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Trends in nanomaterial-based solid-phase microextraction with a focus

on environmental applications - A review

Khaled Murtada

PII: S2214-1588(19)30062-5
DOI: https://doi.org/10.1016/j.teac.2019.e00077
Reference: TEAC 77

To appear in: Trends in Environmental Analytical Chemistry

Received Date: 19 November 2019

Revised Date: 4 December 2019
Accepted Date: 5 December 2019

Please cite this article as: Murtada K, Trends in nanomaterial-based solid-phase

microextraction with a focus on environmental applications - A review, Trends in
Environmental Analytical Chemistry (2019), doi: https://doi.org/10.1016/j.teac.2019.e00077

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Trends in nanomaterial-based solid-phase microextraction with a

focus on environmental applications - A review

Khaled Murtada 1* k.a.murtada@gmail.com ; kmurtada@uwaterloo.ca

Palestine Academy for Science and Technology (PALAST), Ramallah, Palestine.

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*
Corresponding author. (K. Murtada)

1
Current Affiliation: Department of Chemistry, University of Waterloo, 200 University

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Avenue West, Waterloo, Ontario, N2L 3G1, Canada.

Graphical abstract
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Highlights
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 Nanomaterials (NMs) are used for SPME in various environmental samples.
NMs can be used in various SPME configurations.
NMs exhibit unique intrinsic properties.
Various environmental applications could be done by applying the properties
of NMs.

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ABSTRACT

Effective solid-phase microextraction (SPME) in environmental field represents a crucial step

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for the adequate extraction of several analytes. Several materials have been traditionally
developed for SPME of several analytes from environmental samples, even though their
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several restrictions such as post-treatment required, elevate costs and limited efficiency.
Recently, nanomaterials (NMs) have emerged as a promising substitute for SPME in
environmental applications of traditional techniques, due to their small size and their high
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specific surface-area which enhances their high reactivity. In this present review different
NMs which have recently been utilized as SPME sorbent for environmental applications are
classified into eleven main groups, namely nanoparticles, nanofibers, nanoflakes,
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nanocomposites, nanorods, nanotubes, nanohorns, nanosheets, nanocubes, nanospheres and

polymer-based NMs. Application of these NMs in SPME modes and configurations for
environmental analysis has been reviewed. The study discusses not only the advantages but
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also the major limitations of using such NMs.

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Abbreviations

(MIL)-53(Al) Material of Institute Lavoisier MIP Molecularly

imprinted polymer
AgNPs Silver nanoparticles MMCNSs Monodisperse microporous
carbon nanospheres
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AuNPs Gold nanoparticles MMIP Magnetic molecularly
imprinted polymer
BSA Bovine serum albumin MOF Metal organic framework
CLC-DAD Capillary liquid chromatography with diode-array detector MOF-
HCNCs Metal-organic framework-hollow carbon nanocubes
ETAAS Electrothermal atomic absorption spectrometry
MWCNT@IL/PANI Ionic liquid functionalized multi-walled carbon
nanotubes-polyaniline
FAAS Flame atomic absorption spectrometry MWCNTs Multi-
walled carbon nanotubes
GC-CD-IMS Gas chromatography-corona discharge ion mobility spectrometry
OAMNPs Oleic acid coated magnetite nanoparticles
GC-ECD Gas chromatography-electron capture detector o-SWNHs Oxidized

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single walled carbon nanohorns
GC-FID Gas chromatography-flame ionization detector PAHs Polycyclic
aromatic hydrocarbons

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GO Graphene oxide PEG-PEG-g-CuO NPs Poly(ethylene
glycol)-poly(ethylene glycol) grafted flower-like cupric oxide nanoparticles
HF-SPME -p
Hollow fiber solid phase microextraction
mesoporous organosilica based on alkylimidazolium ionic liquid
HPLC High performance liquid chromatography
PMO-IL

PPy-MWCNTs-TiO2
Periodic
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Polypyrrole/multi-walled carbon nanotubes /titanium oxide
HPLC-FD High performance liquid chromatography with fluorescence detection
SDS Sodium dodecyl sulfate
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IC Ion chromatography SERS Surface enhanced Raman

spectroscopy
ICP-OES Inductively coupled plasma optical emission spectrometry SLPME
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Solid-liquid phase microextraction

IMS Ion mobility spectrometry SQT-FAAS Slotted
quartz tube-flame atomic absorption spectrometry
MDSPME Magnetic dispersive solid phase microextraction TFME Thin film
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microextraction
ZnO/PT/SBA-15 ZnO/polythiophene/ hexagonally ordered silica
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Ti-Ni-O CNTs Titanium-nickel oxide composite nanotubes

VASPME Vortex assisted solid phase microextraction TiO2/NiOCNSs Titanium
and nickel oxide composite nanosheets

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Keywords: solid-phase microextraction, nanomaterials, nanoparticles, nanosheets,
nanocomposites, environmental applications.

1. Introduction

The quality of analysis in environmental matrices fundamentally depends on the chosen

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sample treatment [1]. Therefore, an efficient environmentally friendly monitoring approach
usually requires and there is an increasing demand for strategies reducing the matrix

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interferences, especially in case of volatile organic compounds (VOCs) and persistent organic
pollutants (POPs) occurring at low levels in complex or difficult volatile matrices. These
cases require minimizing the final volume of target analytes to higher concentration of
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analytes at low quantification limits [2]. Furthermore, there is a indigence for environmentally
friendly sustainable procedures that apply minimized the volume of spent organic solvents
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[2]. Another aspect of analytical method and procedures development is automation [3].
There are many advantages commonly attributed to automation include low time-consuming,
lower sample contamination, increase of simplicity and improved the repeatability. These are
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some of the most important advantages for the application of solid-phase microextraction
(SPME) technique [3].
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SPME is a miniaturized extraction technique developed in 1990 [4]. SPME has been
considered as a modern alternative to current sample preparation, and has a very wide range
of applications [5]. The SPME procedure involves the sorption of the target analytes onto the
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surface of a coated fiber. The extraction is followed by desorption of the trapped analytes to
proceed their analytical determination. Desorption process is usually carried out by a thermal
step (place the SPME fiber in the gas chromatography (GC) injection port) or by exposing the
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SPME fiber that has been coated to a small volume of organic solvent where analytes dissolve
(when combining SPME combined liquid chromatography (LC) or capillary electrophoresis
(CE)). Autonomously on the desorption step, the SPME coating material is able to maintain
its integrity and could be used repeatedly. Fig. 1 shows a general scheme of the main
procedure to carry out SPME analysis. However, several limitations are also encountered. For

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instance, the aforementioned SPME techniques require the correct selection of a robust
sorbent to be successfully applied under variable conditions. Additionally, the efficiency of
extraction, the reusability and disposal of the sorbents with several analytes in environmental
samples must be estimated, representing some of the major issues to consider. Also,
performing such techniques is not exempt of difficulties and higher costs. Alternatively,
nanomaterials (NMs) possess certain features which makes this discipline attractive to
overcome the drawbacks found when using the conventional extraction techniques, although
the correct selection of the NMs with an adequate conformation or structure must be
necessary considered.

NMs are conducted at the nanoscale objects, usually ranging from 1 to 100 nanometer (nm)
[6]. NMs have unique physical, thermal, optical chemical, morphological and mechanical

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characteristics which enable them to be applied in many several applications. One of the most
interesting properties of NMs is their high surface area to volume ratio because of their high

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surface atoms fraction. On the other hand, there are some limitations in the application of
NMs originated from the high surface energy of small particles. NMs usually have higher
surface energy and tend to agglomerate or adsorb other molecules to decrease their surface
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free energy. The agglomeration leads to diminishing of the sorbent specific surface area.
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Nevertheless, in recent years, application of NMs in SPME and sample preparation has
attracted the attention of many researchers. Hundreds of papers reporting SPME applications
in the environment have been published in the last decade. For instance, Khajeh et al. have
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discussed classification, preparation, and applications of different NMs as sorbents for

environmental analysis [7]. Xu et al. have reviewed the applications of NMs as a sorbent for
different purposes [8]. In another review, the preparation and application of nano-imprinting
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technology in sample preparation was presented [9]. This review paper will present a
comprehensive study of recently published articles on the applications of NMs in SPME for
environmental analysis. Various frequently used NMs will be classified in different classes
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such as nanoparticles, nanofibers, nanoflakes, nanocomposites, nanorods, nanotubes,

nanohorns, nanosheets, nanocubes, nanospheres and polymer-based NMs for environmental
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analysis will be reviewed.

