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International Journal of Environmental Analytical
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ISSN: 0306-7319 (Print) 1029-0397 (Online) Journal homepage: http://www.tandfonline.com/loi/geac20
Recent advances of adsorbents in solid phase

extraction for environmental samples
Junping Xiao, Jingjie Wang, Huili Fan, Qingxiang Zhou & Xudong Liu
To cite this article: Junping Xiao, Jingjie Wang, Huili Fan, Qingxiang Zhou & Xudong Liu
(2016): Recent advances of adsorbents in solid phase extraction for environmental
samples, International Journal of Environmental Analytical Chemistry, DOI:
10.1080/03067319.2016.1150459
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Published online: 15 Mar 2016.
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INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY, 2016
http://dx.doi.org/10.1080/03067319.2016.1150459
REVIEW
Recent advances of adsorbents in solid phase extraction for

environmental samples
Junping Xiaoa, Jingjie Wanga, Huili Fana, Qingxiang Zhoub and Xudong Liua
a
School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing,
China; bCollege of Geosciences, China University of Petroleum, Beijing, China
Downloaded by [University of California, San Diego] at 01:33 22 March 2016
ABSTRACT ARTICLE HISTORY

In recent years, some new and sensitive analytical instruments Received 19 December 2014
have been invented or existing instruments have been improved, Accepted 28 January 2016
which have resulted in many advanced achievements. However, Published online xx xxx xxxx
sample pre-treatment techniques still play important and irre- KEYWORDS
placeable roles in the analysis of pollutants. Among the developed ion imprinting material;
sample pre-treatment techniques, solid phase extraction is the magnetic material;
most often used method and has been widely applied worldwide. mesoporous materials; core-
In solid phase extraction, adsorbent is the key part to achieve high shell materials; carbon
sensitivity and enrichment efficiency, which is the hot topic in nanotubes; TiO2 nanotube
analytical and environmental fields in recent years. In order to arrays; solid phase extraction
deeply understand the prospect of solid phase extraction, this
review summarises the recent advances of adsorbents including
ion imprinting materials, magnetic materials, core-shell materials,
mesoporous materials, carbon nanotubes, TiO2 nanotube arrays
and some other new materials.
1. Introduction
With the rapid development of science and technology, more and more pollutants
entered into the environment. According to the statistics of World Health Organization
(WHO), the scarcity of water resources has created challenges for over 40% of the world
population, that is to say, more than 2 billion people have no access to enough or clean
water [1]. The severe water pollution has attracted considerable attention. In order to
control and monitor such pollutions, various analytical technologies have been devel-
oped such as gas chromatography–mass spectrometry (GC-MS) [2], high-performance
liquid chromatography (HPLC) [3], ultra-high-performance liquid chromatography
coupled to tandem mass spectrometry (UPLC-MS/MS) [4], flame atomic absorption
spectrometry (FAAS), inductively coupled plasma atomic emission spectrometry (ICP-
AES), and inductively coupled plasma mass spectrometry (ICP-MS). Some of them are
expensive, the requirements for the operators are very strict and the running cost is also
very high. On the other hand, for the new instruments the requirement for the samples
is also very rigid and that is to say, the sample should be very ‘clean’. Hence, the clean-
up step is necessary in the analytical process of the analytes. In general, the ‘clean-up’
CONTACT Junping Xiao xiao1229@163.com; Qingxiang Zhou zhouqx@cup.edu.cn

© 2016 Taylor & Francis
2 J. XIAO ET AL.
procedure will also result in the enrichment of the target analytes at the same time. So
the sample pre-treatment techniques have been focused on for many years.
Up to date, many sample pre-treatment methods have been developed based on
various principles such as liquid–liquid extraction (LLE) [5], dispersive liquid–liquid
microextraction (DLLME) [6,7], stir bar sorptive extraction (SBSE) [8,9], solid-phase micro-
extraction (SPME) [10], supercritical fluid extraction [11], microwave assisted extraction
[12–14], accelerated solvent extraction [15]and solid phase extraction (SPE) [16–18].
Among them, SPE has been developed to be an efficient method, which is strongly
recommended for use due to its merits such as rapidness, low cost, low consumption of
organic solvents, short extraction time, high enrichment factor and wide scope based on
different adsorbents with different properties. However, in solid phase extraction the
core part is the adsorbent with good adsorption ability for many pollutants or a kind of
pollutant. So it has been a hot topic to synthesise, screen and exploit new adsorbents in
recent years. Thus, significant efforts have been made to develop and characterise new,
advanced adsorbent materials. Some reviews have focused on the different sorbents
such as nanomaterial, titanium dioxide nanotubes, magnetic adsorbents, polymeric
sorbents and molecularly imprinted sorbents, or combination of nanoparticles and
continuous flow systems, magnetic solid phase extraction, state-of-the-art SPE, etc.
[19–31]. This review is a summary of several new advanced materials in SPE for achieving
a high enrichment factor and sensitivity.
2. Ion-imprinted materials
Molecular imprinting technology has become a powerful technology, which has high
selectivity [32] and also exhibited its merits in the enrichment of some special com-
pounds. Molecularly imprinted material has drawn much more attention from the
analytical researchers due to its excellent selectivity and high enrichment capacity and
has achieved many applications as SPE adsorbent since it was introduced. For metal
ions, molecular imprinting generally is regarded as ionic imprinting. In other words,
molecularly imprinted polymer for ions usually is considered as ionic imprinted polymer
(IIP). The ion imprinting process is similar to molecular imprinting, in which template
ions are introduced to facilitate the recognition sites with appropriate functional mono-
mers. After removing the template, the vacated spaces only permit the entry of the ions
with similar size to the template ion. The ion-imprinted materials are mostly used in pre-
concentration and separation of trace metal elements in environmental samples and
water samples.
The first ion-imprinted polymer was reported in 1976 [33], and ion-imprinted poly-
mers for solid phase extraction of metal ions in environmental samples have been
widely reported [34]. Cd(II)-imprinted polymer has been synthesised for extraction of
trace cadmium (II) from water samples [35]. The synthesised particles have excellent
selectivity for Cd(II) compared with Cu(II), Zn(II) and Hg(II). The maximum adsorption
capacity was 32.56 mg g−1, and the detection limit was 0.14 μg L−1 analysed by
inductively coupled plasma atomic emission spectrometry (ICP-AES). Singh et al. synthe-
sised another Cd(II)-imprinted polymer by the copolymerisation of phenol and formal-
dehyde in the presence of Cd(II)–SPANDS complex in acidic medium [36] to remove Cd
(II) from aqueous solutions; the removal rate was 95% and the material could be reused
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 3
for five cycles. Besides, there are many research works on the ion-imprinted materials for
some other metal ions such as K(I), Pb(II) and Hg(II) [37–40]. These applications of ion-
imprinted materials are listed in Table 1 [38,41–53]. In a recent study, Yordanova et al.
synthesised polymeric ion-imprinted nanoparticles to adsorb and enrich Hg(II) in surface
waters [54]. The adsorbent was prepared by dispersion polymerisation in the presence of
Hg(II) complexes with chelating agent 1-pyrrolidinedithiocarboxylic acid as template
species. Low limits of quantification were achieved as 0.015 μg L−1 for Hg(II) and
0.02 μg L−1 for methylmercury. Xu et al. was excited by the T–Hg(II)–T interaction and
prepared a new functional monomer, 3-isocyanatopropyltriethoxysilane (IPTS) bearing T
bases (T-IPTS), with T group as recognition element for the imprinting of Hg(II), and then
a novel Hg(II)-sensitive IIPs were prepared by sol–gel process. This Hg-IIPs–T demon-
strated their excellent and highly selective enrichment of Hg(II), and the dynamic linear
range was in the range of 0.08 ~ 50 μg L−1 and LOD was 0.03 μg L−1. Their work
contributed much to this field and provided new directions for the design of new ion-
separation materials [55]. Zhang et al. utilised dithizone–Hg(II) as the template and 3-
aminopropyltriethoxysilane as functional monomer to synthesise a novel kind of Hg-IIPs,
which also resulted in good selectivity and reusability, and provided better sensitivity
with LOD of 0.015 μg L−1 for Hg(II) and 0.02 μg L−1 for organic mercury [56]. Wang et al.
prepared a new Cd(II)-imprinted sorbent with interpenetrating polymer network (IPN)
structure through free radical/cationic hybrid photopolymerisation to selective enrich-
ment of Cd(II) from water samples [57]. The results indicated that the imprinted gel had
higher selectivity for Cd(II) in comparison to the non-imprinted gel and the relative
selectivity coefficients for Cd(II)/Cu(II), Cd(II)/Ni(II) and Cd(II)/Pb(II) were 7.64, 7.58 and
7.59, respectively. Arslan et al. developed a novel Cu(II)-ion-imprinted polymer using 2-
thiozylmethacrylamide (TMA) for online pre-concentration of Cu(II) before determination
by inductively coupled optical emission spectroscopy (ICP-OES) [58]. The result showed
that the as-synthesised adsorbent had higher selectivity for Cu(II), which was about
30 times higher than that of NIP. The IIP also exhibited excellent selectivity for Cu(II)
against the competing transition metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn.
The relative standard deviation and limit of detection of the method were 3.2% and
0.4 μg L−1, respectively.
Some other new developments opened possibilities in a surprising direction. Wang
et al. first reported a new material as silica-based ion-imprinted composite hydrogels for
selective metal ion adsorption [59]. They synthesised Cu(II)-imprinted composite hydro-
gel (Cu(II)-ICH) by in situ free-radical polymerisation. In these new materials, silica
nanoparticles were introduced, which significantly enhanced the mechanical properties
of the Cu(II)-ICH. Adsorption studies demonstrated that the selectivity coefficient of Cu
(II)-ICH for Cu(II) was 5 times larger than that of the non-imprinted composite hydrogel
(NICH) and these materials had strong selectivity for Cu(II) compared with other heavy
metal ions such as Pb(II), Cd(II) and Ni(II). More recently, gold ion imprinted polymer-
coated multi-walled carbon nanotubes were synthesised to adsorb and determine gold
ion in environmental water samples [60]. The maximum capacity is higher than 67 mg g−1
and the detection limit was lower than 0.041 ng mL−1.
In order to achieve better selectivity with SPE adsorbent, some authors have prepared
adsorbent using the surface imprinting method. These materials exhibit obvious advan-
tages, such as high binding capacity, fast mass transfer and binding kinetics, and
4
J. XIAO ET AL.
Table 1. Applications of ion-imprinted material for the extraction of pollutants from waters.
Analytes Method Monomer Cross-linking agent Detection technique LODs (ngmL−1) Ref.
Cd(II) Hydrothermal sol–gel 3-thiocyanatopro-pyltriethoxysilane epichlorohydrin FAAS n.r. [40]
Cd(II) surface imprinting carboxymethyl chitosan glutaraldehyde FAAS n.r. [41]
Cd(II) precipitation polymerisation 4-vinyl pyridine ethyleneglycoldimethacrylate FAAS 0.2 [42]
Tl(III) thermal copolymerisation methyl methacrylate Ethyleneglycol dimethacrylate ETAAS 0.02. [43]
Pb(II) bulk polymerisation n-methacryloyl-(L)cysteine ethylene glycol dimethacrylate FAAS 50.2 [44]
Pb(II) bulk polymerisation 2-vinylpyridine ethylene glycol dimethacrylate FAAS 0.42 [45]
Pb(II) inverse emulsion polymerisation 4-vinylbenzo-18-crown-6 ethylene glycol dimethacrylate AAS n.r. [37]
Ni(II) precipitation polymerisation 5-vinyl-8-hydro-xyquinoline ethylmethacrylate divinylbenzene ICP-OES 0.26 [46]
Cs(I) precipitation polymerisation methacrylic acid ethyleneglycoldimethacrylate FAES 0.7 [47]
Sc(III) n.r. methacrylic acid ethylene glycol dimethacrylate ICP-MS 13 [48]
Pd(II) copolymerisation 4-vinylpyridine (VP) and styrene divinylbenzene ETAAS 0.012 [49]
Sn(IV) bulk polymerisation methacrylic acid ethylene glycol dimethacrylate GF-AAS 1.3 [50]
Ru(III) bulk polymerisation 4-vinylpyridine and styrene divinylbenzene ETAAS 0.26 [51]
Mo(IV) surface imprinting isonicotinic acid tetraethyl orthosilicate ICP n.r. [52]
avoiding grinding and sieving, so they were focused on and widely applied as adsorbent
materials. Yu and his co-workers introduced the concept of surface-imprinting polymers
in 1992 [61]. They synthesised a metal ion-imprinted structure on the carboxylated
microsphere surface. In the surface imprinting process, silica is commonly used as the
support material because of its stable properties no matter in acidic or alkaline solutions.
A Cr(III)-imprinted aminopropyl-functionalised silica gel adsorbent was synthesised by a
surface imprinting technique [62], which has demonstrated good adsorption capacity for
chromium (III) and total chromium in natural waters, in which Cr(VI) was reduced to Cr
(III) with hydroxyammonium chloride. The detection limit for Cr(III) was 0.11 ng mL−1 and
the maximum adsorption capacity was 11.12 mg g−1, which was much higher than that
of the non-imprinted adsorbent (3.81 mg g−1). Dey et al. reported Cr(III)- and Fe(III)-
imprinted amino-functionalised silica gel adsorbents (APTS-Cr(III)-Si and APTS-Fe(III)-Si)

