Trends in Analytical Chemistry 82 (2016) 199–207

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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

Current sample preparation methodologies for analysis of emerging

pollutants in different environmental matrices
K. Mogolodi Dimpe, Philiswa N. Nomngongo *
Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, P.O. Box 17011, Johannesburg 2028, South Africa

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

Keywords:
Emerging contaminants such as pharmaceuticals, personal care products, and endocrine disrupting com-
Emerging pollutants
pounds are ever-present in environmental matrices and they are known to pose negative effects on living
Sample pretreatment methods
Pharmaceuticals
organisms. The determination of these pollutants in different environmental matrices (such as water, soil,
Personal care products and sediments, among others) frequently requires separation techniques that are capable of high effi-
Endocrine disrupting compounds ciency, unique selectivity and high sensitivity. However, direct analysis of these pollutants in complex
Environmental samples matrices is difficult. For this reason, rapid, inexpensive, efficient and environmentally friendly sample
Chromatographic techniques preparation techniques have been developed prior to chromatographic quantification. Therefore, the aim
of this article is to review recent publications (2010–2016) on modern sample preparation techniques
combined with chromatographic techniques for identification and quantification of emerging pollut-
ants in environmental matrices. These sample preparation techniques include solid phase extraction, solid
phase microextraction, liquid-liquid extraction, microwave-assisted extraction, liquid-phase microextraction
techniques, stir bar sorptive extraction, and pressurized liquid extraction, among others.
© 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................ 200

2. Sample preparation techniques ................................................................................................................................................................................................................... 200
2.1. Solid phase extraction (SPE) ............................................................................................................................................................................................................ 200
2.2. Solid phase microextraction (SPME) ............................................................................................................................................................................................ 201
2.3. Dispersive solid phase (micro) extraction (DSPE/DSPME) .................................................................................................................................................... 201
2.4. Microwave-assisted extraction (MAE) ......................................................................................................................................................................................... 202
2.5. Liquid-liquid extraction (LLE) ......................................................................................................................................................................................................... 202
2.6. Liquid phase microextraction techniques (LPME) ................................................................................................................................................................... 202
2.7. Pressurized liquid extraction (PLE) ............................................................................................................................................................................................... 203
2.8. Stir bar sorptive extraction (SBSE) ................................................................................................................................................................................................ 203
2.9. Other sample preparation techniques ......................................................................................................................................................................................... 203

Abbreviations: ASE, accelerated solvent extraction; BDE, bromodiphenyl ether; BFRs, brominated flame retardants; BSAs, benzenesulfonamides; BTRs, benzotriazoles;
BTs, benzothiazoles; BZPs, benzodiazepines; CTAB, cetyltrimethylammonium bromide; DDT, dichlorodiphenyltrichloroethane; DEET, N,N-Diethyl-meta-toluamide; DI-
SPME, direct-immersion solid phase microextraction; DLLE, dispersive liquid-liquid extraction; DSPE, dispersive solid phase extraction; DSPME, dispersive solid phase
microextraction; DVB, divinylbenzene; EDCs, endocrine disrupting compounds; ESE, enhanced solvent extraction; GC-FID, gas chromatography–flame ionization detection;
GC-MS, gas chromatography–mass spectrometry; GC-NCI-MS, gas chromatography negative chemical ionization mass spectrometry; HF-LPME, hollow fiber liquid-phase
microextraction; HLB, hydrophobic-hydrophilic balanced; HPLC, high performance liquid chromatography; HPLC-DAD, high performance liquid chromatography-diode array
detector; HSE, high-pressure solvent extraction; HS-SPME, headspace solid phase microextraction; IL-USA-DLLME, ionic liquid-based ultrasound assisted dispersive liquid-
liquid microextraction; LC-MS, liquid chromatography coupled to mass spectrometer; LC-MS/MS, liquid chromatography time-of-flight mass spectrometry; LLE, Liquid-
liquid extraction; LOD, limit of detection; LOQ, limit of quantification; LPME, Liquid Phase Microextraction; MNP, magnetic nanoparticles; MWCNTs, multiwalled carbon
nanotubes; MAE, Microwave assisted extraction; MS-DLLME, magnetic stirring assisted dispersive liquid–liquid microextraction; NPs, nanoparticles; NSAIDs, nonsteroidal
anti-inflammatory drugs; PAHs, polycyclic aromatic hydrocarbons; PBDE, polybrominated diphenyl ethers; PCBs, polychlorinated biphenyls; PDMS, polydimethylsiloxane;
PFE, pressurized fluid extraction; PLE, pressurized liquid extraction; QuEChERS, quick, easy, cheap, effective, rugged and safe; RDSE, rotating disk sorptive extraction; RSD,
relative standard deviation; SBSE, stir bar sorptive extraction; SUPRAS, supramolecular solvents; SPE, solid phase extraction; SPME, solid phase microextraction; TCC, triclocarban;
TCS, triclosan; TG-MS, thermogravimetry-mass spectrometry; UA-LLME, ultrasound-assisted liquid-liquid microextraction; UPLC-MS/MS, ultra performance liquid chroma-
tography coupled to mass spectrometer; UV, ultraviolet; VA-DLLME, vortex-assisted dispersive liquid–liquid microextraction; WWTP, wastewater treatment plant; XPS, x-ray
photoelectron spectroscopy.
* Corresponding author. Tel.: +27 115596187; Fax: +275596425.
E-mail address: pnnomngongo@uj.ac.za or nomngongo@yahoo.com (P.N. Nomngongo).

