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Trends in Analytical Chemistry 68 (2015) 4877

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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 achievements in solidied oating organic drop


microextraction
Pilar Vias a,*, Natalia Campillo a, Vasil Andruch b
a Department of Analytical Chemistry, Faculty of Chemistry, Regional Campus of International Excellence Campus Mare Nostrum, University of Murcia,
E-30100 Murcia, Spain
b Department of Analytical Chemistry, Pavol Jozef afrik University, SK-04154 Koice, Slovak Republic

A R T I C L E

I N F O

Keywords:
Complexation
Derivatization
Disperser solvent
Green analytical chemistry
Liquid-phase microextraction
Real sample analysis
Sample pre-treatment
SFODME
Solidied oating organic drop
microextraction
Solvent microextraction

A B S T R A C T

We give an overview of achievements in solidied oating organic drop microextraction (SFODME). We


focus on the types of analyte investigated, the types of sample analyzed, the sample-pre-treatment procedures used, including derivatization and complexation, and we cover the articles available on-line up
to 30 November 2014. SFODME has been applied to the determination of organic compounds and inorganic analytes. Although most extraction methods based on SFODME have been applied to water samples,
the technique has also been used for analysis of other types of samples. We also briey discuss the effects
of different variables. We discuss the various modalities of SFDOME. Tables summarize the applications, selected experimental conditions and the most important parameters of SFODME.
2015 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.
4.

Introduction ...........................................................................................................................................................................................................................................................
A brief history of solvent microextraction .................................................................................................................................................................................................
Principle of solidied oating organic drop microextraction ..............................................................................................................................................................
Applications to the determination of organic compounds ...................................................................................................................................................................
4.1.
Types of analyte .....................................................................................................................................................................................................................................
4.2.
Types of sample .....................................................................................................................................................................................................................................
4.3.
Sample (aqueous phase) volume .....................................................................................................................................................................................................

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Abbreviations (techniques and parameters): AA, Alcoholic-assisted; AAS, Atomic absorption spectrometry; AFS, Atomic uorescence spectrometry; BE, Back-extraction;
CAD, Charged aerosol detection; CE, Capillary electrophoresis; CLC, Capillary liquid chromatography; CV, Cold vapor; D, Displacement; DAD, Diode-array detection; DLLME,
Dispersive liquid-liquid microextraction; DMAE, Dynamic microwave-assisted extraction; DS, Directly suspended; DSDME, Directly suspended droplet microextraction; ECD,
Electron-capture detection; EF, Enrichment factor; ETAAS, Electrothermal atomic absorption spectrometry; ETV, Electrothermal vaporization; FAAS, Flame atomic absorption spectrometry; FI, Flow injection; FID, Flame ionization detection; FLD, Fluorescence detection; FPD, Flame photometric detection; GC, Gas chromatography; HF, Hollow
ber; HG, Hydride generation; HPCE, High-performance capillary electrophoresis; HPLC, High-performance liquid chromatography; ICP, Inductively coupled plasma; IP, Ion
pair; LC, Liquid chromatography; LL, Ligandless; LLE, Liquid-liquid extraction; LOD, Limit of detection; LOQ, Limit of quantication; LPME, Liquid-phase microextraction;
MAE, Microwave-assisted extraction; MS, Mass spectrometry; MS/MS, Tandem mass spectrometry; MSA, Magnetic stirring-assisted; MWCNT, Multiwalled carbon nanotube;
OES, Optical emission spectrometry; SA, Surfactant-assisted; SD, Solvent demulsication; SDME, Single-drop microextraction; SFODME, Solidied oating organic drop
microextraction; SFVCDME, Solidied oating vesicular coacervative drop microextraction; SM, Supramolecular; SPE, Solid-phase extraction; SPME, Solid-phase microextraction;
UA, Ultrasound-assisted; UAE, Ultrasound-assisted extraction; UASEME, Ultrasound-assisted surfactant-enhanced emulsication microextraction; UHPLC, Ultra-high performance liquid chromatography; USAE, Ultrasound-assisted emulsication; USAEME, Ultrasound-assisted emulsication-microextraction; UV-Vis, Ultraviolet-visible spectrometric
detection; VA, Vortex-assisted; VALLME, Vortex-assisted liquid-liquid microextraction; VASEME, Vortex-assisted surfactant-enhanced-emulsication microextraction.
Abbreviations (chemicals): APDC, Ammonium pyrrolidinedithiocarbamate; BDTA, Benzyldimethyltetradecylammonium chloride-dihydrate; BPHA, N-benzoyl-Nphenylhydroxylamine; 5-Br-PADAP, 2-(5-Bromo-2-pyridylazo)-5 diethylaminophenol; BTEX, Benzene, toluene, ethyl benzene and xylene; CTAB, Cetyltrimethylammonium
bromide; DAB, 3,3-Diaminobenzidine; DDTC, Diethyldithiocarbamate; DDTP, Diethyldithiphosphate; DMF, Dimethylformamide; DMSO, Dimethylsufoxide; DPC,
1,5-Diphenylcarbazide; EDC, Endocrine-disrupting compound; Fmoc-Cl, 9-Fluorenylmethyl chloroformate; HDEHP, Di-2-ethylhexylphosphoric acid; HOC, Halogenated organic
compound; HQ, Hydroxy quinoline; IBCF, Isobutyl chloroformate; iBuOH, 2-Methyl-1-propanol; IL, Ionic liquid; OCP, Organochlorine pesticide; OPE, Organophosphate ester;
PAH, Polycyclic aromatic hydrocarbon; PAN, 1-(2-Pyridylazo)-2-naphthol; PBDE, Polybrominated diphenyl ether; PCB, Polychlorinated biphenyl; PE, Phthalate ester; SDBS,
Sodium dodecylbenzenesulfonate; SDS, Sodium dodecylsulfate; THF, Tetrahydrofuran; THM, Trihalomethane; TTA, 2-Thenoyltriuoroacetone.
* Corresponding author. Tel.: +34 868 887 415; Fax: +34 868 887 682.
E-mail address: pilarvi@um.es (P. Vias).
http://dx.doi.org/10.1016/j.trac.2015.02.005
0165-9936/ 2015 Elsevier B.V. All rights reserved.

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

5.

6.

7.

4.4.
Sample pre-treatment ..........................................................................................................................................................................................................................
4.5.
Application of derivatization in solidied oating organic drop microextraction (SFODME) ....................................................................................
4.6.
Salt addition and pH .............................................................................................................................................................................................................................
4.7.
Extraction temperature .......................................................................................................................................................................................................................
4.8.
Figures of merit ......................................................................................................................................................................................................................................
Applications to the determination of inorganic compounds ...............................................................................................................................................................
5.1.
Types of analyte .....................................................................................................................................................................................................................................
5.2.
Sample (aqueous phase) volume .....................................................................................................................................................................................................
5.3.
Sample pre-treatment ..........................................................................................................................................................................................................................
5.4.
Application of complexation in SFODME ......................................................................................................................................................................................
5.5.
Salt addition and pH .............................................................................................................................................................................................................................
5.6.
Extraction temperature .......................................................................................................................................................................................................................
5.7.
Figures of merit ......................................................................................................................................................................................................................................
Different modalities of solidied oating organic drop microextraction ........................................................................................................................................
6.1.
Nature and volume of the extraction solvent ..............................................................................................................................................................................
6.1.1.
Organic compounds ..............................................................................................................................................................................................................
6.1.2.
Inorganic compounds ..........................................................................................................................................................................................................
6.2.
Selection of the disperser solvent for DLLME-SFO .....................................................................................................................................................................
6.3.
Stirring rate ..............................................................................................................................................................................................................................................
6.4.
Extraction time .......................................................................................................................................................................................................................................
6.5.
Disruption of the cloudy solution ....................................................................................................................................................................................................
Concluding remarks and future trends ........................................................................................................................................................................................................
Acknowledgments ...............................................................................................................................................................................................................................................
References ..............................................................................................................................................................................................................................................................

1. Introduction
An inevitable requirement in modern chemistry is that chemical procedures have the least possible impact on the environment
[1]. Analytical chemistry is no exception to this trend [24]. An analytical procedure comprises several steps, and sample pre-treatment
is probably the most laborious and tedious of them. The development of novel, simple, green and low-cost sample pre-treatment
procedures has therefore been an important topic in this area over
the past two decades.
In the mid-to-late 1990s, Dasgupta and co-workers published a
remarkable series of papers on the potential application of a
microdrop. They demonstrated the usefulness of the unique features of liquid drops through a series of novel liquid-drop-based
systems [510]. These works can be considered as the beginning of
miniaturization in analytical chemistry. Miller and Synovec also discussed various aspects of drop-based analytical measurements [11].
Another interesting, challenging task is automation, the direct coupling of the sample preparation step with the detection system.
Automated systems offer a number of advantages, such as minimizing the errors associated with manual handling, reducing consumption
of sample and reagent, and improving sensitivity and precision.
Liquid-liquid extraction (LLE) is among the oldest preconcentration
and separation techniques. However, in a conventional design, LLE
has many well-known drawbacks and limitations, the most important of which are the large volumes of sample and extraction solvent
required, and consequently the large amount of waste generated,
as well as the low preconcentration factors provided, making necessary the evaporation of the extract to dryness and the subsequent
re-dissolution in a smaller volume.
Some earlier attempts to miniaturize LLE can be found at the end
of the twentieth century. Liu and Dasgupta reported a drop-indrop system, in which the aqueous phase was continuously delivered
to the surface of a drop and was aspirated away from the bottom
part of it; thus, the organic drop (1.3 L) was enclosed in the aqueous
drop. The feasibility of the suggested arrangement was demonstrated by the determination of an anionic surfactant through the
formation of an ion associated with Methylene Blue reagent and its
extraction into chloroform [12].
Jeannot and Cantwell reported another approach to miniaturization of solvent microextraction: a small drop (8 L) of a waterimmiscible organic solvent was located at the end of a Teon rod

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63
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71
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immersed in a stirred aqueous sample solution. After the extraction, the probe was withdrawn from the aqueous solution, and the
organic phase injected into an analytical instrument for quantication
[13].
There are several valuable, well-founded review articles devoted
to solvent microextraction; Table 1 lists a selection. However, until
now, only two review articles have directly addressed solidied oating organic drop microextraction (SFODME) [29,30]. In them, the
authors focused on the experimental factors that affect the extraction eciency and the coupling of SFODME with various detection
techniques, such as gas chromatography (GC), liquid chromatography (HPLC, LC), atomic absorption spectrometry (AAS) and
inductively-coupled plasma optical emission spectrometry (ICPOES), so we do not include these aspects of SFODME here.
Our review focuses on the types of analyte and sample analyzed using SFODME and includes articles available up to 30
November 2014. Tables summarize the application of SFODME.
2. A brief history of solvent microextraction
Numerous variations of solvent microextraction have already been
developed, including single-drop microextraction (SDME) [31,32],
hollow-ber liquid-phase microextraction (HF-LPME) [33], dispersive liquid-liquid microextraction (DLLME) [34,35], solidied oating
organic drop microextraction (SFODME) [36], ultrasound-assisted
emulsication-microextraction (USAEME) [37], ultrasound-assisted
surfactant-enhanced emulsication microextraction (UASEME) [38],
directly suspended droplet microextraction (DSDME) [39,40] and
vortex-assisted liquid-liquid microextraction (VALLME) [41].
Electrodriven LME techniques have high eciency in the extraction of charged analytes in short times [26].
Until now, the majority of papers have reported manually performed solvent-microextraction procedures. However, several articles
can be found describing procedures with various levels of automation (from semi-automated to fully automated); we discussed recent
efforts at automation of solvent microextraction in a previous paper
[42]. We therefore list certain procedures here, but we do not discuss
them in detail.
Anthemidis et al. suggested automated DLLME, in which the droplets of organic phase containing a complex of the analyte are retained
on a microcolumn [43,44], while a different option is based on a
ow-batch approach [45,46]. Another eld of study has been

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P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Table 1
Selected review articles devoted to solvent microextraction (arranged chronologically)
First Author

Year

Topic/Title

Ref.

Miller

2000

[11]

Anthemidis

2009

Dadfarnia
Rezaee

2010
2010

Sarafraz-Yazdi
Asensio-Ramos
Mahugo-Santana

2010
2011
2011

Tankiewicz

2011

Cruz-Vera

2011

Abadi

2012

Pic

2013

Delgado-Povedano

2013

Kokosa

2013

Hu

2013

Spietelun

2014

Bosch Ojeda

2014

Review of analytical measurements


facilitated by drop formation technology
Homogeneous and dispersive liquidliquid extraction for inorganics
LPME, determination of metals
Evolution of dispersive liquid-liquid
microextraction method
Liquid-phase microextraction
LPME, applications in food analysis
LPME, determination of emerging
pollutants
Solventless and solvent-minimized
sample preparation techniques
Sample treatments based on dispersive
(micro)extraction
LPME combined with UV-Vis
spectrophotometry
Ultrasound-assisted extraction for food
and environmental samples
Ultrasound-assisted emulsicationextraction
Advances in solvent-microextraction
techniques
LPME, analysis of trace elements and
their speciation
Green aspects, developments and
perspectives of LPME techniques
Vortex-assisted liquidliquid
microextraction

[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]

3. Principle of solidied oating organic drop microextraction


An aliquot of sample solution is put into a suitable glass vessel.
A 1-L volume of an appropriate extraction solvent is added, usually
by rapid injection into the aqueous sample using a syringe, or, alternatively, it can be placed on the sample surface at the center of
the vortex in DS-SFODME [39,40,52,53]. The extractions solvent should
satisfy not only the general criteria for an extraction solvent in LLE,
but also the one specic criteria of SFODME, namely, it should have
a melting point near room temperature, in the range 1030C. The
solution is then agitated (usually by magnetic stirring) for a prescribed period of time; it is in this step that the analytes are extracted
into the organic phase. After centrifugation, the glass vessel is immersed in an ice water bath, and the oated organic solvent solidies
after a short period of time. Afterwards, the solidied solvent is transferred to a conical vial using a small spatula, quickly melted at room
temperature and injected (as a whole, as an aliquot or after proper
dilution) into the analytical instrument for quantication. Besides
magnetic stirring, sample agitation can be performed using ultrasound energy (USAE-SFODME) [54] or vortex mixing (VA-SFODME)
[55], or agitation can be replaced by application of a disperser solvent
(DLLME-SFO) [56] and enhanced by manual shaking [57] or using
surfactants (SA-SFODME) [58].
The application of SFODME to the determination of organic and
inorganic compounds is summarized in Tables 2 and 3, respectively.

[28]

4. Applications to the determination of organic compounds


4.1. Types of analyte
automation of SDME [47,48]. Mitani et al. described on-line LPME
based on a drop-in-plug sequential injection lab-at-valve platform for metal determination [49], while Burakham et al. applied
the lab-at-valve system for the development of on-line LPME procedures [50,51].
SFODME, like other solvent microextraction techniques, quickly
attracted the attention of researchers and remains very popular
among analytical chemists, as evidenced by its appearance in a continually growing number of original papers (Fig. 1).

The majority of SFODME procedures reported until now (61%)


have been devoted to the determination of organic analytes. The
technique has been applied to the determination of various classes
of organic compounds that are widely used in different areas of
human activity, but at the same time they (or their metabolites) may
pose risks (Fig. 2).
Persistent organic compounds are of worldwide concern, because
some of them are recognized as potential carcinogens and show tumorigenic and endocrine-disrupting activities in mammals. They

Fig. 1. The distribution of articles devoted to solidied oating organic drop microextraction (SFODME) from 2007 to 2014 (30 November) (Based on the data in Tables 2
and 3).

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

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Fig. 2. Applications of solidied oating organic drop microextraction (SFODME) to the determination of organic compounds.

exist ubiquitously in the atmosphere, soil, water and food {e.g., polycyclic aromatic hydrocarbons (PAHs) [36,5961]; halogenated organic
compounds (HOCs) [56]; trihalomethanes (THMs) [62,63]; polychlorinated biphenyls (PCBs), considered to be target compounds
of environmental regulations [6466]; volatile aromatic hydrocarbons, such as benzene, toluene, ethyl benzene and xylene (BTEX)
[6770]; nitrobenzene isomers [71,72]; mono nitrotoluenes [73];
aliphatic amines [74]; aromatic amines, including aniline and other
substituted derivatives [75]; and, chlorinated anilines [76]}.
Another group of analytes comprises ame-retardants {e.g., organophosphate esters (OPEs) [77], decabrominated diphenyl ether
[78] and polybrominated diphenyl ethers (PBDEs)}, which are well
known for their anti-aming properties [79,80].
Phthalate esters (PEs) are polymer additives and plasticizers that
can migrate from the material to the environment and, consequently, pollute water, soil, air and food products [8184]; esters of
p-hydroxybenzoic acid, commonly known as parabens, are widely
used as preservatives [85]; and, methyl methacrylate [86],
benzotriazole ultraviolet stabilizers [87] and volatile aldehydes, recognized as biomarkers of cancers [88], have also been determined
after pre-concentration by SFODME.
Phenolic compounds are released in aquatic environments as pollutants during the production of plastics, drugs, pesticides and
petrochemicals. An EC directive [57] species a legal tolerance level
of 0.1 g L1 for each phenolic compound and 0.5 g L1 for the sum
of all compounds in water intended for human consumption, and
different methods have been proposed for determining phenols
[8994], nitrophenolic compounds [57] and alkylphenols [95].
Pesticides provide many benets for increasing agricultural production, but their presence in water is strictly regulated by legislation
to concentrations in the range <10100 ng L1. Several types of pesticides have been determined using SFODME {e.g., organophosphorus
pesticides [96101], OCPs [65,66,102106], pyrethroids [65,66,
107109], triazole and triazine herbicides [110115], neonicotinoids
[116], fungicides [52,117126] or pesticide mixtures [61,127130].
Different types of drugs have also been determined using SFODME
techniques {e.g., endocrine-disrupting compounds (EDCs) [131135],
growth promoters [136], lovastatin and simvastatin [137], nicotine and cotinine (which are considered as biological markers of
exposure to tobacco smoke) [138], duloxetine [139], antibiotics, such
as kanamycin [140], macrolide antibiotics [141] and sulfonamides
[61], haloperidol [142], antifungal drugs [143], opiates and their derivatives [144], antidepressant drugs [145,146], amphetamines
[58,147], carvedilol [148], propanolol [149], and compounds containing a pyrazole ring [150]}.