for solid phase extraction of Cr(III) and Fe(III) from aqueous solutions [63]. They found
that the two adsorbents were efficient in removal of divalent as well as trivalent cations.
In case of APTS-Cr(III)-Si the equilibrium time for Cr(III) was reached within a time period
of 10 ~ 20 minutes and in the case of APTS-Fe(III)-Si, the metal uptake follows the order
Fe(III) > Cr(III) > Zn(II) > Mn(II) for all metal ions, the equilibrium time was found to be
within a time period of 20 ~ 30 minutes. Buhani et al. synthesised a Cd(II)-imprinted
mercapto-functionalised silica gel sorbent via a surface imprinting technique for selec-
tive adsorption of Cd(II) ion [64]. The process of the Cd(II) ion imprinting is illustrated in
Figure 1. The results show that the adsorption capacity of Cd(II)-IIP was 83.89 mg g−1,
which was significantly higher than that of NIP (35.91 mg g−1). Furthermore, the
Figure 1. The process of Cd(II) ion imprinting [64].

6 J. XIAO ET AL.
selectivity coefficients of Cd(II)-IIP sorbent for Cd(II) were higher than Cd(II)-IIP sorbent
for Ni(II), Cu(II) and Zn(II), and the selectivity coefficients of the adsorbent for Cd(II) in the
presence of Ni(II), Cu(II) and Zn(II) are 99.798, 93.045 and 86.617, respectively. In another
study, an ordered mesoporous silica SBA-15 was used as supported material to synthe-
sise Pb(II) ion-imprinted polymer with surface molecular imprinting technology as
described by Yan et al. [65]. The Pb(II)-IIP offered advantages of selectivity towards
targeted Pb(II) compared with raw SBA-15 and NIP, and the maximum adsorption
capacity for Pb(II) was 38.01 mg g−1 under the optimum condition. Cai et al. reported
a new Pb(II)-IIPs, which was prepared based on ionic interactions via the synergy of dual
functional monomers of methacrylic acid and vinyl pyridine. The Pb(II)-IIPs exhibited
high binding capacity and excellent selectivity for Pb(II) over other metal ions such as Cu
(II), Cd(II), Zn(II) and Mn(II) with selective coefficients above 30, and the LOD was
0.06 μg L−1 with Pb(II)-IIPs used as SPE adsorbents [66]. Hu et al. developed a novel
restricted accessed material (RAM) – Cu(II) ion-imprinted polymer by surface imprinted
emulsion method, which exhibited a high selectivity for Cu(II) and good macromolecules
exclusion property. Under the optimal conditions, the adsorption capacity of RAM-IIP for
Cu(II) was 15.9 mg g−1, the pre-concentration factor was 30 and the LOD for Cu(II) was
0.17 µg L−1 [67]. Hu et al. first prepared Cd(II) imprinted 3-mercaptopropyltrimethoxysi-
lane (MPTS)-silica coated stir bar by sol–gel technique based on a double-imprinting
concept and established an SBSE method for Cd(II) ions at trace level from water
samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection.
The results demonstrated that the established method was rapid, selective, sensitive and
applicable for the analysis of trace Cd(II) in environmental water samples [68]. Their
group also prepared a novel Cd(II)-ion imprinted magnetic mesoporous silica material
for selective magnetic solid phase extraction of Cd(II) at trace level prior to graphite
furnace atomic absorption spectrometry. The results showed that a 50-fold enrichment
was achieved [69].
Another new trend in ion imprinting is to combine the surface-imprinting technique
with magnetic materials. Based on this principle, a Cu(II) magnetic ion-imprinted poly-
mer (MIIP) was synthesised for the removal of Cu(II) ions from river water [70]. The
process was divided into two steps: first the silica layer was modified onto the Fe3O4
surface by the sol–gel method, and then the complex of Cu(II) and 3-aminopropyl-
triethoxysilane (APTES) was grafted onto the surface of the Fe3O4@SiO2 particles. The
results showed that the synthesised adsorbents had high adsorption efficiency, and
were stable up to five adsorption cycles without obvious decrease in the adsorption
capacity for Cu(II). The maximum adsorption capacity for Cu(II) was 26.25 mg g−1. A
magnetic surface-imprinted adsorbent was prepared for Th(IV) ion [71]. The results
demonstrated that the adsorption maximum capacity was 42.54 mg g−1 and that the
adsorption behaviour of Th(IV) followed a pseudo-second-order kinetic model. Up to
now, research works on such aspects are very few.
Although ion-imprinted materials are widely used in water sample pre-treatment and
received satisfactory results, the material has some drawbacks. For example, ion imprint-
ing methods frequently suffer from memory effect or leaching problems. For ion-
imprinted materials, the monomer played a great role because it affected the affinity
of the material and determined the accuracy and selectivity of recognition sites. So to
design and synthesise new monomers for imprinting ions without functional groups are
still great challenges. There are much work to do in exploiting new polymerisation
methods for ion imprinting to improve imprinting efficiency and adsorption capacity.
3. Magnetic materials
Magnetic nanoparticles (MNPs) are a new material, and increasing research interest has
been put on their potential application in solid phase extraction. The advances of the
magnetic nanoparticles are obviously that it is easily prepared and the cost is very low.
Most importantly, the use of MNPs can simplify the pre-concentration procedure and make
the separation very easy. Actually, since it was introduced in 1973 [72], magnetic materials
have been widely used in various aspects such as enzyme immobilisation [73], DNA extrac-
tion [74], chemosensor [75] and catalysis [76]. However, the term magnetic solid phase
extraction (MSPE) was first introduced by Safarikova and Safarik in 1999 [77], who used
magnetic charcoal as adsorbent for extraction of reactive copper phthalocyanine dye. In the
MSPE procedure, the magnetic adsorbent is added to the sample solution containing the
analytes, and the analytes are adsorbed onto the magnetic sorbent after a short time of
stirring. The adsorbent with captured analytes is then separated using an appropriate
external magnetic field. The process was illustrated in Figure 2. Compared with the tradi-
tional adsorbent, the magnetic separation greatly improved the separation efficiency and
avoided the time-consuming column passing or filtration that was often involved in an SPE
procedure. In general, the materials with magnetism can be used as the magnetic cores. In
contrast, magnetic materials such as Fe3O4, Fe2O3, MnO2, CoFe2O4, NiFe2O4, Fe nanoparti-
cles, and alloys containing ferric and nickel and so on, and could be used as the magnetic
cores. Due to the easy preparation and low cost, Fe3O4 is often used as the magnetic core for
preparing new adsorbents. Recently, other magnetic cores have also been introduced and
more magnetic materials are developed for use. Chen et al. have reviewed the magnetic
Figure 2. The process of magnetic solid-phase extraction [74].

