analytes is placed in a disposable polyethylene pipette. 2(d)). the test tube is transferred to a beaker containing crushed ice. After centrifugation. One microliter of the separated extractant is injected into GC for analysis.2. the separated toluene is injected into a gas chromatograph for analysis. The drawbacks of this method are limited to the solvent chosen (low melting point) which is suitable for use in warm climates. / J. 1(b)). 2(f)). a low-density solvent. the extracting phase containing the target OPPs is easily recovered by syringe. Hu et al. After removal of the plunger and sealing of the syringe with a silicone-plug. Most of the devices use narrow necks or ports to gather the extractant drops [19–22]. is used as the extraction solvent for DLLME and no disperser solvent is used. it is not suitable for extracting volatile compounds. The organic phase rises to the top of the mixture and concentrates in the narrow open tip of the flask upon addition of pure water into the extraction mixture through the other port. To meet recent concerns about the costs and environmental hazards of waste solvent disposal. a holder fabricated in-house is used to hold the sealed conical-bottom glass tubes. In this approach. 2(a)). such as specially designed centrifugation tubes and pipette collection tubes. This method does not require a narrow-necked port to collect the extractants and the device is very easy to clean. an IL of low toxicity such as [C8 MIM][PF6 ] is used instead of the highly toxic solvent normally used in DLLME. 1-Octanol. A uniformly distributed cloudy suspension is produced by further aspiration and expulsion of about 2 mL of the cloudy sample by syringe. Ku et al. In this method [16] (Fig. and a 100 ␮L glass syringe is used to inject the extraction solvent and to recover the extractant.-I. The apparatus for this method is simple and the extraction time is less than 4 min. a mixture of 0. This method affords very rapid extraction and recovery of the extractant. fine droplets of cyclohexane accumulate in the upper layer of aqueous solution. one of which has a capillary tip [22] to extract ultraviolet (UV) filters in environmental water samples (Fig.15. 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. and is easily withdrawn by a 10. DLLME with special extraction devices Recently.0 ␮L microsyringe. This method is faster than many DLLME methods because it does not require centrifugation. Additional water is added from the opening of NNGT. In this method. This method uses a 5 mL syringe as the sample vial instead of a centrifuge tube. the extraction solvent toluene is injected slowly into aqueous sample in a centrifuge glass vial in an ultrasonic water bath. This method is rapid and easily recovers the extractant. Hexanol and acetone are used as the extraction solvent and disperser solvent. After centrifugation. however. The extraction solvent (toluene) is then injected into the sample solution by using a 100 ␮L glass syringe. Finally. water must be injected to allow the extracted organic drop to reach the level of the neck or port of the tube or flask. The up-and-down shaker model FS-6 was used to shake the mixture of extraction solvent and aqueous sample. the barrel is held upside down and the needle is removed. many researchers have attempted to use lowertoxicity solvents with density lower than that of water in DLLME. Ultrasound radiation is applied to accelerate the emulsification of microliter volumes of low-density organic solvent in aqueous solutions to enhance the efficiency of OPPs microextraction from the sample. In 2009. and enables extraction in a disposable polyethylene pipette. 1. Chromatogr. resulting in extraction times similar to those of DLLME and shorter than that of LLME-SFO [14. The extraction is accelerated by magnetic agitation. no centrifugation step is necessary. the extraction phase accumulates on the surface of the aqueous solution. port. the aqueous mixture is centrifuged. Since hexanol is lighter than water. In this method. The flask is employed to facilitate the DLLME process. if the laboratory is not air conditioned. It is thereafter withdrawn by microsyringe for HPLC analysis. designed a special flask equipped with two narrow open ports. performed an up-and-down shaker assisted DLLME that uses an ionic liquid (IL) to preconcentrate three UV filters from field water samples [25]. It can be applied in the extraction of samples that are non-volatile and have large volumes. Leong et al. 2(c)) for the determination of PAHs in water samples [21]. Zhang et al. The extraction solvent 1-octyl-3-methylimidazolium hexafluorophosphate ([C8 MIM][PF6 ]) (40 ␮L) and the disperser solvent methanol (200 ␮L) are used to extract the UV filters. developed [23] a DLLME method based on a molecular complex for analysis of polar compounds in aqueous solution (Fig. The principle of this method is the hydrogen bonding between the extractant and the analytes. Dispersions in various special extraction devices are described in Table 2.5 mL of acetone and 10 ␮L of 2-dodecanol is rapidly injected by syringe into a 5 mL water sample. The upper phase is injected into a gas chromatograph for separation. After extraction. 2(b)) [20]. Farajzadeh et al. the extraction phase is raised and fills the narrow neck of NNGT. As a result. the organic phase floating on the aqueous solution is concentrated in the narrow neck of the pipette.18]. After ultrasonication and centrifugation. This device is easy to operate. To save time and effort. developed a DLLME method that uses a special device to enrich glycyrrhizic acid from aqueous extracts of licorice (Fig. and the extractant volume is easily read from the scale on the capillary tube. One possible way of enabling the application of such solvents in DLLME is the use of special extraction devices. the pipette is placed in a 10 mL Eppendorf tube and is agitated by a vortex mixer. the plunger of the 5 mL syringe is slowly pushed to transfer the recovered extractant into a graduated capillary tube. this method uses an extraction solvent of low toxicity and low volatility. reported a centrifuge glass vial fabricated in-house for ultrasound-assisted emulsification microextraction (USAEME) (Fig. A mixture of the extractant TBP and the disperser solvent methanol is rapidly injected into the sample solution by syringe. or nozzle) of devices can assist the collection of the low-density extraction solvent from the samples.