http://dx.doi.org/10.1016/j.trac.2016.05.023
0165-9936/© 2016 Elsevier B.V. All rights reserved.
200 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207

3. Novel solid and liquid phase materials ..................................................................................................................................................................................................... 204

3.1. Nanomaterials ....................................................................................................................................................................................................................................... 204
3.2. Ionic liquids (ILs) ................................................................................................................................................................................................................................. 204
3.3. Supramolecular solvents (SUPRAS) ............................................................................................................................................................................................... 204
4. Conclusion and future prospects ................................................................................................................................................................................................................. 204
Acknowledgements .......................................................................................................................................................................................................................................... 205
References ............................................................................................................................................................................................................................................................ 205

1. Introduction Table 1
Emerging pollutants found in the environment [7,17,18]

The presence of emerging pollutants in environmental matri- Chemical name Sources or use
ces has been reported in the literature and their occurrence in the Paracetamol Analgesic/Antipyretic
environment poses a significant risk to the ecosystem. According Amoxycillin Broad spectrum antibiotic
to EPA [1], emerging pollutants are classified as pollutants that have Metoprolol succinate β- blocker for blood pressure control
found their way to humans and animals due to the newly discov- N,N-Diethyl-meta-toluamide (DEET) Mosquito repellent
Triclosan Disinfectant, antimicrobial
ered source. These pollutants have no guidelines or legislative Benzophenone Fixative for perfumes and soaps
intervention that is currently available to regulate their presence Dieldrin, Aldrin, Endrin, β-endosulfan Organochlorine pesticides
in the environment [2–6]. Human activity such as personal care, Bisphenol A Plasticiser
healthcare, and industrial operations entails the use of chemicals Benzo[a]pyrene Regulated PAHs, used in cancer
research
that produces or generates waste [7]. The latter contains contami-
Tributyltin, cyhexatin Organotin compounds
nants that are in water systems. The contaminants in the waste are vinclozolin Fungicide
usually resistant to degradation. Therefore, they tend to accumu- Atrazine, simazine, terbutylazine, Herbicides
late in the environment which eventually becomes a hazard to living 2,4-D, 2,4,5-T
organisms [7]. For this reason, this contaminant calls for legisla-
tive intervention because of their elevated levels in our water bodies
[2]. Emerging pollutants include products that are intensively used
of new sample preparation methods that will be specific to differ-
in large quantities on daily basis such as health and beauty prod-
ent kinds of emerging pollutants. Due to the fact that there is a
ucts [2,8]. These pollutants are mainly categorized into synthetic
myriad of emerging pollutants, this review focuses on emerging pol-
(man-made compounds) and natural chemicals (hormones ex-
lutants such as pharmaceuticals, PCPs, and EDCs present in the
creted by invertebrates and vertebrates) [9].
environment.
In the last decades, extensive studies have proven the presence
of emerging pollutants (parent compound) and their metabolites
in groundwater, storm wastewater, drinking water, surface water, 2. Sample preparation techniques
plants and wastewater [9]. However, the common playground of
emerging contaminants is the industrial and domestic wastewa- Direct analysis of emerging pollutants in complex matrices is dif-
ter treatment plants (WWTPs) which receive wastewater coming ficult because in some samples they are present low concentrations
from human activities and of industrial discharges [10,11]. The in- and are associated with the sample matrix [19]. For this reason, it
dication of these organic pollutants is mostly evident in municipal is difficult to predict their transport and fate in the environment
WWTPs [9] and other sources (agricultural and industrial activi- because of the lack of information about them [2]. In order for re-
ties) that spread the pollutants in various water sources such as river, searchers to overcome such a predicament, sample preparation step
dams, lakes and oceans [10]. Biosolids (sewage sludge) is one of the needs to be carefully examined [2]. Sample preparation may include
by-products that attract emerging pollutants and are eventually filtration, pH adjustment, extraction, clean-up and pre-concentration
applied in an agricultural soil as a fertilizer [12]. Emerging pollut- procedures to ensure that the analytes are found at a suitable con-
ants present in fertilizers poses a possibility of getting into centration level [20]. Currently, sample preparation is moving
agricultural produce (food) which will have a negative impact on towards environmental friendliness, low cost, miniaturization, au-
the quality of the food and may be a hazard to human health [13]. tomation and simplicity [21]. The following section discusses the
In addition, stormwater runoff is one of the possible sources of application of different sample preparation techniques such solid
emerging pollutants such as plasticizers, flame retardants, and pes- phase extraction, solid phase microextraction, microwave assisted
ticides [9]. There are numerous types of emerging contaminants in extraction, liquid-liquid extraction, liquid phase microextraction,
the environment. These pollutants include pharmaceuticals (acidic pressurized liquid extraction and stir bar sorptive extraction method,
and basic), personal care products (PCPs), pesticides, surfactants, among others, that have been used for preconcentration and ex-
endocrine disrupting compounds (EDCs), disinfection byproducts traction of different emerging pollutants in different matrices.
and detergents [14–16]. Among the aforementioned types of emerg-
ing pollutants, pharmaceuticals, personal care products, and 2.1. Solid phase extraction (SPE)
endocrine disrupting compounds are of great interest. Table 1 sum-
marizes some different types of pharmaceuticals, personal care Solid phase extraction is one of the most extensively used sample
products, and endocrine disrupting compounds that have re- preparation technique for environmental samples [11,21,22]. This
ported in the in environmental matrices. technique was first developed in the 1980s and ever since then, it
In this review, the most recent published work regarding the has proven to be the most powerful tool for the isolation and pu-