Cork taint, which is one of the most common, unpleasant offavors found in wine, is mainly caused by the appearance of
haloanisoles and halophenols [151,152]. Biogenic amines, which are
markers for levels of microbiological food contamination, are found
in many foods and alcoholic beverages [153]. Flavonoids are polyphenolic compounds that play an important role as potent natural
antioxidants [154], and quercetin is one of the most abundant avonoids present in fruits and vegetables [155]. Other antioxidants
include tanshinones [156], as well as lignans [157].
Vitamins are essential to the health of humans and other vertebrates. Methods have been proposed for determining fat-soluble
vitamins [158], -carotene [159] and hydrosoluble vitamins {e.g.,
thiamine and cobalamine [160]}.
Amino acids exhibit structural diversity and high polarity, so their
analysis has been a respectable testing eld for any novel analytical method [161]. Sudan dyes have been widely used as organic
colorants in all aspects of the chemical industry, though they represent a threat to public health once they enter the food chain [162].
4.2. Types of sample
Most extraction methods based on SFODME have been applied
to the analysis of water samples due to the simplicity of this matrix,
representing 48.1% of the total number of studies surveyed. However,
the application of the technique in other elds increased in recent
years. For more complex samples, due to the interaction of the matrix
components with organic solvents, it is more dicult to obtain a
oating organic drop appropriate for injection in chromatography,
and, as a result, sample pre-treatment is essential.
Other types of sample analyzed include soil and sediments, each
of which represents 2.3% of the samples analyzed. Applications to
biological uids included urine (12%) and serum, plasma or blood
(9%). Food analysis is an emerging area, and a great variety of matrices analyzed (23.3%). The technique has been applied to the
analysis of cosmetics and personal-care products (3%).
4.3. Sample (aqueous phase) volume
Decreasing the ratio of organic solvent volume to sample volume
increases the preconcentration factor. The sample volume can also
inuence the convection eciency and may inuence the extraction eciency in given extraction times. In most cases, the volumes
of samples were in the range of 520 mL. Typically, the largest analytical response was obtained at a sample volume of 20 mL. Upon
further increasing the sample volume, the relative peak areas

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P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

decreased, because, when stirring the solution at a xed rate with


a completely lled vial, convection is insucient in the aqueous
phase, resulting in less extraction. Nevertheless, one can also nd
articles in which higher sample volumes, such as 25 mL [96], 30 mL
[67,97,107], 40 mL [79] or even 200 mL [132], and 210 mL [106], were
chosen as optimal.
4.4. Sample pre-treatment
The treatment for water samples normally includes only ltration and, in some cases, adjusting the pH and adding a salt.
A combination of solid-phase extraction (SPE) and DLLME-SFO
was designed and employed for sample preparation of organic compounds from water samples. The use of this combination enabled
lower limits of detection (LODs) and higher enrichment factors (EFs)
to be achieved. The SPE column is a key factor in the isolation and
purication eciency of the target analytes. Multiwalled carbon
nanotubes (MWCNTs) were chosen as the sorbent to isolate and to
concentrate OCPs because of their large surface area [106]. Also, other
SPE conditions, including the ow rate of the sample solution, the
breakthrough volume, the types and the volume of eluting solvent
and the salt concentration, were also tested in order to achieve acceptable recoveries upon extraction of large volumes (210 mL) of
samples for environmental estrogens [132].
The treatment of soil samples includes extraction with water and
sonication [112,140]. For sediments, extraction with water and
shaking [78], or extraction with methanol and sonication [80,120]
were applied.
For urine samples, most procedures included using a supernatant after centrifugation, adjusting the pH value, sometimes dilution
with water or an organic solvent, such as acetonitrile, and adding
a salt. After shaking and centrifugation, the extract can be used as
the sample for the SFODME step [58,79,90,93,98,136138,141143,
146,147,150,158]. Most treatments for serum samples included adjusting the pH value, sometimes dilution with water or an organic
solvent to remove proteins, and the addition of a salt. After shaking
and centrifugation, the extract can then be used as the aqueous phase
for the SFODME step [88,93,142144,146,148,150,159].
For food samples, procedures required:

only ltration and centrifugation, or dilution with water for fruit


juices, wine and honey [52,66,110,115,116,121,122,124,126,128,
151153,158,163];
extraction with an organic solvent and centrifugation [162];
extraction with an organic solvent and microwave-oven digestion for fruits [66,117] and cereals [113];
extraction with an organic solvent and sonication for tomato
[130], fruits and vegetables [155], summer crops [101] or tea
[109]; and,
using water and sonication for tobacco [161].

Due to its advantages over traditional techniques, the QuEChERS


method was the most common method employed for sample preparation; it was used for analysis of fungicides in grapes [123].
Traditional Chinese medicines were simply submitted to SFODME
or diluted with water [154,156,157]. For cosmetics, the treatment
included extraction with an organic solvent and dilution with water
[82], or the use of an organic solvent and an acid, assisted by sonication [85].
4.5. Application of derivatization in solidied oating organic drop
microextraction (SFODME)
Sometimes a derivatization step is needed prior to detection.
When using HPLC with uorescence detection (FLD), derivatization
was included for estrogenic hormones using p-nitrobenzoyl chloride

at 35C [131,133] and 9-uorenylmethyl chloroformate at pH 8.5 for


detection of kanamycin in wastewater and soil samples [140].
When using UV detection, volatile aldehyde biomarkers in human
blood samples used 2,4-dinitrophenylhydrazine as a derivatization
reagent and formic acid as a catalyzer, and biogenic amines [153]
were derivatized using p-benzoyl chloride at pH 10.
Amino acids were derivatized with isobutyl chloroformate (IBCF)
in aqueous solution, extracted and then determined in tobacco
samples using GC and mass spectrometry (MS) detection [161]. The
use of GC also required a previous derivatization step to convert polar
and non-volatile analytes into volatile derivatives, so this step was
carried out for phenolic compounds [91] and for haloanisoles and
halophenols using acetic anhydride and potassium carbonate [151].
4.6. Salt addition and pH
The salting-out effect has been used universally in LLE and solidphase microextraction (SPME). Sodium chloride was added into the
sample solution to increase the ionic strength, to decrease the solubility of the analytes in the sample solution and to enhance the
extraction eciency. However, the decrease in extraction eciency observed at higher salt concentrations can be explained by the
addition of a salt being able to restrict the transport of the analytes
to the extracting drop due to the increase in sample viscosity. By
increasing the salt concentration, the diffusion of analytes towards
the organic solvent becomes more and more dicult. In addition,
NaCl dissolved in water might change the physical properties of the
Nernst diffusion lm and thus reduce the rate of diffusion of the
target analytes into the drop.
Frequently, the effect of salt addition on extraction eciency was
evaluated by increasing the NaCl concentration up to 30% (w/v). In
some studies, the extraction eciency of the analytes was not
changed by increasing the concentration of NaCl, and so it ceased
being used (32% of the total published studies). Other experiments showed an increase in the extraction eciency in the presence
of salt, so values in the range 130% (w/v) NaCl were selected.
The value of pH plays a signicant role in the extraction of ionizable compounds. Thus, very different pH values were selected in
different applications {e.g., pH 3 for quercetin [155]; pH 4 for pyrethroids [109]; pH 2 [91], 4 [90], 5 [93] or 6 [92,94] for phenolic
compounds; pH 5 [127] or 6 for triazole fungicides [114]; pH 5 for
decabrominated diphenyl ether [78]; pH < 6 for benzotriazole ultraviolet stabilizers [87]; pH 6 for OCPs [104,105], parabens [85],
synthetic antioxidants [163] and estrogens [134]; pH > 6 for
pyrazoline derivatives [150]; pH 6.4 [58] and pH 10.2 [147] for amphetamines; pH 7 for methyl methacrylate [86], fungicides [120,124],
insecticides [128] and OCPs, PCBs and pyrethroid pesticides [65];
pH 7.6 for haloanisoles and halophenols [151]; pH 8.5 for kanamycin [140] and antifungal drugs [143]; pH 9 for nicotine, cotinine [138]
and opium alkaloids [144]; pH 10 for lovastatin [137] and haloperidol [142]; pH 11 for herbicides [112], anilines [75] and
chloroanilines [76]; and, pH 12 for carvedilol [148], volatile aldehydes with formic acid [88], chlorpyrifos with 0.2% (v/v) acetic acid
[97], nitrophenols in 0.8 M HCl [57], neonicotinoids in HCl [116],
aliphatic amines in 3% (w/v) NaHCO3 [74], macrolide antibiotics with
sodium carbonate [141] and antidepressant drugs with KOH [146]}.
4.7. Extraction temperature
Generally, in LPME experiments, higher EFs can be obtained by
increasing the temperature, because heating facilitates the mass
transfer of analytes from the sample to the organic solvent and
thus increases the eciency of the extraction. Normally, a simple
water bath was employed to heat the sample solution. The effect
of sample-solution temperature on extraction eciency was typically studied in the range 1080C. Results showed that, by

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

increasing the temperature, the extraction eciency was increased up to a maximum value near 5070C. However, in other
cases (70% of the studies), values near room temperature up to
40C were selected.

4.8. Figures of merit


Table 2 sets out the linearity and the LODs obtained in the
SFODME methods developed for organic analytes.

53

5.2. Sample (aqueous phase) volume


For the volume of the aqueous phase submitted to the SFODME
procedure, the most frequently selected values (in ~87% of cases)
were 525 mL, though some authors used volumes as high as 100 mL
[194,205,207] and 160 mL [192], while intermediate values were
4060 mL [168,182,216,229]. However, such volumes can lead to
diculties with phase separation due to the solubility of the organic
solvent in an aqueous sample.

5.3. Sample pre-treatment


5. Applications to the determination of inorganic compounds
5.1. Types of analyte
Inorganic analytes have also been preconcentrated using SFODME,
although there have been fewer applications than those for organic
compounds. A total of 30 elements have been preconcentrated by
applying classic SFODME or one of its variants (Fig. 3).
Aluminum [165,166], thallium [167169], lead [170179] and
bismuth [179] are the metals from columns 1315 in the Periodic
Table of Elements that have been determined. Antimony [180182],
arsenic [183186], selenium [187190] and tellurium [191] are the
metalloids that have been microextracted using SFODME. With respect
to the transition metals, cadmium [177,179,192196], chromium
[178,197199], cobalt [178,179,199204]], copper [199,204214],
gold [169,215], iron [166,214,216,217], manganese [199,218], mercury
[179,219,220], molybdenum [55,221], nickel [178,196,203,204,222],
palladium [179,223225], rhodium [226], silver [227,228], vanadium [229,230], yttrium [231], zinc [54,213] and zirconium [232]
have all been quantied using SFODME. Several lanthanides europium [233], dysprosium [231], lanthanum [233] and ytterbium
[233] and the actinide uranium [234] have all been determined
in different types of sample. Copper has been the element most
studied using the SFODME technique, followed by lead, cobalt and
cadmium.
Most of the proposed methods have been developed for the determination of the total metal content; nevertheless, several of them
include speciation studies. Thus, the speciation of antimony [181,182],
arsenic [183186], chromium [198], iron [217], selenium [190] and
thallium [168] has been carried out by submitting the sample to
chemical reactions in order to change the oxidation state of the
analyte. Readers can also nd some details in the last paragraph of
sub-section 5.6 (below). The quantication of iron in its two oxidation states has been achieved by Moghadam et al. [216] using
chemometric methods.

The simplicity of water samples means that, in many cases, there


is no need for sample pre-treatment prior to preconcentration. Filtration to remove particulate matter from a suspension, especially
for environmental water, and, in some cases, acidication in order
to prevent adsorption of the metal ions on the inner ask walls, are
the unique treatments carried out. Water samples are generally ltered through 0.45-m pore-size membrane lters shortly after being
collected; they are then kept at 4C until needed for analysis. Several
authors recommend that the plastic and glass materials used in the
analysis be maintained in acid over 24 h and then rinsed with highpurity water; such a practice is very common in all metal-analysis
procedures [54,179,189].
Even though, for most SFODME procedures, the matrix of water
samples does not inuence the analysis, Dadfarnia et al. [188] found
a relatively high degree of interference in the speciation of selenium in waters. They proposed using cation-exchange resins to
remove the interfering metals. The combination of the SPE and
SFODME steps has been proposed as an ultra-preconcentration technique [185] for the determination of arsenic in water, increasing the
sensitivity with respect to similar determinations [186] since the
preconcentrated sample volume is increased considerably. In this
case, the SPE eluate is used as a disperser solvent.
Minimal sample treatment has been proposed for beverage and
urine samples, as their matrices, slightly more complex than waters,
did not prevent microextraction being accomplished. Filtration is
also the only treatment required for beverages [196,209], as is centrifugation prior to ltration for urine samples [198].
When dealing with solid samples, the analytes need to be extracted from the matrices in order to obtain solutions suitable for
SFODME. Wet digestion by mixtures of mineral acids and, occasionally, hydrogen peroxide is the most widely used technique
[168,169,175,191,195,196,210,211,214,220,221,225,226,228]. Sometimes, digestion is assisted by microwaves [55,190,233], thus
decreasing the risk of contamination or analyte loss as well as

Fig. 3. Applications of solidied oating organic drop microextraction (SFODME) to the determination of inorganic compounds.

54

Table 2
Applications of solidied oating organic drop microextraction (SFODME) to the determination of organic compounds (arranged in alphabetical order)
Analyte

Sample

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Alachlor and atrazine

Water

DLLME-SFO

HPLC-UV

5 mL water; pH 5; 1% (w/v) NaCl

LR: 0.1200 g L1
LOD: 0.020.05 g L1

[127]

Aliphatic amines

Water (environmental)

DLLME-SFO

HPLC-DAD

5 mL water; 3% (w/v) NaHCO3

LR: 0.05500 and 0.1


500 g L1
LOD: 0.0050.02 g L1

[74]

Alkylphenols

Water (lake, river)

SFODME

UPLC-UV

5 mL water; 1.5 g NaCl

Tobacco

DLLME-SFO

GC-MS

Amphetamine and
methamphetamine

Urine

VASEME-SFO

HPLC-UV

1 g ground tobacco; 10 mL water; sonication


bath, 10 min; centrifugation, 5 min,
4000 rpm; ltration; 2 mL sample; 80 L
iBuOH-pyridine mixture (3:1, v/v) and 60 L
IBCF; sonication, 1 min; without salt
addition
Urine diluted to 1:5, using water
Sample: 5 mL; pH 6.4; 0.3% (w/v) NaCl

LR: 1500; 21000;


5500 ng mL1
LOD: 0.21.5 ng mL1
LR: 0.5200 g mL1
LOD: 0.122.82 g mL1

[95]

Amino acids

1 mL acetone with 30 L 1-undecanol;


centrifugation, 5000 rpm, 4 min; cooling,
ice bath, 4 min; 25 L injected
20 L 1-undecanol; 1 mL acetonitrile;
16 L PITC; water bath, 45C; shaking,
2 min; centrifugation, 4000 rpm, 3 min;
cooling, ice bath, 5 min; 10 L injected
10 L 1-hexadecanethiol; manual shaking,
90 sec; centrifugation, 5000 rpm, 2 min;
cooling, 5 min; 20 L injected
40 L 2-dodecanol; 500 L acetone;
shaking, 2 min; centrifugation, 5000 rpm,
3 min; cooling, ice bath, 5 min; 1 L
injected

LR: 102000 g L1
LOD: 2 and 3 g L1

[58]

Amphetamines

Human urine

DLLME-SFO

HPLC-UV

LR: 103000 g L1
LOD: 28 g L1

[147]

Anilines

Water (tap, river)

DLLME-SFO

GC-MS

2 mL urine to 5 mL with water;


centrifugation, 10 min, 5000 rpm; ltration
of supernatant; dilution to 5 mL using 2%
(w/v) K2CO3 solution; pH 10.2
5 mL water; pH 12; ltration

31 L 1-undecanol; 56.5 L (70 g L1)


SDS; vortex mixing, 5000 rpm, 30 s;
centrifugation, 4000 rpm, 5 min; cooling,
ice bath, 5 min; 20 L injected
30 L 1-undecanol; 300 L acetonitrile;
centrifugation, 5000 rpm, 4 min; cooling,
ice bath, 5 min; 25 L injected