8 J. XIAO ET AL.
material of combined silica, octadecylsilane, polymers and surfactants to the separation and
the pre-concentration of pollutants in water samples [78]. Li et al. reviewed the synthesis
and characterisation of magnetic materials and their application for biological macromole-
cules proteome and contaminants in food samples [79]. Besides magnetic materials used for
pre-concentration metal/metalloid, DNA were also reported [80,81]. Aguilar-Arteaga et al.
summarised the progress of magnetic material on the synthesis, characterisation and
applications in analytical chemistry [82]. Herein we focus on the recent progress in the
application of magnetic and modified magnetic materials as adsorbent to remove inorganic
and organic contaminants from environmental water samples.
Magnetic materials have been widely investigated to remove inorganic contaminants
from water samples. Parham et al. used magnetic iron oxide nanoparticles as the
adsorbent for extraction of fluoride ions in water [83]. They synthesised the magnetic
iron oxide nanoparticles by co-precipitation of ferrous and ferric chlorides in ammonium

hydroxide solution with constant stirring. Under the optimum conditions a pre-concen-
tration factor of 50 was achieved and the recovery was up to 99%. The limit of detection
and limit of quantification were 0.015 and 0.042 μg mL−1. δ-MnO2 has a large surface
area, microporous structure and hydroxyl functional groups, which made it capable of
adsorbing metals. Besides, the point of zero charge of δ-MnO2 is about 2.5 and which
also ensures that it is predominantly applied for removal of cations. Thus, Höll et al.
synthesised manganese dioxide (δ-MnO2) with magnetic properties as adsorbent to
remove Cd(II), Ni(II) and Pb(II) ions [84]. The result demonstrated that the adsorption
equilibrium reached within 30 min for Cd2+ and the maximum adsorption capacities for
Cd(II), Ni(II) and Pb(II) were 0.599, 0.623 and 2.18 mmol g−1 at pH 7, pH 7 and pH 6,
respectively.
Generally, the adsorption scope of the new material is very limited, and to widen the
scope is the effective way to completely utilise the advantage of the material. The often
used method is to modify the material according to the properties of the analytes.
Hence the coating material is very important for target analytes, and we can design and
modify an appropriate coating according to the target analytes, which can be inorganic
or organic materials. Zhang et al. [85] prepared carbon-coated Fe3O4 nanoparticles by a
hydrothermal method, and which was used for solid-phase extraction of polycyclic
aromatic hydrocarbons (PAHs) from environmental water samples. Excellent enrichment
performance was achieved using only 50 mg of sorbents for the extraction of PAHs from
1000 mL water samples. The detection limits of PAHs were in the range of 0.2–0.6 ng L−1
with the detection of HPLC-FLD. This is the first time that Fe3O4@C nanoparticles were
used for the pre-treatment of environmental water samples. Heidari et al. investigated
carbon-coated Fe3O4 nanoparticles as adsorbent for magnetic solid phase extraction and
monitoring of trace amounts of organophosphorus pesticides (OPPs) from environmen-
tal water samples [86]. The detection limit was down to 4.3–47.4 pg mL−1 and the
enrichment factors were in the range of 330–1200. They successfully applied the method
for the determination of OPPs in spiked water samples and satisfied spiked recoveries
were obtained. Fe3O4@C nanoparticles were also used to trap organic dyes from aqu-
eous solution and good results were achieved [87]. Polyaniline is a polymer and contains
several benzene rings in the molecular structure, which improves the surface properties
of Fe3O4@C nanoparticles and enhances the adsorption ability for aromatic pollutants by
π–π interaction. Meng et al. prepared Fe3O4@C@polyaniline microspheres by
hydrothermal method [88]. The experiments proved this concept and achieved good
enrichment ability for phenolic compounds such as phenol, 2,4-dichlorophenol, 2,4,5-
trichlorophenol, pentachlorophenol and bisphenol. This was achieved due to the strong
π–π interaction between polyaniline and aromatic compounds. The results obtained
from a gas chromatography–mass spectrometry experiment demonstrated that the
linear ranges were very wide with good linearity (r2 > 0.991), and the limits of quanti-
fication were in the range of 2.52–29.7 ng mL−1. The method developed was validated
with real water samples and the spiked recoveries were satisfied in the range of 85.3–
110.6%.
Graphene is a new carbonaceous material, and also a material with good adsorption
ability for many compounds. So it may be a good layer material for modification of
Fe3O4 magnetic nanoparticles. The graphene-modified Fe3O4 magnetic nanoparticles

(Fe3O4@G MNPs) were prepared and used as the adsorbent for the magnetic solid-phase
extraction of triazine herbicides such as atrazine, prometon, propazine and prometryn in
environmental water samples prior to high-performance liquid chromatography diode
array detection [89]. The detection limits of the method were in the range of 0.025–
0.040 ng mL−1. Graphene oxide has very similar structure of graphene and has more
hydroxyl and carboxy groups, and it is also a good coating material for enrichment.
Zeng et al. used Fe3O4 nanoparticle grafted graphene oxide (Fe3O4@GO) as the adsor-
bent for extraction of 2,4,4ʹ-trichlorobiphenyl (PCB 28) from water samples [90]. The
results showed that Fe3O4@GO was an effective absorbent for PCB 28 as it required only
30 min to adsorb trace levels of PCB 28 from a 200 mL water sample. It was the first
study to use graphene oxide modified magnetic nanocomposites for the extraction of
POPs from water samples. Meanwhile, Fe3O4@GO also demonstrated good adsorption
activity for protein [91]. The Fe3O4@GO submicron particles, synthesised by a simple self-
assembly process, showed a high adsorption capacity for BSA, and the adsorption
capacity was 181.8 mg g−1 and the adsorption equilibrium was reached within 30 min.
Ye et al. synthesised magnetic graphene composites to extract phthalate acid esters
from environmental water before determining by gas chromatography–mass spectro-
metry (GC-MS) [92]. The results showed that the proposed method had good linearity
(r2 > 0.997), satisfactory precisions (RSD < 8.5%) and high recoveries (88–110%). The
limits of quantification were in the range of 0.035–0.19 μg L−1 and the limits of detection
were in the range of 0.010–0.056 μg L−1. The limits of detection for carbamates in pears
and cucumbers were found to be in the range of 0.08–0.2 ng g−1, which was much lower
than that of some other existing methods. Xian et al. used polyacrylic acid modified
graphene oxide/Fe3O4 (Fe3O4@GO@PAA), which enhanced the water solubility of the
magnetic graphene nanocomposites, and could react with metal ions, which was
successfully used to remove Cu(II), Cd(II) and Pb(II) ions from aqueous solution [93].
The results showed that the adsorbent had high stabilities and removal efficiencies for
Cu(II), Cd(II) and Pb(II) ions. This material had good stability and reusability keeping the
removal rate over 85% after five cycles. Hu et al. modified Fe3O4 with TiO2 nanoparticles
and obtained high-magnetisation Fe3O4@SiO2@TiO2 nanoparticles, which were used for
solid phase extraction of trace amounts of Cd(II), Cr(III), Mn(II) and Cu(II) from environ-
mental waters. In this procedure, molecular malachite green carbinol base (MGCB), a
light-induced hydroxide ion emitter, was applied to adjust pH value of solution for
10 J. XIAO ET AL.
quantitative adsorption instead of the conventional used buffer. The LODs were 4.0, 2.6,
1.6 and 2.3 ng L−1 for Cd(II), Cr(III), Mn(II) and Cu(II), respectively [94].
Another modified strategy for magnetic nanoparticles (MNPs) is to modify with
organic molecules. For example, dodecylbenzene sulfonate was coated onto magne-
tite nanoparticles, and further used as adsorbent for solid phase extraction of ultra-
trace amounts of ammonium in water samples [95] in which ammonium was oxi-
dised to nitrite and then determined by spectrometry after reacting with sulfaben-
zamide. The results showed that the limit of detection was 3.2 ng L−1 and the
recovery was 99%. Fe3O4 magnetic nanoparticles modified with sodium dodecyl
sulfate (SDS) also demonstrated good merits to remove methyl violet from aqueous
solutions [96], and the maximum adsorption was 416.7 mg g−1 which was calculated
based on the Langmuir model. Cetyltrimethylammonium bromide (CTAB) is a better