2. SPME procedures for environmental analysis using nanomaterials

The complete development of a SPME method, requires a number of intermediate steps

between sample collection and the final results including sample pretreatment, SPME,
desorption, and detection. The first step in these steps is sample collection from an
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environmental system. The most popular sample is water. In the next step, the environmental
sample is exposed to the SPME unit. The aim of this step is to clean up and pre-concentrate
the sample in order to get higher selectivity and sensitivity.

To this end, various SPME configurations have been developed such as in-tube, fiber, in-
needle, in-tip, thin-film, and stir-bar microextraction, depicted in Fig. 2. These configurations
can be chosen for a specific aim based on their advantages and disadvantages. The advantages
of SPME are that the method is solvent free, online, and suitable for volatile compounds. The
disadvantages are losing and breakable fibers, desorption, and low sensitivity.

In SPME technique, there are two modes (Fig. 1). The first one is based on direct immersion
of the sorptive materials to the samples, while another mode is based on the sorptive

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extraction of volatile or semi-volatile compounds from the headspace of the samples. In both
cases, application of NMs has motivated researchers to increase the efficiency and selectivity
of the SPME methods.

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2.1. Direct immersion method (DI-SPME)

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In DI-SPME method, the NMs is in direct contact with the sample which contains the target
analytes. NMs should be able to separate all of the target analytes in sample while releasing
the other interfering compounds of the matrix. In this regard, the NMs should have enough
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sorption capacity to adsorb all of the target analytes, and should have specific interaction with
them. Then, elution by organic solvent or increasing the temperature should easily release the
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target analytes completely before introduce to the detection system. Furthermore, in order to
increase sorption capacity, the utilization of NMs with high surface areas can be the best
solution. Nowadays, nanosorbents are extensively used in environmental applications because
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of their properties such as, high sorption capacity, and in some cases high selectivity.

2.2. Headspace method (HS-SPME)

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Here, the sample is placed into a vial is sealed with a cap, and the NMs are exposed to the
headspace of the sample (gas, solid, or liquid) to extract the target volatile or semi-volatile
analytes. This method increase the selectivity because the number of volatile substances in
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environmental samples is high. The ideal NMs for HS-SPME are the same sorbents used in
DI-SPME method. However, the desorption step in HS-SPME is usually thermal desorption,
and the NMs should have high chemical and thermal stability at desorption temperatures.

3. Applications of nanomaterials in SPME for environmental applications

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As SPME still is the most widely used microextraction technique. There are many
modifications made to this technique. In its classical and commercially available form, the
SPME device consists of a fused silica or stainless steel fiber coated or uncoated with a thin
layer of sorbent. The fiber mounted on syringe-like device. Researchers have used different
strategies to improve SPME extraction efficiency for environmental applications by using
different NMs. Therefore, the use of NMs in SPME techniques has received great attention in
the analytical and environmental fields due to enhanced properties while offering high
selectivity for some target analytes. The interest of NMs in SPME for clean-up and
pretreatment of environmental samples is increasing. Many current NMs have been applied
for the SPME of analyte(s) from environmental samples, include nanoparticles, nanofibers,
nanoflakes, nanocomposites, nanorods, nanotubes, nanohorns, nanosheets, nanocubes,

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nanospheres and polymer-based NMs (Fig. 3). The essential parameters involved in SPME
process such as surface modification, type of SPME, sample matrix, analyte(s), sample
volume, extraction time, linear range, limit of detection, instrumentation, and SPME recovery

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are discussed (Table 1).

3.1. Nanoparticles -p
Nanoparticles (NPs) are particles with size range from 1 to 100 nm, can be either simple or
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complex nature (metallic, semiconductor, or polymeric) and have a wide range of
environmental applications: air, soil, and water. Furthermore, NPs can be used as sorbents for
an efficient SPME of many analytes in different environmental samples [10]. Due to the
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unique properties of NPs such as small size, large surface-area and high catalytic activity,
NPs emerged as a promising alternative to conventional materials for SPME of analytes from
environmental samples, which often result in tiresome and expensive procedures.
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In one study, SPME fiber coatings based on gold nanoparticles (AuNPs) was investigated.
The method was applied to the determination of organochlorine pesticides (OCPs) from
different water samples using GC-ECD [10]. A new magnetic in-tube SPME based on SiO2
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NPs supported Fe3O4 NPs for extraction of triazines from river water prior their determination
by CLC-DAD was developed [11]. A new AuNPs-thiol silane film/SPME fiber and coupled it
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with IMS for the analysis of organic compounds in exhaled breath was investigated [12]. A
novel AgNPs-coated SPME fiber was prepared based on electroless plating technique was
investigated. Good extraction performance of the SPME fiber was applied for to the
extraction of phthalate esters and polycyclic aromatic hydrocarbons (PAHs) in aqueous
solution followed by GC-FID [13]. A nanostructured TiO2-based SPME fiber was fabricated.
The modified fibers have been used for headspace SPME coupled with GC-ECD for the
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determination of dichlorodiphenyltrichloroethane and its degradation products in different
water samples [14]. A new SPME fiber based on carbon ceramic with copper NPs followed
by GC-FID was investigated. The method was applied for the extraction and determination of
some nitro explosive compounds in soil samples [15]. A new SPME fiber based on Co3O4
NPs on a Platinum wire was fabricated. The fiber was successfully applied to the
determination of benzene, toluene, ethylbenzene and xylene (BTEX) compounds in river
water and sewage water samples [16]. Liu et al. developed SPME fibers by coating a steel
wire with Cr2O3 NPs coupled with GC-FID. The fabricated fiber has been used to detect
aromatic hydrocarbons in standard water and rainwater samples [17]. Sun et al. developed a
novel SPME fiber based on carbon NPs. The fiber was used to extract phthalate esters and
PAHs in aqueous samples (food-wrap, cigarette ash and snow water) by using GC-FID [18].

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In another study, diamond NPs were coated onto stainless steel wires as an extraction
material, then it was filled into a polyether ether ketone (PEEK) tube for in-tube SPME. The
extraction tube was evaluated with different types of analytes including PAHs, estrogens and

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plasticizers in aqueous solution of cigarette smoke and soil solution by using HPLC-UV [19].

Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) have attracted interest wide-ranging due to their
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outstanding catalytic activities strong magnetism and high specific surface-area. Several in-
tube SPME methods have been developed based on Fe3O4 MNPs coupled with HPLC-DAD
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for determination of several analytes from different water samples [20]. A magnetic on-line
in-tube SPME based on silica supported Fe3O4 MNPs followed by CLC-DAD to determine
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OPs in wastewater samples was developed [21]. An in-tube magnetic SPME based on the use
of sodium dodecyl sulfate coated Fe3O4 MNPs was developed. The in-tube SPME coupled
with HPLC-UV was used for the analysis of fluoroquinolones in water and urine samples
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[22].

3.2. Nanofibers

Nanofibers usually possess diameters lower than 100 nm and have been widely used in
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several environmental applications. They can be considered as one of the safest NMs due to
their extreme length and can be easily incorporated onto into the frequently different media or
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support/substrate. They also have high porosity, large surface-to-volume ratio, and more
functionality. As a consequence, they have been used in several applications.

