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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
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.
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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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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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
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
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).
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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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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.
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Fig. 3. Applications of solidied oating organic drop microextraction (SFODME) to the determination of inorganic compounds.
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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.
Water
DLLME-SFO
HPLC-UV
LR: 0.1200 g L1
LOD: 0.020.05 g L1
[127]
Aliphatic amines
Water (environmental)
DLLME-SFO
HPLC-DAD
[74]
Alkylphenols
SFODME
UPLC-UV
Tobacco
DLLME-SFO
GC-MS
Amphetamine and
methamphetamine
Urine
VASEME-SFO
HPLC-UV
[95]
Amino acids
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
DLLME-SFO
GC-MS
LR: 0.5200 g L1
LOD: 0.070.29 g L1
[75]
Antidepressant drugs
DLLME-SFO
GC-MS
[145]
Antidepressant drugs
USAE-SFODME
HPLC-UV
LR: 101000 g L1
LOD: 3 g L1
[146]
Antifungal drugs
SFODME
HPLC-DAD
LR: 0.1300 g L1
LOD: 0.010.1 g L1
[143]
SFODME
GC-FID
[67]
BTEX
Water
SFODME
GC-FID
LR: 0.02300 g L1
LOD: 0.070.18 g L1
[68]
BTEX
SFODME
GC-FID
LR: 0.20400 g L1
LOD: 0.040.09 g L1
[69]
BTEX
SFODME
DLLME-SFO
GC-FID
[70]
[161]
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
IL-SFODME
HPLC-UV
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
LR: 0.055 mg L1
LOD: 0.08 g mL1
[159]
2-agonists
Bovine urine
VA-DLLME-SFO
CE-UV
[136]
Biogenic amines
VA-DLLME-SFO
LC-UV
[153]
Bisphenol A
Water (environmental)
AA-DLLME-SFO
HPLC-UV
[89]
Bisphenol A
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
[129]
DLLME-SFO
FLD
[148]
Chlorinated anilines
Water (environmental)
USAE-SFODME
HPLC-UV
[76]
Chlorpyrifos
Water (environmental)
DLLME-SFO
GC-FPD
LR: 0.054 g L1
LOD: 0.02 g L1
[96]
DLLME-SFO
HPLC-UV
LR: 150 g L1
LOD: 0.100.12 g L1
[97]
SFODME
GC-MS
[98]
DLLME-SFO
HPLC-UV
LR: 3.51400 ng g1
LOD: 2.3 pg g1
[78]
[90]
55
Urine
[128]
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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
DLLME-SFO
HPLC-DAD
Diethofencarb and
pyrimethanil
DLLME-SFO
HPLC-DAD
[71]
Diethofencarb and
pyrimethanil
UA-DLLME-SFO
GC-ECD
[118]
Dinitrobenzenes
Duloxetine
Human plasma
VA-DLLME-SFO
HPLC-FLD
[139]
Estrogenic hormones
Water
DLLME-SFO
HPLC-FLD
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
Fat-soluble vitamins
(A, D2, D3)
SFODME
HPLC-UV
LR: 5500 g L1
LOD: 1.03.5 g L1
[158]
Fenvalerate
Tomato
DLLME-SFO
HPLC-UV
[130]
Flavonoids
SFODME
HPLC-UV
MSA-SFODME
HPLC-UV
Fungicides
DS-SFODME
HPLC-DAD
[154]
Fungicides
Traditional Chinese
medicines
Water and wine
Fungicides
Sediments
UA-DLLME-SFO
HPLC-DAD
LOD: 0.10.5 g g1
[120]
Fungicides
UASEME-SFO
HPLC-DAD
LR: 51000 g L1
LOD: 0.41.4 g L1
[121]
10 mL sample
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
[72]
[132]
[134]
[119]
[52]
[117]
Table 2 (continued)
Sample
Mode
Detection
Sample pretreatment
Extraction conditions
LR/LOD
Ref.