emerging pollutants will be thoroughly covered, especially the rification of target analysis [23]. The advantages of SPE include
sample preparation methodologies that applied for analysis of these simplicity, flexibility, high selectivity, automation, rapidity, higher
pollutants in environmental samples. The review also discusses the enrichment factors, and the absence of emulsion and use of differ-
advantages and disadvantages of various sample preparation tech- ent sorbents [24]. The latter include reversed-phase hydrophobic-
niques as well as future perspectives related to the development hydrophilic balanced (HLB) polymeric sorbents, alkyl-modified silica
 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207
Table 2
Solid phase extraction techniques used for extracting emerging pollutants in various environmental samples
Emerging pollutant Family of Adsorbent
pollutant
TCS and TCC Antimicrobials Oasis HLB
Caffeine Pharmaceutical Oasis HLB, Supelclean
envi-chrom P, Supelclean
LC-SAX and Oasis MCX
Naproxen and diclofenac Pharmaceuticals Oasis HLB 6 cc
Twenty different Pharmaceutical Lipophilic-hydrophilic
compounds balanced Oasis HLB
BDE-47, BDE-99, BDE-100, Flame retardant C18-silica
BDE-153 additives
Tribromophenol, PCPs and BFRs Fe3O4/C magnetic
tetrabromobisphenol A, nanoparticles
dibromodiphenyl ether,
dibromobiphenyl and
pentachlorophenol
Sixty- two compounds Pharmaceuticals Oasis HLB and
and EDCs Oasis HLB 96
(C-18 non-polar phase), molecular imprinted sorbents and others
[23,25–27]. Among other sorbents, HLB based sorbents are the most
preferred solid phase materials due to the improved recoveries and
good extraction efficiency for emerging pollutants [25]. These sor-
bents are advantageous because they are stable in wide pH ranges,
no silanol interactions and no effect on sorbent drying. Moreover,
depending on HLB sorbents used, they are able to retain acidic, basic,
and neutral analytes [28]. HLB sorbents include polyamide, poly [n-
vinylpyrrolidone-divinylbenzene (DVB)], methacrylate DVB and
hydroxylated polystyrene DVB (such as OASIS HLB, STRATA XL, Super
select HLB and Bond Elut Plexa), among others [28]. Like any other
analytical procedure, the main disadvantages of SPE include the use
of a significant amount of organic solvents (still lower than LLE),
disposable cartridges, and discs with a special manifold [29].
However, the researchers tend to overlook these limitations such
a number of researchers have reported on the application of SPE
for preconcentration of different emerging pollutants in environ-
mental matrices. Selected solid phase extraction based methods
reported in the literature for the analysis of emerging pollutants are
summarized in Table 2.
2.2. Solid phase microextraction (SPME)
Microextraction techniques are described as non-exhaustive
sample preparation technique that utilizes a little volume of the ex-
traction phase (μL) relative to the sample volume [20]. Solid phase
microextraction is a reliable and effective alternative extraction
method to SPE [21]. The configuration of SPME can be classified
into dynamic and static techniques. The static techniques are
carried out in stirred sample mode. These include thin-film, fiber
microextraction, and rotating disk sorptive extraction (RDSE) [20].
On the other hand, methods such as in-tube SPME, in-tip and in-
needle microextraction and capillary microextraction are classified
as dynamic techniques [20]. The SPME procedure is the solvent free
technique that utilizes fused silica fibers coated with a polymeric
adsorbent [37]. The SPME method has the advantage over other ex-
traction methods because it requires less manipulation (simplicity)
and is not tedious as compared to other methods [10]. The advan-
tages of SPME also include small sample volumes; analyte
concentration from liquid, gaseous and solid samples; solvent-
free extraction technique and easily automated to allow high-
throughput analysis [38]. The extraction and preconcentration of
the analyte occur by a thin layer of a suitable polymer at the surface
of a fused silica fiber [39,40]. However, the main limitation of this
technique is related to polymeric extractant phase and the desorption
201
Matrix Levels Detection Ref.
found/recoveries
River water and 3.4–1098 ng L−1 HPLC-MS/MS [30]
wastewater
Hospital wastewater Up to 9099 ng L−1 HPLC [31]
River water 2–20 and 5–38 ng g−1 GC-MS [32]
Hospital wastewaters 5 ng L−1-2 mg L−1 LC-MS/MS [33]
Fish, egg and chicken 91 and 140 pg g−1 GC-MS/MS [34]
Tap water, River water 0–110.0% XPS and TG-MS [35]
Freshwater 34–125% UPLC–MS/MS) [36]
invertebrates
process [41,42]. This challenge can be solved by using hollow fibre
membrane of metal oxide based membrane. This will involve the
use of a membrane as the adsorption material that integrates sam-
pling, extraction, and preconcentration into a single step and inherits
the advantages of SPME and membrane separation [41].
The idea of using SPME is to adsorb analytes on a fiber coated
with a stationary phase expressed from a syringe. The sensitivity
of SPME depends on the partition coefficient between the fiber sta-
tionary phase and the sample [38,42]. The SPME technique can be
divided into three modes of extraction which are the headspace ex-
traction (HS-SPME), the direct-immersion extraction (DI-SPME) and
the membrane protected SPME [25]. Different SPME procedures have
been reported in the literature for extraction and preconcentration
of emerging pollutants in different matrices. The application of solid
phase microextraction methods are reported by Manzo et al. [37]
Wang et al. [38] and Manzo et al. [43], among others.
2.3. Dispersive solid phase (micro) extraction (DSPE/DSPME)
Dispersive solid phase (micro) extraction (DSPE/DSPME) is a
sample preparation technique which was introduced in 2003 by
Anastassiades and coworkers [44]. It involves single extraction of
the sample using a solid adsorbent and followed by a clean-up
process [45]. Dispersive solid phase (micro) extraction is regarded
as a promising and a straightforward sample preparation tech-
nique that is greener than other techniques in analytical chemistry,
which is applicable in a wide range of environmental samples such
as food, water, and soil [46]. Dispersive solid phase extraction is a
highly developed form of SPE, however, DSPE forms the fraction
of the so-called quick, easy, cheap, effective, rugged, and safe
(QuEChERS) [47–49]. However, the extraction performance of DSPE
chiefly dependent on the choice of the adsorbent materials [47]. In
DSPE, sorbents such as bonded silica, activated carbon, and primary
secondary amine are directly dispersed into the sample solution
instead of being packed in SPE columns [46]. Subsequent to the ex-
traction process, the adsorbent-containing adsorbed analytes is
separated by filtration or centrifugation [47]. This method allows
the full interaction of the sorbent and the sorbent particles, ac-
complishing a great capacity per amount of sorbent and avoiding
the blockage of cartridges in traditional SPE [44–49]. However, the
main drawback of using DSPE/DSPME is the inability to change
solvent between the extraction and preconcentration steps [50]. Ap-
plications of both DPSE/DSPME techniques for preconcentration of
emerging pollutants in different environmental samples are sum-
marized in Table 3.
202 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207