In one study, in-tube SPME based on polyaniline functionalized basalt fiber was developed.
The extraction and analysis processes were carried out by connecting it to HPLC-DAD. The
method was applied for determination of three ultraviolet filters as model analytes in

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environmental water samples [23]. A new SPME fiber based on poly(dimethylsiloxane)-
coated carbon nanofibers for extraction and determination of PAHs form water samples, by
using GC-FID was fabricated [24]. A SPME fiber based on polyurethane nanofiber was
developed. The method was assessed for SPME of chlorobenzenes, from environmental
samples followed by GC-MS using a homemade SPME syringe [25]. A novel SPME fiber
based on polypyrrole-polyamide nanofiber was fabricated. The applicability of the new
nanofiber was examined as an extracting medium to isolate malathion as a model pesticide
from aqueous samples [26]. In another study, SPME fiber based on electrospun polyamide-
polyethylene glycol nanofiber was investigated. The fabricated fiber coupled with GC-MS
was applied for determination of some phenols compounds in aqueous samples [27]. The
SPME fiber based on modified silica fiber by self-assembled AuNPs for determination of

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PAHs in environmental water samples using HPLC-UV was developed [28]. An in-needle
SPME based on polyethylene terephthalate nanofiber film by a simple and low-cost
electrospinning method and used as a novel SPME adsorbent of chromium (VI) in water

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samples was developed [29]. In-tube SPME based on carbon fibers packed into a poly(ether
etherketone) tube was investigated. Coupled to HPLC, the in-tube SPME was applied to
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analyze some PAHs in environmental aqueous samples [30]. A polyimide nanofiber
membrane was electrospun and applied as sorbent for thin film microextraction. The method
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applied for the analysis of phenols in environmental water samples followed by GC-MS [31].
Nanofibers mat based SPME in 96-well plate format as a novel high-throughput sample
preparation technique prior to the determination of cationic dyes in wastewater samples using
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HPLC-DAD were fabricated [32]. A nanostructured polysiloxane as a coating for in-needle

SPME of chlorobenzenes from water, wastewater, sludge and sediment samples followed by
GC-ECD was investigated [33].
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3.3. Nanoflakes

Nanoflake is a flake (that is, an uneven piece of material with one dimension substantially
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smaller than the other two) with at least one nanometric dimension (between 1 and 100 nm).

In one study, ZnO nanoflakes were electrochemically grown on a nickel-titanium alloy wire
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for use in SPME of polychlorinated biphenyls (PCBs) which then were quantified by HPLC-
UV. Satisfactory accuracy and precision were achieved when PCBs were determined by this
method in spiked rain water, river water and wastewater samples [34]. In another study, a
novel silica based SPME fiber was fabricated by the immobilization of silica nanoflakes onto
they hydrothermally treated nickel-titanium alloy wire. The fiber exhibited the high extraction
capability and good extraction selectivity for PAHs in water samples [35].
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3.4. Nanocomposites

Nanocomposites have been widely used in environmental applications as well as for the
extraction of analyte(s). Nanocomposites are defined as solids consisting of a combination of
NMs such as polymer, and graphene based NMs, which enhance its overall adsorption
capability.

In one case study, SPME fiber based on ZnO/polythiophene/hexagonally ordered silica

(ZnO/PT/SBA-15) nanocomposites deposited on a stainless steel wire was investigated. The
applicability of this nanocomposite coating was assessed using a SPME device and GC-MS
for the extraction of some PAHs from the headspace of aqueous samples [36]. In another
study, SPME fiber based on zinc oxide/polypyrrole nanocomposites was fabricated. Coupled

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with GC-FID, the developed method was applied for the extraction of aliphatic hydrocarbons
from water and soil samples [37]. A novel on-line in-tube SPME method followed by HPLC-
UV for preconcentration and determination of trace amounts of parabens in some water, milk,

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and juice samples was fabricated. An effective adsorbent based on magnetic MoS2-Fe3O4
nanocomposite for dSPME of lead(II) and copper(II) prior to their determination by FAAS
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was developed [38]. A SPME fiber based on SiO2-polyethylene terephthalate nanocomposites
was developed. The applicability of new fiber coatings were examined by HS-SPME of some
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environmentally important volatile organic compound (BTEX) from aqueous samples,
followed by GC-MS [39]. HS-SPME of volatile aromatic hydrocarbons using a steel wire
coated with an electrochemically prepared nanocomposite consisting of polypyrrole, carbon
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nanotubes, and titanium oxide was developed. The method was successfully applied to real
water samples, followed by GC-FID detection [40]. A sol-gel/nanoclay composite as a SPME
fiber coating for the determination organophosphorus pesticides in water samples was
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investigated [41]. In another study, SPME fiber based on mesoporous carbon-zirconium oxide
nanocomposite derived from carbonized metal organic framework was developed. The
developed fiber was applied for the determination of benzene, toluene, ethylbenzene and m-,
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p-xylenes compounds in different water and wastewater samples [42]. A new SPME fiber
based on polypyrrole and manganese dioxide nanocomposites was developed. The developed
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fiber was applied for determination and extraction of cyproheptadine and ketotifen from water
samples, followed by GC-FID [43]. A SPME fiber based on nanoscale graphitic carbon
nitride/copper oxide hybrid composites coupled with GC-FID for determination of PAHs in
water and soil samples was fabricated [44].

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3.5. Nanorods

Nanorods are nanoscale objects within a 1-100 nm size range. They can be synthesized by
direct chemical synthesis from different metals such as gold, silver, or from semiconducting
materials.

In one case, high efficiency SPME fibers by growing arrays of ZnO nanorods on fused silica
was fabricated. The prepared SPME fibers were applied to extraction of 1,4-dichloro-
nitrobenzene, biphenyl and acenaphthene in environmental water samples by using head
space technique prior to detection by GC-MS [45]. In another study, a new and highly
efficient stationary phase based on the SnO2 nanorods coating on fused silica using a
hydrothermal process was investigated. The extraction properties of the fiber were

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investigated using HS-SPME mode coupled with GC-MS detection for PAHs from
environmental water samples [46]. A thin film microextraction (TFME) technique based on
phenyl carbamate functionalized ZnO nanorods were on a cellulose filter paper was

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fabricated. The modified cellulose paper was applied for the extraction of three phenylurea
herbicides from different water samples by using HPLC-UV [47]. A new SPME fiber based
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on platinum wire coated with polypyrrole-coated ZnO nanorods was fabricated. The coated
wire was applied to SPME of amitraz and teflubenzuron pesticides from environmental water
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samples, then quantified by GC-MS [48]. A SPME fiber based on TiO2 nanorods on the
surface of titanium wire by hydrothermal synthesis was fabricated. The established method
was used for extraction of PAHs and terphenyls from rainwater and aqueous solution of coal
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ash, with DI-SPME mode coupled with GC-FID [49].

3.6. Nanotubes
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Nanotubes are hollow tubular nanostructures with diameters in the nanometer regime and
lengths ranging, in general, from the nanometer to the micrometer regime.

The most popular types of nanotubes are carbon nanotubes (CNTs), such as single walled
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(SWCNTs) and multi walled (MWCNTs). CNTs display exceptional several properties which
has resulted in their widespread application. Due to their high surface area, these NMs are
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employed as support, through each of them has unique structure, properties and applications.

In one case study, CNTs/layered double hydroxide coated fiber for the HS-SPME of phenols
from water samples was developed [50]. SPME fiber based on ionic liquid functionalized
MWCNTs-polyaniline coating was fabricated. Coupled with GC-FID, the fabricated fiber was
applied for determination and extraction of benzoic acid esters in perfume samples [51].