LR: 0.5200 g L1
LOD: 0.070.29 g L1

[75]

Antidepressant drugs

Water (tap, drinking, lake)

DLLME-SFO

GC-MS

5 mL water; 0.5 g NaCl; ltration

LR: 0.040.12 g mL1


LOD: 0.00850.0285 g mL1

[145]

Antidepressant drugs

Human urine and plasma

USAE-SFODME

HPLC-UV

Plasma and urine diluted at ratios of 1:4 and


1:1 with water; 5 mL; 0.5 M KOH; 5% (w/v)
NaCl

LR: 101000 g L1
LOD: 3 g L1

[146]

Antifungal drugs

Plasma and urine

SFODME

HPLC-DAD

LR: 0.1300 g L1
LOD: 0.010.1 g L1

[143]

Benzene, toluene, xylene

Water (river, lake, sewage)

SFODME

GC-FID

2 mL plasma or urine mixed with


acetonitrile at 1:2 ratio; stirring, 10 min,
1200 rpm; centrifugation, 15 min,
5000 rpm; transparent solution diluted to
8 mL with water; pH 8.5; 7% (w/v) NaCl
30 mL water; without salt addition

15 L cyclohexane; 0.5 mL ethanol;


centrifugation, 5000 rpm, 3 min; cooling,
ice bath, 5 min; 1 L injected
30 L n-hexadecane; 0.5 mL acetonitrile;
centrifugation, 3500 rpm, 7 min; cooling,
ice bath, 5 min; 2 L injected
30 L 1-undecanol; sonication, 20 min,
35 kHz, 320 W; centrifugation, 3500 rpm,
3 min; cooling, ice bath; mixed with
mobile phase in the ratio 1:1 v/v; 20 L
injected
10 L 1-dodecanol; stirring, 550 rpm,
35 min, 57C; cooling, ice bath, 5 min

LR: 0.01100 g mL1


LOD: 0.050.10 ng mL1

[67]

BTEX

Water

SFODME

GC-FID

10 mL water; without salt addition

LR: 0.02300 g L1
LOD: 0.070.18 g L1

[68]

BTEX

Water (tap, well, river)

SFODME

GC-FID

5 mL; without salt addition; ltration

LR: 0.20400 g L1
LOD: 0.040.09 g L1

[69]

BTEX

Water and snow

SFODME
DLLME-SFO

GC-FID

8 mL water; 0.2 g mL1 NaCl

15 L n-decanol; stirring, 400 rpm, 30C,


30 min; cooling, ice bath, 10 min; 1 L
injected
15 L 1-undecanol; stirring, 1200 rpm,
15 min, 40C; cooling, ice bath; 2 L
injected
20 L 1-undecanol; stirring, 35C; cooling,
ice bath; centrifugation, 5000 rpm, 3 min;
2 L injected
SFODME: 20 L 1-undecanol; stirring,
400 rpm, 60 min; cooling, ice bath, 5 min.
DLLME-SFO: 20 L 1-undecanol; 0.48 mL
acetone; stirring, 5000 rpm, 2 min;
cooling, ice bath, 5 min; 1 L injected

LR: 0.5210 g mL1


LOD: 0.150.31 g L1

[70]

[161]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

(continued on next page)

Table 2 (continued)
Analyte

Sample

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Benzotriazole ultraviolet
stabilizers
Benzoylurea insecticide

Seawater

VA-DLLME-SFO

HPLC-MS/MS

5 mL water; pH < 6; 8% (w/v) NaCl

IL-SFODME

HPLC-UV

50 mL juice; centrifugation, 4000 rpm,


10 min; supernatant ltered
Sample: 8 mL; 2% (w/v) NaCl; pH 7

LR: up to 25 g L1
LOD: 0.0010.090 g L1
LR: 0.5500 g L1
LOD: 0.030.28 g L1

[87]

Fruit juice

Beta-carotene

Human serum

DLLME-SFO

HPLC-UV

1 mL serum; 3 mL acetone; centrifugation,


10 min, 4000 rpm; 0.2 M NaNO3; 1.2 mL
acetone extract to DLLME

LR: 0.055 mg L1
LOD: 0.08 g mL1

[159]

2-agonists

Bovine urine

VA-DLLME-SFO

CE-UV

LR: 0.1510.0 mg L1 and


151000 g L1
LOD: 1.8037.0 g L1

[136]

Biogenic amines

Alcoholic beverages (wine,


rice wine, beer)

VA-DLLME-SFO

LC-UV

LR: 0.058.0 g mL1


LOD: 0.0050.01 g mL1

[153]

Bisphenol A

Water (environmental)

AA-DLLME-SFO

HPLC-UV

4 mL bovine urine; ltration; adjust pH 10.5


using 0.1 M NaOH; mix with acetonitrile at
2:1 (v/v) ratio; add 1 g NaCl; vortex mixing,
30 s; centrifugation, 1 min, 5000 rpm; 1 mL
extract to DLLME
Beverage diluted to 1:101:20 (v/v) in
water; ltration
Sample: 2 mL; 1 mL 0.5 M borate buffer
pH 10; 125 L 3% benzoyl chloride in
acetonitrile; sonication, 30 min, 30C
Water; 22% (w/v) NaCl

20 L 1-dodecanol; 400 L methanol;


vortex mixing, 2 min
50 L 1-dodecanol; 10 L [P14,6,6,6]PF6;
45C; stirring, 1000 rpm, 20 min and
750 rpm, 10 min; centrifugation, no need;
solvent collection; cooling, ice bath, 5 min;
diluted with 40 L ethanol
30 L 2-decanol; 1.2 mL acetone extract;
centrifugation, 4000 rpm, 5 min; cooling,
ice bath; mixed with 200 L acetone; 25 L
injected
50 L 1-undecanol; 1 mL acetonitrile
extract; 5 mL water; vortex mixing, 30 s;
centrifugation, 5000 rpm, 5 min; cooling,
20C
BE: pH 2; 15 L injected
50 L 1-dodecanol; 450 L methanol;
vortex mixing, 1 min; centrifugation,
3600 rpm, 5 min; cooling, ice bath, 10 min;
diluted to 90 L with methanol; 20 L
injected
158 L 1-octanol; 500 L methanol

[89]

Bisphenol A

Water and urine

VA-DLLME-SFO

CE-UV

LR: 1100 g L1
LOD: 0.10 g L1
LR: up to 100 g L1
LOD (g L1): 0.8 (water) and
2.5 (urine)

Carbamate and
Peach juice drink
benzoylurea insecticides
Carvedilol
Human plasma

SFODME

HPLC

LR: 0.0110.0 g mL1

[129]

DLLME-SFO

FLD

75 L 1-undecanol; 0.5 mL acetonitrile;


centrifugation, 6000 rpm, 5 min; cooling,
ice bath, 10 min; methanol to 1 mL

LR: 40300 ng mL1


LOD: 18 ng mL1

[148]

Chlorinated anilines

Water (environmental)

USAE-SFODME

HPLC-UV

LR: 0.05500 ng mL1


LOD: 0.010.1 ng mL1

[76]

Chlorpyrifos

Water (environmental)

DLLME-SFO

GC-FPD

25 mL water; 0.5 g NaCl

LR: 0.054 g L1
LOD: 0.02 g L1

[96]

Chlorpyrifos and its main Water


degradation product TCP

DLLME-SFO

HPLC-UV

30 mL water; 0.2% (v/v) acetic acid;


ltration; 3.75 g NaCl; 40C

LR: 150 g L1
LOD: 0.100.12 g L1

[97]

Chlorpyrifos and its oxon


metabolite

SFODME

GC-MS

5 mL urine; without salt addition; ltration

LR: 0.055.0 ng mL1


LOD: 3.84.8 ng L1

[98]

DLLME-SFO

HPLC-UV

0.1 g sediment; 10% (w/v) NaCl; 7 mL water;


shaking; pH 5 with HCl

60 L 1-dodecanol; sonication, 2 min,


43 kHz, 80 W; centrifugation, 4000 rpm,
6 min; cooling, ice bath, 2 min; diluted
with mobile phase (1:1)
40 L 1-dodecanol; 1.5 mL methanol;
stirring, 5 min; centrifugation, 3400 rpm,
3 min; cooling, ice bath; dissolved with
60 L ethyl acetate
70 L 1-dodecanol; 1 mL methanol;
stirring, 11 min; centrifugation, 3400 rpm,
3 min; cooling, ice bath; dissolved with
70 L methanol; 100 L injected
10 L 2-dodecanol; stirring, 800 rpm,
40 min, 70C; deep freeze, 10 min;
centrifugation, 4000 rpm, 3 min; 7 L
injected
35 L dodecanol; 1 mL methanol; stand,
10 min; centrifugation, 5500 rpm, 10 min;
10 L injected

LR: 3.51400 ng g1
LOD: 2.3 pg g1

[78]

Decabrominated diphenyl Supercial sediments


ether

Plasma; acetone with 1:1 ratio; vortex


mixing, 20 s; centrifugation, 10 min,
6000 rpm; 1 mL clear supernatant diluted
with 10 mL water; 1.5 g NaCl; pH 12 with
1 M NaOH
10 mL water; pH 11; without salt addition;
ltration

90 L 1-undecanol; 1.5 mL acetone; vortex


mixing, 1 min; centrifugation, 5000 rpm,
5 min; cooling, 20C, 5 min
BE: 20 L 0.1 M NaOH; vortex mixing,
1 min; centrifugation, 4000 rpm, 1 min

[90]

55

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P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Urine

Water: 10 mL; pH 4 with 0.1 M HCl


Urine: 4 mL supernatant; pH 4 with 0.1 M
HCl; acetonitrile at 2:1 (v:v) ratio; 1 g NaCl;
vortex mixing, 1 min; centrifugation,
4000 rpm, 1 min; 1 mL acetonitrile extract to
DLLME

[128]

56

Table 2 (continued)
Analyte

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Dichloro-nitrobenzene
Water (well, river, sea)
and dichloro-nitroaniline

Sample

SFODME

GC-ECD

14 mL water; 0.8 g NaCl

Apple pulp and peel

DLLME-SFO

HPLC-DAD

Diethofencarb and
pyrimethanil

Water (tap, lake)

DLLME-SFO

HPLC-DAD

0.5 g apple pulp, vacuum freeze- drying;


5 mL acetonitrile; microwave irradiation,
30 min, 80C; 0.4 mL acetonitrile extract to
DLLME
5 mL water; without salt addition; ltration

LR: 5100, 5170, and 20


1400 ng L1
LOD: 1.210 ng L1
LR: 8800 and
8400 g kg1
LOD: 1.21.6 g kg1

[71]

Diethofencarb and
pyrimethanil

Water (tap, lake, waste)

UA-DLLME-SFO

GC-ECD

5 mL water; 0.08 g mL1 NaCl

LR: 0.42000 and 0.2


1000 g L1
LOD: 0.24 and 0.09 g L1
LR: up to 10 g L1
LOD: 0.0190.079 g L1

[118]

Dinitrobenzenes

Duloxetine

Human plasma

VA-DLLME-SFO

HPLC-FLD

LR: 2.5200 ng mL1


LOQ: 2.5 ng mL1

[139]

Estrogenic hormones

Water

DLLME-SFO

HPLC-FLD

Water (tap, commercial)

DLLME-SFO

HPLC-UV

LR: 0.0020.25 mg L1
LOD: 0.0050.50 g L1
LR: 0.05100 g L1
LOD: 3.348.4 ng L1

[131]

Estrogens

Estrogens

Water

UASEME-SFO

HPLC-FLD

Water (environmental)

AA-DLLME-SFO

HPLC-UV

LR: 0.022.0 mg L1
LOD: 1.065.04 g L1
LR: 0.1500 g L1
LOD: 0.010.1 g L1

[133]

Estrogens

1 mL plasma; 0.9 mL 15% (w/v) ZnSO4


solution-acetonitrile (50/40, v/v); vortex
mixing, 20 min, 4C, 15 min; centrifugation,
4000 rpm, 5 min; supernatant to DLLME
Water; 6.4% (w/v) NaCl; derivatization with
6 mg p-nitrobenzoyl chloride, 35C, 20 min
210 mL water; without salt addition; SPE
with carbon nanotubes 30 mg, ow rate of
water, 2 mL min1
Water; derivatization with 5 mg
p-nitrobenzoyl chloride, 35C, 2 min
10 mL water; pH 6

10 L 1-undecanol; stirring, 1000 rpm,


25 min, 50C; cooling, ice bath, 5 min; 2 L
injected
10 L 1-undecanol; 0.4 mL acetonitrile
extract; 5 mL water; 1.4 g NaCl;
centrifugation, 4000 rpm, 2 min; cooling,
ice bath, few minutes; 5 L injected
20 L 1-dodecanol; 0.5 mL methanol;
centrifugation, 4000 rpm, 2 min; cooling,
ice bath, 2 min; 5 L injected
8 L 1-dodecanol; 200 L methanol;
sonication, 1 min; centrifugation,
4000 rpm, 1 min; cooling, ice bath, 1 min;
1 L injected
50 L 1-undecanol; vortex mixing;
centrifugation, 4000 rpm, 5 min; cooling,
ice bath, 5 min; mixed with 150 L
methanol; 50 L injected
93.6 L extractant; 0.4 mL dispersant

Fat-soluble vitamins
(A, D2, D3)

Tap water, urine, fruit juice

SFODME

HPLC-UV

LR: 5500 g L1
LOD: 1.03.5 g L1

[158]

Fenvalerate

Tomato

DLLME-SFO

HPLC-UV

LR: 5500 g kg1


LOD: 0.6 g kg1

[130]

Flavonoids

SFODME

HPLC-UV

MSA-SFODME

HPLC-UV

Fungicides

Water and honey

DS-SFODME

HPLC-DAD

LR: 0.0110.00 g mL1


LOD: 1.00.01 ng mL1
LR: 12000 g L1
LOD: 0.140.26 g L1
LR: 51000 ng mL1
LOD: 0.201.95 ng mL1
(water) and 1.14
11.06 ng g1 (honey)

[154]

Fungicides

Traditional Chinese
medicines
Water and wine

Fungicides

Sediments

UA-DLLME-SFO

HPLC-DAD

LOD: 0.10.5 g g1

[120]

Fungicides

Juices and red wine

UASEME-SFO

HPLC-DAD

LR: 51000 g L1
LOD: 0.41.4 g L1

[121]

10 mL sample

3 mL water or diluted honey; without salt


addition
Water: ltration
Honey: 1.5 g; 10.5 g water; vortex mixing,
ultrasonication; ltration
5 g dried sample; 30 mL methanol-water
(70:30); ultrasound, 20 min, 25C;
evaporation to dryness, 40C; redissolution
in 10 mL methanol; pH 7 with 0.03 M HCl or
0.025 M NaOH; 1 mL extract to DLLME
8 mL sample; ltration

35 L dodecanol; 40 L Tween-20;
sonication, 15 min, 62.5 W
220 L 1-octanol; 700 L ethanol; stirring,
1250 rpm; centrifugation, 3000 rpm,
10 min
15 L 1-undecanol; stirring, 1000 rpm,
60 min, 55C; cooling, ice bath, 5 min;
whole melted solvent injected
150 L 1-undecanol; centrifugation,
4000 rpm, 2 min; 1 mL of this mixture
injected into 5 mL water containing 0.01 g
NaCl; centrifugation, 4000 rpm, 4 min;
cooling, ice bath, 5 min
40 L 1-dodecanol; stirring, 40 min; 20 L
injected
1-dodecanol; no centrifugation
20 L 1-dodecanol; stirring, 900 rpm,
90 min, 30C; cooling, ice bath, 5 min;
diluted with 10 L methanol

80 L 1-dodecanol; 0.2 mL methanol; 3 mL


water; 0.02 g NaCl; sonication;
centrifugation, 1100 rpm, 9 min; cooling,
ice bath, 5 min; redissolution in 5 mL
methanol; 10 L injected
30 L 1-dodecanol; 24 L 10 mM Tween80; sonication, 1 min, 40 kHz, 100 W,
25 2C; centrifugation, 3800 rpm, 3 min;
cooling, ice bath, 1 min; mixed with
methanol at ratio 1:1; 20 L injected

[72]

[132]

[134]

[119]
[52]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

20 mL sample; without salt addition.


