Trends in Analytical Chemistry 72 (2015) 181–192

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Recent advances in dispersive liquid-liquid microextraction for

pesticide analysis
W. Ahmad, A.A. Al-Sibaai, A.S. Bashammakh, H. Alwael, M.S. El-Shahawi *,1
Department of Chemistry, Faculty of Science, King Abdulaziz University, P. O. Box 80203, Jeddah 21589, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords:
Dispersive liquid-liquid microextraction (DLLME) techniques have attracted considerable interest because
Complex matrix
they are cost effective, easy to operate, and reliably preconcentrate trace levels of analytes in complex
Dispersive liquid-liquid microextraction
Emerging pesticide
matrices. This comprehensive review is concerned with principles, applications and developments of DLLME
Green aspects techniques for analysis of trace emerging pesticides in water. DLLME techniques have had few cou-
Nanotechnique plings to spectrofluorimetric methods and relatively none with electrochemical techniques. We highly
Pesticide analysis recommend thin-layer stripping voltammetric techniques at surface-modified electrodes and
Surface-modified electrode spectrofluorimetric techniques coupled and implemented with DLLME. Great attention should be focused
Thin-layer stripping voltammetry on developing low-cost, precise methods for analysis of trace concentrations of pesticides in various bi-
Trace analysis ological and environmental samples. We describe milestones and the combination of nanotechniques
Water analysis
in the DLLME field, green aspects, advantages and shortcomings of known DLLME protocols.
© 2015 Published by Elsevier B.V.

Contents

1. Introduction ........................................................................................................................................................................................................................................................ 182

1.1. Theory and fundamentals of DLLME ............................................................................................................................................................................................. 182
1.2. Analytical parameters affecting extraction efficiency of DLLME ......................................................................................................................................... 182
1.3. Calculations in DLLME ....................................................................................................................................................................................................................... 183
1.4. Classification in DLLME ..................................................................................................................................................................................................................... 183
2. Analytical applications of DLLME in the analysis of pesticides ........................................................................................................................................................ 183
2.1. DLLME combined with gas chromatography (GC) ................................................................................................................................................................... 183
2.2. DLLME combined with high-performance liquid chromatography (HPLC) .................................................................................................................... 184
2.3. DLLME combined with other techniques .................................................................................................................................................................................... 187
3. Advantages of DLLME ...................................................................................................................................................................................................................................... 187
4. Milestones, green aspects, shortcomings and developments in DLLME ........................................................................................................................................ 187
5. Limitations and outlook on the future trends of DLLME .................................................................................................................................................................... 190
6. Conclusion ........................................................................................................................................................................................................................................................... 190
References ............................................................................................................................................................................................................................................................ 191

Abbreviations: AS-DLLME, Auxiliary solvent dispersive liquid-liquid microextraction; CPE, Cloud-point extraction; DLLME, Dispersive liquid-liquid microextraction; DLLME-
SFOD, Dispersive liquid-liquid microextraction based on solidification of floating organic droplet; EF, Enrichment factor; ER, Extraction recovery; GC, Gas chromatography;
Gas GC-FID, chromatography-flame-ionization detection; GC-MS, Gas chromatography-mass spectrometry; GC-TMS, Gas chromatography-tandem mass spectrometry; HFME,
Hollow-fiber-protected microextraction; HPLC, High performance liquid chromatography; HPLC-DAD, High performance liquid chromatography-diode array detection; LLE,
Liquid-liquid extraction; LLME, Liquid-liquid microextraction; LLLME, Liquid-liquid-liquid microextraction; MA-DLLME, Microwave assisted dispersive liquid-liquid microextraction;
OCP, Organochlorine pesticide; OPP, Organophosphorus pesticide; PCP, Personal-care products; RR, Relative recovery; SDME, Single-drop microextraction; SME, Surface-
modified electrode; SPE, Solid-phase extraction; SPME, Solid phase microextraction; SFE, Supercritical fluid extraction; USA-DLLME, Ultrasound-assisted dispersive liquid-
liquid microextraction; WHO, World Health Organization.
* Corresponding author. Tel.: +966 12 6952000 Ext 64422; Fax: +966 12 6952292.
E-mail address: malsaeed@kau.edu.sa; mohammad_el_shahawi@yahoo.co.uk (M.S. El-Shahawi).
1 On sabbatical leave from Department of Chemistry, Faculty of Science, Damiatta University, Damiatta, Egypt.