Table 3
Dispersive solid phase (micro) extraction technique used for extraction of emerging pollutants in various environmental samples

Sorbents Emerging pollutant Family of pollutant Matrix Levels found/recoveries Detection Ref.

CTAB)-coated Fe3O4 Estrogens (17beta-estradiol EDCs Pork 93.3–106.7% HPLC [51]

(E2), estrone (E1) and
diethylstilbestrol
IL-graphene oxide Steroids and B-blockers EDCs and PCPs wastewater 87–98% HPLC-DAD [52]
Pb-MONTs PBDEs Flame retardants Water 80.5–119.2% GC–NCI-MS [47]
MNPs-nylon 6 composite Bisphenol A EDC Milk 86.7–99.5% HPLC-UV [53]
Graphene oxide Ibuprofen, gemfibrozil, Acidic pharmaceuticals Water 1 to 16 ng L−1 GC-MS [48]
naproxen, ketoprofen, and
diclofenac
Polypyrrole-Fe3O4 Citalopram and sertraline Antidepressant drugs Urine and plasma 93–98% HPLC-UV [54]
nanocomposite
−1
Fe3O4 MNPs @ MWCNTs Ofloxacin and lomefloxacin Antibiotics Urine and plasma 12–15 ng mL Spectrofluorimetry [55]