(d) special flask equipped with two narrow open ports (DLLME). / J. Leong et al. (b) glass tube with narrow neck (DLLME). (c) centrifuge glass vial designed in-house (USAEME).-I. A 1335 (2014) 2–14 Fig. (f) 5 mL syringe as sample vial (DLLME) and (g) disposable polyethylene pipette (LDS-SD-DLLME).6 M. Diagram of the special device used in dispersion LPME with low-density extraction solvent: (a) special extraction vessel (DLLME). . 2. (e) 5 mL polyethylene Pasteur pipette (DLLME). Chromatogr.

the median lethal dose (LD50 ) 6150 mg kg−1 ) instead of the highly toxic solvents normally used in DLLME. In particular. In 2010. [33] reported a novel SI-DLLME (Fig. and a disperser solvent is employed in this method. in this manner.2. is used to adjust the density of the extraction solvent–auxiliary solvent mixture to facilitate its separation from the aqueous sample by centrifugation.0 ␮L) are rapidly injected into the sample solution and the resulting mixture is shaken by hand for a few seconds. A 5 mL sample solution containing Au (III) is prepared in conical microcentrifuge tubes. 3(b)). droplets of the organic phase are retained in a microcolumn. and chelating agent is mixed with a stream of aqueous sample through an online system. the organic solvent is sedimented at the bottom of the conical test tube. This method does not require the use of special devices. 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 1.5 mL glass syringe. A 5 mL sample solution is placed in a 5 mL polyethylene Pasteur pipette by using a 5 mL syringe. Auxiliary solvent to adjust the density of DLLME Kocúrová et al. A 0. No centrifugation is required in this procedure. The auxiliary solvent (a chlorinated solvent). 145 ␮L) is vigorously injected by using a 0. there are many extraction methods use disperser solvent or surfactant to assist the dispersion of the extraction solvent. Chromatogr. the extraction requires only 2–3 min. [19] [20] [21] [22] [23] [24] [26] 7 extraction apparatus is easy to clean. and is therefore faster than conventional DLLME or similar techniques. 2(g)). The demulsification solvent acetone (500 ␮L) is then injected into the aqueous solution to break up the emulsion and separate it into two layers. A layer of sediment containing a mixture of toluene and CCl4 accumulates at the bottom of the tube. This method does not require centrifugation and an extraction solvent that is denser than water. extraction solvent.2. 1. The liquid organic drop is transferred along with some of the water into a microtube (3 mm × 15 mm) by syringe. it is better to centrifuge the collected phases in the microtube for about 1 min before injection. this method requires a microcolumn for retention of the analytes and several hundred microliters of solvents for elution of the analytes. [28]. as little as 50 ␮L of the acid is sufficient for extraction. The mixture is gently shaken and centrifuged. LT-DLLME was developed by Leong et al. After extraction. because it further removes water. 40% (w/v)) is added to the sample to minimize emulsion formation by the extraction solvent before centrifugation. a liquid organic drop accumulates between the water surface and the glass wall of the centrifuge tube. This improved solvent collection system can protect the instrument from damage by the injected water and increase the reproducibility of the results. This method permits a solvent that is less dense than water to be used as extraction solvent.2. and expands the applicability of DLLME to a wider range of solvents. This method also demonstrates that propionic acid is suitable as a disperser solvent. two clear phases are obtained. This novel method combines the advantages of conventional DLLME and the use of lower-density solvent and lower volumes of toxic solvents. Fig. The disperser solvent propionic acid and the extraction solvent 1-bromo-3-methylbutane (10. an extraction solvent.31]. 