http://dx.doi.org/10.1016/j.trac.2015.04.022
0165-9936/© 2015 Published by Elsevier B.V.
182 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
1. Introduction
Advancement in sample pre-treatment techniques in the past
decade was mainly focused on miniaturization, simplification and
automation in order to lower costs of both materials and person-
nel. Hence, the main aim of sample preparation is to clean up and
to concentrate the target analyte and finally to execute it in a form
that is well-matched with the desired analytical instrument. Liquid-
liquid extraction (LLE), Soxhlet extraction, chromatography,
distillation, and absorption [1] are conventional practices for sample
preparation that suffer from the different drawbacks, such as being
time consuming, tedium, consumption of large amounts of toxic sol-
vents, and, to some extent, complications in automation. The trend
has resulted in several microextraction techniques [e.g., solid-
phase microextraction (SPME), single-drop microextraction (SDME)
and dispersive liquid-liquid microextraction (DLLME)]. Most of these
techniques are simple, fast and consume less extraction solvents than
conventional sample-preparation techniques [1].
Interest in miniaturizing sample pre-treatment techniques started
with the introduction of SPME by Pawliszyn and co-worker [2]. Since
then, several other microextraction methods have been developed.
DLLME was introduced by Rezaee et al. in 2006 [3] as a conse-
quence of the demands for rapid, economical and environmentally
benign sample-pretreatment techniques. DLLME was originally de-
veloped for water samples, but was afterwards also applied to other
matrices, such as soil and foodstuffs. The extraction mechanism is
based on the different affinities of the analytes to the aqueous sample
and the organic extractant. The major advantages include simplic-
ity, minimal use of harmful solvents, rapid extraction and low cost.
This technique is one of the most outstanding due to the large
number of publications since its inception. The main aim of this tech-
nique is:
• to overcome and to overpower the demerits of conventional tech-
niques in order to reduce both personnel and material expense;
and,
• to achieve promising results in terms of recovery and enrich-
ment factor (EF).
DLLME, as a powerful sample-preparation and preconcentration
technique, has attracted great attention due to its wide range of ap-
plications to organic and inorganic contaminants in different
matrices. Among the most inspected analytes employing DLLME are
pesticides. A number of reviews on DLLME have been published
[4–20]. Few of these reviews were focused on analysis of pesti-
Fig. 1. Steps in dispersive liquid-liquid microextraction protocols.
cides in complex matrices by DLLME [6,15,16,18]. Hence, an
independent comprehensive study on pesticides was very much
needed. Most of the reported pre-treatment methods suffer from
many drawbacks (e.g., high cost, multiple steps and time consum-
ing, costly HPLC solvents), while DLLME offers a stable system with
short analysis time, good reproducibility, ruggedness and cost
effectiveness.
This review presents various chemical classes of pesticides ana-
lyzed by a variety of DLLME protocols grouped by analytical
technique. In this article, we cover the best practices for pesti-
cides with special emphasis on further advancement and future
trends in the microextraction techniques for pesticide analysis.
1.1. Theory and fundamentals of DLLME
DLLME uses a ternary solvent system in which a small amount
of a blend of extraction and disperser solvents is rapidly injected
into an aqueous sample containing the analyte. After shaking the
mixture, a cloudy solution is obtained and tiny fine droplets of the
extraction solvent are formed. The surface area between water and
the extraction solvent becomes infinitely large, so rapid, effective
mass transfer occurs. The mixture is then centrifuged and the
sedimented phase is collected with a micro syringe for subse-
quent analysis. Fig. 1 shows the process.
1.2. Analytical parameters affecting extraction efficiency of DLLME
Development of strategies and techniques allowing the selec-
tion of representative samples continues to be the main focus of
research in pre-treatment and clean-up. In DLLME, several factors
influence the extraction efficiency, including type and volume of the
extraction solvent, type and volume of the disperser solvent, pH of
the sample, effect of salt, extraction time, centrifugation time, and
sample volume. These parameters have to be optimized for high ex-
traction efficiency. The most important task in the process is the
selection of an appropriate extraction solvent, based on several re-
quirements. It must be immiscible in water and should form tiny
droplets in it. It must have higher affinity towards the analyte. Its
volume should be carefully optimized and its compatibility with the
desired instrument is also considered. Rezaee et al. [3] used carbon
tetrachloride, carbon disulfide and 1,1,2,2- tetrachloroethylene in their
very first experiment.
Optimizing the disperser-solvent type and volume is as
important as optimizing the extraction solvent. The function of
the disperser solvent is to empower the extracting solvent to
 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
Fig. 2. Microextraction protocols.
partition itself uniformly in the aqueous sample, in order to achieve
good extraction efficiency. The ratio of volume of extracting solvent
to disperser solvent should be carefully considered. The volume of
the sedimented phase is significantly influenced by disperser type
and volume. Acetone, methanol and acetonitrile are commonly used
as disperser solvents.
Optimal pH and salt concentration should be established. Ex-
traction and centrifugation times should be carefully optimized.
Extraction time is defined as the time interval between the injec-
tion of the mixture of disperser and extraction solvent, and
centrifugation. Centrifugation is important for phase separation and
is time consuming compared to other parameters. It is usually
5–10 min. A long centrifugation time causes phase separation to dis-
solve [21].
1.3. Calculations in DLLME
In DLLME, the analyte EF and extraction recovery (ER) should be
taken into consideration. Rezaee et al. [3] defined EF in the follow-
ing equation:
EF = Csed C0
where Csed is the analyte concentration in the sedimented phase and
C0 is the initial analyte concentration in the sample. ER is defined
as the ratio of the amount of analyte in the sedimented phase to
the initial concentration in the sample:
ER = (nsed n0 ) × 100 = Csed × Vsed C0 × V0
where nsed is the amount of the analyte in the sedimented phase,
n0 is the initial analyte amount in the sample, Vsed is the volume
of the sedimented phase and V0 is the volume of the aqueous phase:
ER = Vsed V0 × EF × 100
The relative recoveries (RR) can be calculated from the equa-
tion:
RR = Cfounded − Creal Cadded
where Cfounded is the analyte concentration measured from the sample
after analyte addition, Creal is the native analyte concentration and
Cadded is the amount of the analyte that was added to the sample.
183
1.4. Classification in DLLME
A large number of papers have been published since the incep-