Filtration and two-times dilution for urine
and juice fruit
1 g tomato; 5 mL acetone; sonication,
30 min, room temperature

50 L dodecanol; 0.2 mL methanol; 20 L


injected

[117]

Table 2 (continued)
Sample

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Fungicides

Wine

DLLME-SFO

GC-MS

5 mL diluted (1:1) wine; without salt


addition

LR: 1300 ng mL1


LOQ: 0.23.2 ng mL1

[122]

Fungicides

Grape

UA-DLLME-SFO

HPLC-UV

LR: 0.36 and 360 mg L1


LOQ: 0.22 mg kg1

[123]

Fungicides

Fruit juice

UA-DLLME-SFO

HPLC-UV

QuEChERS: 5 g sample; 5 mL acetonitrile;


vortex mixing, 1 min; 4 g MgSO4 and 1 g
NaCl; vortex mixing, 30 s; centrifugation,
3800 rpm, 5 min; 500 L acetonitrile extract
to DLLME
5 mL juice; pH 7

50 L 1-undecanol; 1 mL acetone;
centrifugation, 3000 rpm, 10 min; cooling,
18C, 10 min; 12 L injected
100 L 1-undecanol; 500 L acetonitrile
extract; 5 mL water; sonication, 2 min;
centrifugation, 3800 rpm, 5 min; cooling,
ice bath; 20 L injected

LR: 0.053.0 mg kg1


LOD: 550 g L1

[124]

Fungicides mixture

Water

UA-DLLME-SFO

HPLC-DAD

8 mL water; 4% (w/v) NaCl; ltration

LR: 0.5500 ng mL1


LOD: 0.020.2 ng mL1

[125]

Haloanisoles and
halophenols

Wine

USAE-SFODME

GC-ECD

5 mL wine; pH 7.6; 2% (w/v) NaCl;


derivatization with 80 L acetic anhydride

LR: 10500 ng L1
LOD: 2.25 ng L1

[151]

Haloanisoles and volatile


phenols

Wine

USAE-SFODME

GC-MS/MS

5 mL wine; 5% (w/v) NaCl

100 L dodecanol; 1 mL acetonitrile;


sonication, 1 min; stand, 10 min;
centrifugation, 3000 rpm, 3 min; cooling,
ice bath, 5 min; 50 L dissolved in 50 L
acetonitrile
50 L 1-dodecanol, 200 L methanol;
sonication, 2 min; centrifugation,
4000 rpm, 10 min; cooling, ice bath, 1 min;
dissolved in 25 L methanol; 10 L
injected
400 L cyclohexanol; sonication, 5 min,
40 kHz, 100 W, 70C; centrifugation,
5000 rpm, 3 min; cooling, ice bath; 0.5 L
injected
425 L cyclohexanol; sonication, 6 min,
70C, 40 kHz, 100 W; centrifugation,
5000 rpm, 3 min; cooling, ice bath

[152]

Halogenated organic
compounds

Water (tap, lake)

DLLME-SFO

GC-ECD,
GC-MS

5 mL water; 1.5 g NaCl; ltration

Haloperidol

Human urine and plasma

USAE-SFODME

HPLC-DAD

Kanamycin

Wastewater and soils

DLLME-SFO

HPLC-FLD

LR: 0.5500 ng mL1


LOD: 0.012 ng mL1

[140]

Lignans

Traditional Chinese
medicines
Rat urine

SFODME

HPLC-UV
HPLC-UV

LR: 1.05 10328.8 g mL1


LOD: 0.080.4 ng mL1
LR: 201000 g L1
LOQ: 20 g L1

[157]

DLLME-SFO

Urine diluted 1:1 with water


2 mL plasma; 100 L HCl; 100 L
triouroacetic acid; centrifugation,
3000 rpm, 10 min; supernatant dilution at
the ratio 1:2 with water
Sample: 4 mL; pH 10; 4% (w/v) NaCl
Water: 2.5 mL; 500 L Fmoc-Cl solution
(0.26 mg mL1); 200 L borate buffer
(pH 8.5); 15 min
Soil: 5 g; 10 mL water; ultrasonic bath, 25C,
1 h; centrifugation, 4000 rpm, 20 min;
supernatant ltered
10 mL sample; 500 L 1 M HCl; 2 mL 4.27 M
NaCl
Urine centrifugation, 12000 rpm, 10 min;
1 mL supernatant; 4 mL 10% (w/v) NaCl;
pH 10; vortex mixing, 1 min

LR: 10500 ng L1
(haloanisoles);
12000 g L1 (volatile
phenols)
LOD: 2.854.0 ng L1
LR: 0.01500 and 0.02
500 g L1
LOD: 0.0050.05 g L1
LR: 41000 g L1
LOD: 1.53 g L1

Methyl methacrylate

Wastewater

DLLME-SFO

GC-FID

5 mL water; pH 7; 20% (w/v) NaCl

[86]

Neonicotinoid pesticides

Fruit juice and water

VASEME-SFO

HPLC-UV

10 mL sample; centrifugation fruit juice,


5000 rpm, 10 min; ltration; 0.3% (w/v)
Na2SO4; 50 L 0.05 M SDS, 400 L 1 M HCl

LR: 12250 g L1
LOD: 8 g L1
LR: up to 5 g mL1
LOD: 0.10.5 g L1

Lovastatin and
simvastatin

10 L 2-dodecanol; 0.5 mL acetone;


centrifugation, 6000 rpm, 5 min; cooling,
ice bath, 5 min; 2 L injected
30 L 1-undecanol; sonication, 20 min,
25C; centrifugation, 4000 rpm, 5 min;
cooling, ice bath; 10 L injected

50 L dodecanol; 50 L ethanol; stirring,


900 rpm, 20 min; cooling, 20C, 5 min;
50 L methanol; 20 L injected

25 L 1-dodecanol; 200 L methanol;


centrifugation, 4000 rpm, 5 min; cooling,
ice bath; mixed with 50 L methanol;
20 L injected
15 L 2-dodecanol; stirring, 1000 rpm,
30 min, 40C; cooling, ice bath, 5 min
150 L 1-octanol; vortex mixing, 1 min;
centrifugation, 5000 rpm, 10 min

[56]

[142]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

[137]

[116]

(continued on next page)


57

58

Table 2 (continued)
Sample

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Nicotine and cotinine

Urine

SFODME

HPLC-UV

15 mL urine centrifugation; 10 mL
supernatant; 7 g NaCl; pH 9 with 0.1 M
NaOH

LR: 0.015.00 g mL1


LOD: 0.002 g mL1

[138]

Nitrophenols

Water

USAE-SFODME

UHPLC-UV

10 mL water; 0.8 M HCl; 2 g NaCl

LR: up to 1000 g L1
LOD: 0.53.2 g L1

[57]

Nitrotoluene compounds

Water (well, sea)

SFODME

GC-FID

8 mL water; 3% (w/v) NaCl

LR: 0.5200 g L1
LOD: 0.30.5 g L1

[73]

Macrolide antibiotics

Human urine

DLLME-SFO

LC-CAD

Urine diluted ten-fold with water; 5 mL; 9%


(w/v) NaCl; 100 L saturated Na2CO3

LR: 0.104.00 and 0.025


1.00 g mL1
LOD: 1040 ng mL1

[141]

Opium alkaloids

Human plasma

DLLME-SFO

HPLC-UV

LR: 1.51000 g L1
LOD: 0.55 g L1

[144]

Organochlorine pesticides Water (river, tap,


agricultural)
Organochlorine pesticides Water (lake, tap)

SFODME

GC-ECD

1 mL plasma; 1 mL 15% (w/v) ZnSO4


solutionacetonitrile 50/40 (v/v); vortex
mixing, 20 min, 4C, 15 min; centrifugation,
4000 rpm, 5 min; supernatant diluted to
5 mL using water; 1% (w/v) NaCl; pH 9
20 mL water; 0.25 M NaCl

100 L 1-undecanol-CHCl3 (v/v 1:1); 10 mL


extract; shaking, 1 min, 25C;
centrifugation, 3000 rpm, 3 min; cooling,
20C, ice bath, 5 min; 10 L injected
12 L 1-undecanol; manual shaking,
3 min; sonication, 3 min, 40 kHz, 335 W,
25 3C; centrifugation, 5000 rpm, 3 min;
cooling, ice bath; diluted with 30 L
DMSO, 20 L injected
5 L 1-undecanol; stirring, 600 rpm,
30 min, 60C; cooling, ice bath, 5 min; 1 L
injected
60 L 1-dodecanol; 440 L methanol;
centrifugation, 3500 rpm, 5 min; cooling,
ice bath, 5 min; 40 L diluted to 120 L
with methanol; 20 L injected
30 L 1-undecanol; 500 L acetone;
centrifugation, 4000 rpm, 5 min; cooling,
ice bath, 5 min; 25 L injected

GC-ECD

5 mL water; 0.8 g NaCl; ltration

LR: 252000 ng L1
LOD: 719 ng L1
LR: 0.02520 g L1
LOD: 0.0110.11 g L1

[102]

DLLME-SFO

Organochlorine pesticides Water (farmland)

SD-DLLME-SFO

GC-MS

5 mL water; pH 6; 1.8 g NaCl

LR: 0.0252.00 g L1
LOD: 0.0120.024 g L1

[104]

Organochlorine pesticides Water (river, piped,


farmland)
Organochlorine pesticides Water (river, well)

SFODME

GC-ECD

Water; pH 6; 15% (w/v) NaCl

GC-ECD

200 mL water; SPE with MWCNT; elution


with 2 mL acetone; 2 mL acetone extract to
DLLME

LR: 5100 ng L1
LOD: 0.240.78 ng L1
LR: 0.51000 ng L1
LOD: 0.10.39 ng L1

[105]

DLLME-SFO

Organophosphate esters

Water (tap, bottled, river)

VA-DLLME-SFO

UHPLC-MS/MS 8 mL water; 2 g NaCl

LR: 1.0200 g L1
LOD: 0.020.07 g L1

[77]

Organophosphorus
pesticides
Organophosphorus
pesticides

Water

SFODME

GC-FPD

20 mL water; 3 M NaCl

VA-DLLME-SFO

HPLC-DAD

20 mL water; 1 g NaCl; ltration

LR: 0.10100 g L1
LOD: 0.010.04 g L1
LR: 1200 ng mL1
LOD: 0.10.3 ng mL1

[99]

Water

Organophosphorous
pesticides

Summer crops

DLLME-SFO

HPLC-UV

LR: 5800 g kg1


LOD: 14 g kg1

[101]

Parabens

Water and cosmetics

SFVCDME

HPLC-UV

1 g sample; 5 mL acetone; sonication,


25 min, room temperature; 150 L
1-undecanol; centrifugation, 5000 rpm,
2 min; 1 mL acetone extract to DLLME
Sample: 24 mL; pH 6; without salt addition
Water: ltration, dilution 1:1 by water, pH
adjusted at 6, adding EDTA (2 mg L1)
Cosmetics: 5 mg; 2 mL methanol; 8 mL
water; 1 mL HCl; sonication, 10 min;
dilution to 150 mL with water and pH
adjusted at 6

8 L 1-dodecanol; stirring, 750 rpm,


30 min, 65C; 2 L injected
10 L hexadecane; 200 L acetonitrile;
centrifugation, 5000 rpm, 3 min; cooling,
ice bath, 5 min; 1 L injected
50 L n-hexadecane; 250 L acetone;
demulsier 750 L acetone; cooling, icebath
n-Hexadecane; stirring, 55C, 10 min;
cooling, ice bath
10 L 1-dodecanol; 2 mL acetone extract;
5 mL solution 4% (w/v) NaCl;
centrifugation, 6000 rpm, 5 min; cooling,
ice bath, 5 min; 1 L injected
400 L 1-undecanol; 300 L methanol;
vortex mixing, 2 min; centrifugation,
3000 rpm, 5 min; cooling, ice bath, 5 min;
diluting to 0.5 mL with methanol
10 L 1-undecanol; stirring, 1250 rpm,
20 min, 60C; cooling, ice bath, 5 min
15 L 1-dodecanol; 200 L methanol;
vortex mixing, 1 min; centrifugation,
3500 rpm, 3 min; cooling, ice bath, 5 min;
15 L methanol added and injected
30 L 1-undecanol; 1 mL acetone extract;
5 mL water; centrifugation, 4000 rpm,
5 min; cooling, ice bath, 5 min; 20 L
injected
30 L supramolecular solvent; stirring,
850 rpm, 30 min, 30C; cooling, ice bath,
3 min, 600 rpm; 20 L injected

LR: 0.5100 g L1
LOD: 0.20.5 g L1

[85]

[103]

[106]

[100]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

Table 2 (continued)
Sample

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Pesticides

Water (tap, river, lake)

UA-DLLME-SFO

GC-FID

5 mL water; 1% (w/v) NaCl; ltration

LR: 0.20200 g L1
LOD: 0.110.48 g L1

[164]

Phenolic compounds

Water (tap, mineral, river)

SFODME

GC-MS

LR: 0.02300 g L1
LOD: 0.0050.68 g L1

[91]

Phenolic compounds

Water (tap, river, spring)

VA-DLLME-SFO

HPLC-UV

10 mL water; ltration; pH 2; saturated salt


conditions; derivatization with 40 L acetic
anhydride, 0.5% (w/v) K2CO3, shaking 2 min
6 mL water; pH 6; without salt addition;
ltration

8 L 1-dodecanol; 300 L acetonitrile;


ultrasonication, 3 min; centrifugation,
4000 rpm, 5 min; cooling, ice bath, 5 min;
1 L injected
9 L 1-undecanol; stirring, 15 min,
1200 rpm, 55C; cooling, ice bath

LR: 10800 ng mL1


LOD: 0.11.50 ng mL1

[92]

Phenolic pollutants

Human urine and blood

USAE-SFODME

HPCE

LR: 0.05100 g L1
LOD: 0.010.04 g L1

[93]

Phthalate esters

Water (tap, bottled, river)

SFODME

GC-MS

Cosmetic and water

USAE-SFODME

HPLC-DAD

10 mL water; 20% (w/v) NaCl


30 mg cosmetic, 100200 L methanol, up
to 10 mL water

LR: 0.05100 g L1
LOD: 0.020.05 g L1
LR: 0.05800 and 0.05
1000 g L1
LOD: 0.0050.01 g L1

[81]

Phthalate esters

Phthalate esters

Water and cosmetics

VA-DLLME-SFO

CLC-UV

300 L water or 300 mg cosmetic; 150 L


ethyl acetate; submitted to LLE, UAE o MAE;
redissolution with 300 L methanol

LR: 0.550 g mL1


LOD: 0.020.17 g mL1

[83]

Plasticizers

Water (kept in PET-bottles)

SFODME

GC-FID

20 mL; 1 M NaCl

LR: 0.210 g L1
LOD: 0.010.03 g L1

[84]

Polybrominated diphenyl
ethers

Water (environmental) and SFODME


human urine

HPLC-DAD

LR: 0.575 and 5500 g L1


LOD: 0.010.04 g L1

[79]

Polybrominated diphenyl
ethers

Sediments

VA-DLLME-SFO

GC-MS

40 mL sample; without salt addition


Water was ltered. Urine was removed,
protein by methanol and ltered
1 g dried sample; 1.2 mL methanol;
ultrasound leaching, 40 2C, two cycles of
9.2 min; centrifugation, 2000 rpm, 10 min;
0.4 mL liquid phase to DLLME

LR: up to 1000 pg g1
LOD: 0.51.8 pg g1

[80]

Polycyclic aromatic
hydrocarbons

Water (tap, well, sea)

SFODME

GC-FID

20 mL water; without salt addition;


ltration

Water (tap, lake, waste)

DLLME-SFO

HPLC-DAD

10 mL water; without any pretreatment

LR: 0.2300 and


5400 g L1
LOD: 0.071.67 g L1
LR: 0.150 and
1500 ng mL1
LOD: 0.0451.1 ng mL1

[36]

Polycyclic aromatic
hydrocarbons

70 L 1-dodecanol; 500 L methanol;


vortex mixing, 1 min; centrifugation,
4000 rpm, 5 min; cooling, ice bath, 5 min;
methanol to 300 L, 20 L injected
40 L 2-dodecanol; sonication, 5 min,
45C; centrifugation, 2500 rpm, 3 min;
cooling, ice bath; BE of 5 L in 45 L
methanol-buffer solution (9:1, v/v)
7 L 1-dodecanol; stirring, 750 rpm,
25 min, 60C
30 L 1-undecanol; sonication, 12 min,
35 kHz, 320 W, 12 min, 25C;
centrifugation, 3500 rpm, 5 min; cooling,
ice bath, 5 min
20 L 1-dodecanol; 30 L acetone; vortex
mixing, 1 min; centrifugation, 3000 g,
5 min; cooling, ice bath, 5 min; 0.5 L
injected
12 L acetophenone/1-undecanol (1:8);
stirring, 30 min, 1250 rpm, 60C; cooling,
ice bath, 5 min; 2 L injected
25 L 2-dodecanol; stirring, 900 rpm,
60C; 25 min; cooling, ice bath, 10 min;
5 L injected
26.5 L 1-dodecanol; 0.1 mL methanol;
1 mL 6.15 M NaCl; vortex mixing; 4.4 mL
40C water; cooling, ice bath, 10 min; 3 L
iso-octane; vortex mixing; nal volume
achieved was 20 L; 1 L injected
8 L 1-undecanol; stirring, 1250 rpm,
30 min, 60C; cooling, ice bath, 5 min; 2 L
injected
100 L 1-dodecanol; 200 L methanol;
centrifugation, 4000 rpm, 2 min; cooling,
ice bath, 5 min; mixed with 50 L
methanol; 20 L injected

Polycyclic aromatic
hydrocarbons
PAHs, pesticides, phenols
and sulfonamides

Soil

DLLME-SFO

[60]

Water

DLLME-SFO

HPLC-UV

10 mL water; 50 mg NaCl; pH adjusted


depending on analytes

DLLME-SFO

GC-ECD

5 mL water; 0.1 g NaCl; ltration

LR: 0.020.5 mg kg1


LOD: 0.1729.13 g kg1
LR: 52000 ng mL1; 10
400 ng mL1; 15
150 ng mL1
LR: 52500 ng L1
LOD: 3.35.4 ng L1

Polychlorinated biphenyls, Water (tap, lake, industrial) DLLME-SFO


organochlorine and
pyrethroid pesticides

GC-ECD

5 mL water; pH 7; without salt addition

LR: 5.02000 ng L1
LOD: 1.48.3 ng L1

[65]

Polychlorinated biphenyls Water (tap, lake)

2 mL serum or urine mixed with acetonitrile


at 1:2 ratio; centrifugation, 12000 rpm,
3 min; dilution with water to 10 mL; 6% (w/
v) NaCl; pH 5
10 mL; without salt addition; ltration

100 L 1-dodecanol; 200 L methanol;


water bath, 30C, 3 min; centrifugation,
4500 rpm, 10 min; cooling, ice bath, 2 min
8 L 1-undecanol; 1 mL acetonitrile;
centrifugation, 3500 rpm, 2 min; cooling,
ice bath, 1 min; 1 L injected
5 L 1-dodecanol; 600 L methanol;
centrifugation, 4000 rpm, 3 min; cooling,
ice bath; 1 L injected

[82]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

[59]

[61]

[64]

(continued on next page)


59

60

Table 2 (continued)
Analyte

Mode

Detection

Sample pretreatment

Extraction conditions

LR/LOD

Ref.