2.4. Microwave-assisted extraction (MAE)
The application of MAE for extraction of emerging pollutants from
the environment matrices has been an attractive method over the
past years [3]. The MAE uses the microwave energy to irradiate the
liquid sample that is in contact with the solvent [3,25]. The energy
that the microwave uses is non-ionizing radiation that causes mol-
ecules to move by migration of ions and rotation of dipoles [3]. The
effect of the microwave energy is dependent on the nature of the
matrix and the solvent used [25]. However, the principle of MAE
is based on the impact of microwaves on molecules caused by dipole
rotation and ionic conduction [3]. This technique has the advan-
tage of decreasing the extraction time and the sample volume for
the extraction of organic analytes from solid samples [11]. Another
advantage of using MAE is that it can be used with closed or opened
vessels and on the other hand it can irradiate multiple samples si-
multaneously [36]. However the main disadvantages include a
limited amount of sample (0.5 g) to be processed, does not permit
the addition of solvents or reagents during operation, the absence
of selectivity and long cooling times after pretreatment [56]. Despite
these limitations, MAE is extensively used for solid samples such
as soil, sewage sludge, food and sediments for extraction of PAHs,
PCBs, flame retardants, PCPs, pharmaceuticals and many more en-
vironmental samples [3]. Table 4 gives a summary of more recent
applications of MAE methods for extraction of emerging pollut-
ants in various environmental samples.
2.5. Liquid-liquid extraction (LLE)
Liquid-liquid extraction technique is one of the oldest well-
explored sample preparation technique that uses the immiscibility
properties of organic solvents to partition target analytes from raw
extract to the extractant [63,64]. It is a non-selective clean-up method
and widely used solvents are ethyl acetate, hexane, isooctane,
toluene, chloroform and methylcyclohexane [63]. The use of large
volumes of organic solvents which are environmentally unfriend-
ly is the main drawback of LLE [63]. It has been used for the
extraction of pharmaceuticals and hormones in aquatic samples
because of its simplicity and rapidity but SPE is preferred over LLE
simply because it can overcome LLE drawbacks [63]. Despite its draw-
backs, LLE has been recently reported for extraction of emerging
pollutants [65–67].
2.6. Liquid phase microextraction techniques (LPME)
Liquid phase microextraction techniques such dispersive liquid-
liquid microextraction (DLLME), ultrasound-assisted liquid-liquid
microextraction (UA-LLME) and hollow fiber liquid-phase
microextraction (HF-LPME), among others, has gained attention due
to the advantages they have over the LLE techniques [68]. Disper-
sive liquid-liquid microextraction has recently been introduced and
it uses a ternary solvent system in which small volumes of extract-
ing solvent is dispersed by the action of a second solvent [69].
Whereas in UA-LLME, ultrasound radiation is utilized for the ac-
celeration of mass transfer process [70]. Hollow fiber liquid-phase
microextraction is preferred because of its low cost, great reduc-
tion in the volumetric ratio of the acceptor and the sample phases,
sample clean-up and high enrichment factor [71]. The principles of
HF-LPME are more or less the same with SPME. However, in HF-
LPME the solvent is placed inside the channel of the hollow fiber
and the pores of its walls and an aqueous solution (acceptor) is then
injected into the channel [72]. The analytes are usually extracted
through the organic phase inside the pores of the hollow fiber and
straight into an acceptor solution [72]. However, the process of per-
forming HF-LPME is relatively slow and the lack of commercially
available equipment [73]. On the other hand, DLLME has its limi-
tation such as the use of the extraction solvents that are usually
limited to solvents of higher density than water in order to be settled

Table 4
Microwave assisted extraction technique used for extraction of emerging pollutants in various environmental samples

Emerging pollutant Family of pollutant Matrix Levels Detection Ref.

found/recoveries

Naproxen and diclofenac Pharmaceuticals River water 2–38 ng g−1 GC-MS [32]
Ciprofloxacin, ofloxacin, and enrofloxacin Antibiotics Sewage sludge 614–836 ng g−1 LC-MS [57]
Ketoprofen, ibuprofen, naproxen, and diclofenac NSAIDs Sewage sludge 0.3–66.7 ng g−1 GC-MS [58]
1H-benzotriazole, 5-methyl- 1H-benzotriazole, benzothiazole, BTRs, BTs and BSAs Soil 70–117% HPLC-UV [59]
2-hydroxybenzothiazole, 2-methylthiobenzothiazole,
benzenesulfonamide, toluenesulfonamide
Demeton-s-methyl, phorate, diazinon, tolclofos-methyl, Organophosphorus Vegetables 80.7–106.7% GC-MS [60]
malathion, fenthion, quinalphos, and fenamiphos pesticides
Ciprofloxacin, Enrofloxacin, Levofloxacin and Norfloxacin Fluoroquinolone Compost 88 ng g−1. UPLC–MS [61]
antibiotics
BDE- 28, BDE-49, BDE-47, BDE-66, BDE-100, BDE-119, BDE-99, Brominated flame Airbone particulate 0.063–0.212 pg m−3 GC-MS/MS [62]
BDE-155, BDE-154, BDE-153, BDE-139 and BDE-183 retardants matter
 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207 203