tion of the DLLME technique in 2006. Several new advances occurred
in time to overcome possible disadvantages and drawbacks of the
process, hence leading to different modifications in DLLME, and, most
often, for each modification a different acronym was assigned by
the researcher. Sometimes, there are more than two or three ac-
ronyms for the same DLLME method, so it is often difficult to
differentiate them or it leads to complications. We have made an
effort to arrange all those acronyms in four general groups, as shown
in Fig. 2.
The four bases of classification are:
(i) mixed mode extraction;
(ii) extraction based on assisting dispersion;
(iii) extraction based on use of ionic liquids (ILs); and,
(iv) extraction based on solvent density in its acronym, and any
other type not fitting into the other three groups.
2. Analytical applications of DLLME in the analysis of
(1) pesticides
Classification of applications of DLLME continues to play a key
role in searching for structure in data. Thus, it allows meaningful
generalization about large amounts of data to be performed by rec-
ognizing a few basic patterns among them. The techniques coupled
(2) with DLLME techniques can be summarized as follows.
2.1. DLLME combined with gas chromatography (GC)
It is evident from the large number of publications that DLLME
is mainly used for the analysis of pesticides. Fig. 3 shows the rel-
(3) ative percentages (%) of articles published each year with respect
to pharmaceuticals and other analytes. Moreover, the most favor-
able analytical technique is GC, since it has rapidly developed in a
short time. The extraction solvent in DLLME should be less soluble
(4) or immiscible with water in order to achieve adequate phase sep-
aration, followed by direct injection into GC.
Table 1 shows applications of DLLME in combination with GC
for pre-concentration and determination of pesticides. As can be
seen, pesticides are mostly analyzed in an aqueous matrix because
184 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
Fig. 3. Evolution of the percentage (%) of publications devoted to DLLME for separation and subsequent determination of pesticides, pharmaceutical and other chemicals
per year (2010–14).
they are directly introduced to water for agricultural purposes and
with personal-care products (PCPs), such as shampoos and sprays
[15]. Due to their continual supply, pesticides have become persis-
tent in the environment, causing adverse effects to health. The World
Health Organization (WHO) and various national governmental in-
stitutions have established residue limits and published guidelines
and policies for quantification of pesticide residues in different kinds
of waters, including environmental, drinking and irrigation waters
[16].
Xiong et al. [22] developed a DLLME method based on solidifi-
cation of floating organic droplet (DLLME-SFOD) for the
determination of chlorpyrifos in environmental water samples fol-
lowed by GC-flame-photometric detection (GC-FPD). The ER was
79.02% and the EF was 232.42.
Alves and co-workers [23] determined six organophosphorus pes-
ticides (OPPs) in water utilizing DLLME prior to GC-mass
spectrometry (GC-MS). In their method, chloroform was used as the
extraction solvent and 2-propanol as disperser. The limit of detec-
tion (LOD) of the method was 1.5–9.1 ng L−1. The method was
validated for tap, well and irrigation waters with relative recover-
ies 46.1–129.4%.
A new method, ultrasound-vortex-assisted DLLME (US-VA-
DLLME) for OPPs and triazines, resulted in excellent LODs of
0.007–0.07 ng mL−1 [24]. Similarly OPPs were analyzed by combin-
ing supercritical fluid extraction (SFE) with DLLME in marine
sediment samples [25]. This method has been applied to real soil
and marine samples with satisfactory results. OPPs were analyzed
in fruit, vegetables, dried herbs and water [26,27]. Table 1 summa-
rizes analysis of organochlorine pesticides (OCPs) [28–32]. Mudiam
et al. [28] analyzed endosulfan and its metabolite in soil
and urines. OCPs were also analyzed by low-density magnetofluid
DLLME (LMF-DLLME) in water with good LODs [29]. In peach
and pulps, OCPs were investigated by DLLME-SFOD as dodecanol
with a density lower than water was used with EFs of 409–1089
[30].
Sousa and co-workers [33] developed a methodology for the
analysis of carbamates and carbofuran in water using DLLME-GC-
MS. Chlorobenzene was used as extracting solvent and methanol
as disperser solvent. A total sample volume of 10 mL satisfactorily
obtained LODs of 0.04 μg L−1 for carbamates and 0.02 μg L−1
for organophosphorus pesticides. Similarly, Chen et al. [34] pro-
posed a low-density extraction solvent-based solvent-terminated
DLLME (ST-DLLME) combined with GC-tandem MS (GC-TMS) for
determination of carbamate pesticides in water samples with
good recoveries of 94.5–104% at all spiked levels for all carba-
mates used.
Triazoles are one of the major classes of pesticides having prop-
erties, such as high chemical and photochemical stability, and low
biodegradability, which make them persist in soil, food and water
for a long time with some endocrine-disrupter properties. Triazoles
are preconcentrated by coupling stir-bar sorptive extraction with
DLLME (SBSE-DLLME) with LODs up to 0.53–24 ng mL−1 [35]. A new
air-assisted LLME technique, similar in principle, has been devel-
oped for analysis of triazoles in water, vegetables and juices with
EFs of 713–808 [36].
Pyrethroids have been analyzed by DLLME-GC [37–41], includ-
ing analysis of cypermethrin in rat tissues by low-density solvent
DLLME (LDS-DLLME [37] followed by GC-ECD with good recover-
ies and EFs. With tomato as the matrix, pyrethroids were analyzed
by Li et al. [38] with recoveries of 89–109%, and in soil [39] with
recoveries 83.6–98.5%.
2.2. DLLME combined with high-performance liquid
chromatography (HPLC)
Table 2 shows that DLLME coupled with HPLC is also a popular
separation and determination technique for pesticide analysis.
However, in contrast to GC, in most cases, the extraction solvent con-
taining the analyte after extraction has to be reconstituted in a
solvent more compatible with HPLC columns, whereas, in some
cases, it can be directly injected into the column. Table 2 summa-
rizes the analysis of pesticides utilizing DLLME-HPLC.
Carbamates have been successfully studied with DLLME tech-
niques [42–45]. Among them, ultrasound-assisted emulsification
microextraction (USAEME) has been successfully used for analysis
of six carbamates in water with excellent EFs of 170–246 [42]. In
watermelon and tomatoes, five carbamates were determined by
DLLME with LODs of 0.5–1.5 ng g−1 [43].
OPPs are widely found in water due to their application in ag-
riculture and other areas. Mostly toxic in nature, their presence in
water is a threat to humans and wild-life. DLLME seems to be the
most promising method for pre-concentration of OPPs because of
their presence in trace concentrations [46–49], so it is analyzed in
various matrices, including an UA-DLLME-SFOD for the determi-
nation of organophosphorus pesticides in environmental water [46].
The EFs were 215–557. This method has been successfully
Table 1
DLLME combined with GC for the analysis of pesticidesa