1.3. 3(a)). 1. The organic and aqueous phases then immediately separate in the microtube. Alternatively. [29] developed an adjusting-density DLLME (ASDLLME) technique.5 mL mixture of the disperser solvent methanol. 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 flask 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 GC–MS Analytes OPPs Glycyrrhizic acid PAHs UV filters OPPs Phenols PAHs Extraction solvent Cyclohexane n-Hexanol Toluene 1-Octanol Toluene TBP n-Hexane Ref. Andruch et al. Except for the methods that use a special flask [22] for magnetic agitation or use an up-anddown shaker [25] to disperse the extraction solvent. In .M. / J. other methods using higher-density extraction solvent have been introduced to overcome the drawbacks of normal DLLME. A 1335 (2014) 2–14 Table 2 Dispersion in different special extraction devices. an auxiliary solvent. The organic solvent is easily collected by syringe and then injected into the GC instrument for analysis. However. used DLLME combined with an improved solvent collection system to separate water and organic solvent in the collected extractant drop [27]. The eluent is then transferred by a nebulizer for analysis by flame atomic absorption spectrometry (FAAS) analysis [30. Chang et al. and the auxiliary solvent carbon tetrachloride (CCl4 . The selected extraction solvent is less toxic than chlorinated solvents in normal DLLME. DLLME with automated online sequential injection Anthemidis and Ioannou developed an automated on-line sequential injection dispersive liquid–liquid microextraction SIDLLME system for metal preconcentration [30–32] (Fig. DLLME with low-toxicity solvent In addition to the many DLLME methods that have been developed to use low-density organic solvents. the extraction solvent toluene (145 ␮L). Guo and Lee [26] reported a LDS-SD-DLLME method for the determination of 16 priority PAHs in environmental samples (Fig. Potassium hydroxide (88 ␮L. and then a microsyringe is used to collect and inject it into a gas chromatograph for further analysis. After centrifugation. This method uses lowertoxicity brominated.1. or injected into a graphite tube for electrothermal atomic absorption spectrometry (ETAAS) measurement [32]. Notably.1. Low-density-solvent based solvent demulsification DLLME (LDS-SD-DLLME) All of the aforementioned extraction devices possess advantages and drawbacks in terms of ease of operation and manifold complexity. After centrifugation. the extractant may be transferred to a graphite atomizer for atomic absorption spectroscopy. A 7 mL sample of water is spiked with PAHs. The mixture of disperser solvent.0 mL syringe to form an emulsion. 1. Moreover. and the process is fully automated. some brominated solvents are less toxic than the conventional low-density solvents in DLLME or dispersion LPME. The extractant is removed by syringe and then analyzed by UV–visible spectrometer.-I. DLLME with higher-density extraction solvent 1. which is denser than water. 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.2. iodinated and other halogenated solvents such as 1-bromo-3-methylbutane (1-bromo-3-methylbutane. The upper layer (about 35 ␮L n-hexane) is collected and analyzed by gas chromatography–mass spectrometry (GC–MS).2. Leong et al. A quaternary system consisting of an aqueous sample.3.