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SPME fiber based on ZnO nanotube arrays on SiO2 substrate was fabricated. The feasibility
of ZnO nanotube arrays adopted for HS-SPME was evaluated by extracting volatile organic
compounds in water samples, followed by GC-MS [52]. HF-SPME device based on
MWCNTs-COOH was developed. The developed HF-SPME was applied to totally extract a
group of pesticides from aqueous and human hair samples followed by HPLC-DAD analysis
[53]. In another study, a new thin-film based on MWCNTs-COOH/polydimethylsiloxane
coating was developed for 96-blade SPME system followed by HPLC-UV [54]. A SPME
fiber based on poly(ethylene glycol) modified with MWCNTs was investigated. The method
was successfully applied to the analysis of real water and urine samples, followed by GC-FID
[55]. A SPME fiber based on polypyrrole-CNTs-SiO2 film coated on a steel wire was
developed. The prepared fiber was used as an absorbent for the HS-SPME of benzene,

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toluene, ethylbenzene, and o-xylene, followed by gas chromatographic analysis [56]. A
SPME fiber coated with porous CNTs-SiO2 nanohybrids was investigated. The developed
method was applied for the determination of some organophosphorus pesticides in vegetables,

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fruits and water samples [57]. A new SPME fiber based on titanium-nickel oxide nanotubes
(Ti-Ni-O CNTs) coating was grown in situ on a nitinol wire by rapid anodic oxidation was
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developed. Thereafter the extraction performance of the Ti-Ni-O CNTs coating was examined
for the analysis UV filters in environmental water samples coupled with HPLC-UV detection
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[58].

3.7. Nanohorns
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Nanohorns are the conical shaped nanostructures sometimes also called as nanocones. The
most popular types of nanohorns are carbon nanohorns (CNHs), such as single walled
(SWCNHs) and multi walled (MWCNHs) are the conical shaped carbon nanostructures.
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CNHs material is expected as a hopeful applicant for several applications (hydrogen storage,
biological applications, drug carriers, biofuel cells, biosensors and photo-thermal cancer
treatment).
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Despite the potential of SWNHs, few are the references which describe their use for analytical
purposes probably due to their scarce commercialization. In one such case, SPME fiber based
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on o-SWNHs immobilized on a microporous hollow polypropylene fiber has been developed.

The method was applied to the determination of volatile organic compounds from water
samples [59].

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3.8. Nanosheets

Nanosheet is a two-dimensional nanostructure with thickness in a scale ranging from 1 to 100

nm. A typical example of a nanosheet is graphene, the thinnest two-dimensional material
(0.34 nm) in the world. It consists of a single layer of carbon atoms with hexagonal lattices.

In one case study, a new fabrication based on graphene coated SPME fiber was developed.
The method was tested by HS-SPME of PAHs in environmental samples followed by GC-MS
analysis [60]. A novel SPME fiber based on phenyl functionalized TiO2-nanosheets coating
on a titanium wire was fabricated. The established SPME-HPLC-UV method was
successfully applied to selective concentration and sensitive determination of target PAHs
from real environmental water samples [61]. A SPME fiber based on polypyrrole/graphene

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oxide coating on a platinum wire was developed. The fiber was applied to the direct SPME
and GC-FID analysis of phthalate esters in two real samples of boiling water of cheap
disposable clear plastic drinking cups [62]. A selective dispersive SPME method based on

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magnetic graphene oxide as an efficient sorbent for the separation and preconcentration of
gold ions in different water samples, determined by the flow injection flame atomic
-p
absorption spectrometry (FI-FAAS) was investigated [63]. A new SPME fiber based on Zn-
ZnO nanosheets coating on an etched stainless steel wire substrate was developed. The
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fabricated SPME fiber was investigated for the concentration and determination of ultraviolet
filters from real environmental water samples coupled to HPLC-UV [64]. A hollow fiber
SPME based on graphene oxide-silica was fabricated. The developed method was applied for
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SPME of trace heavy metals (Mn, Co, Ni, Cu, Cd and Pb) in environmental water samples,
followed by on-line inductively coupled plasma mass spectrometry (ICP-MS) detection [65].
SPME fiber based on titanium and nickel oxide composite nanosheets (TiO2/NiOCNSs) was
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fabricated. The extraction performance of the developed SPME fiber was investigated for the
concentration and detection of ultraviolet filters in different environmental water samples
coupled to HPLC-UV [66]. In another study, a SPME method based on copper 1,4-
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benzenedicarboxylate-MOF nanosheets incorporated in polyimide resin as a coating material

was investigated. Coupled with GC-MS and DI-SPME technique, the fiber was evaluated
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through the analysis of five PAHs in aqueous samples [67]. In another study, bamboo
charcoals were modified using Fe3O4 nanosheets. The materials used as a novel SPME fiber
coating, for the extraction of seven polybrominated diphenyl ethers (PBDEs) in
environmental water samples, followed by GC-MS [68].

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3.9. Nanocubes

Nanocubes are cube shaped particles with narrow size distributions, such as silver, gold,
titanium oxide nanocubes and others. Nanocubes show interesting plasmon coupling
properties, photoluminescence, optical properties and catalytic properties. Furthermore,
nanocubes have been applied in SPME for extraction of analytes from environmental
samples.

In one such case, SPME fiber based on zeolitic imidazole framework-8 derived double-
shelled hollow ZnO/nanocubes was developed. The ZnO/carbon coated fiber was used to
investigate its simultaneous SPME ability for polar and nonpolar compounds (benzene
compounds and chlorophenols) from environmental water samples. The double shelled

of
hollow ZnO/carbon nanocubes improve the sensitive extraction for the target analytes.
Compared with the commercial fiber, the ZnO/carbon coated fiber shows better extraction
performance owing to the combined effect of the ZnO/carbon and double-shelled hollow

ro
structure [69].

Likewise, metal-organic framework derived hollow carbon nanocubes (MOF-HCNCs) were

-p
prepared and further coated on the surface of stainless steel wires as SPME fibers for the
determination of PAHs from the real water samples. The extraction efficiency of MOF-
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HCNCs-coated fiber was found superior as compared to solid carbon nanocube coated fiber
and commercial fibers. It is due to their unique hollow structure, hydrophobic interactions,
and π-π interactions [70].
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3.10. Nanospheres

The nanospheres are the simplest type of nanoparticle with only one adjustable geometrical
na

parameter (radius) which exhibits resonant responses under optical excitation. Nanospheres
are formed by dense polymeric matrix whereas nanocapsules are nanoscale shells made up of
natural or synthetic polymers.
ur

In one study, SPME fiber based on nanospherical metal-organic framework UiO-66 has been
used to extract hydrophobic PAHs from actual water samples. MOFs can provide more sites
Jo

for adsorption, and the state of nanospheres can also change the hydrophobicity of the
material, which makes it easier to extract the hydrophobic analytes [71]. In another study, the
monodisperse microporous carbon nanospheres (MMCNSs) were applied in SPME. A good
repeatability and reproducibility were obtained, due to the excellent monodispersity of the
MMCNSs. The MMCNSs fiber exhibited superior extraction ability for PAHs and

14
organochlorine pesticides, compared with the commercial polydimethylsiloxane
/divinylbenzene (PDMS/DVB) fiber and the fiber prepared with its precursor, the
monodisperse microporous polystyrene nanospheres [72].

3.11. Polymer-based nanomaterials

Polymer-based NMs such as those based on organic, inorganic and hybrid polymers, as well
as on molecularly imprinted polymers (MIPs) have been successfully applied in SPME for
extraction of analytes.

Magnetic molecularly imprinted polymer (MMIP) based on Fe3O4@SiO2 nanoparticles has

been developed. The MMIP-Fe3O4@SiO2 sorbent was then used in the development of a
simple, selective, and relatively fast magnetic dispersive solid phase microextraction

of
(MDSPME) method for the separation, cleanup, and preconcentration of diazinon from
various matrices [73]. Then, the preconcentrated analyte was determined by HPLC-UV.

ro
In one study, a novel imazethapyr molecularly imprinted polymer (MIP) coated SPME fiber
was developed. The method based on imazethapyr MIP-SPME coupled with HPLC was
-p
established for determination of five imidazolinones in spiked rice, peanut, and soil samples
with the satisfactory recoveries and precision [74].
re
4. Future perspectives

Most of the methods here discussed were performed at a laboratory, and no green synthetic
lP

materials were used. Even considering the reusability of many NMs and the low reagents
consumption associated to their application, these alternative green materials and methods
should be considered as future approaches to be developed. In this sense, supercritical carbon
na

dioxide medium (sc-CO2) used to synthesize and modify NMs may be further developed [75].
More indeed, prepared NMs from natural products such as the clay-based halloysite
nanotubes could also be applied for SPME in environmental samples. Consequently, these
ur

green NMs represent an eco-friendly and remarkably efficient alternative, also considering
their potential tunable surface chemistry for environmental applications. Additionally, new
Jo

kind of NMs applicable at wide pH ranges could also represent a remarkably interesting
alternative to applied for SPME from environmental samples.