and easier coated layer for modification, and the CTAB-coated Fe3O4 nanoparticles
were used to remove of perfluorinated compounds from environmental water sam-
ples and surprising results were obtained [97]. The results indicated that only 50 mg
sorbent were able to extract 800 mL environmental water samples and the enrich-
ment factor was up to 1600. The detection limits by high-performance liquid chro-
matography electrospray tandem mass spectrometry were below 0.31 ng L−1.
Besides, the CTAB-coated Fe3O4 nanoparticles also exhibited excellent removal per-
formance for arsenate from water or extraction efficiency for antidepressant drugs
from biological fluid, respectively [98,99]. Polymer is a promising coating layer in the
modification and polystyrene is an often-used coating. The polystyrene-coated mag-
netic nanoparticles (MNPs/PSt) were prepared by emulsion polymerisation and they
were also successfully used in the extraction of five pyrethroids with high enrichment
factors from environmental water samples [100]. Madrakian et al. used arsenazo III
modified maghemite nanoparticles (A-MMNPs) for removal and pre-concentration of
U(VI) from aqueous samples [101]. Under optimised conditions, the pre-concentration
factor and LOD were 400 and 0.01 ng mL−1, respectively. The maximum adsorption
capacity for U(VI) was 285 mg g−1. Hu et al. prepared a novel magnetic material, Al3+
immobilised Fe3O4@SiO2@iminodiacetic acid, and investigated its applicability for the
pre-concentration of gold nanoparticles and ions in water samples. They found that
gold nanoparticles and ions could be simultaneously trapped by this material and
eluted sequentially by NH3·H2O and Na2S2O3 solution, and mercaptosuccinic acid
played an important role in the quantitative recovery of gold nanoparticles and
ions. The LODs for gold nanoparticles and ions were 0.31 and 0.39 ng L−1, respec-
tively. This method provided a good tool for the monitoring of the pollution of gold
nanoparticles and ions [102].
Fe2O3 has strong magnetism, and will be used for the extraction and adsorption of
pollutants. Recently, Bhattacharya et al. investigated γ-Fe2O3 nanotubes to adsorb Cd(II),
Ni(II) and Co(II) in binary and ternary systems from wastewaters [103]. It was the first
time for the study of Cd(II), Ni(II) and Co(II) onto maghemite nanotubes in single, binary
and ternary system. The maximum adsorption capacity of Cd(II), Ni(II) and Co(II) adsorp-
tion by γ-Fe2O3 nanotubes were 94.33, 86.206 and 60.60 mg g−1, respectively, which
indicated the strong adsorption ability; the extraction efficiencies were much higher
than other works.
4. Core-shell materials
Core-shell materials are a new kind of material in recent years, and which have achieved
many more applications. In analytical and environmental fields, they are also drawing
much attention. Especially, core-shell materials have demonstrated their potential as
adsorbents to extract inorganic and organic contaminants from water samples [104–
107]. Core-shell material is a new kind of material, which is generated for the purpose of
improving the surface structure to achieve better adsorption ability, photocatalytic
ability, conductive properties, high surface area, better dispersion, functionality and so
on, and so one or more materials are coated onto the subject material to form core-
shell-like material. Both the core materials and shell materials can be inorganic or
organic materials, which make the core-shell material various and widen the application
fields. Hence, core-shell materials have drawn much more attention and achieved many
applications in chemosensor [75], extraction of PAHs [108], DNA purification [109] as well
as protein recognition and separation [110]. Paria et al. have investigated the classes,
properties and synthesis mechanisms of core-shell nanoparticles and their application
[111]. Here we will discuss the use of the core-shell material in solid phase extraction for
purifying and pre-treating environmental water samples.
Silica-coated core-shell materials have attracted considerable attention because silica
is stable under weak acidic or alkaline conditions, and silica has high mass exchange and
shows a very high thermal resistance. Usually silica shell layer acts as a protecting
coating to prevent the aggregation of the core materials, improve their chemical
stability and provide better protection against toxicity because the core material may
be unstable under acidic or alkaline conditions. However, its use is limited because of
serious parameters, for example, strong alkaline condition, which make silica unstable.
Meanwhile, in more cases, its presence makes it easy and convenient to modify with
functional groups for achieving the required properties. Silica-coated core-shell materials
have been widely used in the extraction of diverse pollutants from water and biological
samples. Luo et al. prepared Fe3O4@SiO2 core-shell material with solvo-thermal reduc-
tion and modified Stöber method, and two-dimensional planar graphene sheets were
coated onto the surface of Fe3O4@SiO2 core-shell material by simple adsorption. The
obtained material exhibited good adsorption and reproducibility for six sulfonamide
antibiotics and the limits of detection were in the range of 0.09–0.16 ng mL−1. These
were attributed to the large surface area and two-dimensional planar structure [112].
Zhu et al. developed a method for detection and adsorption of Hg2+ in water samples
using 1,8-naphthalimide-functionalised Fe3O4@SiO2 core/shell magnetic fluorescent
nanoparticles as the adsorbent [113]. Under the optimised conditions the maximum
adsorption capacity for Hg2+ was higher than 30 mg g−1 and the detection limit for Hg2+
was 3.4 nmol L−1. Furthermore, common coexisting ions had no interference with the
separation and determination. Natural water samples were used to validate the pro-
posed method and the spiked recoveries were all above 98%. While 3-(dansylamino)
propyltriethoxysilane (DAP) functionalised Fe3O4@SiO2 was synthesised for simultaneous
detection and removal of Hg(II) in aqueous solution [114]. Under the optimal conditions,
the detection limit of DAP-Fe3O4@SiO2 for Hg(II) was at the 10–8 M level and the
adsorbent showed excellent fluorescence sensitivity and selectivity towards Hg(II) over
other metal ions. When this adsorbent was used to remove Hg2+ from waste water, the
12 J. XIAO ET AL.
removal efficiency was up to 95%. Recently, Fe3O4@C@layered double hydroxide

(Fe3O4@C@e-component composite) was prepared to extract uranium (VI) ions from
aqueous solutions [104]. The result showed that the maximum adsorption capacity of
Fe3O4@C@Ni−Al LDH for uranium (VI) ion was 174.1 ± 0.2 mg g−1. In a more recent
study, Song et al. designed and prepared polyaniline-coated magnetic particles with
bowl-shaped morphology (Fe3O4@C@PANI microbowls), and which was used to extract
and determine pyrethroids in tea drinks [115]. The results showed that the new material
demonstrated good adsorption activity for pyrethroids pesticides, and the method had
good linearity (r = 0.9992–0.9998). The LODs of pyrethroid pesticides were in the range
of 0.025–0.032 ng mL−1 and spiked recoveries were in the range of 72.1–118.4%. Lu et al.
synthesised core-shell Fe3O4@C@polyaniline (PANI) composite microspheres as the
adsorbent for removal of methyl orange (MO) dye from water samples [116]. They
found that the adsorbent had an excellent adsorption capability of 120.2 mg g−1 for
MO and kept about 81% of the removal efficiency after five adsorption–desorption
cycles. Wang et al. prepared magnetically separable polyaniline (Fe3O4@SiO2-PANI) to
remove humic acid (HA) from aqueous solutions [117]. The adsorption capability for HA
was 36.36 mg g−1 and the adsorption could be well described by Langmuir model. The
more applications of core-shell materials are listed in Table 2 [112,118–127].
Other applications of core-shell materials in solid phase extraction are the imprinted
core-shell material, and their applications in environmental sample pre-treatment have
been widely reported. Gao et al. exploited carbon nanotubes (CNTs) to design a new
nanomaterial in which molecularly imprinted polymers are used to coat carbon nano-
tubes (CNTs). This new material was applied to remove estrone from water samples
[128]. This new core-shell structure estrone-imprinted polymers nanocomposite
(CNTs@Est-MIPs) was synthesised by a semi-covalent imprinting strategy and the
adsorption capacity for estrone was 113.5 μmol g−1. The method was used to analyse
the real water samples, and good recoveries were achieved in the range of 96.14–
98.03%. Gao et al. prepared a core-shell molecularly imprinted polymer to extract
trace triclosan in environmental water samples [129]. These core-shell composites
were synthesised by anchoring MIP shells on the surface of carbon nanotubes (CNTs)
via a surface molecular imprinting sol–gel process. The as-synthesised adsorbent had
good stability because it could be used for over six cycles with loss of less than 6.9% and
the recoveries from spiked river water and lake water samples were in the range of 92.1–
95.3% and 90.7–93.6%, respectively. In a recent study, Fe3O4@SiO2 mesoporous micro-
spheres were synthesised to extract and determine Sudan dyes in environmental water
samples with ultrafast liquid chromatography (UFLC) [130]. Under the optimised condi-
tions the results indicated that the enrichment factor was 500 and the detection limits
were in the range of 0.082–0.12 ng mL−1. The results showed that mesoporous structure
of SiO2 coating increased the surface area and enhanced the adsorption capacity.
Polydopamine coating (PDA), as reported by Lee et al., is able to form on virtually all
types of material surfaces such as metals, oxides, semiconductors, ceramics and syn-
thetic polymers [131]. Polydopamine-coated materials as the promising adsorbents have
aroused great interests in sample preparation due to their desirable characteristics of
easy preparation, environmental friendly and high adsorption capacity. In recent years
the polydopamine-coated polymer had been widely applied in water sample pre-treat-
ment. Niu et al. prepared core-shell polydopamine-coated Fe3O4 nanoparticles to enrich
Table 2. The applications of core-shell material in environmental samples.