In this approach. much less volume of organic solvent is used as compared with DLLME. Regueiro et al. a 10 mL sample is placed in a 15 mL conical-bottom glass centrifuge tube. In 2008. sample and all reagents are drawn into the holding coil of the sequential injection analysis (SIA) manifold. solid phase microextraction (SPME). 2. the method. A mixture of the extraction solvent is then added at a high flow rate to form a cloudy suspension and to extract the analytes.1. Air-assisted liquid–liquid microextraction (AALLME) Farajzadeh and Mogaddam developed an AALLME method for extraction and preconcentration of phthalate esters from aqueous samples prior to GC analysis [35]. Manual shaking for assisting dispersion Tsai and Huang reported DLLME with very low consumption of solvent (DLLME–LSC) method [34]. Extracts are stored at −20 ◦ C until analysis by GC–MS.41]. This method is a rapid and convenient procedure for qualitative and quantitative analyses of OCPs. rapid.37] and vortex-assisted emulsification [24.-I. The large surface area of the organic solvent droplets increases the rate of mass transfer from the water sample to the extractant. Manual shaking may be done for dispersion and extraction. 2. Chloroform is removed by using a syringe and the remaining extract is transferred to a 100 ␮L glass insert in a 1. ultrasound-assisted emulsification for extended periods may lead to decomposition of analytes. developed a novel method based on USAEME and GC–MS for the analysis of synthetic musk fragrances (Fig.1. and the resulting mixture is delivered into a conical tube. USAEME is an efficient. 3. Table 3 shows the extraction solvents and extraction times for various techniques. A similar approach of extraction reported by Fontana et al. In their method. the cationic surfactant cetyltrimethylammonium Fig. Various techniques for assisting dispersion 2. and 5 ng of the surrogate standard PCB-166 in acetone is added to the sample. Diagram of (a) SI-DLLME with retention microcolumn and (b) SI-DLLME with conical tube. The extraction phase consequently separates rapidly at the bottom of the conical tube. 4(b)). 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. Afterward. [37] developed USAEME for concentration of analytes.38] reduce the consumption of solvent. / J.23] followed by HPLC has been developed for the extraction and determination of chlorophenols in environmental water samples (Fig. A number of reports indicated that the use of manual shaking in USAEME improves the extraction efficiency and lowers the ultrasonic extraction time. Ultrasound-assisted emulsification Ultrasound-assisted [36. Surfactant-assisted emulsification Surfactant-assisted DLLME (SA-DLLME) [22. In DLLME-LSC. requires little organic solvent.8 mL GC vial. However. and allows efficient extraction in a short period.8 M. phase separation is performed by centrifugation.4. In this method.3. A 100 ␮L solution of 5 ng of PCB-195 (internal standard) in chloroform is added as extractant. the extraction phase is transferred to a microvolume Z-flow cell for spectrophotometric detection. It is environmentally friendly because of the low consumption of organic solvent. 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). and is suitable for extraction of various organic compounds in aqueous samples. A 13 ␮L mixture of the extraction solvent TCE and the disperser . 2. Lin and Fuh used ultrasound with occasional manual shaking to form a cloudy suspension. 4(a)) [36]. The online DLLME methods achieved a major breakthrough in DLLME and overcame the difficulties of rapidly extracting analytes and collecting the organic solvent in online analysis. and obtained good results [42]. Other fast and novel USAEME methods that use low-density solvent were developed by Lee’s group [43–45]. which minimizes decomposition of analytes [40. 2.1. Leong et al. It is simple. [36] and Fontana et al.1. fine 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. 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.2. and LPME.1. simple. Ultrasound-assisted emulsification has been found to improve efficiency by increasing the rate of mass transfer between the two immiscible phases. or as a premixing step before extraction. Regueiro et al. The extraction solvent is dispersed by aspiration and expulsion of the sample mixture by syringe instead of using disperser solvent. 2. After extraction. The resulting emulsion is then disrupted by centrifugation and the organic phase is sedimented at the bottom of the conical tube. uses ultrasound and surfactant [39]. Chromatogr. and the enriched analytes are determined by GC–FID. A 1335 (2014) 2–14 solvent diethyl ether at a ratio of 6:4 is added to the tube. 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. This method requires less volume of organic solvent and does not use a disperser solvent. and then the tube is shaken vigorously for 90 s.1. and inexpensive alternative to other extraction techniques such as solid-phase extraction (SPE).