Polychlorinated biphenyl, Peach juices, pulp and


organochlorine pesticide peels
and pyrethroid pesticides

Sample

DLLME-SFO

GC-ECD

0.5 g vacuum freeze-dried peach pulps and


peels; 5 mL acetone; microwave irradiation,
30 min, 60C
5 mL juice (diluted 1:1 with water)

LR: 102000 ng L1
LOD: 2.818.5 ng L1

[66]

Propranolol enantiomers

Human plasma

DLLME-SFO

HPLC-FLD

8 L 1-dodecanol; 0.4 mL acetone extract;


5 mL water; sonication, 2 min;
centrifugation, 4000 rpm, 2 min; cooling,
ice bath; diluted with methanol 1:10; 1 L
injected
1-undecanol

[149]

2-Pyrazoline derivatives

Tap water, urine and serum SFODME

GC-FID

Pyrethroids

Water (tap, well, river,


reservoir)

SFODME

GC-ECD

20 mL sample; pH > 6; without salt addition.


Two and 20-times dilution for urine and
serum, respectively
30 mL water; 12% (w/v) NaCl; ltration

LR: 0.5100 ng mL1


LOQ 0.5 ng mL1
LR: 25800 g L1
LOD: 510 g L1
LR: 0.1580 g L1
LOD: 2.050 ng L1

[107]

Pyrethroids

Water

DLLME-SFO

GC-ECD

5 mL water; 0.16 g mL1 NaCl; ltration

LR: 102000 ng L1
LOD: 1.42.9 ng L1

[108]

Pyrethroid pesticides

Tea

VA-DLLME-SFO

GC-ECD

0.2 g powder sample; 2.3 mL ethanol;


sonication, 45 min; centrifugation, 5 min;
2 mL ethanol extract to DLLME

LR: 5100 g kg1


LOD: 0.080.5 g kg1

[109]

Quercetin

Apple, grape, onion and


tomato

DLLME-SFO

FI-UV-Vis

LR: 50 1085.0 M
LOD: 108 M

[155]

Tanshinones

Traditional Chinese
medicinal injections

VA-DLLME-SFO

HPLC-UV

Sample; 10 mL methanol; left over night;


sonication, bath, 40 min; ltration;
supernatant diluted to 50 mL with water;
10 mL extract; pH 3 with HCl
4 mL sample

LR: 0.05100 and 0.05


40 g mL1
LOD: 2.324.62 ng mL1

[156]

Thiamine and cobalamine Serum and urine

SFODME

HPLC-UV

[160]

Triclosan and
2,4-dichlorophenol

Water (environmental)

VA-DLLME-SFO

HPLC-MS/MS
HPLC-UV

5 mL water; pH 6; without salt addition;


ltration

LR: 5400 g L1
LOD: 3.19.2 g L1
LR: 0.0210 and 0.05
50 g L1
LOD: 0.0020.02 g L1

Triazine herbicides

Water and sugarcane

DLLME-SFO

GC-MS

LR: 0.01100 ng mL1


LOD: 0.0080.037 ng mL1

[110]

Triazine herbicides

Water

SFODME

HPLC-UV

5 mL sample; 5% (w/v) NaCl. Juice:


centrifugation, 15 min, 3500 rpm; 5 mL of
juice diluted with water
Peel of sugarcane washed and the wash
water analyzed; ltration
5 mL sample; 2% (w/v) NaCl

[111]

Triazine herbicides

Soil

SFODME

GC-FPD

LR: 0.2200 and


1200 g L1
LOD: 0.030.10 g L1
LR: 102000 and
2500 g kg1
LOD: 0.21.0 g kg1

Triazine herbicides

Cereals

DMAE-SFO

HPLC-UV

LR: 51000 ng g1
LOD: 1.11.5 ng g1

[113]

10 L 1-dodecanol; 0.3 mL methanol; 0.5 g


NaCl; water to 5 mL; vortex mixing, 30 s;
centrifugation, 3000 rpm, 5 min; cooling,
ice bath, 5 min; 10 L methanol added;
5 L injected

12 L 1-dodecanol; 300 L acetonitrile;


vortex mixing, 30 s; centrifugation,
3000 rpm, 4 min; cooling, ice bath; 10 L
injected
10 L 1-undecanol; 100 L acetonitrile;
centrifugation, 4000 rpm, 3 min; cooling,
ice bath, 5 min; 2 L injected

16 L 1-dodecanol; stirring, 1050 rpm,


30 min, 60C
10 L 1-dodecanol; stirring, 1000 rpm,
25 min, 65C; cooling, ice bath, 5 min; 1 L
injected

1 g cereal; 4 g quartz sand; 90 L


1-dodecanol; 1 mL methanol; microwave
heating, 600 W, water ow rate
1.5 mL min1; 1.5 g NaCl; centrifugation,
4000 rpm, 3 min; cooling, ice bath, 5 min;
20 L injected

[150]

[94]

[112]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

10 g soil; 13 mL water; pH adjusted to 4 by


0.1 M HCl; ultrasound shaken in a water
bath, 10 min; centrifugation, 3500 rpm,
5 min; supernatant ltrated; above
procedures were repeated three times;
ltrate combined; pH 11 with 0.1 M NaOH

8 L 1-undecanol; stirring, 1250 rpm,


30 min, 70C; cooling, ice bath, 5 min; 1 L
injected
13 L 1-dodecanol; stirring, 15 min,
1200 rpm, 55C; cooling, ice bath, 5 min;
1 L injected
8 L 1-dodecanol; 500 L methanol;
centrifugation, 3500 rpm, 2 min; cooling,
ice bath; 1 L injected
30 L 1-dodecanol; 2 mL ethanol extract;
5 mL water; pH 4; vortex mixing, 1 min,
centrifugation, 4000 rpm, 5 min; cooling,
ice bath; 1 L injected
80 L 1-undecanol; 100 L methanol;
centrifugation, 2000 rpm, 3 min; cooling,
ice bath, 5 min; diluted with ethanol (1:1)

Table 2 (continued)
Analyte

Sample

Mode

Detection

Sample pretreatment

Water (lake, stream, well)

VA-DLLME-SFO

HPLC-DAD

10 mL water; 1.5 g NaCl; pH 6; ltration

Triazole fungicides

Juice

USAE-SFODME

HPLC-UV

0.5 mL ltrate juice; 9.5 mL water; 250 g L1


NaCl

Trihalomethanes

Drinking water

SFODME

GC-MS

10 mL water; 3 M NaCl

Trihalomethanes

Water (tap, swimming


pool)

DLLME-SFO

GC-ECD

18 mL water; 0.9 g NaCl

Steroid hormones

Water (tap, river)

DLLME-SFO

HPLC-UV

5 mL water; 0.3 g NaCl; ltration

Strobilurin fungicides

Fruit juice

UASEME-SFO

HPLC-DAD

5 mL juice (diluted at 1:1 ratio with water);


1% (w/v) NaCl

Sudan dyes

Foodstuffs and water

DLLME-SFO

HPLC-UV

Synthetic antioxidants

Beverages

DLLME-SFO

HPLC-UV

10 mL sample; 1 g NaCl
Water: ltration
Food: 2 g; 5 mL ethanol; shaking, 20 min,
30C; centrifugation, 4000 rpm, 10 min;
dried under nitrogen; diluted to 10 mL with
10% (w/v) NaCl (pH 7)
5 mL beverage; ltration; pH 6; 0.3 g NaCl

Volatile aldehyde
biomarkers

Human blood

DLLME-SFO

HPLC-DAD

Serum; 750 L methanol; 500 L of


supernatant diluted with water to 5 mL;
0.75 g NaCl; 30 L 20 mM 2,4dinitryophenyl hydrazine; 40 L formic acid;
40C; 10 min

12 L 1-dodecanol; 200 L methanol;


vortex mixing, 1 min; centrifugation,
3500 rpm, 3 min; cooling, ice bath, 5 min;
mixed with 12 L methanol; 15 L injected
50 L 1-undecanol; sonication, 18 min;
30C; centrifugation, 4200 rpm, 10 min;
mixed with 20 L methanol
7 L 1-undecanol; stirring, 15 min,
750 rpm; 60C; cooling, ice bath, 4 min;
1 L injected
50 L 1-undecanol; 0.7 mL acetone;
manual shaking, 1 min; centrifugation,
3000 rpm, 10 min; cooling, fridge, 15 min;
1 L injected
10 L 1-undecanol; 200 L methanol;
centrifugation, 4500 rpm, 3 min; cooling,
ice bath; mixed with 35 L DMSO; 25 L
injected
30 L 1-undecanol; 15 L 5 mg mL1
Tween-80; sonication, 1 min, 60 kHz, 30C;
centrifugation, 3000 rpm, 5 min; cooling,
ice bath, 10 min; 10 L diluted with mobile
phase (1:1) injected
100 L 1-dodecanol; 400 L of ethanol;
water bath, 20 min, 70C; centrifugation,
4500 rpm, 5 min; cooling, ice bath, 5 min;
mixed with 50 L methanol; 20 L injected

90 L 1-octanol; 1 mL methanol;
centrifugation, 4000 rpm, 5 min; 20 L
injected
50 L 1-dodecanol; 50 L methanol;
centrifugation, 4000 rpm, 2 min; cooling,
ice bath, 5 min; mixed with 50 L
methanol; 5 L injected

LR/LOD

Ref.
mL1

LR: 0.5200 ng
LOD: 0.060.1 ng mL1

[114]

LR: 20890 g L1
LOD: 10.917.2 g L1

[115]

LR: 0.10100 g L1
LOD: 0.030.08 g L1

[62]

LR: up to 100 ng mL1


LOQ: 0.051.3 ng mL1

[63]

LR: 51000 g L1
LOD: 0.83.1 g L1

[135]

LR: 510000 ng mL1


LOD: 24 ng mL1

[126]

LR: 11250 ng g1
LOD: 0.100.20 ng g1 and
0.03 g L1

[162]

LR: 0.051 and 0.005


1 g mL1
LOD: 0.852.73 ng mL1
LR: 0.015 M
LOD: 7.90 and 2.34 nM

[163]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Triazole fungicides

Extraction conditions

[88]

61

62

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

reducing the time required in comparison with classic wet-acid digestion. Classic dry calcination in an oven, in order to obtain ashes
before digestion treatment, has also been recommended in some
instances [176,181,212,230].
As previously stated, several SFODME applications tackle the determination of inorganic species in different oxidation states. When
a complexing agent reacts with only one form of an inorganic analyte,
this can be exploited for the purpose of speciation, and the
microextraction has to be applied in two sample aliquots in which
the metal ion is in different oxidation states. Thus, oxidation or reduction processes have to be included in the sample pre-treatment.
In such cases, a mixture of sodium thiosulfate and potassium iodide
was used to reduce As(V) [183186], concentrated nitric acid to
oxidize Fe(II) [217], hydroxylamine hydrochloride to reduce Cr(VI)
[198], both ascorbic acid/potassium iodide [181] and L-cysteine/
hydrochloric acid [182] to reduce Sb(V), and hydrobromic acid [188]
and hydrochloric acid [190] were used for the reduction of Se(VI).
The total concentration of the analyte was then obtained from the
treated sample aliquot, and speciation was achieved by the difference with respect to the non-treated aliquot.
5.4. Application of complexation in SFODME
A neutral form is required to extract inorganic ions into
an extractant organic phase. For this reason, practically all
SFODME applications for metals are based on the formation of
hydrophobic chelates, sothiocarbamates [e.g., ammonium
pyrrolidinedithiocarbamate (APDC) and diethyldithiocarbamate
(DDTC)] have been used in the determination of arsenic [183186],
selenium [189,190], lead [171,173,175,176,179], antimony [181,182],
cobalt [179,201,204], copper [204,208], palladium [179,224,225], tellurium [191], mercury [179,220], silver [228], nickel [204,222] and
cadmium [179]. In addition, 8-hydroxyquinoline (8-HQ) has been
proposed for chelating copper [209,211,212], cadmium [195], molybdenum [55,221] and cobalt [200], and the latter was also
complexed with 2-nitroso-1-naphthol [202]. Another naphthol used
to a greater extent is 1-(2-pyridylazo)-2-naphthol (PAN). The chelation of cadmium [193], copper [206,210,213], zinc [54,213], cobalt
and nickel [203], thallium [167,168] and several rare-earth elements [231,233] has been carried out with PAN, while the SFODME
determination of lead [170,172,174], cadmium and nickel [196] has
been accomplished in water and tea using dithizone. For the speciation of arsenic [185] and selenium [188], diethyldithiophosphate
(DDTP) and 3,3-diaminobenzidine (DAB) have been used,
respectively.
The use of surfactants has also been considered for SFODME.
Anionic surfactant sodium dodecylbenzenesulfonate (SDBS) has been
added to the organic phase to facilitate the extraction of the hydrophilic complex formed between Cu(II) and Neutral red; in this
way, the chelate acquires a more hydrophobic character [207]. Triton
has been used with a similar objective for the determination of
cadmium and nickel [196] as well as cobalt [202] in water samples.
Some authors have formed ion pairs (IPs) to achieve the extraction of metals into an organic drop [166,169,187,192,197]. Moghadam
et al. [166] proposed the simultaneous determination of iron and
aluminum by extracting the IP formed between the cationic complexes of Fe(III)-morin and Al(III)-morin, with ClO4 as the bulky
counter anion. Surfactants are in some cases also involved in IP formation [169,187,192,197]. Dadfarnia et al. [192] determined cadmium
using CdI42 complexes extracted in an organic solvent containing
methyltrioctylammonium chloride. Gold and thallium were extracted into 1-undecanol through the formation of IPs between the
surfactant benzyldimethyltetradecyl ammonium and metal chlorocomplexes (AuCl4 and TlCl4) [169]. A hydrophobic IP was formed
between the cationic complex of Cr(VI) with 1,5-diphenylcarbazide
(DPC) and anionic surfactant SDS [197]. An indirect IP-DLLME-SFO

procedure has been developed for the determination of selenium:


in this case, the triiodide anion, formed in the reduction of Se(VI),
reacts with the surfactant cetyltrimethylammonium bromide (CTAB)
contained in the extractant phase [187].
The chelating agent in about 75% of cases was added to the
aqueous phase in order to extract the chelate thus formed
[165,180,185,224,227]; however, some authors prefer to dissolve this
agent in the extractant phase and to add the mixture to the sample
solution [190,203,229].
The extraction of ionic analytes using SFODME has also been proposed in the absence of a chelating agent. The preconcentration of
rhodium can be achieved through a ligandless (LL) SFODME procedure, in the form of its hydroxide in 1-dodecanol from a basic
aqueous solution [226]. As previously indicated, the presence of
anionic surfactants in organic phase has been shown to extract
analytes eciently from acid aqueous solutions. The micelles formed
when the surfactant concentration is higher than its critical micellar concentration (CMC) cause adsorption or binding of the cations
[194]. The addition of SDBS at a concentration higher than its CMC
produces an aggregation of surfactant molecules forming spherical micelles with negative charge that extract metal ions from the
aqueous phase. In this way, an LL-SFODME procedure has been proposed for the determination of cadmium in water samples [194].
Coacervates composed of reverse micelles formed with decanoic acid
and tetrahydrofuran (THF) were used to extract Cr-DPC-SDS IPs [197].
Lopez-Garca et al. proposed a saving in reactives by using undecanoic
acid for the preconcentration of lead, cadmium [177] and mercury
[219]. This weak acid acts as a complexing and extracting agent.
However, the effect of coexisting ions in real samples always
needs to be considered for the recovery of the analytes when inorganic compounds are determined. The interference may be the
result of competition from other ions for the chelating agent and
their subsequent coextraction with the analyte. The interference
caused by Cd(II), Zn(II) and Cu(II) in the determination of Co and
Ni was removed by adding EDTA [203]. Rezaee et al. [165] found
that Fe(III) and Cu(II) can interfere with the extraction recovery of
Al(III) ions and proposed their elimination using SCN and ascorbic acid/potassium iodide solutions, respectively. The interference
by Fe(III) in the determination of Se(IV) was also eliminated using
EDTA [189]. An important degree of interference was observed in
the extraction of Se(IV) as a piazoselenol complex in 1-undecanol,
with a cation-exchange resin used to eliminate the interfering
cations [188]. The introduction of displacement reactions in a
microextraction procedure can improve the selectivity of the method
[228].
5.5. Salt addition and pH
A decrease in analyte solubility in the aqueous phase leads to
an increase in extraction eciency; nevertheless, high salt concentrations reduce the analyte diffusion rate to the organic phase and
thus decrease the extraction eciency. In those procedures for which
the presence of salt benets extraction, concentrations between
0.01 M [204,223] and ~0.2 M [226] were generally selected, with the
use of sodium chloride and sodium nitrate. Salt concentrations in
the 1.74 M range have also been recommended [184,209,212].
The pH selected for the aqueous phase is that which favors formation of the chelate and maintains it in a suitable form to be
extracted {e.g., when APDC is the chelating agent, an acidic medium
is always used, in most cases with the pH adjusted to between 1
[183,186] and 3 [176,189]}.
5.6. Extraction temperature
Room temperature is generally selected during the extraction step
because the solubility of the organic phase can increase at high tem-

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

peratures, and the complex of the inorganic analyte can be degraded.