Application Recovery
Analytes fields Adsorbent material Kinetic model pH (%) Detection LOD Ref.
Hg(II) water samples naphthalimide functionalised n.r. 5–10 >98.55 fluorescence 3.4 nM [112]
Fe3O4@SiO2
Hg(II) water samples thiol-modified Magnetic Silica n.r. 6 >96% CV-AAS 0.06 ng mL−1 [118]
Pb(II) aqueous Fe3O4@SiO2–NH2 pseudo-second- 5–6 n.r. n.r. n.r. [119]
solutions order
solvent green 7 waste-waters Fe3O4/SiO2/CTAB pseudo-second- neutral and n.r. n.r. n.r. [120]
order alkaline
Methylene Blue water solution Fe3O4/SiO2-GO pseudo-second- n.r. n.r. UV/visible n.r. [121]
order spectrophotometer
pesticides water samples C18-modifie Fe3O4@SiO2 n.r. 3 70.2–110.2 GC-MS 0.001 ~ 0.008 g L−1 [122]
humic acid drinking water Fe3O4@ SiO2-PEI pseudo-second- 4–6 128.64 UV–vis spectrophotometer n.r. [123]
order
Hg(II) water samples SH-Fe3O4-NMPs pseudo-second- 4.0–6.0 129.9– GB/T 5750.6–2006 n.r. [124]
order 256.4
bisphenol A water samples Fe3O4@C@CHI n.r. Natural pH 99.4–102.6 HPLC-FLD. n.r. [125]
phthalates water samples C18-functionalised Fe3O4@mSiO2 n.r. n.r. n.r. GC–MS 25 ~ 77μg L−1 [126]
Cu(II), Pb(II), Cd Water Samples amino-functionalised Fe3O4@SiO2 n.r. 7 n.r. AAS n.r. [127]
(II)
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
13
14 J. XIAO ET AL.
polycyclic aromatic hydrocarbons (PAHs) from environmental water samples [132] and
the results showed that the adsorbent had high extraction efficiency for PAHs. High
extraction efficiency resulted in high sensitivity with LODs in the range of 0.5–1.9 ng L−1
under optimised conditions. Li et al. synthesised magnetic glassy carbon modified
Fe3O4@PDA core-shell nanoparticles to determination of lead (II) and cadmium (II)
[133], and good sensitivities were achieved. More recently, Zhang et al. [134] utilised
polydopamine polymer decorated magnetic nanoparticles (Fe3O4@PDA) to remove
multiple pollutants. They selected dyes (methylene blue and tartrazine) and heavy
metal ions (Cu(II), Ag(I) and Hg(II)) as target pollutants. The result demonstrated that
Fe3O4@PDA had great potential for the removal of multiple pollutants and the max-
imum adsorption capacities calculated from Langmuir adsorption isotherm for methy-
lene blue, tartrazine, Cu (II), Ag(I) and Hg(II) were 204.1, 100.0, 112.9, 259.1 and
467.3 mg g−1, respectively. Duan et al. reported that graphene hydrogel with functio-
nalisation of polydopamine was an effective sorbent material for Pb(II), Cd(II), synthetic
dyes and aromatic pollutants [135]. The maximum adsorption capacity was all above
200 mg g−1 for the analytes.
Besides, some nonmagnetic core-shell materials also have good adsorption ability for
pollutants. Related research works have covered nonmagnetic core-shell materials and
achieved successful applications. For example, core-shell structured hydroxyapatite (HA)/
meso-silica was synthesised as the sorbent to remove methylene blue (MB) from aqu-
eous solutions [136]. The results showed that the as-synthesised adsorbent had a high
adsorption capacity of 134.0 mg g−1. Core-shell polyaniline/polystyrene nanocomposite
was synthesised and used for removal of Cr(VI) from aqueous solutions [137]. Under the
optimised conditions, the adsorption capacity of the adsorbent for Cr(VI) ions in terms of
monolayer adsorption was 19 mg g−1. Core-shell material based on poly(methyl metha-
crylate) (PMMA) cores and poly(ethyleneimine) (PEI) shells (PMMA/PEI) has been synthe-
sised and used to remove heavy metal pollutants [138]; the experimental results showed
that the adsorption capacity was 14 mg g−1.
Core-shell nanomaterials have many advantages such as enhancing the sensitivity
and selectivity. Meanwhile, reasonable modification will endow them with new char-
acteristics for enrichment and widen the scope of application. The core-shell nanoma-
terials can be designed and prepared based on the chemical and physical properties of
the target analytes, and the obtained functionalised materials will demonstrate the
expected physicochemical stability, life span and selectivity; all these will be given
more efforts and open a great prospect for their application in this field.
5. Mesoporous materials
In the early 1990s, pore sized and highly ordered mesoporous silica, known as MCM-41,
showed regularly ordered pore arrangement, high specific surface area, very narrow
pore size distribution and pore diameters in the range of 2–10 nm, which was synthe-
sised for the first time by researchers at the Mobil Oil Corporation [139]. Since then the
mesoporous materials attracted much attention in various fields of physics, chemistry
and material science. Because of its distinctive properties such as large surface area,
thermal and chemical stability, tunable mesoporous channels as well as modifiable
surface properties, mesoporous materials will be an ideal material for SPE. Sierra et al.
reviewed the preparation of hybrid mesoporous silica functionalised with chelating

ligands for extraction of heavy metals [140], Zhao et al. explained the application of
mesoporous materials in extraction of metal ions, organic compounds and peptides/
proteins [141]. We focused on the recent development of mesoporous materials used as
sorbents in solid phase extraction.
Anbia et al. [142] investigated the effect of cationic template on the adsorption of
chromium (VI), furfural and copperphthalocyanine-3,4,4,4-tetrasulfonic acid tetrasodium
salt (CuPc) on MCM-41 and MCM-48 mesoporous materials. The results showed that
adsorbents reached equilibrium in less than 2 h and the materials without surfactant did
not show significant affinity for the analytes. In order to increase the selectivity and
create a stronger link, the adsorbent materials are usually modified with organic or
inorganic groups to obtain specific binding sites on the silica surface. This chemical
modification can make the mesoporous silicas more attractive for many adsorption
applications compared with their unmodified mother-material.
Amino group can chelate with many metal ions to form metal-complex, and so
amino-functionalisation is an important way to increase the adsorption ability of the
material. SBA-15 mesoporous silica material was modified with amino group to form
NH2-SBA-15 which was used to trap hexavalent chromium from water samples [143]. The
modification enhanced the adsorption of hexavalent chromium and the enrichment
factor was 44 and the LOD was 0.2 μg L−1 by FAAS. Ahmadi et al. chemically modified
MCM-41 by (3-aminopropyl) triethoxysilane groups and 5-nitro-2-furaldehyde as adsor-
bent to pre-concentrate and determine uranium and thorium in water samples prior to
ICP-OES [144]. The results show that the synthesised adsorbent has good stability,
reusability and high adsorption capacity. The adsorption capacities of the modified
MCM-41 for uranium (VI) and thorium (IV) were 47 and 49 mg g−1, respectively. The
limits of detection obtained for uranium (VI) and thorium (IV) were 0.3 μg L−1. Hu et al.
modified ordered mesoporous silica with 3-(2-aminoethylamino) propyltrimethoxysilane
(AAPTS) and packed as a micro-column for separating and pre-concentrating inorganic
arsenic species in natural water samples [145]. Their result showed that As(V) was
selectively adsorbed on the micro-column in the range of pH 3–9, while As(III) could
not be retained in the studied pH range and passed through the micro-column directly.
They achieved total inorganic arsenic by oxidation of As(III) to As(V) with 50.0 μmol L−1
KMnO4 and the concentration of As(III) was obtained by subtracting As(V) from total As.
The adsorption capacity of AAPTS modified ordered mesoporous silica for As(V) was
10.3 mg g−1, and the LOD of the method for As(V) was 0.05 μg L−1, and the enrichment
factor was 100. Thiol group is an important group and can react with some metal ions
selectively, and so it is often used to develop highly selective enrichment methods and
determination methods. Wu et al. synthesised thiol-functionalised MCM-41 mesoporous
silica by evaporation-induced self-assembly to remove Cu(II), Cr(III), Pb(II) and Ag(I) from
water samples [146]. The synthesised adsorbent has a large surface area of 421.9 m2 g−1
and which resulted in the largest adsorption capacity with high pore diameter (centred
at 5.27 nm). C18 can also be used as a functional group to modify mesoporous silica
materials (SM-C18 and SBA-15-C18), which were used as stationary phases for pre-
concentration of seven steroid hormones (estrone, estradiol, estriol, ethinyl estradiol,
diethylstilbestrol, testosterone and progesterone) from milk. The results indicated that
mesoporous silicas had a high surface area, high pore volume and a homogeneous
16 J. XIAO ET AL.
distribution of the pores and both silicas presented a similar degree of functionalisation,
and SBA-15-C18 silica exhibited good extraction performance for the seven steroid
hormones with high recoveries [147]. C18 functionalised mesoporous silicas (SBA-C18
and SM-C18) also exhibited good enrichment ability for 17β-estradiol in water media
[148]. Meanwhile, bi-functionalised mesoporous silica with octadecyl and aminopropyl
groups would have different properties different from only C18 modification, and the co-
modification with C18 and amino groups showed excellent adsorption capacity for 12
endocrine disruptors, with high recoveries near 100% except estriol and prednisolone
with recoveries of 66% and 82%, respectively [149]. Carpio et al. first investigated the
possibility of periodic mesoporous organosilica (a phenylene-bridged material, Ph-PMO)
for the enrichment of fenuron, simazine, atrazine, carbaryl and terbutryn in grape must,
and the results demonstrated that periodic mesoporous organosilica had comparable
adsorption ability for the target analytes and the performance was even better than that
achieved with C18 and HLB materials, which indicated that periodic mesoporous orga-
nosilica would have a great potential in the adsorption of pollutants [150]. Hu et al.
reported a micro-column solid phase extraction with Ti-containing mesoporous silica for
the separation/pre-concentration of Cr(III), Cd(II), Pb(II) and Cu(II) in environmental water
samples in combination with inductively coupled plasma mass spectrometry. They
found that the adsorption process was described with Freundlich adsorption isotherm
and multilayer adsorption, and the strong adsorption resulted from the hydroxyl groups
on the surface of the material. The reported SPE-ICP-MS method provided good sensi-
tivity for heavy metals with low LODs of 19, 39, 7 and 13 pg mL−1 for Cr(III), Cu(II), Cd(II)
and Pb(II), respectively [151]. Chen et al. prepared a novel adsorbent of thiacalix[4]arene
tetracarboxylate derivative modified mesoporous TiO2 and developed a simultaneous
determination of trace metals based on micro-column separation-pre-concentration
online coupled to plasma optical emission spectrometry. They found that the adsorption
capacities of thiacalix[4]arene tetracarboxylate derivative modified mesoporous TiO2 for
V, Cu, Pb and Cr were 14.0, 11.7, 17.7 and 14.5 mg g−1, respectively. The detection limits
of the method were 0.09, 0.23, 0.50 and 0.15 μg L−1, respectively [152].
The modified mesoporous materials will also play an important role in the enrichment
and removal of organic contaminants. He et al. prepared an ordered mesoporous carbon
containing basic nitrogen functional groups to adsorb Reactive Red dyes [153]. The
results indicated that this novel functionalised ordered mesoporous carbon could
increase the adsorption capacity of Reactive Red 2 at 298 K by around 40% and 100%
as compared with the unmodified carbon and a commercial activated carbon,
respectively.
6. Carbon nanotubes (CNTs) and graphene