5. Conclusions

15
SPME is widely prescribed approach for the extraction of several analytes in environmental
applications. NMs are an ideal alternative for SPME of several analytes in environmental
samples over the traditional techniques, as it is a secure, clean and energy efficient method.
NMs have been widely used in SPME of environmental samples, such as nanoparticles,
nanofibers, nanoflakes, nanocomposites, nanorods, nanotubes, nanohorns, nanosheets,
nanocubes, nanospheres and polymer-based NMs. Many advantages associated with these
NMs are high specific surface-area, good catalytic activity, easy synthetic routes, and good
properties (electrical optical, mechanical and physical). Efficient SPME recoveries have been
accomplished using these NMs at differing surface modification, type of SPME,
environmental sample matrix, analyte(s), sample volume, extraction time, linear range, limit
of detection, analytical instrumentation, and SPME recovery. However, these NMs have

of
several restrictions such as toxicity of different classes of NMs and particle agglomeration.
The NMs are generally expected to be unstable at different conditions.

ro
Declaration of interests
-p
The authors declare that they have no known competing financial interests or personal
re
relationships that could have appeared to influence the work reported in this paper.
lP
na
ur
Jo

16
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ro
-p
re
lP
na
ur
Jo

31
Figure captions

of
ro
Fig. 1. General scheme for the extraction and desorption steps in the SPME analysis.
-p
re
lP
na
ur
Jo

32
 of
ro
-p
re
lP

Fig. 2. Various SPME configurations: (A) fiber; (B) in-tube; (C) thin-film; (D) magnetic; (E)
in-tip; and (F) stir-bar. Reprinted from Ref. [76].
na
ur
Jo

33
 of
Fig. 3. Nanomaterials used in SPME.

ro
-p
re
lP
na
ur
Jo

34
 f
Table 1. Recent applications of different NMs in SPME for environmental analysis.

oo
Sample Linear Limit of
Surface Type of Sample Extraction Detection Recovery
Nanomaterials Analyte(s) volume range (µg L- detection Ref.

pr
modification SPME matrix time (min) technique (%)
1
(mL) ) (µg L-1)

e-
101.86-

Pr
Nanoparticles OAMNPs VASPME Tap water Indium 30 - 20-100 6.02 SQT-FAAS [77]
105.97

Heptachlor,

l Tap water,
dieldrin,
na
methoxychlor,
pond water,
AuNPs Fiber 4,4’-DDT, 2,4’- 15 60 0.59-10 0.13 GC-ECD 85-97.1 [10]
And well
ur

DDT, α-
water
endosulfan and
Jo

β-endosulfan

35
 f
SiO2-BSA Aqueous

oo
Fiber Diclofenac - - - - GC-MS - [78]
NPs sample

Simazine,

pr
SiO2-Fe3O4
in-tube River water atrazine and 0.1 - 3.0-40 0.3-0.4 CLC-DAD 99-110 [11]
NPs
terbutylazine

e-
Naphthalene,

Pr
methyl-

naphthalene,

biphenyl,
River water
PMO-IL l
Fiber anthracene, 10 40 0.01-10 0.004-0.009 GC-MS - [79]
na
and dam water
fluorene,

acenaphthene,
ur

fluoranthene

and pyrene
Jo

36
 f
AuNPs-thiol Exhaled Xylene and 1.1-32, 16-

oo
Fiber - 15 0.7-8.0 IMS 85-95 [12]
silane breath toluene 112

Double-

pr
distilled water,

river water,

e-
Mn doped ZnS UA- Auramine O and
tap water, 12 - 3.0-5000 0.91-0.61 UV–Vis 92.8-97.7 [80]
NPs DSPME malachite green
mineral water,

Pr
rain water and

wastewater

l 4-chlorophenol,
na
2,4-
Tap water,
Polyamidoami dichlorophenol,
Fiber well water and 12 15 0.002-1.0 0.0006-0.1 GC-MS 80-97 [81]
ur

ne dendrimers 2,6-
sea water
dichlorophenol
Jo

and

37
 f
2,4,6-

oo
trichlorophenol

HF- 600-

pr
TiO2NPs Water samples Pb (II) 6 30 0.2 FAAS 99.3 [82]
SLPME 3000000

e-
Lead (II) Tap water

dioxide NPs double-

UA- Eriochrome 94.85-

Pr
loaded on distilled water 10 - 5.0-2000 0.43 UV-Vis [83]
DSPME Cyanine R 101.42
activated and

carbon wastewater

l
na
Escherichia coli
ZnAl-AgNPs Fiber - - 30 - - GC-FID - [84]
bacterial
ur

Aqueous
Latex NPs Fiber Atrazine - - - - GC-FID 100 [85]
sample
Jo

38
 f
2-hydroxy-4-

oo
methoxybenzop

henone, 2-

pr
ethylhexyl-4-

methoxycinnam

e-
River water
ate, 2-
Ti-TiO2-ZrO2 Fiber and 15 30 0.5-500 0.032-0.082 HPLC-UV 82.2-106.6 [86]
ethylhexyl

Pr
wastewater
4-(N,N-

dimethylamino)

benzoate and 2-
l
na
Ethylhexyl

salicylate
ur

2,4-
Nitrogen- River water,
dihydroxybenzo
containing Fiber rain water and 15 50 0.02-200 0.006-0.203 HPLC-UV 89.2-119 [87]
Jo

phenone,
carbon NPs wastewater
benzophenone-

39
 f
3, ethylhexyl

oo
dimethyl p-

aminobenzoate,

pr
ethylhexyl

methoxycinnam

e-
ate and

ethylhexyl

Pr
salicylate

Naphthalene,
Mercaptounde River water,
anthracene,
canol l wastewater
na
Fiber phenanthrene, 10 40 0.05-300 0.01-0.044 HPLC-UV 94.5-107.5 [88]
modified and snow
pyrene and
AuNPs water
benzo[a]pyrene
ur

Malachite green
Aquaculture
Jo

ZnO nanorods
Fiber and crystal - 120 50-5000 nM 1.9 nM SERS - [89]
decorated with water
violet

40
 f
Au@Ag core-

oo
shell NPs

Dichlorodiphen

pr
yltrichloroethan

e,

e-
River water dichlorodipheny 0.0002-
TiO2NPs Fiber 10 40 0.005-5.0 GC-ECD 67-85 [14]
and well water ldichloroethylen 0.00098