Table 5
Liquid-phase microextraction techniques for extracting emerging pollutants in environmental samples

Extraction Emerging pollutant Family of Matrix Levels Detection Ref.

technique pollutant found/recoveries

IL-USA-DLLME 2-Hydroxy-4-methoxybenzophenone, 3-(4methylbenzylidene) Ultraviolet filters Surface 86–114% HPLC-UV [69]

camphor(MBC), 2-ethylhexyl 2- cyano-3,3-diphenylacrylate, seawater and
2-ethylhexyl4-dimethylaminobenzoate, ethylhexyl salicylate and pool water
homosalate
UA-DLLME Phthalates EDCs Food and water 72–109% GC-FID [70]
HF-LPME 10 organochlorine pesticides EDCs Textile samples 95.8–244.5 ng g−1 GC-MS [71]
UA-DLLME Imazethapyr, bensulfuron, and uniconazole Phytocites Soil 87.10 and 95.01%. HPLC [76]
UA-DLLME Musk fragrances PCPs Wastewater 850–2800 ng L−1 GC-MS [77]
UA-DLLME Ethylhexyl salicylate (EHS), 3,3,5-trimethyl-cyclohexylsalicylate Salicylate and River water and 74–92% GC-MS [78]
(HMS), 2-hydroxy-4-methoxybenzophenone (BP-3), 2,4-dihydroxy- benzophenone-type municipal
benzophenone (BP-1) and2,2_-dihydroxy-4-methoxybenzophenone ultraviolet filters wastewater

by centrifugation [74]. Overall, the use of membranes in LPME
acts as a barrier between the sample phase and the acceptor phase
which increases the extraction time and reduces the extraction
rate [75]. Furthermore, air bubbles that are created on the surface
of the HF decreases the reproducibility of the extraction and also
reduces the transport rate [75]. Table 5 summarizes different
liquid phase microextraction techniques that are reported in the
literature.
2.7. Pressurized liquid extraction (PLE)
Pressurized liquid extraction is commonly known as acceler-
ated solvent extraction (ASE), pressurized fluid extraction (PFE),
enhanced solvent extraction (ESE) and high-pressure solvent ex-
traction (HSE) [11,25,79]. Pressure is normally applied using the
extraction solvents at higher temperatures above the boiling point.
For this reason, higher temperatures are used to better promote the
analyte solubility [11]. The use of high temperatures reduces the
surface tension of solvents and the viscosity which assist in reach-
ing areas of matrices easily, enhancing the extraction rate [11,80].
The pressure increase retains the solvents in the liquid state even
at higher temperatures. The advantages of PLE are the reduction of
solvent volume and the time it takes to perform sample prepara-
tion [80]. The number of publication regarding PLE research have
been increasing exponentially and this technique has been applied
for the extraction of organic samples such as PAHs, PCBs, DDTs,
dioxins, PBDE, pharmaceutical and PCPs [80]. Lately, PLE has been
used for extraction organic compounds in food samples, sewage
sludge and other environmental samples [63]. Table 6 summa-
rizes selected recent application of PLE methods. The major drawback
of PLE is that a sample clean-up is still mandatory once the extrac-
tion is done and it uses expensive specialized equipment. In addition,
high extraction temperature might cause decomposition of other
thermally unstable analytes of interest [81].
2.8. Stir bar sorptive extraction (SBSE)
The SBSE was initially introduced in 1999 as a newly emerging
sample preparation technique [88]. Stir bar sorptive extraction is
a solvent-free extraction that is usually performed on a 1.5 cm long
glass magnetic stirrer coated with polydimethylsiloxane (PDMS)
[19,22]. The coating of the stir bar with PDMS is sometimes a draw-
back due to polar compounds being poorly extracted because of the
non-polarity of the PDMS polymer [88]. The SBSE procedure has the
capability of extracting organic compounds from liquid samples and
the principle of SBSE is based on immersing the stir bar in the liquid
phase and being continuously stirred for a period of time [88,89].
The stir bar is set to capture the analytes by partition during stir-
ring but stirring at high speed can result in the damage of the
extracting phase [88,89]. SBSE has been largely applied for the ex-
traction of atrazine, PAHs, PCBs, PBDEs, sunscreens, pharmaceuticals
and EDCs [89–91].
2.9. Other sample preparation techniques
There are several new extraction techniques that have been used
to clean-up and pre-concentrate emerging pollutants from a wide
variety of sample matrices. For instance, Racamonde et al. [92] de-
veloped a new sorptive microextraction method based on FPSE for
determination of NSAIDs from environmental water samples. The four
NSAIDs (ibuprofen, naproxen, ketoprofen and diclofenac) in envi-
ronmental water samples were quantified by GC-MS. Under optimum
experimental conditions, the LODs ranged from 0.8 ng L−1 to 5 ng L−1,
enrichment factors ranged from 162 to 418, absolute extraction ef-
ficiencies varied from 27 to 70% and a good trueness (82–116% relative
recoveries). These analytical performances indicated that the pro-
posed method can be readily used for routine environmental pollution
monitoring. Other applications of FPSE are reported by Lakade, et al.
[93], and Montesdeoca-Esponda et al. [94], among others.