Analyte Matrix Extraction Solvent Disperser Solvent EF LOD Method Others Ref
−1
Chlorpyrifos Water 1-Dodecanol (40 μL) Methanol (1.5 mL) 232.42 0.02 μg L DLLME-SFO Centrifugation time 3 min and [22]
0.5 g NaCl,
6 OPPs Water CHCl3 2-Propanol – 1.5–9.1 ng L−1 DLLME – [23]
OPPs & Triazine Wine 1,2-Dichloroethane (250 μL) – 210–232 0.007– 0.07 ng mL−1 USVA-DLLME Sample volume 10 mL, pH 8, [24]
vortex time 30 sec,
ultrasonication time 10 min
7 OPPs Soil &marine CCl4 (17 μL) Acetonitrile (1.0 mL) 67–144 0.001–0.009 mg kg−1 SFE-DLLME Sample volume 5 mL, pH 6, [25]
sediment sample optimum pressure 150 bar
−1
10 OPPs Fruit, vegetables, CCl4 (80 μL) Acetonitrile (1.0 mL) 51–99 0.12–4.92 ng kg DLLME No salt added, centrifugation [26]

W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192

dried herbs time : 5 min
3 OPPs Water Carbon Disulfide (30 μL) Methanol (1.0 mL) – 0.047–0.201 μg m L−1 DLLME Sample volume 5 mL, [27]
centrifugation time 3 min
Endosulfan & its Soil and Urine Tetrachloro ethylene (58 μL) Acetone (1.27 mL) – 0.316–2.494 ng g−1 (soil) UA-DLLME Na2SO4, (7% w/v) [28]
metabolite 0.049–0.514 ng g−1 (urine)
OCPs Water n-Octane Magnetofluid (50 μL) – 156–196 1.8–8.4 ng L−1. LMF-DLLME NaCl added (3% m/v), [29]
extraction time 4 min
OCPs Peach, pulps & 1-Dodecanol (8 μL) Acetone (0.4 mL) 409–1089 2.8–18.5 ng L−1 DLLME-SFO No salt added, sample volume [30]
peels 5 mL
14 OCPs River water Carbon disulfide (13.5 μL) Acetone (0.50 mL) 647–923 0.05–0.001 μg L−1 DLLME – [31]
20 OCPs Water CCl4 (10 μL) Acetone (1.5 mL) – 0.21–11.65 ng L−1 DLLME Centrifugation time 5 min, no [32]
salt added
Carbamates & Water Chlorobenzene (80 μL) Methanol (500 μL) – 0.04 μg L−1, 0.02 μg L−1, DLLME Sample volume (10 mL), no [33]
Organophosphorus salt added
−1
4 Carbamates Water Toluene (50 μL) Acetonitrile (1 mL) – 0.001–0.50 ng mL ST-DLLME Sample volume 5 mL, [34]
extraction time 10 min and
pH 7.
Triazole Water 1,1,2,2-Tetrachloro-Ethane – 282–1792 0.53–24 ng mL−1 SBSE-DLLME NaCl (30 % m/v) [35]
(25 μL)
Triazole Water, vegetables Toluene (35 μL) – 713–808 0.53–1.13 ng mL−1 AALLME Centrifugation time 2 min pH [36]
and juices not significant, NaCl (10% w/v),
Cypermethrin Biological matrix n-Hexane (100 μL) Acetone (300 μL) 477–659 0.043–0.314 ng mg−1 LDS-DLLME No salt added, pH 4 [37]
3 Pyrethroids Tomato CHCl3 (40 μL) Acetonitrile (1.0 mL) – 0.3–0.5 μg kg−1 DLLME – [38]
3 Pyrethroids Soil Tetrachloro ethylene (50 μL) Acetone 128–138 0.45–1.13 ng g−1 MSPD-UA-DLLME pH 6.3, ultrasonication time [39]
2 min
4 Pyrethroids Water 1-Dodacanol (8 μL) Methanol (500 μL) 475–790 1.4–2.9 ng L−1 DLLME-SFO NaCl (16% m/v), extraction [40]
time: 90 s
−1
9 Pyrethroids Water Chlorobenzene (15 μL) Acetone (0.3 mL) 728–1725 0.2–0.7 μg L USA-DLLME Centrifugation for 5 min, [41]
extraction for 2 min
a Abbreviations: AALLME, Air-assisted liquid-liquid microextraction; [D(i-C )IM][PF ], 1,3-Diisooctylimidazolium hexafluorophosphate; DLLME-SFO, Dispersive liquid-liquid microextraction based on solidification of floating
8 6
organic droplet; LDS-DLLME, Low-density solvent dispersive liquid-liquid microextraction; LMF-DLLME, Low-density magnetofluid dispersive liquid-liquid microextraction; ME-VADLLME, Matrix-extraction-vortex-assisted dis-
persive liquid-liquid microextraction; MSPD-UA-DLLME, Miniaturized pre-treatment procedure combining matrix solid-phase dispersion with ultrasound- = assisted dispersive liquid-liquid microextraction; SBSE-DLLME, Stir-
bar sorptive extraction dispersive liquid-liquid microextraction; SFE-DLLME, Supercritical fluid extraction coupled with dispersive liquid–liquid microextraction; ST-DLLME, Solvent-terminated dispersive liquid–liquid microextraction;
UA or USA–DLLME, Ultrasound-assisted dispersive liquid-liquid microextraction; USVADLLME, Ultrasound-vortex-assisted dispersive liquid–liquid microextraction.

185
 186
Table 2
DLLME combined with HPLC for analysis of pesticidesa

Analyte Matrix Extraction Solvent Disperser solvent EF LOD Method Other Ref

6 Carbamate Water CHCl3–C6H5Cl (1:1, v/v) – 170–246 0.1–0.3 ng mL−1 UASEME Water sample 5 mL, no salt addition, [42]
(150 μL) 3 min extraction time
−1
5 Carbamates Water melon and CHCl3 (40 μL) Acetonitrile (1.0 mL) 80–177 0.5–1.5 ng g DLLME NaCl (5% w/v), extraction time not [43]
tomatoes significant
N-Methyl Carbamates Water CHCl3 (126 μL) Acetonitrile (1.5 mL) – 0.0001 and 0.0005 μg mL−1 DLLME Sample volume 5 mL, NaCl (4.7%w/v), [44]
extraction time 1 min, natural pH
Carbamates Fruits and vegetables Trichlormethane (35.0 μL) Acetonitrile (1.0 mL) 5400–7650 5–60 pg kg−1 SPE-DLLME Sample volume 5.0 mL, NaCl (20% w/v) [45]
OPPs Environmental water 1-Dodecanol (15 μL) Methanol (200 μL) 215–557 0.1–0.3 ng mL−1 DLLME-SFO Sample volume 20 mL, 1g NaCl, [46]
extraction time 1 min
Dichlorvos Water [BMIM][PF6] (65 μL) THF (260 μL) 215 0.2 μg L−1 RTIL–DLLME NaCl (25% w/v), [47]
Sample volume, 8 mL
pH 5
OPPs and Carbamates Tea 1-Octanol (50 μL) – 130–185 0.13–0.61 μg L−1 MSA-DLLME Sample volume, 12 mL [48]
NaCl (20% m/v), pH not significant
3 OPPs Water CHCl3 (250 μL) Methanol (1.5 mL) 20.7–26.4 2 ng mL−1 for Fenitrothion, DLLME No Salt added, pH not significant [49]