/ J. and uses minimal surfactant as emulsifier instead of traditional organic dispersive solvents. the sample solution is injected into a mixture of the extraction solvent toluene and the surfactant CTAB. After centrifugation. 4. which accelerated mass transfer to the organic phase. ultrasound-assisted back-extraction is done by addition of extraction solvent. Dispersion techniques Manual shaking Air-assisted emulsification Ultrasound-assisted emulsification Surfactant assisted emulsification Vortex-assisted emulsification Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification Vortex-assisted supramolecular solvent microextraction Homogeneous ionic liquid microextraction Method DLLME-LSC AALLME USAEME SA-DLLME VALLME LDS–VSLLME VASUSME HILME Extraction solvent TCE Chloroform Chloroform 1-Octanol Octanol Toluene Octyl alcohol and THF [C4 MIM][PF4 ] Extraction time (min) 1. After several steps. ultrasound-assisted emulsification for extended periods may cause analytes to decompose.5. it may limit the selection of detection methods for analytes. 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. . Li et al. In this method. The resulting mixture is transferred to a glass tube with conical bottom and then vortexed to form an emulsion.M. as a result. resulting in fast and efficient analyte transfer. 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. The extractant octanol (50 ␮L) was mixed with 20 mL of aqueous sample without adjusting the ionic strength or pH. Li et al. After extraction and phase separation by centrifugation. and the resulting mixture is shaken for 1–3 min to disperse the organic phase. compared the extraction droplets produced in manual-assisted emulsification. described vortex-assisted liquid–liquid microextraction (VALLME) for the analysis of alkylphenols [38]. In addition. the spent sample is removed and the toluene extract is collected and analyzed by GC–MS.-I. A 1335 (2014) 2–14 Table 3 Extraction solvent and extraction time of different dispersion techniques.1. vortex-assisted emulsification.5 10 3 2 1 2 6 Ref [34] [35] [36] [22] [38] [48] [49] [50] 9 bromide (CTAB) is used as a dispersing agent.1 mol L−1 hydrochloric acid (pH 2) and 100 ␮L of 100 g L−1 Triton X-114 and manual shaking of the mixture. Zhang and Lee developed VALLME [47] and vortex-assisted surfactant-enhanced-emulsification liquid–liquid microextraction based on low-density solvent (LDS-VSLLME) [48]. Ultrasoundassisted and vortex-assisted emulsification reduced the volume of organic solvent required. (b) VALLME. Compared with ultrasound-assisted emulsification. In 2013. homogenization or emulsification with ultrasound was faster because formation of submicron droplets greatly increased the contact surface between the two liquids. Yiantzi et al. 2. and ultrasound-assisted extraction (USE) [49]. 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. However. Vortex-assisted emulsification In 2010. An extraction solvent is injected rapidly into the aqueous sample containing CTAB. and that ultrasound-assisted Fig. After extraction. Chromatogr. Micrographs of droplets show that vortex-assisted emulsification dispersed analytes well in the emulsion. the mixture is centrifuged and the organic phase is subjected to HPLC analysis. consequently. In this method. coacervative ultrasound-assisted back-extraction was developed to extract and preconcentrate OPPs from honey samples prior to GC–MS [39]. Diagram of the extraction process of (a) USAEME. the floating octanol phase was easily collected with a microsyringe. This method has a total extraction time of less than 1 min. The analytes were agitated with a vortex mixer. an aliquot of 10 mL 50 g L−1 honey blend solution is conditioned by addition of 100 ␮L of 0. Leong et al. The vortex agitator was set at 2500 rpm for 2 min extraction time. and (c) HLLE.5 <0. surfactant in the final extractant is greatly reduced [46].

5. This method is fast and simple. which is used as an ion-pairing agent.1. homogeneous ionic liquid microextraction with microwave-assisted emulsification was developed for the extraction of active constituents from fruits of Schisandra chinensis and Schisandra sphenanthera [50]. Leong et al. and affords very high EFs and short analysis time. suitable for the extraction of active constituents in natural products.1. 10 mg of sample powder. A 1335 (2014) 2–14 Fig. In this method. Chromatogr. A cloudy mixture is formed because of formation of fine droplets of [C4 MIM][PF6 ] homogeneously dispersed in an emulsion.8 g of ammonium hexafluorophosphate ([NH4 ][PF6 ]). After centrifugation. The mixture was then centrifuged and the extractant was injected into the GC for analysis. The analytes were collected from large volumes of aqueous solutions (100 mL) into the sorbent SPE C18 (100 mg). is added. emulsification over-emulsified the mixture and resulted in incomplete phase separation. 0. Combination of techniques for extraction and analysis with DLLME 2. After the sealed vessel was shaken. Solid-phase extraction combined with DLLME SPE and DLLME coupled with GC were used for determination of 13 OPPs in aqueous samples [51]. This method is 2. Eluates were collected into a 10 mL screw-cap glass test tube. . After the vessel is cooled to ambient temperature. Diagram of extraction by (a) MSPD–DLLME and (b) D-␮-SPE.6. The C18 SPE cartridge was used in separation of the desired compounds by elution with 1 mL of acetone. the IL phase deposits at the bottom of the centrifuge tube. Upon formation of [C4 MIM][PF6 ]. it was exposed to microwave radiation at 200 W for 6 min. Microwave-assisted emulsification In 2012. 2.-I. 150 ␮L of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4 MIM][BF4 ]).2. the analytes are extracted into the IL phase. / J. 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.10 M. and 10 mL of deionized water were combined in a microwave extraction vessel.2.