Table 6
Pressurized liquid extraction technique for the extraction emerging pollutants in environmental samples

Emerging pollutant Family of pollutant Matrix levels found/recoveries Detection Ref.

Ninety-seven compounds EDCs, PCPs and Marine sediment 70–100% GC-MS [82]
Pharmaceuticals
Heptachlor, aldrin, dacthal and endrin, PCBs, PBDEs, EDCs Atmospheric Up to 88.8% GC-MS [83]
particulate matter
Benzophenone-3, ethylhexyl methoxycinnamate and octocrylene UV-filters Fish 11.2–241.7 ng g−1 LC-MS/MS [84]
Atrazine, simazine, cyanazine, sebuthylazine, deisopropylatrazine, Pesticides Water and soil 0.46 to 2.26 ng g−1 LC-MS/MS [85]
deethylatrazine and deethylterbuthylazine
Glucocorticoids (betamethasone, cortisol (hydrocortisone), EDCs Sludge 5.2–6.0 μg kg−1 UHPLC-MS/MS [86]
cortisone, dexamethasone, flumethasone, methylprednisolone,
prednisolone, prednisone and triamcinolone acetonide)
Ifosfamide and cyclophosphamide Pharmaceuticals Sludge 11.4–42.5 μg kg−1 HPLC-MS [87]
204 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207
On the report, Gago-Ferrero et al. [95] proposed the develop-
ment and validation of a new method based on ultrasound-assisted
extraction and LC-MS/MS for the simultaneous determination of 148
substances in sewage sludge. The proposed method displayed rel-
atively good analytical performance with LODs values below 10 ng g−1
and absolute recovery in the range 50–110% for more than 77% of
the studied compounds. The developed method enabled the iden-
tification and quantification of antibiotics, analgesic and/or anti-
inflammatory drugs, antiepileptics, benzodiazepines, antipsychotics,
antidepressants, opiates, opioids, cocaine, amphetamines, canna-
binoids, and their metabolites. Similar reports have been developed
by Sousa et al. [96], Peng et al. [97], Komesli et al. [98], and others.
Racamonde et al. [99] developed a method for the simultane-
ous determination of 17 benzodiazepines (BZPs) and related
pharmaceutical (zolpidem) in water using LC–MS/MS after extrac-
tion with low-cost polymeric sorbents. The method displayed good
figures of merit such as high enrichment factors, relatively low LODs,
and LOQs as well as quantitative recoveries 87–117%. Other methods
for extraction and determination of emerging pollutants in differ-
ent matrices are reported in the literature [100].
3. Novel solid and liquid phase materials
3.1. Nanomaterials
Nanotechnology is the technology that plays a crucial role in
addressing effective and innovative solutions to a number of environ-
mental challenges [101]. Nanomaterials are significant because they have
the potential of providing a solution to environmental clean-up pre-
venting pollution and playing a role in monitoring and remediation of
environmental pollutants [101].The use of nanomaterials in the ex-
traction and microextraction context has undergone rapid growth in
recent years [102]. For this reason, their inclusion in the sample prep-
aration process helps to simplify the procedure because of their high
surface-to-volume ratio, high reactivity, unique mechanical, thermal and
electronic properties [103]. Nanomaterials such as carbon nanotubes,
zeolites, nanofibers and metallic NPs as well as hybrid (combination
of different NPs) or rather a nanocomposite have been utilized for ex-
traction and preconcentration of emerging pollutants [102,104]. Other
applications of nanoadsorbent have been reported by Hao et al. [105]
and Zhang et al. [106].
3.2. Ionic liquids (ILs)
Ionic liquids (ILs) are ionic compounds made up of discrete cations
and anions often liquid at or beneath 100°C [52,107,108]. Ionic liquids
have outstanding properties such as miscibility, high solvation in-
teraction, negligible vapour pressure, high thermal stability, good
conductivity and tunable viscosity [52]. In analytical chemistry, ionic
liquids are regarded as green solvents for most of the chemical pro-
cesses and are they usually used replace conventional solvent [107].
Although, ionic liquids have been attractive features, some have
drawbacks. For instance, their synthesis process is complex, costly
and difficult to purify [107]. In addition, pyridinium or imidazolium-
based ionic liquids are not completely “green” because their toxicity
is the same or more than that of traditional organic solvents [108].
Despite these drawbacks, the applications of IL have been docu-
mented in analytical chemistry especially in liquid phase based
microextraction of emerging pollutants [109]. Other recent reports
on the application of ILs for extraction of emerging pollutants are
documented in the literature [110–112].
3.3. Supramolecular solvents (SUPRAS)
The supramolecular solvent is a chemical term referring to the
nano-structured liquids that are generated from amphiphiles through
a sequential self-assembly process that occurs on two scales, which
are molecular and the nanoscale [113,114]. The most appealing prop-
erty of SUPRAS is their potential to extract amphiphilic compounds
such as drugs, pesticides, bisphenols, surfactants, bioactive com-
pounds and mycotoxins [114]. In addition, SUPRAS has the capability
to extract organic compounds in a wide polarity range from both
solid and liquid samples [114]. Recently, hemimicelles/admicelles
(supramolecular assemblies) has been discovered as an efficient
sorbent material for extracting and preconcentrating organic and