W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192

3 ng mL−1 for others
DDT and Its Metabolites Water [C8MIM][ PF6] (50 μL) [C4MIM][BF4] (300 μL) – 0.21–0.49 μg L−1 MILs-DLLME pH 7 extraction time 5 min, no Salt [50]
added
Benzoylurea Water [C6MIM][PF6] (70 μL) Acetonitrile (300 μL) 261–302 0.05–0.15 μg L−1 MR-IL-DLLME No salt added, vortex extraction time [51]
90 s
Urea derivatives Water CH2Cl2 (200 μL) – 78–160 0.04–0.4 μg L−1 US-DLLME Sonication time 30 s, No salt added, pH [52]
not significant
Benzoylurea Waste water [C8MIM][PF6] Methanol – 0.5–1.0 ng L−1 TCIL-DLLME Vs – [53]
US-IL-DLLME
Pyrethroid Complex environmental [N8881][Tf2N] Methanol – – MA-DLLME pH 5, Microwave conditions, 200 W [54]
matrices and 60 s
4 pyrethroids Water and vegetables 1-Octanol (200 μL) APTS magnetic nano 51–108 0.05–2 ng mL−1 (water) DLLME-D-μ-SPE Extraction time 3 min, vortexed for [55]
particles 0.02–2.0 ng g−1 (vegetables) 3 min
6 Pyrethroid Fruit juice CHCl3 (300 μL) Methanol (1.25 mL) 62–84 2–5 μg L−1 DLLME Sample volume 5 mL, centrifugation [56]
5 min
3 Pyrethroids Tomato [Bmim][PF6] (80 μL) Acetonitrile (300 μL) 42–48 8.1–14.3 mg kg−1 IL-DLLME pH 5, no salt added, extraction time [57]
10 min
Imidacloprid Tomatoes Tetrachlo ethane (30 μL) – 375 0.045 mg kg−1 UDLLME Sample volume 5 ml, ultra sonication [58]
for 10 min, no salt added, extraction
time 6 min
6 Neonicotinoid Soil Dichloromethane Acetonitrile – 0.0005–0.003 μg mL−1 DLLME – [59]
Neonicotinoids Insecticides Honey CHCl3 (100 μL) Acetonitrile – 0.2 − 1.0 ng g−1 for DAD and SPE-DLLME NaCl (10% w/v) [60]
0.02 − 0.13 ng g−1 for MS/MS
2,4-Dichlorophenoxyacetic Water 20 mg DeA in 1.0 mL THF – 148–157 0.5–0.8 μg L−1 RM-DLLME pH 2, sample volume 10 mL [61]
acid and 4-chloro-2- centrifugation time 5 min, extraction
methylphenoxyacetic time few seconds, no salt added
6 fungicide residues Juices and red wine 1-Dodecanol (30 μL) – – 0.4 -1.4 μg L−1. UASEME-SFO Sample volume (5 mL), extraction time [62]
for 1 min, no salt added, Tween 80 (10
mmol L−1) as emulsifier,
Strobilurin fungicides Fruit juice 1-Undecanol (30 μL) – 95–135 2–4 ng mL−1 UASEME-SFO Sample volume (5 mL) [63]
Surfactant 0.015 mg mL−1 Tween
80,ultrasonic time 1 min, NaCl (1%
w/v)
5 Fungicides Fruit juice 1-Dodecanol – 25–56 5–50 μg L−1 UA-DLLME Fruit juice sample 5 mL [64]
a Abbreviations: APTS, Aminopropyl triethoxysilane; [BMIM][PF6], 1-Butyl-3-methylimidazolium hexafluorophosphate; [C4MIM][BF4], 1-Butyl-3-methylimidazolium tetrafluoroborate; [C8MIM][PF6], 1-Octyl-3-
methylimidazolium tetrafluorophosphate; [C6MIM][PF6], 1-Hexyl-3-methylimidazolium hexafluorophosphate; DDT, Dichlorodiphenyltrichloroethane; DeA, Decanoic acid; D-μ-SPE- DLLME, Dispersive micro-solid-phase extraction
combined with dispersive liquid-liquid microextraction; IL-DLLME, Ionic liquid dispersive liquid-liquid microextraction; MA-DLLME, Microwave-assisted dispersive liquid-liquid microextraction; MILs-DLLME, Mixed ionic liquids
dispersive liquid-liquid microextraction; MR-IL-DLLME, Magnetic retrieval of the ionic liquid dispersive liquid-liquid microextraction; MSA-DLLME, Magnetic stirring-assisted dispersive liquid-liquid microextraction; [N8881][Tf2N],
Trioctylmethylammonium bis(trifluoromethylsulfonyl)imide; RM-DLLME, Reverse micelle-mediated dispersive liquid-liquid microextraction; RTIL-DLLME, Room-temperature ionic liquid dispersive liquid-liquid microextraction;
TC-IL-DLLME, Temperature-controlled ionic liquid dispersive liquid-liquid microextraction; THF, Tetrahydrofuran; UDLLME, Ultrasonic dispersion liquid-liquid microextraction; USAEME, Ultrasound-assisted emulsification microextraction;
US-IL-DLLME, Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction.
 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
validated in real water samples. Wang et al. [47] also developed
room-temperature IL DLLME (RTIL-DLLME) for the analysis
of dichlorvos in water with an LOD of 0.2 μg L −1 . In tea,
OPPs and carbamates were analyzed by magnetic stirring-
assisted DLLME (MSA-DLLME) with LODs of 0.13–0.61 μg L −1
[48].
Dichlorodiphenyltrichloroethane (DDT) and its metabolites have
been determined by mixed ILs DLLME (MILs-DLLME) in environ-
mental water using hydrophobic IL [C8MIM][PF6] as extractant and
hydrophilic IL [C4MIM][BF4] as disperser solvent [50]. Under the
optimum experimental conditions, the LODs reached 0.11–0.49 μg L−1,
the linear range was 1–100 μg L−1 and recovery percentages of the
spiked samples were 85.7–106.8%.
Substituted ureas, especially benzoylurea, are powerful insect
regulators. They are widely used for controlling numerous pests by
inhibiting the synthesis of cuticle chitin. Due to its high consump-
tion, its presence in the environment and foodstuffs is one of the
risks faced by the general population. Zhang et al. [51] introduced
a novel method magnetic retrieval of the IL DLLME (MR-IL-DLLME)
for analysis of five benzoylurea (BU) insecticides in environmen-
tal water samples and it was successfully applied in real water
samples with good recoveries and RSDs. BU was also studied in
natural water [52] and wastewater [53] by two DLLME tech-
niques, namely temperature-controlled IL (TCIL-DLLME), and
USA-IL-DLLME.
Pyrethroids are synthetic insecticides widely used in agricul-
ture, households, forestry, horticulture and some other fields.
The pyrethroids class of pesticides has low toxicity towards mammals
and birds and low environmental persistence. However it pos-
sesses high toxicity towards aquatic arthropods, fish and honey
bees, even at low concentrations. The low toxicity of pyrethroid
compared to organochlorine, organophosphorus and carbamate