Since the CNTs were discovered in 1991 [154], they have attracted much attention for
their unique properties such as large surface area, stability and mechanical strength,
which make them an ideal material for SPE. Hence there are many applications in
many fields. Herrera-Herrera et al. have reviewed CNTs in separation science [155], and
Herrero Latorre et al. have summarised the advances of CNTs as SPE adsorbents for the
determination of metal species in combination with atomic spectrometry [156].
Generally, the CNTs can be classified as single-walled CNTs (SWCNTs) and multi-walled
CNTs (MWCNTs). The first case is formed by a single rolled graphite lamella in a
cylinder and the latter is formed by several concentrically arranged CNTs arranged
around a common axis. Salam et al. used multi-walled carbon nanotubes (MWCNTs) to
adsorb and remove Sb(III) from model solutions and environmental water samples
[157]. The results show that the adsorption of Sb(III) by MWCNTs from the model
solution followed pseudo-second-order kinetics with good correlation coefficient.
SWCNTs and MWCNTs were also used as adsorbents for the pre-concentration of
heavy metals, 4-nitrophenol in environment samples [158–162]. Oxidisation is the
simplest modification method and has received much attention in recent years. The
oxidised CNTs had been widely used for solid phase extraction. Chen et al. used
oxidised single-walled carbon nanotubes for extraction and determination of Cu, Co
and Pb in water samples before analysis by ICP-MS[163]. The SWNTs were oxidised by
concentrated nitric acid, which enhanced the adsorption of heavy metal ions. Under
the optimised conditions the LODs for Cu, Co and Pb were 39, 1.2 and 5.4 pg mL−1,
respectively. Oxidised multi-walled carbon nanotubes as adsorbent had exhibited the
high removal efficiency of manganese from water [164], the removal rate of manga-
nese by MWCNT reached up to 96.82%, and the equilibrium was achieved within
354 min and the adsorption was fit for the pseudo-second-order model. Besides,
modified with functional groups which can form complexes with metal ions on CNTs
surface is an important way for modification. Multi-walled carbon nanotubes were
modified with ethylenediamine, which had advances for the extraction and pre-con-
centration of heavy metal ions [165]. Under the optimum conditions, the maximum
adsorption capacity of the adsorbent for Cr(III), Fe(III) and Pb(II) was found to be 39.58,
28.69 and 54.48 mg g−1, respectively. Diphenylcarbazide-modified multi-walled carbon
nanotubes were used for extraction of ultra–traces of Cd(II) from water samples and
also from food products [17]. The nitrogen in the diphenylcarbazide can complex with
Cd(II), which can enhance the selectivity. Under the optimum experimental conditions,
the adsorption capacity of the modified MWCNT was 86 mg g−1 for cadmium ions, the
pre-concentration factor was 360 and the detection limit was 0.05 ng mL−1. It would
be a good idea to combine the merits of magnetic nanoparticles and multi-walled
carbon nanotubes, because multi-walled carbon nanotubes have large specific surface
area, and have high adsorption capacity for many analytes, and the magnetic nano-
particles provide the advantage of rapid separation, which avoids the low flow rate,
small sample volume and labour-intensive procedure of the conventional solid phase
extraction with multi-walled carbon nanotubes as the adsorbents. This core-shell
material provides more advantages and draws much attention from the researchers.
Wang et al. developed a method for extracting and determining Se(IV) using mag-
netic multi-walled carbon nanotubes as adsorbent and analysed by hydride generation
atomic fluorescence spectrometry [166]. Under the optimised conditions the enhance-
ment factor of the proposed method for Se(IV) was 100 and the limit of detection was
0.013 μg L−1. Huang et al. used magnetic multi-walled carbon nanotube (MMWCNTs)
composites to extract linear alkylbenzene sulfonates (LAS) from environmental water
samples [167]. High-performance liquid chromatography (HPLC) was used to determine
linear alkylbenzene sulfonates in water samples. The results indicated that the synthe-
sised material had good stability and reuse property because it remained 95.0% recovery
for the target LAS even after a fifty-run of adsorption and desorption cycle. The
18 J. XIAO ET AL.
detection limits were in the range of 0.013–0.021 µg L−1 and the spiked recoveries of
LAS homologues in environmental water samples were in the range of 87.3–106.3%.
MWCNTs by oxidation or modification with amino group has exhibited good enrichment
ability of metal ions; however, in order to achieve high adsorption efficiency, more
amino groups can be grafted onto the surface of MWCNTs. Recently, a report described
a method to prepare multi-amino groups modified MWCNTs on which polypropylene
amine dendrimers (POPAM) were grafted, and the increased amino groups markedly
increased the adsorption capacity of gold and palladium and the enrichment factor up
to 360. The LODs based on this material were 0.08 and 0.12 ng mL−1 for gold and
palladium, respectively [168]. The preparation process of POPAM-grafted MWCNTs is
shown in Figure 3. Nabid et al. developed a new way for modifying MWCNTs by poly 1,8-
diaminonaphthalene and MWCNTs-COOH for providing active amino groups, which

could chelate with metal ions and realising the enrichment of heavy metal ions. This
was a good idea and this hybrid material earned high selectivity to cadmium and lead
and the maximum capacity for cadmium and lead ions was 101.2 and 175.2 mg g−1, and
the LODs based on this material were 0.09 and 0.7 ng mL−1 [169]. Hu’ group prepared 3-
(2-aminoethylamino) propyltrimethoxysilane modified multi-walled carbon nanotubes
and developed a method with microcolumn solid phase extraction coupled to ICP-MS
for simultaneous speciation analysis of inorganic arsenic, chromium and selenium. The
method was simple, selective and cheap. They also developed stir bar adsorptive
extraction methods with amino modified multi-walled carbon nanotubes/polydimethyl-
siloxane and polyaniline/hydroxyl multi-walled carbon nanotubes composite-coated stir
Figure 3. The preparation process of POPAM-grafted MWCNTs [161].