However, temperatures below 20C prevent the extractant from being
eciently dispersed. Nevertheless, 35C has been selected as the
extraction temperature for the determination of uranium [234] and
mercury [220], and, for SFODME using undecanoic acid, an extraction
temperature of 50C has been applied in order to keep the organic
solvent in liquid form [177,219].
5.7. Figures of merit
Table 3 summarizes linearity, LODs and EFs obtained in the
SFODME methods developed for inorganic analytes. For these species,
EFs between 12 [206] and 1520 [185] were found in the literature.
Nevertheless, comparison of the different values is dicult, because
the authors used different criteria to obtain the EFs.
6. Different modalities of solidied oating organic drop
microextraction
Tables 2 and 3 show the main features of the published procedures that focus on the determination of organic and inorganic
species using SFODME for preconcentration purposes. Most of these
methods applied the microextraction step in the conventional mode;
the rest employed some kind of modication (Fig. 4).
In DLLME-SFO, the use of a disperser solvent to increase the
contact surface between the organic extractant and the aqueous
phase produces a cloudy solution with no need for agitation, although some authors recommend agitation of the ternary mixture.
In any case, the time required to achieve the extraction equilibrium is reduced considerably compared with conventional SFODME.
In USAE-SFODME, dispersion of the extraction solvent is achieved
with the assistance of ultrasound energy instead of a disperser
solvent, and the method has been used with numerous applications. Fazelirad and Taher [169] compared the extraction eciency
achieved when dispersing the extraction solvent using ethanol or
by applying ultrasound energy. Similar results were found in both
cases, and, in this case, USAE-SFODME was selected in order to decrease organic solvent consumption.
A UASEME-SFO method for the determination of cadmium and
nickel using Triton to improve the emulsication has also been
developed [196].

63

VA-SFODME has been used for the determination of molybdenum [55,221], cobalt [202] and duloxetine [139]. VA has also been
used to accelerate reaching extraction equilibrium in DLLME-SFO
for the determination of benzotriazole ultraviolet stabilizers [87],
phenolic compounds [92], organophosphorus pesticides [100],
triazole pesticides [114], bisphenol A [90], 2 -agonists [136],
duloxetine [139], PBDEs [80], PEs [83], and triclosan and 2,4dichlorophenol [94].
When the analyte is microextracted with coacervates composed of reverse micelles using extraction and disperser solvents
and solidication of the enriched organic drop, the technique is
known as supramolecular solvent (SM)-DLLME-SFO. Coacervates are
immediately produced in the solution and the extraction equilibrium rapidly reached. Lead [175], chromium [197] and parabens [85]
have been determined in water and cosmetic samples using SMDLLME-SFO. The reverse micelles were formed using decanoic acid
and were dispersed in a THF-water mixture. THF acts as a dispersant and in assembling the micelles.
BE into aqueous acid medium from an enriched organic phase
obtained by SFODME was required for the determination of selenium by HG-AFS, because the high viscosity and low volatility of
the extraction solvent made it incompatible with hydridegeneration analysis [189]. In this case, the BE step was assisted by
ultrasound. BE has also been recommended for the determination
of mercury in waters with a high calcium content in order to
overcome the drawback caused by a high background appearing
during electrothermal atomization [219]. The same methodology
was applied for determination of several organic compounds using
CE [90,93,136].
Afzali et al. used a modied DLLME-SFO for the determination
of lead [171] and palladium [225] in water samples. A displacement reaction takes place, in which the targeted metal substitutes
another metal, whose complex has lower stability. The technique,
called displacement (D)-DLLME-SFO, has proved effective in decreasing interferences from coexisting metal ions and improving
the selectivity of the procedure without using masking agents.
For the determination of lead, zinc is displaced from its complex
with APDC [171], whereas, for the determination of palladium,
copper is displaced from its DDTC complex [225]. The displacement procedure was used for the preconcentration of silver by
SFODME [228].

Fig. 4. The different modalities of solidied oating organic drop microextraction (SFODME).

64

Table 3
Applications of solidied oating organic drop microextraction (SFODME) to the determination of inorganic analytes
Analyte

Sample

Mode

Detection

Sample treatment

Water

USAE-SFODME

ETAAS

pH 1; ltration; 10 mL sample;
pH 3.1; 0.7 mL 0.02% of 5-(4-dimethylamino
benzyliden)-rhodanine

Ag

Water and sediments

D-SFODME

ETAAS

Water: ltration, pH 2
Sediment: digestion with HNO3/H2O2; heating
to dryness; dissolution with 0.1 M HNO3
510 mL sample solution; pH 3; without salt
addition

Al

Water

DLLME-SFO

ICP-OES

20 mL sample; pH 4.5; without salt addition;


375 L 0.01 M morin

As speciation

Water

USAE-SFODME

ETAAS

As speciation

Water

SFODME

ETAAS

As speciation

Water

DLLME-SFO

ETAAS

As speciation

Water

DLLME-SFO

ETAAS

Au

Water and
pharmaceuticals

USAE-SFODME

FAAS

Cd

Water

IP-SFODME

FI-FAAS

pH 3; ltration; 5 mL sample; 0.1 ng mL1


APDC; pH 1
Total inorganic As: 1 mL 1% (w/v) Na2S2O3,
1 mL 0.5% (w/v) KI
20 mL sample; 0.1 M HCl; 50 L 130 mg L1
APDC; 4 M NaCl; water bath, 40 min,
1250 rpm, 45C
Total inorganic As: 1 mL 1% (w/v) Na2S2O3,
1 mL 0.5% (w/v) KI
100 mL sample; pH 2.5; 20 L DDTP. SPE, C18
cartridges. As-DDTP elution in 2 mL acetone
Total inorganic As: 1 mL 1% (w/v) Na2S2O3,
1 mL 0.5% (w/v) KI
pH 3; ltration; 5 mL sample; pH 1;
0.08 ng mL1 APDC
Total inorganic As: 1 mL 1% (w/v) Na2S2O3,
1 mL 0.5% (w/v) KI
Water: ltration; pH 1
Pharmaceutical: digestion with HNO3 and heat
10 mL sample; pH 2; without salt addition;
70 L 0.1% (w/v) N-(4-{4[(anilinocarbothioyl)amino]benzyl}phenyl)
-N-phenylthiourea
Filtration; 160 mL sample; pH 1.2; 0.2 M I

Cd

Water

USAE-SFODME

FAAS

Filtration; 6 mL sample; pH 9; 1 mL 0.2 g L1


PAN

Cd

Water

LL-SA-SFODME

FI-FAAS

100 mL sample; pH 4.5; without salt addition

Cd

Water, beverages and


cereals

VA-DLLME-SFO

FAAS

Cereals: pulverization; sieving; dry ashing


digestion with HNO3: ltration
20 mL sample; pH 7; without salt addition;
0.75 mL 0.1 M 8-HQ

Co

Water

SFODME

ETAAS

LR/LOD/EF

Ref.
mL1

30 L 1-undecanol; sonication, 7 min;


centrifugation, 3500 rpm, 5 min; cooling,
3 min; 10 L 0.05 M HNO3 added; 20 L
injected
40 L 0.08 mg mL1 DDTC in 1-undecanol to
5 mL 10 g mL1 Cu(II) at pH 6; stirring, 5 min;
cooling, 5 min. Addition of the solidied
extract to the sample; stirring, 5 min; cooling,
5 min; drop dilution to 500 L with ethanol;
10 L injected
2 mL acetone containing 132 L 1-undecanol;
centrifugation, 4000 rpm, 3 min; cooling,
5 min; drop dilution up to 100 L with
1-propanol; 200 L injected
35 L 1-dodecanol; sonication, 5 min, 25 3C,
40 kHz, 0.138 kW; centrifugation, 5000 rpm,
2 min; cooling; 20 L injected

LR: 0.110 ng
LOD: 0.056 ng mL1
EF: 250

[227]

LR: 0.14.5 ng mL1


LOD: 4.7 ng L1
EF: 250

[228]

LR: 1.0250 g L1
LOD: 0.8 g L1
EF: 128

[165]

LR: 0.052 ng mL1


LOD: 0.004 ng mL1
EF: 152

[183]

15 L 1-undecanol; cooling, 5 min; 10 L


injected

LR: 0.10.7 ng mL1


LOD: 9.2 ng L1
EF: 1000

[184]

60 L 1-undecanol; 2 mL acetone SPE extract;


5 mL water; centrifugation, 5000 rpm, 3 min;
cooling, 5 min; 20 L injected

LR: 10100 ng L1
LOD: 2.5 ng L1
EF: 1520

[185]

1 mL ethanol; 30 L 1-dodecanol;
centrifugation, 5000 rpm, 2 min; cooling;
20 L injected

LR: 0.082 ng mL1


LOD: 0.02 ng mL1
EF: 135

[186]

40 L 1-undecanol; sonication, 3 min;


centrifugation, 2500 rpm, 10 min; cooling;
drop dilution to 285 L with ethanol; 285 L
injected

LR: 1.5400 ng mL1


LOD: 0.45 ng mL1
EF: 34.8

[215]

160 L 0.02 M methyltrioctyl ammonium


chloride in 1-undecanol; stirring, 1200 rpm,
15 min; cooling, 5 min; drop dilution to 250 L
with ethanol; 100 L injected
90 L 1-dodecanol; sonication, 10 min, 40C;
centrifugation, 2000 rpm, 2 min; cooling,
2 min; drop dilution to 500 L with ethanol;
500 L injected
100 L 5 mM SDBS in 1-dodecanol; stirring,
300 rpm, 10 min; cooling, 10 min; drop
dilution to 300 L with methanol; 200 L
injected
100 L 1-dodecanol and 1 mL methanol;
vortex mixing, 1 min; centrifugation,
3500 rpm, 5 min; cooling, 5 min; drop dilution
with 400 L methanol; 400 L injected
1-undecanol using 8-HQ

LR: 0.0830 g L1
LOD: 0.0079 g L1
EF: 635

[192]

LR: 10450 g L1
LOD: 0.66 g L1
EF: 81

[193]

LR: 125 ng mL1


LOD: 0.21 ng mL1
EF: 205

[194]

LR: 150 ng mL1


LOD: 0.3 ng mL1
EF: 133

[195]

LR: 0.0510 ng mL1


LOD: 0.02 ng mL1

[200]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Ag

Extraction conditions

Table 3 (continued)
Analyte

Sample

Mode

Detection

Sample treatment

Water

DLLME-SFO

FAAS

Filtration; 10 mL sample; pH 5; without salt


addition;1 mL 0.2 g L1 APDC

Co

Water

VA-SFODME

FAAS

Filtration; 8 mL sample; pH 3.5; 1.25 104 M


Triton X-114; 2.5 104 M 2-nitroso-1naphthol

Cr

Water

SM-DLLME-SFO

UV-Vis

Filtration; 10 mL sample; 50 L 4 103 M


DPC; 0.2 mL 0.5% (w/v) SDS; 0.5 mL 1 M H2SO4

Cr speciation

Water and urine

SFODME

ETAAS

Cu

Water

SFODME

FI-FAAS

Water: ltration; dilution 1:10. Urine:


centrifugation, 3000 rpm; ltration; dilution
2:10
Total inorganic Cr: reduction with
hydroxylamine hydrochloride
10 mL sample; pH 3.5; 0.2 mL 1 M NaF
100 mL sample; pH 6; without salt addition

Cu

Water

USAE-SFODME

FAAS

Filtration; 8 mL sample; pH 6; without salt


addition; 2 mL 103 M PAN

Cu

Water

SA-SFODME

FI-FAAS

100 mL sample; pH~6; without salt addition;


500 L 0.1% (w/v) Neutral red

Cu

Water

USAE-SFODME

FAAS

Filtration; 5 mL sample; pH 6; 2 mL DDTC;


sonication, 15 min

Cu

Water and beverages

VA-DLLME-SFO

FAAS

Filtration; 20 mL sample; 2 g NaCl; pH 8;


2.5 mM 8-HQ

Cu

Water, sediments and Ni


standard alloy

DLLME-SFO

FAAS

Cu

Hair and tea

DLLME-SFO

FAAS

Cu

Cereals

VA-DLLME-SFO

FAAS

Fe speciation

Water

DLLME-SFO

UV-Vis

Sediment: digestion heating with HNO3


Alloy: digestion heating with HNO3/H2O2;
ltration
10 mL sample; pH 7; 0.5% (w/v) NaCl
digestion heating with HNO3/HClO4;
neutralization
20 mL sample; pH 4; 1% (w/v) NaCl; 0.5 mL
0.01 M 8-HQ
pulverization; sieving; carbonization and
ashing; dissolution in HNO3; ltration
15 mL sample; pH 8; 2 g NaCl; 0.5 mL 100 mM
8-HQ
Filtration; 60 mL sample; pH 4.8; without salt
addition

LR/LOD/EF

1 mL ethanol containing 80 L 1-dodecanol;


centrifugation, 3000 rpm, 3 min; cooling,
2 min; drop dilution to 500 L with ethanol;
500 L injected
30 L 1-undecanol; vortex mixing, 2800 rpm,
60 s; centrifugation, 4500 rpm, 3 min; cooling,
10 min; drop dilution to 400 L with ethanol;
400 L injected
90 mg decanoic acid in 0.6 mL THF;
centrifugation, 4000 rpm, 5 min; cooling,
1.5 min; drop dilution up to 150 L with
acetonitrile; 150 L injected
30 L 103 M TTA in 1-undecanol; stirring,
1250 rpm, 30 min; cooling, 5 min; 10 L
injected

LR: 1.15110 g
LOD: 0.35 g L1
EF: 160

200 L 0.2% DPC in 1-dodecanol; stirring,


500 rpm, 60 min; cooling, 10 min; drop
dilution to 300 L with ethanol; 200 L
injected
60 L 1-dodecanol; sonication, 15 min, 45C;
centrifugation, 2000 rpm, 2 min; cooling,
2 min; drop dilution to 500 L with ethanol;
500 L injected
100 L 0.05% SDBS in 1-dodecanol; stirring,
300 rpm, 20 min; cooling, 10 min; drop
dilution to 300 L with methanol; 200 L
injected
60 L 1-dodecanol; sonication, 15 min;
centrifugation; 2000 rpm, 2 min; cooling,
5 min; drop dilution to 500 L with ethanol;
500 L injected
150 L 1-dodecanol and 1.25 mL methanol;
vortex mixing, 1 min; centrifugation,
3500 rpm, 3 min; cooling, 5 min; drop dilution
with 350 L methanol
0.5 mL ethanol containing 25 L 1-undecanol
and 103 M PAN; centrifugation, 2500 rpm,
2 min; cooling, 5 min; drop dilution to 300 L
with ethanol; 300 L injected
0.5 mL ethanol containing 150 L
1-undecanol; centrifugation, 3500 rpm,
10 min; cooling, 5 min; drop dilution to 500 L
with DMF; 500 L injected
150 L 1-dodecanol and 1.25 mL methanol;
vortex mixing, 1 min; centrifugation,
3500 rpm, 3 min; cooling, 5 min; drop dilution
with 350 L methanol
90 L 0.16 M TTA in 1-undecanol and 0.8 mL
ethanol; centrifugation, 2500 rpm, 3 min;
cooling, 5 min; drop dilution with 40 L
ethanol; 100 L injected

Ref.
L1

[201]

LR: 15400 g L1
LOD: 5.4 g L1
EF: 18

[202]

LR: 140 g L1
LOD: 0.23 g L1
EF: 50

[197]

LR: 0.030.13 g L1
LOD: 0.006 g L1
EF: 327

[198]

LR: 125 ng mL1


LOD: 0.4 ng mL1
EF: 324

[205]

LR: 20600 g L1
LOD: 0.76 g L1
EF: 12.5

[206]

LR: 0.520.0 ng mL1


LOD: 0.18 ng mL1
EF: 541

[207]

LR: 20800 g L1
LOD: 0.327 g L1
EF: 86

[208]

LR: 0.5300 ng mL1


LOD: 0.1 ng mL1
EF: 122

[209]

LR: 0.5300 ng mL1


LOD: 0.16 ng mL1
EF: 33

[210]

LR: 5200 g L1
LOD: 3.4 g L1
EF: 28

[211]

LR: 0.5500 ng mL1


LOD: 0.1 ng mL1
EF: 122

[212]

Fe(II), Fe(III):
LR: 951070,
31350 g L1
LOD: 25, 8 g L1
EF: 125, 162

[216]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Co

Extraction conditions

(continued on next page)


65

66

Table 3 (continued)
Sample

Mode

Detection

Sample treatment

Extraction conditions

LR/LOD/EF

Ref.