inorganic substances [115]. These assemblies are formed from the
adsorption of surfactants on the surface of metal oxides such as silica,
TiO2, ferric oxyhydroxides and alumina [115]. The application of
SUPRAS for extraction and preconcentration of emerging pollut-
ants have reported by Lara et al. [114] and Beiraghi et al. [116],
among others.
4. Conclusion and future prospects
This review describes the occurrence, fate and transport of three
different types of emerging pollutants (pharmaceuticals, personal
care products, and endocrine disrupting compounds) in environ-
mental matrices. In addition, the literature review on emerging
pollutants analysis in environmental samples reveals that tradi-
tional and modern sample preparation techniques have recently
obtained much greater importance. This is because direct analysis
in complex matrices and samples where the pollutants are present
in low content is difficult. A number of sample preparation tech-
niques have been extensively reviewed for their application for
extraction and preconcentration of emerging pollutants.
Amongst the studied sample preparation techniques, SPE is con-
sidered as the most extensively used technique due to its attractive
advantages over other traditional techniques (such as LLE). The ad-
vantages include simplicity, flexibility, high selectivity, automation,
rapidity, higher enrichment factors, and the absence of emulsion
and use of different sorbent materials. Although SPE uses smaller
volumes of potentially toxic solvents as compared to LLE, a signif-
icant amount of organic solvents, disposable cartridges, and discs
with a special manifold are still required, among others. For this
reason, alternative techniques such dispersive solid phase (micro)
extraction have reported. This technique displays superior advan-
tages (over traditional SPE) such rapidity (no conditioning step),
simplicity, high enrichment factors and cost effective due to the re-
duction in sample size, sorbent amount, solvents, and waste.
However, like any other analytical techniques, the main disadvan-
tage of DSPE/DSPME is the inability to change solvent between the
extraction and preconcentration steps.
Despite the limitations of SPE and DSPE/DSPME, the still remain
as the most studied method according to the documented litera-
ture, to date. This is because of the use of different sorbents that
have been developed to accommodate the newly discovered con-
taminants. For this reasons, new sorbents such as carbon nanotubes,
graphene, metal nanoparticles, metal–organic frameworks, and
mesoporous hybrid materials, among others have been to play a sig-
nificant role in increasing the detectability, enrichment efficiency,
and selectivity of pharmaceuticals, EDCs, and PCPs in environmen-
tal matrices. The main features of the abovementioned sorbents
include large surface area and permanent nanoscale porosity, among
others. However, adsorbents such magnetic NPs display disadvan-
tages low stability in acidic media, low dispersibility in different
sample matrices and its low sensitivity towards analytes. There-
fore, it can be concluded that adsorbent has its own advantages and
disadvantages because they are described by certain specific
parameters.
Liquid phase based microextraction techniques have high-
potential in sample preparation due to their inherent advantages over
conventional LLE procedure. These include simple operation, low cost,
 K.M. Dimpe, P.N. Nomngongo / Trends in Analytical Chemistry 82 (2016) 199–207
low solvent consumption, speed, the potential for automation and
high enrichment factors. However, the extraction solvents used in
these techniques are usually are chlorinated solvents, which are unde-
sirable for human and environmental health. Due to environmental
concerns around halogenated organic solvents, scientists have used
alternative solvents such low density organic solvents and ionic liquids.
The latter, are said to be better choices compared to traditional organic
solvents. This is because they have negligible vapor pressure, the pos-
sibilities to tune their chemical structure and versatility. However,
pyridinium or imidazolium-based ionic liquids are not completely
“green” because their toxicity is the same or more than that of tra-
ditional organic solvent. Therefore, there a need to search for solvents
that has similar physicochemical properties as ILs.
The determination of emerging pollutants in solid samples (soils,
sediments, and food matrices) has not been extensively investi-
gated. Therefore, there is a demand for the development of more
sample preparation techniques that will be specific to complex ma-
trices. As the development and improvement of sample preparation
procedures increases, chromatographic techniques hyphenated to
mass spectrometry have been widely used for identification and
quantification of a wide range of different emerging pollutants. For
this reason, the combination of chromatographic techniques with
sample preparation procedures provides great improvement in sen-
sitivity, selectivity, and reduced matrix effects.
Acknowledgements
I would like to thank National Research Foundation (NRF, grant
no. SFH14073184214) for providing financial support and the Uni-
versity of Johannesburg for making this study possible by making
laboratory facilities available.
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