Ku et al. the ␮-SPE device is placed in a 20 mL sample solution. A magnet is held next to the bottom of the vial to attract and isolate the nanoparticles. The eluate was collected in a 10 mL conical tube and then evaporated to 1. Supercritical fluid extraction (SFE) combined with DLLME SFE followed by DLLME [54. 100 mL of standard or sample solution is stirred with a stir bar coated with octadecyl silane for 30 min at 300 rpm. Nanotechniques combined with DLLME Dispersive micro-solid-phase extraction (D-␮-SPE) (Fig. The homogenized mixture was transferred to an empty cartridge (5 cm × 8 mm i. / J. and 100 ␮L of acetonitrile is introduced to the vial to desorb the 1-octanol from the nanoparticles by sonication. 2. Recently. high viscosity. and the sample solution is discarded by decantation. and the final phase was injected into an electrothermal atomic absorption spectrometer for Hg detection.64]. and sensitive determination of analytes in complex matrixes. rinsed with 4.d. Leong et al.0 mL of methanol–water solution. Therefore. flotation-assisted homogeneous liquid–liquid microextraction (FA-HLLME) followed by GC–FID analysis was developed for the extraction of four PAHs in soil samples [76].2. and DLLME. 4(c)). PAHs are extracted from soil samples into methanol and water (1:1. a supramolecular solvent is prepared by mixing 2 mL of octylalcohol and 10 mL of tetrahydrofuran in 38 mL of . 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.M. SFE of PAHs was performed at 313 K and 253. In LDS-DLLME. The filtrate is added into an extraction cell. which contains a mixture of 1. ILs are generally composed of organic cations and inorganic anions [60–63]. 2. This MIM–MSPD–DLLME method combined the advantages of MIM. It was then mixed with 100 ␮L of TCE and 5.2. After centrifugation.0 ␮L of toluene (extraction solvent). and solvent. the dispersed extraction solvent is transferred to the surface of the mixture and then collected by microsyringe. derivatized magnetic nanoparticles are then quickly added to the vial. 5(b)) combined with DLLME [56. was developed for the determination of trace-level phthalate esters in environmental water samples [58]. For SPE step (absorption and elution). MSPD. ILs have low vapor pressure. Finally. A 20 ␮L portion of the toluene phase containing C12S Pd MPCs was used for extraction. good thermal stability. bisphenol-AF. For the dispersion step. 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 the first step of VA-␮-SPE. the PAHs in the sedimented phase were analyzed by GC. tunable miscibility and polarity. The miniaturized MSPD procedure was performed by using small amounts of sample. In particular.0 mL of methanol (homogenous solvent) and 150.4-dichlorophenol. The sedimented organic phase is removed and injected into GC for analysis. Subsequently. The resulting mixture was rapidly injected into 5.2. has been developed for determination of bisphenol-A. 1-octanol is injected rapidly into a vial containing sample solution and the vial is subsequently sealed and vortexed.0 mL of acetonitrile). a simple and efficient two-step method. 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.. An aliquot of the egg yolk sample and MIM sorbent were placed in a small glass beaker and blended together. The sorbent was a miniaturized matrix solid-phase dispersion used for MSPD–DLLME.-I. and good extractability with various organic and inorganic compounds [63.0 mL of water for further purification and concentration of analytes by DLLME. as it does not need centrifugation to separate the organic phase.3. In this approach.5 mL glass vial containing 1 mL of methanol for liquid desorption. After extraction. v/v) by using ultrasound.0 cm × 0. support.5.55] has been developed for extraction and determination of PAHs in marine sediments.2-tetrachloroethane is added to the extracted analytes. This new procedure is different from the conventional homogeneous liquid–liquid microextraction (HLLE) (Fig. In this method. Molecularly imprinted matrix solid-phase dispersion combined with DLLME (MIM–MSPD–DLLME) 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. 2. and the extract is injected into the GC–MS system for analysis.2. 25 ␮L of the extraction solvent 1. The resulting solution is rapidly injected into 5 mL of sodium chloride solution by syringe and then centrifuged. 