Fe speciation

Water

DLLME-SFO

FAAS

[217]

Water

SFODME

ETAAS

LR: 0.23 g L1
LOD: 0.07 g L1
EF: 430

[219]

Hg

Human saliva

SFODME

CV-AFS

1 mL ethanol containing 50 L 1-undecanol;


centrifugation, 4000 rpm, 4 min; cooling,
10 min; drop dilution to 500 L with ethanol;
500 L injected
50 L undecanoic acid at 50C; stirring,
1000 rpm, 10 min and next 300 rpm, 2 min;
cooling; 10 L injected
BE for samples with high Ca content: 25 L 1 M
HCl; 25 L cyclohexane for phases separation
60 L 1-undecanol at 35C; cooling; drop
dilution to 2 mL with ethanol; 2 mL injected

LR: 25250 g L1
LOD: 4.8 g L1
EF: 20

Hg

Filtration; 5 mL sample; pH 3; without salt


addition; 1.1 103 M oxine; dilution to 10 mL
Total inorganic Fe: oxidation with
concentrated HNO3
25 mL sample; pH 5; without salt addition;
heating, 50C

LR: 0.02510 ng mL1


LOD: 2.5 ng L1
EF: 182.4

[220]

Mn

Water

USAE-SFODME

ETAAS

Water and multivitamin


supplements

VA-SFODME

FAAS

LR: 0.510 ng mL1


LOD: 0.3 ng mL1
EF: 160
LOD: 5 g L1
EF: 67

[218]

Mo

Mo

Plants (corn roots and


leaves)

VA-SFODME

FAAS

50 L 1-undecanol; sonication, 5 min;


centrifugation, 6000 rpm, 10 min; cooling;
10 L injected
60 L 1-undecanol; vortex mixing, 2 min;
centrifugation, 2000 rpm, 2 min; cooling,
10 min; drop dilution with 500 L ethanol;
200 L injected
60 L 1-undecanol; vortex mixing, 2 min;
centrifugation, 2000 rpm, 2 min; cooling,
10 min; drop dilution to 500 L with ethanol;
200 L injected

LR: 0.024.0 mg L1
LOD: 4.9 g L1
EF: 67

[55]

Ni

Water

DLLME-SFO

FAAS

LR: 4.23250 g L1
LOD: 1.27 g L1
EF: 158

[222]

Pb

Water

SFODME

ETAAS

10 mL sample; pH 6; without salt addition

Water

D-DLLME-SFO

FAAS

pH 1; ltration; 10 mL sample; 0.4% (w/v)


NaNO3

Pb

Water

SFODME

Nanodrop-UV-Vis

Pb

Water

DLLME-SFO

FAAS

Filtration; 10 mL sample; pH 7; without salt


addition; 1.5 mL 0.2 g L1 APDC

LR: 430 ng L1
LOD: 0.9 ng L1
EF: 497
LR: 4700 ng mL1
LOD: 0.7 ng mL1
EF: 35
LR: No data
LOD: 0.006 g L1
EF: 356
LR: 8.43400 g L1
LOD: 2.53 g L1
EF: 151

[170]

Pb

0.75 mL ethanol containing 80 L 1-dodecanol;


centrifugation, 3000 rpm, 2 min; cooling,
1 min; drop dilution to 500 L with ethanol;
500 L injected
20 L 2 104 M dithizone in 1-undecanol;
stirring, 500 rpm, 5 min; cooling, 5 min; 10 L
injected
Zn-APDC in 1-undecanol-DMF; centrifugation,
2500 rpm, 8 min; cooling, 5 min; drop dilution
to 300 L with DMF; 300 L injected
20 L 103 M dithizone in 1-undecanol;
stirring, 25 min; cooling, 5 min

Pb

Water

DLLME-SFO

ETAAS

Filtration; 5 mL sample; without salt addition;


pH 4; 5 105 M dithizone

LR: 0.0520 ng mL1


LOD: 18 ng L1
EF: 77

[174]

Pb

Water and food (rice and


wheat ours)

SM-DLLME-SFO

ETAAS

Food: digestion by heating with HNO3/H2O2


5 mL sample; without salt addition; 105 M
DDTC; 0.01 M HNO3

LR: 0.130 ng mL1


LOD: 27 ng L1
EF: 52

[175]

Pb

Water and infant


formulae base powder

SFODME

ETAAS

Infant formula: ashing; dissolution with


HCl/HNO3
10 mL sample; pH 3; 50 L 0.5% (w/v) APDC;
stirring, 55C, 10 min

LR: 0.210 g L1
LOD: 0.058 g L1
EF: 113

[176]

Digestion with HNO3/H2O2 at 75C for 6 h;


water dilution
25 mL sample; pH 2; 100 L 0.6% DDTC;
stirring, 500 rpm, 10 min
pH 1; ltration; aliquot of sample; 200 L
0.05% 5-Br-PADAP; 0.8 mL 10% (w/v) NaCl;
water up to 8 mL; pH 10
Multivitamin samples: digestion by heating
with HNO3/H2O2
Aliquot of sample; pH 4.75; 2.5 mL 0.5% (w/v)
8-HQ; water to 8 mL; stand, 10 min
Washing; drying; grinding; microwave
assisted digestion with HNO3/H2O2; water
dilution
8 mL sample; pH 4.75; 2.5 mL 0.5% (w/v)
8-HQ; stand, 10 min
Filtration; 10 mL sample; pH 5; without salt
addition; 1.8 mL (0.2 g L1) APDC

90 L 1-dodecanol and 1 mL ethanol;


centrifugation, 3000 rpm, 3 min; cooling,
2 min; drop dilution to 500 L with ethanol;
500 L injected
0.4 mL methanol containing 35 L
1-undecanol, manual shaking, 30 s;
centrifugation, 3000 rpm, 5 min; cooling,
5 min; 20 L injected
30 mg decanoic acid in 400 L THF; stand,
5 min; centrifugation, 3000 rpm, 5 min;
cooling, 5 min; drop dilution with 40 L
methanol; 20 L injected
20 L 1-undecanol; stirring, 800 rpm, 30 min;
cooling, 5 min; drop dilution with 80 L
ethanol; 10 L injected

[221]

[171]

[172]

[173]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

Table 3 (continued)
Sample

Mode

Detection

Sample treatment

Extraction conditions

LR/LOD/EF

Ref.

Pd

Water

USAE-SFODME

FI-FAAS

Filtration; 10 mL sample; pH 1; 0.01 M NaCl

LR: 1.5100 g L1
LOD: 0.3 g L1
EF: 55

[223]

Pd

Water

USAE-SFODME

FAAS

15 mL sample; pH 2; without salt addition;


5 L 0.37% (w/v) APDC

LR: 2400 ng mL1


LOD: 0.6 ng mL1
EF: 49.9

[224]

Pd

Water and road dust

D-DLLME-SFO

ETAAS

Water: ltration
Dust: drying; digestion with
HNO3/HCl/HF/H2O2; neutralization
14 mL sample; 0.14% (w/v) NaNO3

LR: 0.110 ng mL1


LOD: 0.02 ng mL1
EF: 316

[225]

Rh

Pt-Ir alloys and road dust

LL-DLLME-SFO

FAAS

LR: 103700 g L1
LOD: 1.5 g L1

[226]

Sb

Water and alloys

USAE-SFODME

FAAS

Alloy: heating extraction with aqua regia/HCl


Dust: drying; sieving; digestion heating with
aqua regia; ltration
8 mL sample; pH 11.5; 1% (w/v) NaCl
20 mL sample; pH 6.2; without salt addition;
1 mL 1% BDTA; 1 mL 0.01% (w/v)
bromopyrogallol red

LR: 4900 ng mL1


LOD: 0.62 ng mL1
EF: 67

[180]

Sb speciation

Water, tea and basil

SFODME

ETAAS

40 L 6 103 M acetyl acetone in


1-undecanol; sonication, 5 min; centrifugation,
2400 rpm, 8 min; cooling, 5 min; drop dilution
to 100 L with 1 M HCl in ethanol; 80 L
injected
35 L 1-undecanol; sonication, 2 min;
centrifugation, 2500 rpm, 8 min; cooling,
5 min; drop dilution to 300 L with DMF;
300 L injected
14 mL 43.4 ng Cu(II); 0.7 mL 5% (w/v) NaNO3;
30 L 0.001% DDTC; 450 L ethanol containing
45 L 1-undecanol; centrifugation, 2500 rpm,
8 min; cooling, 4 min; drop dilution with
400 L ethanol and injection into the sample;
centrifugation, 2500 rpm, 5 min; cooling
1 mL ethanol containing 25 L 1-dodecanol;
centrifugation, 4000 rpm, 3 min; cooling,
5 min; drop dilution with 0.5 mL 0.5 M HNO3
in ethanol
45 L 1-undecanol; sonication, 2 min;
centrifugation, 1250 rpm, 8 min; cooling,
10 min; drop dilution to 300 L with ethanol;
300 L injected
50 L 1-undecanol; stirring, 1200 rpm, 10 min;
cooling; 10 L injected

Sb speciation

Water and soils

USAE-SFODME

ETAAS

Se

Water and selenium plus


tablets

IP-DLLME-SFO

UV-Vis

Se

Water, selenium plus


tablets and garlic

DLLME-SFO

UV-Vis

Se(IV)

Water

SFODME-UA-BE

HG-AFS

Water: ltration; pH 5
Tea and basil: ashing; heat digestion with HCl;
ltration
10 or 25 mL sample; pH 5; without salt
addition; 0.5 mL 2 103 M APDC
For total inorganic Sb: 0.5 mL 10% (w/v) KI and
0.5% (w/v) ascorbic acid
Water: ltration
Soil: 5 g shaken with 40 mL water for 2 h;
centrifugation; ltration
40 mL sample; pH 9; 0.6 mL 3% DDTC
For total inorganic Sb: 0.2% L-cysteine and
0.4 M HCl; heating, 50C, 30 min
Water: ltration
Tablets: grinding, heat digestion with HCl;
ltration
20 mL sample; 0.5 mL 4 M HCl; heating,
30 min; 2 mL 0.04 M NaI; pH 3
Water: ltration; cation exchange
Tablets: grinding; heat digestion with HCl;
ltration
Garlic: digestion HNO3/HClO4
20 mL sample; 0.25 mL 20% HCOOH; 0.7 mL
0.023 M DAB; pH 22.5; stand, 30 min;
pH 67; without salt addition
Total inorganic Se: HBr
Filtration; 10 mL sample; pH 3; 100 L
1.2% (w/v) APDC

For 10 and 25 mL sample: [181]


LR: 60450,
20170 ng L1
LOD: 15, 5 ng L1
EF: 187.5, 437.5

50 L 1-undecanol; sonication, 20 min, 35C;


centrifugation, 6500 rpm, 10 min; cooling,
10 min; drop dilution with 0.5 mL methanol
containing 0.1 M HNO3; 20 L injected

LR: 0.0510.0 ng mL1


LOD: 9.89 ng L1
EF: 80

[182]

1 mL ethanol containing 2.6 105 M CTAB and


40 L 1-undecanol; centrifugation; cooling,
5 min; drop dilution with 40 L ethanol

LR: 401000 g L1
LOD: 16 g L1
EF: 250

[187]

100 L 1-undecanol and 150 L ethanol;


centrifugation, 1500 rpm; cooling, 5 min; drop
dilution with 50 L ethanol

LR: 5600 g L1
LOD: 1.6 g L1
EF: 133

[188]

40 L 1-undecanol; stirring, 20 min; cooling


BE: 300 L 5 M HNO3; sonication, 30 min;
cooling; 300 L injected

LR: 0.015.0 g L1
LOD: 7.0 ng L1
EF: 15

[189]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

(continued on next page)


67

68

Table 3 (continued)
Sample

Mode

Detection

Sample treatment

Extraction conditions

LR/LOD/EF

Ref.

Se speciation

Tea leaves and infusions

SFODME

ETV-ICP-MS

20 L 0.02 M APDC in 1-dodecanol; stirring,


900 rpm, 30 min, 45C; cooling; drop dilution
to 100 L with THF; 10 L injected

LR: 0.0110 ng mL1


Se(IV), Se(VI): 0.19,
LOD: 0.26 pg mL1
EF: 500

[190]

Te(IV)

Water and soils

USAE-SFODME

ETAAS

40 L 1-undecanol; sonication, 4 min;


centrifugation, 2500 rpm, 8 min; cooling,
5 min; 20 L injected

LR: 0.010.24 ng mL1


LOD: 0.003 ng mL1
EF: 342

[191]

Tl

Water

USAE-SFODME

ETAAS

Total Se: microwave assisted digestion with


HNO3/H2O2
Suspended and soluble Se: infusion ltration;
acid digestion separately of ltrate and
insoluble residues. Se(VI) reduction with HCl
in the ltrate
10 mL sample; pH 4
Water: Te(VI) reduction in 6 M HCl, 45 min;
pH 1.5; ltration
Soil: heat digestion with HNO3:HCl:HF;
ltration
14 mL sample; 0.33% (w/v) NaNO3; pH 1.5;
1.8 L 0.001% (w/v) APDC
pH 1; ltration; 8 mL sample; pH 5.5; 200 L
0.05% (w/v) PAN

Hair

DLLME-SFO

FAAS

LR: 0.210 g L1
LOD: 0.03 g L1
EF: 200
LR: 6900 ng mL1
LOD: 2.1 ng mL1
EF: 42.7

[167]

Tl speciation

40 L 1-undecanol; sonication, 6 min;


centrifugation, 4000 rpm, 5 min; cooling,
5 min; 20 L injected
2.5 mL ethanol containing 100 L 1-dodecanol;
centrifugation, 3000 rpm, 6 min; cooling,
5 min; drop dilution with 1 mL 0.5 M HNO3 in
methanol

Water

SFODME

UV-Vis

LR: 0.875 ng mL1


LOD: 0.1 ng mL1
EF: 125

[234]

Water

SFODME

UV-Vis

Filtration; 50 mL sample; pH 5; 0.01 M NaCl

Water and parsley

DLLME-SFO

ETAAS

Zn

Water

USAE-SFODME

FAAS

Water: ltration; pH 3
Parsley: carbonization; digestion with HNO3;
ltration
25 mL sample; pH 3; without salt addition
Filtration; 5 mL sample; pH 5; without salt
addition; 2 mL 103 M PAN

LR: 3100 g L1
LOD: 0.94 g L1
EF:38
LR: 201000 ng L1
LOD: 7 ng L1
EF: 184

[229]

50 L 5% HDEHP in 1-dodecanol; stirring,


900 rpm, 40 min, 35C; cooling, 5 min; mixing
with 500 L 0.2% Arsenazo III in methanol;
stand, 10 min
300 L 6.8 103 M oxine in 1-undecanol;
stirring, 1000 rpm, 20 min; cooling; drop
dilution to 500 L with ethanol
80 L 0.03 M BPHA in 1-undecanol and 200 L
acetone; centrifugation, 1500 rpm, 2 min;
cooling, 10 min; 20 L injected

LR: 20450 g L1
LOD: 0.79 g L1
EF: 76

[54]

Zr

Water (containing Hf)

DLLME-SFO

ICP-OES

90 L 1-dodecanol; sonication, 20 min, 40C;


centrifugation, 2000 rpm, 2 min; cooling,
3 min; drop dilution to 500 L with ethanol;
500 L injected
2 mL acetone containing 140 L 1-undecanol;
centrifugation, 5000 rpm, 5 min; cooling,
5 min; drop dilution with 100 L of
1-propanol; 200 L injected

No data

[232]

Multiel-emental
Au, Tl

Water and hair

LL-IP-USAE-SFODME ETAAS

30 L 1-undecanol; sonication, 3 min (or


alternatively 300 L ethanol); centrifugation,
3000 rpm, 5 min; cooling, 10 min; drop
dilution to 100 L with methanol; 20 L
injected

LR: 2.289,
22.2667 ng L1
LOD: 0.66, 4.67 ng L1
EF: 441, 443

[169]

Cd, Ni

Water and tea

UASEME-SFO

30 L 1-dodecanol; 25 L 40 mM Triton X-100;


sonication, 2 min; centrifugation, 3000 rpm,
5 min; cooling, 1 min; drop dilution with 50 L
ethanol; 50 L injected

LR: 0.3100,
0.6180 g L1
LOD: 0.11, 0.20 g L1
EF: 64, 60

[196]

FAAS

Digestion with HNO3


50 mL sample; pH 10; 0.2 mL 1.5 mg mL1 PAN;
3 mL 10% (w/v) NaCl
Total inorganic Tl: heating with 0.01 M [Ce(IV)/
Mn(II)]/0.1 M HNO3
15 mL sample; 0.1 M HClO4; without salt
addition

20 mL sample; 2 M HNO3; 30 L 20% (w/v)


cyanex 272 in 1-propanol

Water: ltration
Hair: drying; digestion with HClO4/HNO3/
H2SO4
20 mL sample; 2 mL 0.1 M hydroxylamine
hydrochloride; 2.5 mL HCl; without salt
addition; 1.6 mL 0.5 M BDTA
Water: ltration
Tea: digestion heating with HNO3/H2O2 to
dryness; dissolution with 5 mL 1 M HNO3 and
dilution
5 mL sample; pH 8; without salt addition;
1.5x105 M dithizone

[168]

[230]

(continued on next page)

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

Table 3 (continued)
Sample

Mode

Detection

Sample treatment

Extraction conditions

LR/LOD/EF

Ref.