pesticides does not rule out the environmental pollution associ-
ated with it. The microextraction techniques considered a bottleneck
of analytical chemistry, especially DLLME, have a wide range of
applications towards pyrethroids in aqueous and non-aqueous
matrices [54–57]. Four pyrethroids were successfully determined
by a microwave-assisted DLLME (MA-DLLME). In addition to solvent
volume, pH and salt addition, microwave conditions are also
carefully optimized [54]. Pyrethroids were also successfully ana-
lyzed by combing dispersive micro-solid-phase extraction with
DLLME (D-μ-SPE-DLLME) in water and vegetables with EFs of
51–108 and LODs of 0.05.2 ng mL−1 and 0.02–2 ng g−1, respectively
[55].
Imidacloprid has been investigated by ultrasonic dispersion LLME
(UDLLME) in a sample of tomatoes [58]. A UD process was applied
to achieve a cloudy solution quickly. Under optimum extraction con-
ditions, the EF was 375. In another study, six neonicotinoids in soil
were processed by DLLME giving recoveries of 55.3–95.6% [59].
Neonicotinoids were also investigated in honey by combining SPE
with DLLME [60].
Chlorophenoxy-acid herbicides are considered potential pollut-
ants. They are persistent, polar in nature, and have high water
solubility, so they are widely found in water. A new DLLME tech-
nique, named reverse micelle-mediated DLLME (RM-DLLME), was
applied for the analysis of water-soluble pesticides 2,4-
dichlorophenoxyacetic acid and 4-chloro-2-methylphenoxyacetic acid
[61]. The LODs of the method were 0.5–0.8 μg L−1 and the repeat-
ability of the proposed method, expressed as relative standard
deviation (RSD), varied in the range of 2.5–3.2%. Linearity was found
to be 1–200 μg L−1.
Fungicides analyzed in different matrices are listed including six
fungicides in juices and red wine [62] with recoveries of 79.5–
113.4%, strobilurin fungicides in fruit juice [63] with recoveries of
82.6–97.5% and other fungicides in fruit juice [64] with recoveries
of 71.8–118.2%.
187
2.3. DLLME combined with other techniques
Other techniques, such as sweeping micellar electrokinetic chro-
matography (MEKC) [65–75] and spectrophotometry [76–78], have
been used for analysis of pesticides (Table 3). Six carbamates in apple
[65], 12 carbamates in juice samples [66], 17 N-methyl carba-
mates in water [67], five sulfonylurea herbicides in soil matrix [68],
neonicotinoid in cucumber [69], phenoxyacetic acids in drinking and
environmental water [70,71], five organophosphorus pesticides [72]
and some other pesticides [73–75] were analyzed by DLLME coupled
with MEKC. The EFs were 87–10,000 under the optimized condi-
tions (Table 3).
Carbaryl [76] was analyzed by DLLME and thiram [77] by DLLME-
D-μ-SPE coupled with spectrophotometric techniques. The LODs of
carbaryl and thiram were 8.0 ng mL−1 and 11.5 ng mL−1, respective-
ly, with RSDs of 1.1–2.7 %.
DLLME with a new disperser, Aliquat 336, was introduced re-
cently for analysis of carbendazim fungicides [78]. Aliquat 336 offered
better extraction efficiency than conventional disperser solvents [78].
3. Advantages of DLLME
In analysis of pesticides, the problems of contamination and loss
of analytes by classical LLE are significantly higher than DLLME, since
DLLME requires only one operational step. DLLME offers rapid, low
cost, short time, reliable, simple operation, high pre-concentration
and recovery factors and environment friendliness. LODs in DLLME
are much better and feasible compared to other liquid-phase
microextraction techniques [7,8]. Table 4 compares the advan-
tages and the drawbacks of different microextraction techniques,
such as SDME, HFME and DLLME.
In DLLME, a syringe is employed for collection and injection of
the extract, so problems are avoided, whereas, in SDME, the
problem of drop dislodgment is common due to the use of a
syringe as the drop holder during extraction [11]. The perfor-
mance of DLLME is much faster than cloud-point extraction (CPE)
because, in many cases, CPE requires heating of the aqueous
solutions for long periods to achieve the cloud-point temperature
[7]. The extraction efficiency of CPE decreases in the presence of
more than 3% of a water-miscible organic solvent (e.g., THF). The
THF solvent is usually used to decrease the viscosity of surfactant-
rich phase and it facilitates sample handling due to dissolution of
the surfactant-rich phase and decrease in the volume of this
phase. The injection of a mixture of solvents, which already
contain the target analytes in an aqueous solution, may be devel-
oped successfully (recovery values are maintained and cleaner
extracts are obtained) [10–14].
4. Milestones, green aspects, shortcomings and developments
in DLLME
This review mainly focuses on recent developments in DLLME
in analysis of pesticides and its applications in conjunction with dif-
ferent analytical techniques for pre-concentration and subsequent
determination of pesticides in complex matrices (Tables 1–3).
Conventional DLLME utilizes solvents heavier than water [3]. The
number of solvents with density greater than water is limited, and
they are mostly halogenated and hazardous. This drawback leads
to many modifications, such as avoiding the centrifugation step, so-
lidifying the floating organic drop (DLLME-SFOD), and adjusting the
solvent density (AS-DLLME) [9]. ILs were also introduced and are
now extensively used in DLLME as extractants. These develop-
ments mainly focused on enhancing the extraction process leading
to different modifications over time. Fig. 4 summarizes the
milestones.
 188
Table 3
DLLME combined with other techniques for analysis of pesticides