bars for phenols and polar and apolar compounds in environmental samples, and good
sensitivity was achieved [170–172].
Graphene and graphene oxide have been mentioned as modified layer above;
however, they can also be used as adsorbents for SPE due to the fact that graphene
is a double-sided polyaromatic scaffold with an ultra-high specific surface area (theo-
retical value 2630 m2 g−1), and graphene oxide earns more polar groups such as
hydroxyl, expoxy, and carboxy groups, which endow graphene oxide with much
stronger polarity and hydrophilicity. All these indicate that graphene and graphene
oxide could be used as promising adsorbents for SPE [173]. Han et al. enriched
organophosphorus pesticides in apple juices with graphene SPE cartridge prior to
GC-MS, and then excellent limits of quantitation for the organophosphorus pesticides
were achieved in the range of 0.15–1.18 ng mL−1 [174]. Pourjavid et al. pre-concen-
trated trace of Co(II) and Ni(II) ions with graphene oxide column SPE in combination
with FAAS, in which the ions were adsorbed onto graphene oxide surface as N-(5-
methyl-2-hydroxyacetophenone)-N′-(2-hydroxyacetophenone) ethylene diamine (MHE)
complex. The study found that the adsorption of ions was achieved at pH 6.0, and the
pre-concentration factor was up to 1250 with passing 1250 mL sample, which allowed
it to be used for the determination of low-levels of metal ions [175]. Shi et al. devel-
oped a sensitive method for the determination of carbamate pesticides with graphene
SPE coupled to ultra-high-performance liquid chromatography–tandem mass spectro-
metry, the LODs for six carbamate pesticides were in the range of 0.5–6.9 ng L−1 and
the enrichment factors were in the range of 34.2–51.7 [176]. Wang et al. prepared a
graphene-coated SPME fibre and developed a simple SPME-GC-MS method for the
simultaneous determination of 16 PAHs in mainstream cigarette smoke. The LODs and
LOQs for 16 PAHs were in the range of 0.02–0.07 and 0.07–0.22 ng cigarette−1. This
method was very easy to operate and have a high selectivity, which could be used as
an excellent alternative for PAHs analysis [177]. As mentioned above, the metal ions
were adsorbed as complex because graphene had a low direct adsorption efficiency of
metal ions. This could be resolved by amino-functionalisation. Behbadhani et al. pre-
pared amino-functionalised graphene nano-sheet by modifying graphene oxide with 3-
aminopropyltriethoxysilane. The amino-modification provided high pre-concentration
factor, high tolerance to interferences and high adsorption capacity. Under optimal
conditions, the extraction efficiency was >97%, the limit of detections were 0.03, 0.05,
0.2, 0.1 and 1 μg L−1 for the ions of cadmium, copper, nickel, zinc and lead, respec-
tively, and the adsorption capacities for these ions were 178, 142, 110, 125 and
210 mg g−1 [178]. Hu’s group prepared GO–silica composite coating, and established
a new online enrichment and determination method for heavy metals in combination
with GO–silica composite coated hollow fibre solid phase micro-extraction and induc-
tively coupled plasma mass spectrometry, and the results showed that this coating
possessed a high adsorption capacity, good preparation reproducibility, excellent
chemical and mechanical stability as well as good reusability. The LODs for Mn, Co,
Ni, Cu, Cd and Pb were 7.5, 0.39, 20, 23, 6.7 and 28 ng L−1, respectively. Meanwhile,
they used graphene oxide to prepare Fe3O4@SiO2@polyaniline–graphene oxide com-
posite and investigate its enrichment for rare earth elements in environmental samples
based on magnetic solid phase extraction coupled to inductively coupled plasma mass
spectrometry. The developed method was very simple, rapid and sensitive, and the
20 J. XIAO ET AL.
LODs were 0.04–1.49 ng L−1. Their group also explored graphene oxide–TiO2 composite
for the pre-concentration of heavy metals and rare earth elements in environmental
samples followed by online inductively coupled plasma optical emission spectrometry
detection and satisfactory results were achieved [179–181].
These results indicated that the graphene modified with specific groups would
increase the adsorption capacity for target analytes, and that they have a great potential
in analytical and environmental fields.
7. TiO2 nanotubes and arrays

TiO2 nanotubes are often used in the photocatalysis. However, due to its relatively large
specific surface areas, it should have a higher enrichment capacity. Hence increasing
attention has been put on TiO2 nanotubes for solid phase extraction in recent years. Our
group used TiO2 nanotubes as adsorbent for pre-concentration of nickel and cadmium
in water samples [182]. The detection limits were 0.25 ng mL−1 for cadmium and
1 ng mL−1 for nickel, respectively. Besides, they also used TiO2 nanotubes as adsorbents
for extraction of trace copper [183], and N-doped TiO2 nanotubes to pre-concentrate
paraquat and diquat prior to capillary electrophoresis [184]. Under optimal conditions,
the detection limits obtained were 1.95 and 2.59 μg L−1. Kef et al. used TiO2 nanotubes
as solid-phase extraction adsorbent for the determination of PAHs in environmental
water samples [185]. After analysis by gas chromatography (GC-FID), the detection limits
were 0.017–0.059 ng mL−1 with a linear range of 0.01–0.8 µg mL−1. TiO2 nanotubes were
also used for water samples enriched with benzoylurea insecticides [186]. The detection
limits were in the range of 0.062–0.21 μg L−1, and the recoveries of spiked samples were
over the range of 82.0–100%.
TiO2 nanotube array is a new nanostructure from TiO2 nanotube particles, and they
will have merits different from nanoparticles. Our group first utilised TiO2 nanotube array
as adsorbent and developed micro-solid phase extraction of fungicides in water samples
[187]. After micro-solid phase extraction, the target analytes were determined by HPLC.
Under the optimal experimental conditions, the detection limits for the targeted fungi-
cides were in the range of 0.016–0.086 μg L−1 (S/N = 3) and the spiked recoveries were
in the range of 73.9–114%. We have successfully developed new methods for enriching
and measuring organochlorine pesticides [188] and pyrethroid pesticides in environ-
mental water samples [189] using TiO2 nanotube arrays. Besides, we also investigated
the applicability of ordered TiO2 nanotube arrays for the enrichment and determination
of polychlorinated biphenyls (PCBs) in water samples [190]. After being determined by
gas chromatography and electron capture detection (GC–ECD), the achieved low detec-
tion limits were in the range of 0.02–0.10 μg L−1 and the adsorbent showed a high
stability. The TiO2 nanotube arrays could be reused for over 200 times without the loss
of the extraction efficiency. Graphene is a good material with excellent adsorption for
many pollutants, which was also considered to modify TiO2 nanotube arrays for enhan-
cing the sensitivity of carbamate pesticides in water samples, and expected enrichment
performance was achieved, and the LODs were in the range of 2.27 ~ 3.26 μg L−1, the
results indicated that graphene modification could change the surface structure and
provide more active sites for adsorption, and the composite exhibited many merits for
potential μSPE of many pollutants [191]. In addition, our group also exploited new ways
Figure 4. Micro-solid phase extraction TiO2 nanotube arrays.
to enhance the extraction of PAHs with TiO2 nanotube arrays in environmental water
samples [192]. A simple method was to modify ordered TiO2 nanotube arrays with CTAB.
The results showed that the CTAB-modified TiO2 nanotube arrays demonstrated excel-
lent enrichment ability for PAHs and the detection limits of targeted PAHs were in the
range of 0.026–0.82 μg L−1 (S/N = 3) and the spiked recoveries were in the range of
75.0–114%. The extraction procedure was depicted in Figure 4.
Some other modified TiO2 nanotubes were also reported. Wang et al. proposed
amino-functionalised titanate nanotubes (NH2-TNTs) as adsorbent to adsorb Cr(VI)
from aqueous solutions [193]. They synthesised the adsorbent by covalently grafting
[1-(2-amino-ethyl)-3-aminopropyl]trimethoxysilane (AAPTS) onto protonated titanate
nanotubes(HTNTs) with great amounts of surface hydroxyl groups. The as-synthesised
adsorbent showed much larger adsorption capacity (153.85 mg g−1) than those on
HTNTs (26.60 mg g−1). Moreover, the adsorption was very fast, and 5 min could result
in 95% Cr(VI) ions adsorbed onto NH2-TNTs.
8. Biosorbents
With the rapid development of the adsorbent materials, there are some new materials
emerged, which are different from the conventional ones and are being used for solid
phase extraction. Biosorption is a new way for SPE, which has been developed and
achieved many applications, and mainly used for removal of heavy metal ions from
water samples. Usually biomass such as bacteria, yeast, algae and fungi has functional
groups that can bind to metal ions, and so these microorganisms could be utilised to be
22 J. XIAO ET AL.
sorbents for SPE by immobilising. Pacheco et al. presented a review on the biosorption
as an analytical tool to improve analytical sensitivity [194].
Bertagnolli et al. found that alginate extraction product from Brazilian brown sea-
weed Sargfassum filipendula showed a high adsorption capacity for Cr(III) and Cr(VI), and
the binding of metal ions was attributed to carboxyl, amino and sulfonate groups, in the
biosorption process, Cr(VI) was reduced to Cr(III) [195]. Meitei et al. investigated Spirodela
polyrhiza biomass to be used as adsorbents for removal of Pb(II) and Cd(II), and found
that the maximum adsorption capacity of Pb(II) and Cd(II) on S. polyrhiza biomass was
137 and 36 mg g−1, respectively [196]. Sartape et al. designed a new way for the removal
of malachite green (MG) dye from water samples with wood apple shell (WAS) as the
adsorbent, and achieved high removal rate of MG dye with 98.87% at an initial con-
centration of 100 mg L−1 and pH 7–9 in 3.3 h. WAS, a fruit-food solid waste, is
abundantly available and eco-friendly and low cost, which has exhibited highly effi-
ciency for the removal of MG dye and may be used as an excellent alternative adsorbent
for removal of such pollutants in the future [197]. Bamboo charcoal is another biomass
that was reported as adsorbent for extraction of atrazine and simazine in environmental
water samples prior to high-performance liquid chromatography–ultraviolet detector
(HPLC-UV) [198]. The results exhibited that an excellent linearity was obtained over the
range of 0.5–30 μg L−1 with correlation coefficients of 0.9991 and 0.9982, for atrazine
and simazine, respectively. Utilisation of walnut shell (WNS) (Juglansregia) as an adsor-
bent for the removal of Cr(VI) ions from aqueous solutions after treatment with citric
acid has been reported [199]. During the modification processes, citric acid converted
into citric acid anhydride after heating, and which was combined with cellulosic hydro-
xyl groups to form an ester linkage and thus introduced carboxyl functional groups to
the cellulosic materials. The additional carboxyl groups ensured higher adsorption
capacity of these materials for positively charged metal ions. The process could be
illustrated in Figure 5. Zhang et al. used eggshell membrane as adsorbent to enrich
arsenic (V) from environmental water samples [200]. Eggshell membrane (ESM) contains
several surface functional groups such as amines, amides and carboxylic groups that
made their use as adsorbent for retain target species possible. Under the optimal
conditions, the breakthrough adsorption capacity was found to be 3.9 μg g−1 and the
detection limit for arsenic (V) was 0.001 μg L−1. Guo et al. used soybean hull as a solid
phase extraction adsorbent after chemically modified with citric acid for extraction and
determination of trace amounts of Cu (II) in food samples by FAAS [201]. The adsorption
capacity of modified soybean hull was found to be 18.0 mg g−1 for Cu (II) and the
detection limit of the proposed method was 0.8 ng mL−1 after analysis by FAAS.
Figure 5. Thermochemical reaction of walnut shell (WNS) and citric acid [186].
9. Metal organic frameworks