Fungicides
Wine
DLLME-SFO
GC-MS
[122]
Fungicides
Grape
UA-DLLME-SFO
HPLC-UV
[123]
Fungicides
Fruit juice
UA-DLLME-SFO
HPLC-UV
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
[124]
Fungicides mixture
Water
UA-DLLME-SFO
HPLC-DAD
[125]
Haloanisoles and
halophenols
Wine
USAE-SFODME
GC-ECD
LR: 10500 ng L1
LOD: 2.25 ng L1
[151]
Wine
USAE-SFODME
GC-MS/MS
[152]
Halogenated organic
compounds
DLLME-SFO
GC-ECD,
GC-MS
Haloperidol
USAE-SFODME
HPLC-DAD
Kanamycin
DLLME-SFO
HPLC-FLD
[140]
Lignans
Traditional Chinese
medicines
Rat urine
SFODME
HPLC-UV
HPLC-UV
[157]
DLLME-SFO
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
[86]
Neonicotinoid pesticides
VASEME-SFO
HPLC-UV
LR: 12250 g L1
LOD: 8 g L1
LR: up to 5 g mL1
LOD: 0.10.5 g L1
Lovastatin and
simvastatin
[56]
[142]
Analyte
[137]
[116]
58
Table 2 (continued)
Sample
Mode
Detection
Sample pretreatment
Extraction conditions
LR/LOD
Ref.
Urine
SFODME
HPLC-UV
15 mL urine centrifugation; 10 mL
supernatant; 7 g NaCl; pH 9 with 0.1 M
NaOH
[138]
Nitrophenols
Water
USAE-SFODME
UHPLC-UV
LR: up to 1000 g L1
LOD: 0.53.2 g L1
[57]
Nitrotoluene compounds
SFODME
GC-FID
LR: 0.5200 g L1
LOD: 0.30.5 g L1
[73]
Macrolide antibiotics
Human urine
DLLME-SFO
LC-CAD
[141]
Opium alkaloids
Human plasma
DLLME-SFO
HPLC-UV
LR: 1.51000 g L1
LOD: 0.55 g L1
[144]
SFODME
GC-ECD
GC-ECD
LR: 252000 ng L1
LOD: 719 ng L1
LR: 0.02520 g L1
LOD: 0.0110.11 g L1
[102]
DLLME-SFO
SD-DLLME-SFO
GC-MS
LR: 0.0252.00 g L1
LOD: 0.0120.024 g L1
[104]
SFODME
GC-ECD
GC-ECD
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
VA-DLLME-SFO
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
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
[101]
Parabens
SFVCDME
HPLC-UV
LR: 0.5100 g L1
LOD: 0.20.5 g L1
[85]
[103]
[106]
[100]
Analyte
Table 2 (continued)
Sample
Mode
Detection
Sample pretreatment
Extraction conditions
LR/LOD
Ref.
Pesticides
UA-DLLME-SFO
GC-FID
LR: 0.20200 g L1
LOD: 0.110.48 g L1
[164]
Phenolic compounds
SFODME
GC-MS
LR: 0.02300 g L1
LOD: 0.0050.68 g L1
[91]
Phenolic compounds
VA-DLLME-SFO
HPLC-UV
[92]
Phenolic pollutants
USAE-SFODME
HPCE
LR: 0.05100 g L1
LOD: 0.010.04 g L1
[93]
Phthalate esters
SFODME
GC-MS
USAE-SFODME
HPLC-DAD
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
VA-DLLME-SFO
CLC-UV
[83]
Plasticizers
SFODME
GC-FID
20 mL; 1 M NaCl
LR: 0.210 g L1
LOD: 0.010.03 g L1
[84]
Polybrominated diphenyl
ethers
HPLC-DAD
[79]
Polybrominated diphenyl
ethers
Sediments
VA-DLLME-SFO
GC-MS
LR: up to 1000 pg g1
LOD: 0.51.8 pg g1
[80]
Polycyclic aromatic
hydrocarbons
SFODME
GC-FID
DLLME-SFO
HPLC-DAD
[36]
Polycyclic aromatic
hydrocarbons
Polycyclic aromatic
hydrocarbons
PAHs, pesticides, phenols
and sulfonamides
Soil
DLLME-SFO
[60]
Water
DLLME-SFO
HPLC-UV
DLLME-SFO
GC-ECD
GC-ECD
LR: 5.02000 ng L1
LOD: 1.48.3 ng L1
[65]
[82]
Analyte
[59]
[61]
[64]
60
Table 2 (continued)
Analyte
Mode
Detection
Sample pretreatment
Extraction conditions
LR/LOD
Ref.