Analyte Matrix Extracting solvent Disperser solvent EF LOD Method Other Ref

W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192

Sweeping micellar electrokinetic chromatography
6 Carbamates Apple CHCl3 (60 μL) Acetone (1 mL) 491–1834 2–3 ng g−1 DLLME Sample volume 5 mL, pH 2.5, no salt [65]
added, extraction time 1 min
12 Carbamates Juice samples CHCl3 (600 μl) Methanol (1500 μl) – 1–7 μg L−1 DLLME Extraction time 5 min, pH 7.5, no salt [66]
added
17 N-Methylcarbamate Environmental and Toluene (636 μl) Acetonitrile (940 μl) – 1–144 ng L−1 DLLME No salt added pH 2.0, [67]
drinking water
−1
Sulfonyl urea herbicides Soil Chlorobenzene (60 μL) Acetone (1.0 mL) 3000–5000 0.5–1 ng g DSPE-DLLME Sample volume 5 mL [68]
pH 2, no salt added,
Neonicotinoid Cucumber CHCl3 (100.0 μL) Acetonitrile(0.8 ml) 4000–10000 0.8–1.2 ng g−1 DLLME Sample volume 5 ml, no salt added, [69]
vortexed for 1 min
Phenoxyacetic acids Drinking water – – – 0.002–0.005 mg L−1 DLLME –- [70]
3 Phenoxy-acid herbicides Environmental Chlorobenzene (180 μL) Acetonitrile (1000 μL) 151–216 1.56–1.91 ng mL−1 DLLME Sample volume 5 mL, no Salt added, [71]
water
Organophosphorus Water Dichloromethane (300 mL) Acetonitrile (2.0 mL) 477–635 3–15 ng mL−1 DLLME Sample volume 10 mL Centrifugation [72]
for 5 min, KI (1.5%)
17 herbicides Natural water CHCl3 (175 μL) 1,4–Dioxane (2 mL) – 0.5–3.0 μg L−1 DLLME-On–line Centrifugation for 10 min, pH 2 [73]
preconcentration
3 Pesticides Apple Carbon tetrachloride (125 μL) Acetone (1.5 mL) 87–95 50–80 ng mL−1 DLLME No salt added, extraction time 3 min [74]
Triazine Water Chlorobenzene (60 μL) Acetonitrile (1 mL) 1750–2100 0.05–0.10 ng mL−1 DLLME NaCl (2% w/v), extraction time 1 min [75]
Spectrophotometry
Carbaryl Water, Fruits Juice 1-Octanol (150 μl) Acetonitrile 2730 8 ng mL−1 DLLME-D-μ-SPE Vortex speed 3200 for 2 min, [76]
Sonication for 4 min
Thiram Water CCl4 (200 μL) Ethanol (1 mL) 58.8 11.5 ng mL−1 DLLME Centrifugation for 5 min [77]
Carbendazim fungicides Water and soil CCL4 Aliquat 336 – 2.1 ng mL−1 DLLME Centrifugation for 5 min [78]
 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192 189

Table 4
Comparison of advantages and drawbacks of DLLME with other microextraction techniques

SDME HFME DLLME

Advantages Inexpensive, simple, easy to operate, nearly
solvent free, more suitable for volatile and semi-
volatile analytes, environmental friendliness,
various extraction modes, ease of automation, high
extraction efficiency
Drawbacks and Problem of drop dislodgment, time consuming,
limitations incomplete equilibrium
Inexpensive, simple, environmentally
friendly, high versatility and
selectivity, headspace and immersion
modes
Poor reproducibility, time consuming,
formation of air bubble
Simple, rapid, inexpensive, high enrichment
factors, environmentally friendly, enormous
contact area between acceptor phase and sample,
fast reaction kinetics, instantaneous extraction,
complete analyte recovery, DLLME can be coupled
with SPE,SFE,SBSE, nanotechniques
Minor restrictions in solvent selection and
automation