Pr
and

dichlorodipheny

ldichloroethane
l
na
Benzophenone-
Sea water,
1,
river water
ur

Fe3O4@SiO2 benzophenone- HPLC-

dSPME and 100 27 - 0.16-1.21 > 87 [90]
@Ionic liquid 2, MS/MS
swimming-
Jo

pool benzophenone-

3,

41
 f
water benzophenone-

oo
6,

benzophenone-

pr
8, 4-

hydroxybenzop

e-
henone,

bisphenol A,

Pr
methylparaben,

ethylparaben,

propylparaben
l
na
and

butylparaben
ur

Tap water,
Co(II), Ni(II) 0.0025-
Alumina NPs - well water, 25 4 0.01-0.25 ETAAS 95-104 [91]
and Cu(II) ions 0.0028
Jo

river water,

42
 f
sea water and

oo
mineral water

Activated

pr
carbon UA- Wastewater 93.27-
Safranin O dye 10 - 25-3500 6.3 UV-vis [92]
modified with DSPME and tap water 99.41

e-
Fe2O3 NPs

Pr
Diethyl

phthalate,

diisobutyl
Polycaprolacta
l River water, phthalate,
na
m
bottled water dibutyl
incorporated Fiber 4 30 0.5-500 0.04-0.193 GC-ECD 90.3-107 [93]
and mineral phthalate,
with MnO
ur

water benzyl butyl

NPs
phthalate and
Jo

di-2-ethylhexyl

phthalate

43
 f
Nitrobenzene,

oo
4-nitrotoluene,

2,4-
Carbon

pr
dinitrotoluene,
ceramic Fiber Soil sample 1g 45 2-160 µg g-1 0.6 µg g-1 GC-FID - [15]
2,6-
copper NPs

e-
dinitrotoluene

and

Pr
trinitrotoluene

Naphthalene,

fluorene,
l Disposable
na
fluoranthene,
paper cup and
AgNPs Fiber phenanthrene, 20 40 0.1-2000 0.02-0.1 GC-FID 82.3-109.7 [13]
instant noodle
dibutyl
ur

barrel
phthalate,
Jo

dioctyl

44
 f
phthalate,

oo
dicyclohexyl

Phthalate and

pr
diallyl phthalate

e-
Dibutyl
Distilled water
Nanosized phthalate and
Fiber and soaking 10 40 0.05-250 0.01 GC-FID 84-117 [94]

Pr
copper diethylhexyl
water
phthalate

Naphthalene,
l
na
acenaphthylene,

Tap water and acenaphthene,

AuNPs in-tube 40 27 0.01-20 0.003-0.015 HPLC-DAD 87-128 [95]
rain water fluorene,
ur

phenanthrene,
Jo

anthracene,

45
 f
fluoranthene

oo
and pyrene

Tap water, Benzene,

pr
landfill toluene,
ZnO NPs Fiber 10 5 0.2-200 0.02-0.11 GC-FID > 88 [96]
leachate and ethylbenzene

e-
wastewater and xylenes

Pr
Benzene,
River water
toluene,
Co3O4 NPs Fiber and sewage 15 14 0.01-500 0.001-0.011 GC-MS 94-115 [16]
ethylbenzene
water
l and xylenes
na
Naphthalene,

Underground acenaphthylene,
ur

AgNPs Fiber 5 60 2.0-300 0.06 GC-FID 74.9-129 [97]

water
acenaphthene,
Jo

fluorene,

46
 f
phenanthrene,

oo
anthracene,

fluoranthene,

pr
pyrene,

benz(a)anthrace

e-
ne, chrysene,

Pr
benzo(b)fluoran

thene,

benzo(k)fluoran

l thene,
na
benz(a)pyrene,

indeno(1,2,3-
ur

c,d)pyrene,

dibenz(a,h)anthr
Jo

acene and

47
 f
benzo(g,h,i)pery

oo
lene

Malathion,

pr
Ceramic- Tap water,
diazinon,
magnetic Fiber well water and 25 40 0.05-400 0.005-0.06 HPLC-UV 85.1-102.5 [98]
phosalone and

e-
graphene NPs river water
chlorpyrifos

Pr
Naphthalene,

anthracene,

phenanthrene,

AuNPs l
Fiber Sea water pyrene, 5 50 0.05-300 10-200 GC-FID 91.9-105.3 [99]
na
acenaphthylene

and
ur

fluoranthene

Fluoride,
Jo

Functionalized
Fiber Tap water chloride, nitrite, 8 50 5.0-5000 3.7 IC 95-115 [100]
latex NPs
bromide, nitrate,

48
 f
sulfate and

oo
phosphate

Estriol,

pr
bisphenol A, β-

estradiol,

e-
estrone,

diethylstilbestro 0.42-0.78;

Pr
Silica NPs in-tube Purified water 6 75 - HPLC-UV - [101]
l, naphthalene, 0.034-0.19

fluorene,

phenanthrene,
l
na
anthracene, and

fluoranthene
ur

River water, 2-hydroxy-4-

0.00043-
AuNPs Fiber rain water and methoxybenzop 15 40 0.004-200 HPLC-UV 77.9-108 [102]
0.57
Jo

wastewater henone,

49
 f
2-ethylhexyl-4-

oo
methoxycinnam

ate, 2-

pr
ethylhexyl-

4-(N,N-

e-
dimethylamino)

benzoate and 2-

Pr
ethylhexyl

salicylate

l Naphthalene,
na
anthracene,

Cr2O3 NPs Fiber Rain water fluorene, 20 10 2.0-400 0.02-0.2 GC-FID 83-113 [17]
ur

fluoranthene

and biphenyl
Jo

50
 f
Ciprofloxacin,

oo
SDS coated
in-tube Water sample enrofloxacin - 13.5 0.1-1000 0.01-0.05 HPLC-UV 92.2-102.2 [22]
Fe3O4 NPs
and ofloxacin

pr
2-hydroxy-4-

methoxybenzop

e-
henon, 3-(4-

methylbenzylide

Pr
Lake water, ne)camphor, 2-

river water ethylhexyl4-

Fe3O4 NPs in-tube 1.5 19 0.25-200 0.04-0.26 HPLC-DAD 70.5-119 [20]
and methoxycinnam
l
na
wastewater ate, octyl

dimethyl-p-

amino-benzoate
ur

and octyl
Jo

salicylate

51
 f
Silica Chlorfenvinpho

oo
supported in-tube Wastewater s and 20 18 - 0.05-0.1 HPLC-DAD 94-97 [21]

Fe3O4 NPs chlorpyrifos

pr
Selenium (IV)
Surface water
Al2O3 NPs dSPME and Selenium 50 15 100-2000 0.0014 ICP-OES > 90 and 5 [103]

e-
samples
(VI)

Pr
Benzene,

PEG-PEG-g- Tap water and toluene, 0.000002- 0.00000025- 85.02-

Fiber 1.5 45 GC-FID [104]
CuO NPs distilled water ethylbenzene 200 0.05 103.31

l and o-xylene
na
Fe3O4@SiO2

@layered Naproxen and 93.5-104.6,

ur

in-tube Water samples - 20 0.1-500 0.07-0.8 HPLC-UV [105]

double indomethacin 94.4-109

hydroxide NPs
Jo

52
 f
(Di-n-butyl

oo
phthalate, di-

cyclohexyl

pr
phthalate and

di-(2-ethyl-

e-
hexyl)

phthalate),
Food-wrap,

Pr
(Fluorine,
cigarette ash 0.005; 92.9-115,
Carbon NPs Fiber anthracene, 10 40 0.01-500 GC-FID [18]
and snow 0.001-0.003 85.5-126
fluoranthene,
l water
na
1,2-

benzophenanthr

ene,
ur

benzo(a)pyrene,

o-terphenyl, m-
Jo

terphenyl and p-

terphenyl)

53
 f
Naphthalene,

oo
diphenyl,

fluorene, trans-

pr
diphenylethylen
GO decorated Tap water and
Fiber e, phenanthrane, - 50 0.02-50 0.002-0.01 GC-FID 84.4-116.3 [106]
with AgNPs rain water

e-
anthracene,

fluoranthene

Pr
and meta-

terphenyl

Naphthalene,
l
na
Tap water, acenaphthene,
Porous
lake water, fluorene,
aromatic 0.0008-
phenanthrene,
ur

Fiber river water 10 30 0.0016-4.0 GC-MS 89.5-103.1 [107]

framework 0.0042
and ground anthracene,
NPs
Jo

water fluoranthene

and pyrene

54
 f
(Benzene,

oo
toluene,

ethylbenzene,
0.00032-

pr
m-xylene and o-
MIL-101(Cr) 0.0017; 80-113,
Fiber River water xylene), 10 3 and 30 0.01-20 GC-MS [108]
NPs 0.00012- 84.8-106

e-
(Acenaphthene,
0.0021
phenanthrene,

Pr
fluoranthene

and pyrene)