5(a)) [53]. which is then vortexed for 6 min.2 bar. Other methods using low-toxicity solvent At present. Chromatogr.0 mL of aqueous solution. and then eluted with 3. Through N2 flotation.57] was developed for GC–MS of PAHs in environmental samples. After the stir bar is removed. hydrophobic magnetic nanoparticles are used to recover the extractant 1-octanol in the DLLME step.8 cm porous polypropylene membrane with heat-sealed edges. The stir bar is subsequently removed and placed in a 1. The organic extract is conveniently collected by using a 50 ␮L microsyringe. and tetrabromobisphenol-A in liquid foods and their packaging materials [49]. vortexassisted micro-solid-phase extraction (VA-␮-SPE) followed by dispersive liquid–liquid microextraction based on low-density solvent (LDS-DLLME). Compared with conventional organic extraction solvents. prepacked with 50 mg of MIM). and the extracted PAHs were collected in 1 mL of acetonitrile. the emulsion is separated into two phases by centrifugation.2. the magnet is again placed next to the vial. it holds great potential in the analysis of trace organic compounds in solid samples. This procedure extends the application of DLLME to solid samples. Last year. This method enables simple. N2 flotation is used to break up the emulsion of organic solvent in water and to finish the extraction process. 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. Each ␮-SPE device was fabricated by packing 4 mg of multiwalled carbon nanotubes in a 1. After extraction. A 1335 (2014) 2–14 11 2. Subsequently. 2 ␮L of the collected organic phase is injected into the GC–FID system for subsequent analysis. The magnet is thereafter removed. In this method.2. 16 ␮L of the extraction solvent chlorobenzene was added to the collecting solvent (1. 2. used an up-and-down shaker and ILs to extract analytes while reducing levels of extracted ILs and the use of disperser solvent [25]. It also potentially lends itself to possible automation. the development of extraction methods includes the use of room-temperature ILs and surfactants. and filtration is subsequent done as a cleanup step. application of ILs in DLLME to determine many various types of contaminants and pesticides in environmental water samples have been reported [57–75].1.0 mL. vortex-assisted supramolecular solvent microextraction.3. In this method.0 mL of acetone–acetic acid solution. and the supernatant is collected into an Eppendorf tube by an automatic pipettor for analysis. A novel and highly efficient 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]. Another new method. selective. Here.4. 2. Analytes were selectively separated in LLME by application of clusters protected by a monolayer of dodecanethiolate-coated Pd (C12S Pd MPCs).

Pb.108–126]. In addition. parabens [106]. fatty acids [105]. Many combinations with DLLME have been reported. bisphenol and bisphenol B [92]. the importance of analysis for contaminants or other harmful substances has been greatly acknowledged. Apart from the combined methods. and applicability to the analytical method. Rh in leaves [124]. alkylphenol [91]. and great potential. [6]. Finally. and proteins [144]. Most of these works focus on water samples or aqueous phases [127–143]. they contain components such as carbohydrates. DLLME has also been applied to the analysis of pharmaceuticals. and Al in fruit juice [148].33. SPE [81. The extraction solvent must have ability to extract target analytes. OPPs [84] and benzoylurea pesticides have been extracted with hexadecane and [C6 MIM][PF6 ] [85].2.0 mL with acetonitrile. polybrominated diphenyl ethers in animal tissue [147]. the mixture is vortexed for 2 min. The numbers of methods that use a two-step preparation have increased in the last few years. and antioxidants [107].95]. animal tissue or offal. the supramolecular solvent. fungicides [81].156].96]. and phenols such as chloramphenicol [86]. DLLME is a novel microextraction technique with great potential in sample pretreatment. other pesticides have been analyzed by using less-toxic extraction solvents in water. pharmaceuticals.121. It can be applied in the analysis of organic compounds (pesticides. This direction of the research may well repay investigation. Besides the above compounds. Zgoła-Grzes´ ıkowiak and Grze´ skowiak summarized the DLLME methods for the analyses of various metals [10]. carbamate pesticides [82].1. A second step that uses a disperser solvent is typically performed [81. 