DLLME has been successfully combined with extraction tech-
niques {e.g., SPE [45], SFE [25], SBSE [35] and some nanotechniques,
such as D-μ-SPE [55]}. Combination of D-μ-SPE with DLLME leads
to higher levels of selectivity and sensitivity, and extends the an-
alytical utility of DLLME in complex matrices [55]. Fig. 5 shows the
general protocol of DLLME with D-μ-SPE.
The analytical applications of DLLME in analysis of pesticides are
limited, since the main disadvantage of DLLME is the consump-
tion of relatively large volumes (i.e., mL) of disperser solvents, which
usually decrease the partition coefficient of analytes into the ex-
tractant solvent [12–18]. This problem is avoided by using ultrasonic
energy or cationic surfactant to disperse the extraction solvent
instead of disperser solvent [14–16].
The EF was improved to be more environment friendly with new
techniques based on DLLME with little solvent consumption (DLLME-
LSC) [14] by combining some ILs in a binary mixture of disperser
and extraction solvents [50]. Recently, some interesting modifica-
tions were introduced to avoid the problems and to expand the
analytical utility of DLLME, and there is an increasing number of
applications of DLLME techniques.
In some cases, extraction solvents with densities and toxicities
lower than those of classical solvents for DLLME have been re-
ported. Despite the feasibility of applying a low-toxicity solvent with
a density lower than that of water, the use of a high-density solvent
is still more desirable due to the simple, convenient collection of
the sedimented phase.
However, there is a limited number of applications of DLLME com-
bined with spectrochemical and electrochemical techniques for analysis
of pesticides in complex matrices. This hot research area will there-
fore attract considerable interest due to the suitability of combining
DLLME with voltammetry at a surface-modified electrode. Voltammetric
techniques (e.g., stripping analysis) have no applications with DLLME.
Most probably, analytical application of voltammetric techniques to
monitoring trace and ultra-trace concentrations of pesticides in dif-
ferent matrices would provide an efficient, low-cost, selective and
excellent approach. However, further work continues on the possible
application of on-line DLLME combined with stripping voltammetric
analysis of such chemicals in various biological and environmental
samples. Further research in this area is still needed to eliminate in-
terferences, and to reduce time and cost.

Fig. 4. Milestones in DLLME.

190 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
Fig. 5. General procedure for coupling dispersive micro solid-phase extraction (D-μ-SPE) with DLLME.
5. Limitations and outlook on the future trends of DLLME
DLLME usually requires phase separation by centrifugation. Micro-
columns packed with suitable sorbents may be used as an alternative
to centrifugation and they may open the door to automation and
on-line coupling of DLLME to analytical instruments.
Amyl acetate-CCl4-acetonitrile mixture systems are generally used
as carrier and aspirated at high flow rate, resulting in formation of
a cloudy state and the extraction of analytes.
Despite the apparent advantages of DLLME, it also has some prob-
lems [e.g., it uses high volumes (i.e., mL) of a polar solvent, it is not
completely suitable for the analysis of analytes in complex matri-
ces, centrifugation must be applied and the extraction solvent must
have a high density and low solubility in water]. The extraction and
auxiliary solvent mixture is immiscible with water and has a density
higher than that of water, so the resulting fine droplets in the mixture
containing the extracted analyte, self-sediment in a short time at
the bottom of conical tube. The use of microcolumn and centrifu-
gation are not required for separation of the extraction phase. The
procedures presented in DLLME are not simple [22–27], so further
research is necessary to complete experiments in this area.
ILs have been successfully used as suitable alternative green ex-
traction solvents to common toxic solvents [4]. However, most ILs
are incompatible with GC analysis, commercially available ILs are
too expensive and their relatively purities are below what would
be typically specified for laboratory solvents. Hence, future activi-
ties should be oriented towards development of new extraction
phases with low toxicity and good GC compatibility. Moreover, com-
plete elimination of disperser solvents is highly desirable, since most
disperser solvents are toxic and the use of organic disperser solvent
usually decreases the performance of extraction of the analyte from
the complex matrices.
DLLME is time consuming when performed in manual mode, due
to the centrifugation step. This time-consuming step can be avoided
by ST-DLLME [34] and some other types of DLLME [22,46]. In spite
of that, applications of DLLME in the analysis of pesticides remain
few.
The experimental parameters affecting uptake performance of
DLLME are usually optimized by employing a step-by-step ap-
proach, in which each factor is varied sequentially. Recent years saw
an upsurge of interest in automation of DLLME using different strat-
egies [17]. However, the complexity of the procedures presented
is far from the simplicity of DLLME, so further modifications and
improvements should be made to make more progress in automat-
ing DLLME. The technique is unsuitable when the number of
influential factors is relatively large, and a step-by-step approach
does not show the interaction among experimental parameters, so
use of experimental designs is highly recommended to achieve the
best extraction conditions quickly and in a relatively small number
of experiments.
DLLME will certainly be used for solid-state samples and con-
nected to other extraction techniques.
6. Conclusion
This review provides a snapshot of the field at this critical stage
covering the recent advances in DLLME for pesticide analysis. We
cover milestones, green aspects, advantages, and drawbacks of the
well-known protocols of DLLME. We provide a brief overview of the
principle of DLLME and manipulation and quantification methods
in droplets including chromatographic and other techniques.
DLLME is a newly developed sample-preparation technique.
However, many improvements have been introduced since its in-
novation in 2006. The rapid development of sample preparation in
the field of analytical chemistry in the past few years will contin-
ue in the foreseeable future, bringing solutions to many challenges
in current bioanalytical, pesticides and drugs analysis.
The widespread application of the DLLME technique is sup-
ported by the usefulness and the automation of the procedures.
DLLME is a clear paradigm in this approach because most of the pub-
lished articles have focused on its automation.
Application of DLLME in analysis of pesticides has received great
attention due to its low cost, high EFs, and high recoveries, and the
short time it takes. Sample preparation involving DLLME for anal-
ysis of pesticides is ecofriendly and offers several advantages, such
as ease of method development and high EFs from low volumes of
water samples, which made it available to virtually all analytical
laboratories.
In the first years of development, DLLME techniques were used
for sample pretreatment for analysis of a wide range of environ-
mental water samples. Thus, DLLME techniques may also be utilized
for green analytical chemistry, since it reduces consumption of haz-
ardous chlorinated organic solvents.
Additional advantages of the well-known protocols of the DLLME
are low instrumental costs and easy operation. DLLME is a highly
versatile sample-preparation method, because not only can it be used
for practically all classes of analytes, but also it is compatible, di-
rectly or after solvent replacement, with most enrichment techniques
(e.g. SPE, SBSE, SFE, and D-μ-SPE), in the extraction of analytes from
various aqueous samples.
 W. Ahmad et al./Trends in Analytical Chemistry 72 (2015) 181–192
The review also highlights the current best practice for analy-
sis of ultra-trace metal ions in various matrices. We also revealed
the need for low-cost methods that can easily be coupled to DLLME
and implemented.
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