NH2- 0.000025-
l
na
functionalized River water Organochlorine 0.00083; 80.3-115,
Fiber 10 60 0.001-1.0 GC-MS [109]
(MIL)-53(Al) and tap water pesticides 0.000051- 77.4-117

NPs 0.00097
ur

Running water
AuNPs 82.65-
Jo

naphthalene,
Fiber and snow 22 40 0.1-300 0.01-0.05 GC-FID [110]
decorated GO fluorene, 126.06
water

55
 f
anthracene,

oo
fluoranthene,

1,4-

pr
dichlorobenzene

, 1,4-

e-
dibromobenzene

, 2-

Pr
bromonaphthale

ne,

l bromobenzene,
na
biphenyl and m-

terphenyl
ur

2-hydroxy-4-
River water,
Mercaptooctyl methoxybenzop
Jo

Fiber wastewater 15 40 0.1-400 0.025-0.056 HPLC-UV 92.1-106 [111]

groups henone, 2-
and rain water
ethylhexyl 4-

56
 f
modified methoxycinnam

oo
AuNPs ate, 2-

ethylhexyl 4-

pr
(N,N-

dimethylamino)

e-
benzoate and 2-

Ethylhexyl

Pr
salicylate

Naphthalene, 2-

Poly(3,4- Lake water, methylnaphthale

l 89.9-106,
na
ethylenedioxyt rain water and ne, 0.0025-
Fiber 10 40 0.01-100 GC-FID 95.7-112, [112]
hiophene)@A soil saturated acenaphthene, 0.025
93.2-109
uNPs water fluorene and
ur

phenanthrene
Jo

57
 f
Naphthalene,

oo
diphenyl,
River water
phenanthrene,
AuNPs Fiber and 15 20 0.05-300 0.008-0.037 HPLC-UV 82.74-110 [113]

pr
fluoranthene
wastewater
and

e-
benzo[a]pyrene

2-hydroxy-4-

Pr
methoxybenzop

henone, 2-
River water,
ethylhexyl 4-
Phenyl- l
na
domestic
(N,N-
SiO2NPs@Ni Fiber 15 40 0.05-300 0.005-0.058 HPLC-UV 80.6-110 [114]
Sewage and dimethylamino)
O/TiO2NSs
rain water benzoate, 2-
ur

ethylhexyl-4-
Jo

methoxycinnam

ate and 2-

58
 f
ethylhexyl

oo
salicylate

Naphthalene,

pr
acenaphthylene,
Aqueous
acenaphthene,

e-
solution of
fluorene,
Diamond NPs in-tube cigarette 60 30 0.016-20 0.005-0.02 HPLC-UV 72-101 [19]
phenanthrene,

Pr
smoke and soil
anthracene,
solution
fluoran-thene

and pyrene
l
na
Naphthalene,
MnO2/PPyNPs River water,
phenanthrene,
coated rain water and
ur

Fiber fluoranthene, 15 35 0.01-500 0.002-0.032 HPLC-UV 93-106 [115]

Ti@TiO2@Si domestic
pyrene and
O2NPs sewage
Jo

benzo[a]pyrene

59
 f
Silica-coated

oo
magnetic NPs Hospital
- Ciprofloxacin 20 10 50-150 0.002 UV-Vis 92.48 [116]
modified with effluent

pr
salicylic acid

Alpha-pinene,

e-
1,8-Cineole,
SiO2NPs
Eucalyptus isopinocarveol,

Pr
incorporated Fiber - 20 - - GC-MS - [117]
leaf aromadendren
PDMS Film
and

neoalloocimene
l
na
2-hydroxy-4-
ur

Polyaniline methoxybenzop
River water
Nanofibers functionalized in-tube henone, phenyl 40 6 0.06-100 0.02-0.05 HPLC-DAD 82-115 [23]
Jo

and sewage
basalt fibers salicylate, 2,4-

dihydroxybenzo

60
 f
phenone and

oo
phenyl

salicylate

pr
Naphthalene,
Poly(dimethyl Well water,
fluorine,

e-
siloxane)- river water,
Fiber phenanthrene, 15 40 0.017-100 0.005-0.02 GC-FID 90.1-99.9 [24]
coated carbon rain water and
anthracene and

Pr
nanofibers wastewater
pyrene

1,4-

l dichlorobenzene
na
, 1,2-
Polyurethane River water dichlorobenzene
Fiber 10 10 0.05-1.0 0.01 GC-MS 94-102 [25]
ur

fiber and tap water , 1,2,4-

trichlorobenzen
Jo

e, 1,2,3-

trichlorobenzen

61
 f
e and 1,2,3,4-

oo
tetrachlorobenez

ne

pr
Polypyrrole-
Tap water and
polyamide Fiber Malathion 10 40 0.1-1.0 0.05 GC-MS 96-98 [26]

e-
river water
nanofiber

Pr
Phenol, 4-

chlorophenol,

Polyamide- 2,4-
River water
polyethylene l dichlorophenol, 0.0008-
na
Fiber and paddy 4 10 0.003-1.5 GC-MS 85-98 [27]
glycol 2,6- 0.025
water
nanofiber dichlorophenol
ur

and 2,4,6-

trichlorophenol
Jo

62
 f
River water,

oo
Modified Naphthalene,
wastewater
silica fiber Fiber fluorene, pyrene 7 20 1.0-500 0.1-0.89 HPLC-UV 84-106 [28]
and mineral
using AuNPs and anthracene

pr
water

Tap water,

e-
Electrospun
sewage,
polyethylene
In-needle ground water Chromium (VI) 25 25 1.8-60 0.6 UV-Vis 96.9-99.1 [29]

Pr
terephthalate
and river
nanofiber
water

l Naphthalene,
na
acenaphthylene,
Rain water
in-tube
acenaphthene,
Carbon and ground 30 30 0.05-50 0.01-0.1 HPLC 92.3-111 [30]
ur

fluorene,
water
phenanthrene,
Jo

anthracene,

63
 f
fluoranthene

oo
and pyrene

2-chlorophenol,

pr
2,6-

dimethylphenol,

e-
Wastewater,
Polyimide 2-nitrophenol, 0.0006-
TFME sea water and 5 20 0.06-10 GC-MS 31.5-249.4 [31]
nanofiber 2,4- 0.008

Pr
tap water
dichlorophenol

and 2,4,6-

trichlorophenol
l
na
P-toluene

sulfonate
Auramine-O,
ur

doped
Disk Wastewater chrysoidine and 10 0.3 1.0-150 0.3-0.5 HPLC-DAD 90.1-99.1 [32]
polypyrrole
rhodamine-B
Jo

functionalized

nanofibers

64
 f
1,4-

oo
dichlorobenzene

Water, , 1,2-

pr
wastewater, dichlorobenzene
Polysiloxane 0.00015-
in-needle sludge, and , 1,2,4- 5 10 0.0005-24 GC-ECD 90-99 [33]

e-
nanofibers 0.075
sediment trichlorobenzen
samples e and 1,2,3,4-

Pr
tetrachlorobenze

ne

l
na
2,4,4′-
Rain water, trichlorobipheny
ur

river water l; 2,4′,5-

Nanoflakes ZnO Fiber 15 25 0.1-200 0.02-0.17 HPLC-UV 76-108 [34]
and waste Trichlorobiphen
Jo

water yl; 2,3′,4,4′,5-

pentachlorobiph

65
 f
enyl and

oo
2,2′,4,4′,5,5′-

hexachlorobiphe

pr
nyl

Naphthalene,

e-
River water,
phenanthrene,
domestic
SiO2 Fiber fluoranthene, - - 0.013-0.108 HPLC-UV 90.8-105.7 [35]