Metal organic frameworks (MOFs) is a new class of porous hybrid materials and consists
of inorganic metal centres and organic linkers by coordinate bonds. MOFs possess
unique characteristics such as structure diversity, large surface area, extraordinary
adsorption affinities, tunable pore sizes and facilely tailorable functionality due to the
variety of metal ions and linkers. Hence these properties inspired the researchers and
related research works were carried out.
Salarian et al. reported that an MOF sustained by a nanosized Ag12 cuboctahedral
node could be applied to selectively extract traces of lead (II) from environmental
water samples. The use of MOF resulted in excellent enrichment and good adsorption
capacity of 120 mg g−1 and LOD of 500 ng L−1 after desorption with EDTA and
determination using FAAS [202]. Haque et al. discovered that MOF-235, an iron
terephthalate, one of the metal-organic frameworks, could be effectively used to
remove harmful dyes methyl orange and methylene blue from contaminated water,
and the adsorption capacities of MOF-235 were much higher than those of activated
carbon [203]. PAHs are important, persistent organic pollutants, and contain two or
more fused benzene rings in linear, angular or cluster arrangements, which have often
been found in the different environmental matrices. To develop highly efficient
detection technology is of crucial importance. Hu et al. synthesised MOFs of Al-MIL-
53-NH2 by hydrothermal method and PDMS/Al-MIL-53-NH2 coated stir bars with sol–
gel method, and established a new method with this novel material as the adsorbents
in combination with high performance liquid chromatography fluorescence detection
(HPLC-FLD) for PAHs. The obtained enrichment factors were in the range of 16.1–88.9,
and the LODs for PAHs were in the range of 0.05–2.94 ng L−1 [204]. They also focused
on the environmental estrogens and developed an efficient enrichment technique
with MOFs-based stir bar adsorptive extraction. They prepared polydimethylsiloxane
(PDMS)/MOFs (including PDMS/MOF-5, PDMS/MOF-199 and PDMS/IRMOF-3) coated
stir bars and which were used to extract seven target estrogens such as 17-β-estradiol,
dienestrol, diethylstilbestrol, estrone, 4-t-octylphenol, bisphenol-A and 17α-ethynyles-
tradiol, and the results showed that PDMS/IRMOF-3 exhibited highest extraction
efficiency, and LODs were low to 0.15–0.35 μg L−1 and the enrichment factors were
in the range of 30.3–50.6-fold [205]. Yan’ group have done many research works on
MOFs for separation, and prepared a thermal and solvent stable MOF MIL-88B with
nanosized bipyramidal cages and large surface area, which was used to prepare an
MIL-88B fibre for developing SPME method to determine polychlorinated biphenyls
(PCBs), another kind of persistent organic pollutants. The results showed that the
enrichment factors for PCBs were in the range of 757–2243, and the LODs were in
the range of 0.45–1.32 ng L−1. The extraction efficiency kept stable without markedly
lost. This excellent enrichment was attributed to the hydrophobicity and dipole–dipole
interactions between PCBs and MIL-88B, and the diphenyl structured PCBs and the
aromatic framework of MIL-88B may be the cause of the strong hydrophobic interac-
tion [206]. Their group also developed another SPME fibre coated with metal-organic
framework UiO-66 for phenols from water samples, and the headspace SPME with
UiO-66 coated fibre provided enhancement factors of 160 (phenol) to 3769 (2,4-
dichlorophenol), and the LODs were in the range of 0.11–1.23 μg L−1. This good
24 J. XIAO ET AL.
extraction performance was attributed to the hydrophobicity of the phenols, the

hydrogen-bond interaction between the hydroxyl groups of the phenols and the Zr-
O sites, and the π–π interaction between the phenols and the UiO-66 framework [207].
10. Conclusions
Chemical pollution really poses a threat for the environment and has attracted increas-
ing attention. Because of the low concentration of pollutants and the complex sample
matrices, separation and pre-concentration before analysis become even more impor-
tant. Solid phase extraction has been widely used due to its intrinsic merits. This review
has summarised recent developments of adsorbents materials of SPE. These materials
offer new possibilities for improving the selectivity and efficiency. Nowadays, new
materials would emerge unexpectedly, which would result in novel discoveries.
Dendrimers are a kind of ideal material for increasing the surface area, and it can be
used to modify magnetic nanomaterial or other SPE adsorbents for achieving unex-
pected extraction performance. Brushes have absorbed much more attention and
achieved many applications, their varieties and specific features such as pH, light or
temperature responses will be utilised to develop new sample pre-treatment techni-
ques. Supramolecular material and the combination of them and the new emerging
material will be a good direction for preparation of new adsorbents. Moreover, the
quantum dots have emerged with attractive properties, but up to now they have not
exhibited their potential. With the rapid development of nanoscience and analytical
chemistry, new adsorbents and modification materials will appear like mushrooms,
which will promote the development of environment pollutants removal and trace
analysis of pollutants for monitoring. These new directions will open a new era and
play great roles in the enrichment and removal of environmental pollution in the future.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by the National Natural Science Foundation of China [grant number
21377167], Program for New Century Excellent Talents in University [grant number NCET-10-0813],
Science Foundation of China University of Petroleum, Beijing [grant number KYJJ2012-01-15].
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International Journal of Environmental Analytical

ISSN: 0306-7319 (Print) 1029-0397 (Online) Journal homepage: http://www.tandfonline.com/loi/geac20

Recent advances of adsorbents in solid phase

To link to this article: http://dx.doi.org/10.1080/03067319.2016.1150459

Published online: 15 Mar 2016.

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Recent advances of adsorbents in solid phase extraction for

ABSTRACT ARTICLE HISTORY

CONTACT Junping Xiao xiao1229@163.com; Qingxiang Zhou zhouqx@cup.edu.cn

imprinted amino-functionalised silica gel adsorbents (APTS-Cr(III)-Si and APTS-Fe(III)-Si)

Figure 1. The process of Cd(II) ion imprinting [64].

Figure 2. The process of magnetic solid-phase extraction [74].

iron oxide nanoparticles by co-precipitation of ferrous and ferric chlorides in ammonium

Fe3O4 magnetic nanoparticles. The graphene-modiﬁed Fe3O4 magnetic nanoparticles

based on the Langmuir model. Cetyltrimethylammonium bromide (CTAB) is a better

removal eﬃciency was up to 95%. Recently, Fe3O4@C@layered double hydroxide

Table 2. The applications of core-shell material in environmental samples.

reviewed the preparation of hybrid mesoporous silica functionalised with chelating

6. Carbon nanotubes (CNTs) and graphene

diaminonaphthalene and MWCNTs-COOH for providing active amino groups, which

Figure 3. The preparation process of POPAM-grafted MWCNTs [161].

7. TiO2 nanotubes and arrays

Figure 4. Micro-solid phase extraction TiO2 nanotube arrays.

9. Metal organic frameworks

extraction performance was attributed to the hydrophobicity of the phenols, the

[46] M. Behbahani, A. Bagheri, M. Taghizadeh, M. Salarian, O. Sadeghi, L. Adlnasab and K. Jalali,

Mater. Sci. Eng. C 47, 114 (2015).

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