3. Pesticides that are commonly analyzed upon extraction by DLLME include OPPs [77]. specially coated nanoparticles and magnetic nanoparticles may be used to assist extraction and to retrieve the extraction solvent. or microwave-assisted extraction [157]. and leaves. By using the new nanotechnique to assist extraction. soil. These above applications illustrate that DLLME is suitable for use in extraction of different types of organic compounds. This review introduces many novel DLLME techniques. DLLME may be a cleanup step before extraction from the food matrix. ions are analyzed through appropriate techniques such as graphite furnace atomic absorption spectrometry [112. Conclusion Many DLLME methods have been developed in recent years.150–157]. triazine herbicides [78]. The above DLLME or dispersion LPME methods have benefits as cleanup and filtering steps to remove impurities of samples.156]. In these methods. / J.147. volatile phenols [93]. aromatic amines [103]. Some of the aforementioned dispersion techniques use very low volumes of organic solvent or no dispersion solvent. The first section discusses various less toxic solvents that are successfully used to develop new methods.0 ␮L of the solution is analyzed by HPLC. heterocyclic insecticides [80]. Application of DLLME for various analytes 3. food. Ions from the liquid phase are then extracted to the extracting solvent as a complex. methomyl [79]. chelating agent is added to the sample to extract the metal ions. used DLLME to extract vegetable oils containing phenolic acids into an aqueous solution [145]. It is then removed and diluted to 1. low cost. rapid. and phenols) and inorganic analytes (Cu. Other novel online DLLME techniques were reported. but not much is known about combinations of extraction methods with DLLME with low-toxicity solvent or dispersion LPME. low solubility in aqueous samples. Because of the increased regulation for food safety.1. metals are the second most common analytes that are extracted by DLLME. Combining other extraction methods with DLLME for analysis of complex samples may be more effective and useful. 3. 500 ␮L of the supramolecular solvent as extraction solvent is added into the sample. 3. Sample preparation can affect the analyte concentration and the cleanliness of the sample prior to further analysis. Inorganic compounds DLLME has been applied to the extraction and concentration of a wide variety of organic compounds and metal ions [10]. DLLME is a popular sample pretreatment step in methods developed for analysis of food. After the sample preparation.102. Food matrixes are notoriously complex. After pesticides. Application of DLLME to various field samples Before 2009. For example. and affords high EF. 10. and many devices that were developed for DLLME. The number of published studies on inorganic analysis assisted by DLLME may increase very rapidly in the near future.1. and n-methyl carbamate pesticides [83]. chlorophenols [94. However. These pesticides are extracted with toxic chlorinated solvents. On the other hand. USE [155.150–154].-I. by shaking or stirring [102. mainly from water samples. respectively. A 1335 (2014) 2–14 distilled water and 10 ␮L of HCl (2 M). forms the top layer of the mixture. For example. and Cd). which is less dense than water. 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. lipids. Chromatogr. DLLME methods have been used in the analysis of various samples such water samples. . Advantages of these techniques include simplicity of operation. triazole pesticides [52]. only a few papers describe the use of DLLME in the analysis of analytes in food samples. anilines [104]. many traditional LPME methods with no dispersing solvent or DLLME have been reported.12 M. Bakar et al. 4. DLLME has been used in the last few years in the extraction and preconcentration of metals for analysis [31.123]. the surface of nanoparticles can be modified to extract various organic compounds and solvents. analytes may be extracted from the food matrix with an organic solvent. disperser techniques. Leong et al. DLLME applications DLLME is simple. fluoroquinolones [90]. inductively coupled plasma optical emission spectrometry [113].147. In these methods. After centrifugation. inflammatory drugs [88]. respectively. 3. these techniques may also be combined with DLLME with lowdensity solvent and high-density solvents to develop other new methods. Organic compounds After DLLME has been introduced by Rezaee et al. Cd in beverage and cereal [119]. Solid samples generally require previous extraction with a suitable solvent to make the analytes available in a liquid matrix [149]. PAHs [54. rapid extraction. Other complex analytes for which DLLME is used for extraction prior to analysis polychlorinated biphenyls in fish [102] and soil [146].2. Furthermore.1. requires low volumes of sample.120.56.124]. Newly prepared functional nanoparticle will extend the usages DLLME in various applications. other organic compounds such as flame retardants and plasticizers [97–102]. glycyrrhizic acid [20]. this review illustrates the application of dispersion LPME methods to allow separation and preconcentration of various types of analytes and samples. urine. clenbuterol [87]. or FAAS [122. and inexpensive. lovastatin [89].154. and new combinations with DLLME.

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