Sample
DLLME-SFO
GC-ECD
LR: 102000 ng L1
LOD: 2.818.5 ng L1
[66]
Propranolol enantiomers
Human plasma
DLLME-SFO
HPLC-FLD
[149]
2-Pyrazoline derivatives
GC-FID
Pyrethroids
SFODME
GC-ECD
[107]
Pyrethroids
Water
DLLME-SFO
GC-ECD
LR: 102000 ng L1
LOD: 1.42.9 ng L1
[108]
Pyrethroid pesticides
Tea
VA-DLLME-SFO
GC-ECD
[109]
Quercetin
DLLME-SFO
FI-UV-Vis
LR: 50 1085.0 M
LOD: 108 M
[155]
Tanshinones
Traditional Chinese
medicinal injections
VA-DLLME-SFO
HPLC-UV
[156]
SFODME
HPLC-UV
[160]
Triclosan and
2,4-dichlorophenol
Water (environmental)
VA-DLLME-SFO
HPLC-MS/MS
HPLC-UV
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
DLLME-SFO
GC-MS
[110]
Triazine herbicides
Water
SFODME
HPLC-UV
[111]
Triazine herbicides
Soil
SFODME
GC-FPD
Triazine herbicides
Cereals
DMAE-SFO
HPLC-UV
LR: 51000 ng g1
LOD: 1.11.5 ng g1
[113]
[150]
[94]
[112]
Table 2 (continued)
Analyte
Sample
Mode
Detection
Sample pretreatment
VA-DLLME-SFO
HPLC-DAD
Triazole fungicides
Juice
USAE-SFODME
HPLC-UV
Trihalomethanes
Drinking water
SFODME
GC-MS
10 mL water; 3 M NaCl
Trihalomethanes
DLLME-SFO
GC-ECD
Steroid hormones
DLLME-SFO
HPLC-UV
Strobilurin fungicides
Fruit juice
UASEME-SFO
HPLC-DAD
Sudan dyes
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
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]
[63]
LR: 51000 g L1
LOD: 0.83.1 g L1
[135]
[126]
LR: 11250 ng g1
LOD: 0.100.20 ng g1 and
0.03 g L1
[162]
[163]
Triazole fungicides
Extraction conditions
[88]
61
62
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
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
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
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
Cd
Water
USAE-SFODME
FAAS
Cd
Water
LL-SA-SFODME
FI-FAAS
Cd
VA-DLLME-SFO
FAAS
Co
Water
SFODME
ETAAS
LR/LOD/EF
Ref.
mL1
LR: 0.110 ng
LOD: 0.056 ng mL1
EF: 250
[227]
[228]
LR: 1.0250 g L1
LOD: 0.8 g L1
EF: 128
[165]
[183]
[184]
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
[186]
[215]
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]
[194]
[195]
[200]
Ag
Extraction conditions
Table 3 (continued)
Analyte
Sample
Mode
Detection
Sample treatment
Water
DLLME-SFO
FAAS
Co
Water
VA-SFODME
FAAS
Cr
Water
SM-DLLME-SFO
UV-Vis
Cr speciation
SFODME
ETAAS
Cu
Water
SFODME
FI-FAAS
Cu
Water
USAE-SFODME
FAAS
Cu
Water
SA-SFODME
FI-FAAS
Cu
Water
USAE-SFODME
FAAS
Cu
VA-DLLME-SFO
FAAS
Cu
DLLME-SFO
FAAS
Cu
DLLME-SFO
FAAS
Cu
Cereals
VA-DLLME-SFO
FAAS
Fe speciation
Water
DLLME-SFO
UV-Vis
LR/LOD/EF
LR: 1.15110 g
LOD: 0.35 g L1
EF: 160
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]
[205]
LR: 20600 g L1
LOD: 0.76 g L1
EF: 12.5
[206]
[207]
LR: 20800 g L1
LOD: 0.327 g L1
EF: 86
[208]
[209]
[210]
LR: 5200 g L1
LOD: 3.4 g L1
EF: 28
[211]
[212]
Fe(II), Fe(III):
LR: 951070,
31350 g L1
LOD: 25, 8 g L1
EF: 125, 162
[216]
Co
Extraction conditions
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
LR: 25250 g L1
LOD: 4.8 g L1
EF: 20
Hg
[220]
Mn
Water
USAE-SFODME
ETAAS
VA-SFODME
FAAS
[218]
Mo
Mo
VA-SFODME
FAAS
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
Water
D-DLLME-SFO
FAAS
Pb
Water
SFODME
Nanodrop-UV-Vis
Pb
Water
DLLME-SFO
FAAS
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
Pb
Water
DLLME-SFO
ETAAS
[174]
Pb
SM-DLLME-SFO
ETAAS
[175]
Pb
SFODME
ETAAS
LR: 0.210 g L1
LOD: 0.058 g L1
EF: 113
[176]
[221]
[171]
[172]
[173]
Analyte
Table 3 (continued)
Sample
Mode
Detection
Sample treatment
Extraction conditions
LR/LOD/EF
Ref.