Co, Ni

Water

SFODME

ETAAS

10 mL sample; pH 7; without salt addition

LR: 560, 550 ng L1


LOD: 0.4, 0.3 ng L1
EF: 502, 497

[203]

Cu, Zn

Water

DLLME-SFO

FI-UV-Vis

pH 7.5; 4 103 M PAN

20 L 6.8 104 M PAN in 1-undecanol;


stirring, 1000 rpm, 30 min; cooling, 5 min;
drop dilution to 500 L with ethanol; 10 L
injected
80 L 1-undecanol and 200 L acetonitrile

Dy, Y
Fe, Al

Water
Water

SFODME
IP-SFODME

ETV-ICP-MS
UV-Vis

Fe, Cu

Water, food (cheese, rice, USAE-SFODME


honey and powdered milk)
and rocks

FAAS

Pb, Cd

Water

SFODME

ETAAS

La, Eu, Yb

Water, shrub and hair

SFODME

ETV-ICP-MS

Ni, Co, Cu

Water

DLLME-SFO

ETAAS

Co, Ni, Pb, Cr

Industrial wastewaters

DLLME-SFO

ETAAS

50 mL sample; pH 7; 0.5% (w/v) NaCl

1.5 mL ethanol containing 80 L 1-undecanol


and 1.5 103 M 5-Br-PADAP; centrifugation,
4000 rpm, 5 min; cooling, 5 min; 10 L
injected

Mn, Cr, Co, Cu

Water

DLLME-SFO

ICP-OES

20 mL sample; pH 6; without salt addition;


TTA with chelating/metal ions molar ratio of 2

2 mL acetone containing 140 L 1-undecanol;


centrifugation, 6000 rpm, 3 min; cooling,
5 min; drop dilution in 100 L 1-propanol;
100 L injected

Co, Pd, Cd, Hg,


Pb, Bi

Water

SFODME

ETV-ICP-MS

Filtration; 10 mL sample; pH 9.5; 0.5% (w/v)


DDTC

30 L 15:85 1-dodecanol/p-xylene mixture;


stirring, 1000 rpm, 20 min; cooling; 10 L
injected

12 mL sample; pH 4; 0.1 mL 6 104 M NaClO4;


0.1 mL 6 105 M morin
Water: pH 2; ltration
Food: Digestion with HNO3/H2O2 and heating
Rock: Digestion with HNO3/HClO4/HF;
evaporation to dryness; dissolution with HCl
Total Fe and Cu: oxidation by heating with
HNO3/H2O2
5 mL sample; pH 3; without salt addition;
0.7 mL 1 g L1 2-mercaptopyridine n-oxide
25 mL sample; pH 5; without salt addition;
heating, 50C
Water: ltration
Shrub and hair: microwave assisted digestion
with HNO3/H2O2
10 mL sample; pH 8; without salt addition
Filtration; 10 mL sample; pH ~ 7; 0.01 M NaCl;
100 L 1.3 103 M DDTC

PAN
60 L 1-undecanol; stirring, 1000 rpm, 15 min;
cooling, 3 min; drop dilution with 60 L
ethanol; the whole diluted extract injected
100 L 1-dodecanol; sonication, 20 min, 40C;
centrifugation, 3500 rpm, 5 min; cooling,
3 min; drop dilution to 500 L with ethanol;
500 L injected

50 L undecanoic acid at 50C; stirring,


1000 rpm, 10 min and next 300 rpm, 2 min;
cooling; 10 L injected
20 L 102 M PAN in 1-dodecanol; stirring,
800 rpm, 30 min; cooling; drop dilution to
100 L with THF; 10 L injected
100 L 1-undecanol and 200 L acetone;
centrifugation, 2200 rpm, 3 min; cooling,
5 min; 10 L injected

LR: 330, 123 g L1


[213]
LOD: 1.5, 0.25 g L1
EF: 85, 86.3
LOD: 0.019, 0.032 pg mL1 [231]
LR: 0.8327, 132 g L1 [166]
LOD: 0.11, 0.17 g L1
LR: 40800,
201200 g L1
LOD: 8.6, 4.1 g L1
EF: 13.1, 13

[214]

LR: 25400, 115 ng L1


LOD: 10, 0.5 ng L1
EF: 380, 420
LR: 0.0110 ng mL1
LOD: 2.1, 0.65,
0.91 pg mL1
EF: 500
LR: 10120, 10100,
7150 ng L1
LOD: 1.2, 1.1, 1 ng L1
EF: 277, 270, 300
LR: 555, 540, 550,
1.025 ng L1
LOD: 1.3 (Co, Ni, Pb),
0.2 (Cr) ng L1
EF: 800
LR: 0.5250 (Mn),
1.25250 (Cr, Co,
Cu) g L1
LOD: 0.10.3 g L1
EF: 57, 96, 76, 93
LR: 0.0120 ng mL1
LOD: 217 ng L1
EF: 20324

[177]

[233]

[204]

[178]

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

Analyte

[199]

[179]

69

70

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

6.1. Nature and volume of the extraction solvent


The selection of a suitable extraction solvent is crucial for optimizing the SFODME process. The extraction solvent must meet
certain requirements:

low volatility and low water solubility in order to remain stable


during the extraction period;
a high anity for analytes;
a melting point near room temperature (in the range 1030C);
and,
in the case of being chromatographically analyzed, to be separated from the analyte peaks in the chromatogram and show good
chromatographic behavior.

6.1.1. Organic compounds


For the extraction of organic compounds, 1-undecanol (melting
point: 1315C) was found to give the best extraction eciency,
while its chromatographic peak was easily distinguished from the
analyte peaks. In addition, because of its stability, low vapor pressure and low water solubility under extraction conditions,
1-undecanol is one of the more frequently selected extraction solvents (accounting for 39% of all published studies). Another
frequently used solvent is 1-dodecanol (appearing in 43% of studies).
Other solvents used include 2-dodecanol [56,86,93,98,161], 2-decanol
[159], n-hexadecane [103105,145], cyclohexanol [151,152], 1-octanol
[116,163], cyclohexane [75], a mixture of acetophenone/1-undecanol
(1:8) [84], a mixture of 1-undecanol/chloroform [138] and
1-hexadecanethiol [95].
Moradi and Yamini reported an ecient, environment-friendly
method for the analysis of parabens using solidied oating vesicular coacervative drop microextraction (SFVCDME) [85]. 1 L of
supramolecular solvent, produced from the coacervation of decanoic acid aqueous vesicles in the presence of tetrabutylammonium
(Bu4N+), was directly injected into an LC, with no need for dilution
or solvent evaporation [85].
Ionic liquids (ILs) consist of organic cations and organic or inorganic anions with some special characteristics, such as negligible
vapor pressure, good chemical and thermal stability, a good ability
to dissolve both organic and inorganic compounds, and good miscibility with both water and organic solvents. Nevertheless, we found
only one article devoted to application of ILs in SFODME mode: Yang
et al. used trihexyl(tetradecyl)phosphonium hexauorophosphate
([P14,6,6,6]PF6) for the determination of benzoylurea insecticide in fruit
juice by HPLC [128].
6.1.2. Inorganic compounds
Among the organic solvents used for extracting inorganic analytes,
1-undecanol is by far the most widely used, specically in 62% of
the published procedures, and 1-dodecanol is the second most used
at 32%. The saturated fatty acids undecanoic acid [177,219] and decanoic acid have been proposed as extractants [175,197].
Guo et al. used a mixture of solvents as extractant phase for the
determination of heavy metals in environmental waters by
ETV-ICP-MS [179]. The relatively high boiling point of 1-dodecanol
prevented the application of high temperatures in the ETV drying
step without analyte losses. However, p-xylene, which also effectively extracts heavy metals and has a lower boiling point than
1-dodecanol, could not be used because of its low viscosity, which
prevented the solidied droplet from being collected. Consequently, a mixture 1-dodecanol/p-xylene was used as extraction solvent,
and it was removed from the graphite tubes at 200C, without
analyte losses [179].
The effect of the organic solvent volume on the analytical signal
was studied in the range 4400 L. Normally, the analytical signal
increases slowly with increasing solvent volume in a narrow range.

It then decreases when the solvent volume is increased. Based on LLE


equations, the rate of the analyte transport into the microdrop is directly related to the interfacial area between the two liquid phases
and inversely related to the organic-phase volume. Thus, by increasing
the drop volume, the effect of the interfacial area predominates and
the analytical signal is increased. By further increasing the microdrop
volume, the dilution effect predominates and the analytical signal decreases. Most of the proposed procedures use extraction solvent
volumes of 520 L (organics) and 2090 L (inorganics), whereas
volumes out of these ranges have been selected less frequently.
6.2. Selection of the disperser solvent for DLLME-SFO
When the extraction solvent and disperser solvent are added to
the aqueous sample solution, the extraction solvent will form very
ne droplets after shaking the solution for a few seconds. The disperser solvent should be miscible with both water and the extraction
solvent, and thus produce very ne droplets of extraction solvent
when the mixture of extraction and disperser solvent is rapidly injected into the aqueous sample. Methanol, ethanol, acetonitrile and
acetone were chosen for most applications. The volume of the disperser solvent varied in the range of 0.052.5 mL.
6.3. Stirring rate
Sample agitation is another important parameter that plays a large
role in enhancing extraction eciency and reducing extraction time,
as the thickness of the diffusion lm in the aqueous phase decreases. In most studies on organic compound preconcentration,
samples were continuously agitated at different rates of up to
1250 rpm using a magnetic stirrer. Normally, the relative peak area
increases by increasing the stirring rate up to a maximum value,
achieved at rates as high as 4001250 rpm [36,52,62,67,71,73,79,
81,84,91,98,99,102,107,111,112,128,140,143,150,158]. Nevertheless, very high stirring speeds can decrease the extraction
eciency due to spattering and damaging the organic droplet
[176,190,194,205,233].
For analysis of inorganic compounds, stirring also enhances the
kinetics of chelate formation; magnetic stirring speeds of 800 rpm
[176,233] to 1250 rpm [198] have been applied in SFODME methods.
Those procedures with stirring speeds around 300 rpm generally corresponded to high sample-volume analysis {i.e., 100 mL [194,205,207]}.
Lpez-Garca et al. [177,219] recommended two steps of different stirring powers, the second at a lower speed in order to group all the
enriched droplets of undecanoic acid. In this case, the centrifugation
step usually applied to disrupt the cloudy solution is omitted.
6.4. Extraction time
SFODME depends on equilibrium rather than exhaustive extraction. To increase the repeatability and the sensitivity of the extraction,
it is necessary to choose an extraction time during which equilibrium is reached between the aqueous and the organic phase. The
relative peak area for each analyte increases by increasing the exposure time and then remains constant, and it is this time that must
be selected. Times of 1030 min [36,62,67,68,71,73,79,8486,91,
99,102,105,107,111,112,128,140,150,162] or higher values of
3090 min [52,67,68,70,73,81,84,86,98,143,158] have been
selected for the extraction of organic compounds. Most of the optimized SFODME procedures for inorganic compounds have applied
extraction times in the 1030 min range. Lower and higher times
have been proposed, such as 5 min [170] and 60 min [205] for the
determination of lead and copper, respectively, in water samples.
In USAE-SFODME procedures, energy is applied by using ultrasound baths for times of 220 min. In VA-SFODME, extraction
equilibrium is achieved in shorter times. Several SFODME

P. Vias et al./Trends in Analytical Chemistry 68 (2015) 4877

applications assisted by vortex agitation are found in the literature


for organic compounds [58,80,83,90,92,100,109,114,116,136,153,156]
and inorganics [55,202,221] with extraction times of 0.52 min.
By contrast, extraction time is not an important variable for
DLLME-SFO, because the surface areas between extraction solvent
and sample solution are innitely large after formation of the cloudy
solution. The mass transfer of analytes from sample solution to extraction solvent therefore happens so fast that the extraction
equilibrium is achieved in a short time, and the analysis time for
the extraction procedure is shortened considerably. The timeconsuming step in DLLME-SFO is the solidication of the oating
extractant in the ice bath for 510 min.
6.5. Disruption of the cloudy solution
In most of the proposed procedures, centrifugation is the way selected to disrupt the cloudy solution. Centrifuging speeds of
4006500 rpm were applied for times of 210 min generally. However,
several authors omit the centrifugation step and aggregate the ne
droplets of the extractant directly while cooling the mixture. A cooling
step is included in all the published procedures, most employing an
ice bath within the mixture, and is maintained in the 310 min range
generally, although Sahin et al. proposed cooling in a refrigerator for
10 min [194,205,207]. The cooling step allows the enriched phase to
be easily collected, generally by being transferred into a conical vial,
where it melts immediately, taking into account the low melting point
of the organic solvents used in SFODME. When undecanoic acid is
used [177,219], heating of the enriched phase to 50C, once separated from the sample, has been recommended, taking into account
its slightly higher melting point and density than commonly used
solvents, such as 1-undecanol and 1-dodecanol. Disruption of the
cloudy state can also be achieved by adding a new portion of disperser solvent, which acts as demulsier [104].
Several authors recommend dilution of the enriched phase prior
to being analyzed in order to decrease its viscosity and thus facilitate
its collection. Ethanol, methanol and acetonitrile are the solvents
most commonly used for this purpose, although 1-propanol and
dimethylformamide have been used to a lesser extent. Chen et al.
[233] indicated the convenience of diluting the extract of
1-dodecanol with THF to facilitate not only sample introduction into
the ETV, but also removal of the organic solvent through the ETV
temperature program. In this way, in the presence of THF, the
removal of the extraction solvent from the furnace has been carried
out at 220C without analyte loss. Moreover, enhancement of sensitivity in experiments with metal complexes in the presence of a
diluent, THF, was attained. The volume of the diluted extract is generally found in the 150500-L range, this value being conditioned
mainly by the minimum volume necessary to carry out the analytical measurement.
7. Concluding remarks and future trends
In the past decade, we have witnessed the attention of analytical chemists constantly growing towards the development of new
microextraction techniques that could better satisfy the requirements of green analytical chemistry.
A considerable proportion of the publications describing SFODME
procedures has been devoted to the analysis of various types of water
samples due to the simplicity of this matrix; however, application
of the technique in other elds, such as analysis of biological uids,
foods, or soil and sediments, increased in recent years. In many cases,
the simplicity of water samples enables avoidance of sample pretreatment before the preconcentration step, or limits it to simple
ltration in order to remove particulate matter, especially in
environmental waters. More complicated aqueous samples, such as
fruit juices, wine and honey, frequently require only ltration and

71

centrifugation or dilution with water. Solid samples, such as foods,


fruits and vegetables, soils and sediments, necessitate the inclusion of a pre-treatment step for extraction of the analyte from the
solid matrices into an aqueous phase suitable for SFODME analysis. The conjunction of SPE and SFODME allows sensitivity to be
increased, since the preconcentrated sample volume is considerably increased. However, there are relatively few publications devoted
to coupling SFODME with SPE or QuEChERS.
Most of the reported SFODME procedures performed the
microextraction step in the conventional mode, while the rest
employed certain modications aimed at improving the stirring
or agitation, and thus reducing the extraction time. This can be
achieved by using a disperser solvent in DLLME-SFO, applying
ultrasound energy in UA-DLLME-SFO and USAE-SFODME, or vortex
mixing in VA-DLLME-SFO and VA-SFODME. The addition of a surfactant can also enhance the SFODME process. In addition to reducing
the use of organic solvents, the current trend in analytical chemistry is towards automating procedures. However, automation of
SFODME is complicated and dicult, and has not yet been
accomplished.
Most of the SFODME methods described for inorganic analysis
were developed for the determination of a total metal content; nevertheless, several of them include speciation studies. We can expect
an increase in publications in this area. However, we did not nd
any articles devoted to SFODME procedures for inorganic anions.
Application of ILs is currently a hot topic in analytical chemistry,
but we found only one article devoted to application of ILs in
SFODME. We also anticipate growth in this eld.
The SFODME method has advantages, such as simplicity, good
accuracy and precision, short extraction times, low costs, and
minimum organic solvent consumption. Since a fresh portion of
organic solvent is used for each extraction, there is no memory effect,
and since the volume of the organic phase is very low, large
preconcentration factors are achievable. Since a specic holder is
not required to support the organic microdrop, stirring the sample
solution at very high speeds is possible. Also, by using a multistirrer, parallel extraction of many samples is possible.
Compared with other microextraction methods, the main drawback of the SFODME method is the limitation in the selection of an
extraction solvent. However, many solvents with suitable melting
points are available.
Acknowledgments
The authors acknowledge the nancial support of the Comunidad
Autnoma de la Regin de Murcia (CARM, Fundacin Sneca, Project
15217/PI/10) and the Scientic Grant Agency of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences
(Grant No. VEGA 1/0010/15). This work was supported in part
through the development of bilateral cooperation between the Slovak
and Spanish universities within the Operational Programme Education nanced by the European Social Fund (ESF) (Project ITMS
26110230084).
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