Pd
Water
USAE-SFODME
FI-FAAS
LR: 1.5100 g L1
LOD: 0.3 g L1
EF: 55
[223]
Pd
Water
USAE-SFODME
FAAS
[224]
Pd
D-DLLME-SFO
ETAAS
Water: ltration
Dust: drying; digestion with
HNO3/HCl/HF/H2O2; neutralization
14 mL sample; 0.14% (w/v) NaNO3
[225]
Rh
LL-DLLME-SFO
FAAS
LR: 103700 g L1
LOD: 1.5 g L1
[226]
Sb
USAE-SFODME
FAAS
[180]
Sb speciation
SFODME
ETAAS
Sb speciation
USAE-SFODME
ETAAS
Se
IP-DLLME-SFO
UV-Vis
Se
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
[182]
LR: 401000 g L1
LOD: 16 g L1
EF: 250
[187]
LR: 5600 g L1
LOD: 1.6 g L1
EF: 133
[188]
LR: 0.015.0 g L1
LOD: 7.0 ng L1
EF: 15
[189]
Analyte
68
Table 3 (continued)
Sample
Mode
Detection
Sample treatment
Extraction conditions
LR/LOD/EF
Ref.
Se speciation
SFODME
ETV-ICP-MS
[190]
Te(IV)
USAE-SFODME
ETAAS
[191]
Tl
Water
USAE-SFODME
ETAAS
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
Water
SFODME
UV-Vis
[234]
Water
SFODME
UV-Vis
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]
LR: 20450 g L1
LOD: 0.79 g L1
EF: 76
[54]
Zr
DLLME-SFO
ICP-OES
No data
[232]
Multiel-emental
Au, Tl
LL-IP-USAE-SFODME ETAAS
LR: 2.289,
22.2667 ng L1
LOD: 0.66, 4.67 ng L1
EF: 441, 443
[169]
Cd, Ni
UASEME-SFO
LR: 0.3100,
0.6180 g L1
LOD: 0.11, 0.20 g L1
EF: 64, 60
[196]
FAAS
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]
Analyte
Table 3 (continued)
Sample
Mode
Detection
Sample treatment
Extraction conditions
LR/LOD/EF
Ref.
Co, Ni
Water
SFODME
ETAAS
[203]
Cu, Zn
Water
DLLME-SFO
FI-UV-Vis
Dy, Y
Fe, Al
Water
Water
SFODME
IP-SFODME
ETV-ICP-MS
UV-Vis
Fe, Cu
FAAS
Pb, Cd
Water
SFODME
ETAAS
La, Eu, Yb
SFODME
ETV-ICP-MS
Ni, Co, Cu
Water
DLLME-SFO
ETAAS
Industrial wastewaters
DLLME-SFO
ETAAS
Water
DLLME-SFO
ICP-OES
Water
SFODME
ETV-ICP-MS
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
[214]
[177]
[233]
[204]
[178]
Analyte
[199]
[179]
69
70
71
72
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