Pr
sewage and -
pyrene and
rain water
benzo(a)pyrene

l
na
Tridecane,

tetradecane,
ur

Water sample
Nanocomposite ZnO/polypyrr pentadecane,
Fiber and soil 10 15 0.25-100 0.08-0.5 GC-FID 85-96 [37]
s ole hexadecane,
Jo

sample
heptadecane,

octadecane,

66
 f
nonadecane,

oo
icosane,

docosane and

pr
tricosane

Magnetic lead(II) and

e-
dSPME Wastewater 10 13 100-1000 1.8-3.3 FAAS 95-105 [38]
MoS2-Fe3O4 copper(II)

Pr
Benzene,

SiO2- toluene, ethyl

Tap water and 0.0007-
polyethylene Fiber benzene, o- 4 10 0.01-1.0 GC-MS 86-102 [39]
dam water 0.0009
terephthalate l xylene and m-
na
xylene

Benzene,
ur

PPy- Mineral water,

toluene,
MWCNTs- Fiber tap water, well 15 35 0.03-500 0.01-0.04 GC-FID 93.7-106.2 [40]
ethylbenzene
Jo

TiO2 water, river

and o-xylene

67
 f
water and

oo
wastewater

River water,

pr
lake water,

well water, Diazinon,

e-
Sol- rain water, parathion,
Fiber 5 45 0.01-2.0 0.003-0.012 GC-CD-IMS 86-104 [41]
gel/nanoclay wastewater fenthion and

Pr
and chlorpyrifos

agricultural

wastewater
l
na
Benzene,

River water toluene,

Mesoporous
ur

Fiber and ethylbenzene 10 15 0.2-200 0.05-0.56 GC-FID 93-107 [42]

carbon-ZrO2
wastewater and m-, p-
Jo

xylenes

68
 f
Polypyrrole/M Cyproheptadine

oo
Fiber Water samples < 10 15 0.3-200 0.7-1.1 GC-FID 26.8-46.9 [43]
nO2 and ketotifen

Naphthalene,

pr
Graphitic acenaphthene,

C3N4 Pond water fluorene,

e-
Fiber 10 25 0.1-1000 0.025-0.4 GC-FID 84.4-108.3 [44]
hybridized and soil phenanthrene,

with CuO anthracene and

Pr
pyrene

Naphthalene,

l biphenyl,
na
bnthracene,
ZnO/PT/SBA-
Fiber River water fluorene, 5 30 0.1-10 0.0082-0.02 GC-MS - [36]
15
ur

acenaphthene,

fluoranthene
Jo

and pyrene

69
 f
oo
1,4-Dichloro-

nitrobenzene, 0.000001-

pr
Nanorods ZnO Fiber Sea water - 30 0.1-10000 GC-MS 91-102 [45]
biphenyl and 0.01

acenaphthene

e-
1,4-dichloro-2-

Pr
Sea water and nitrobenzene, 0.000001-
SnO2 Fiber - 30 0.1-100 GC-MS 93-98 [46]
groundwater biphenyl, and 0.01

acenaphthene

l
na
Phenyl
River water, Monuron,
carbamate
TFME well water and linuron and 15 25 0.2-50 0.04-0.13 HPLC-DAD 92-106 [47]
functionalized
ur

tap water neburon

ZnO
Jo

Polypyrrole- River water 2,4-

Fiber - 30 0.5-300 0.1-0.15 GC-MS 88.9-97.5 [48]
coated ZnO and well water dimethylaniline

70
 f
and

oo
teflubenzuron

Anthracene,

pr
benzo[a]pyrene,

Rainwater and chrysene,

e-
TiO2-nanorod aqueous fluorene,
Fiber 10 35 0.01-200 0.003 GC-FID 85.8-114 [49]
coated Ti wire solution of fluoranthene, m-

Pr
coal ash terphenyl, o-

terphenyl, and

p-terphenyl
l
na
Phenol; 4-
ur

CNT/layered
Chlorophenol;
Nanotubes double Fiber River water 5 30 0.01-300 0.005-0.08 GC-MS - [50]
2,4-
Jo

hydroxide
Dichlorophenol;

71
 f
2,6-

oo
Dichlorophenol

and 2,4,6-

pr
Trichlorophenol

Methyl

e-
benzoate, ethyl
MWCNT@IL/ Perfume
Fiber benzoate, propyl 10 30 0.012-50 0.0061 GC-FID 86.3-110.8 [51]

Pr
PANI samples
benzoate and

butyl benzoate

l Benzene,
na
toluene,

ZnO nanotube Fiber Water samples ethylbenzene, o- - 20 10-600 0.005-0.01 GC-MS 87-108 [52]
ur

, m-and p-

xylene
Jo

72
 f
Diazinon,

oo
fenitrothion,
Wastewater
MWCNTs malathion,
Fiber and distilled 5 40 0.01-25000 0.004-0.095 HPLC-DAD 86.2-98.8 [53]

pr
functionalized fenvalerate,
water samples
phosalone and

e-
tridemorph

2-Nitrophenol,

Pr
4-nitrophenol,

2,4-
Yellow River
MWCNTs- dinitrophenol, 86.13-
l
Fiber and 4 30 10.2-1585 0.25-3.67 HPLC-UV [120]
na
COOH 2,4- 111.56
wastewater
dichlorophenol

and 2,4-
ur

dimethylphenol
Jo

Poly(ethylene Tap water, Aniline, o-

Fiber 10 30 0.001-200 0.0005-0.05 GC-FID 63.7-97 [55]
glycol) river water, Toluidine, N,N-

73
 f
modified well water and Dimethylaniline

oo
MWCNTs wastewater , 2-

Chloroaniline

pr
and 3-

Chloroaniline

e-
Benzene,
Tap water,
Polypyrrole- toluene,

Pr
Fiber well water and 15 30 0.01-200 0.005-0.02 GC-FID 91-106.7 [56]
CNT-SiO2 ethylbenzene
wastewater
and o-xylene

l River water Diazinon,

na
and fenthion,
CNTs@SiO2 Fiber 4 30 0.01-20 0.005-0.02 GC-CD-IMS 89-99 [57]
agricultural parathion and
ur

wastewater chlorpyrifos
Jo

74
 f
3, 2-hydroxy-4-

oo
methoxybenzop

henone; 2-

pr
ethylhexyl 4-

(N,N-

e-
River water dimethylamino)

Ti-Ni-O CNTs and benzoate; 10 10 0.1-300 0.019-0.082 HPLC-UV 88.6-101 [58]

Pr
wastewater polyacrylate; 2-

ethylhexyl 4-

methoxycinnam
l
na
ate and 2-

ethylhexyl

salicylate
ur

Silica- in- Tap water and Naphthalene,

Jo

MWCNTs capillary river water phenanthrene, 3 0.3-1000 0.1-0.3 GC-MS 72-124 [119]
-
monolithic fluoranthene,

75
 f
pyrene,

oo
benz[a]anthrace

ne, and

pr
benzo[a]pyrene

MWCNTs- 96-blade River water 2-nitrophenol,

e-
COOH/PDMS 2,4-

dichlorophenol 1.2 80 5.0-3000 1.0-2.0 HPLC-UV 66-90 [54]

Pr
and 2,4,6-

trichlorophenol

l
na
o-SWNHs Fiber River water, Toluene,

tap water and ethylbenzene, o-

ur

0.0035-
Nanohorns bottled xylene, m- 20 15 0.5-500 GC-MS 83-107 [59]
0.025
mineral water xylene, p-xylene
Jo

and styrene

76
 f
oo
Naphthalene,

acenaphthene,

pr
fluorene,
River water,
phenanthrene,

e-
pond water 0.00152-
Nanosheets GO Fiber anthracene, 25 40 0.005-0.5 GC-MS 72-102 [60]
and soil 0.00272
fluoranthene,

Pr
sample
pyrene and

benzo(b)fluoran

thene
l
na
Naphthalene,
Phenyl-
River water, phenanthrene,
functionalized
ur

Fiber rain water and fluoranthene 15 40 0.05-300 0.008-0.043 HPLC-UV 86.2-112 [61]
TiO2
wastewater and
nanosheets
Jo

benzo[a]pyrene

77
 f
Di-I-butyl

oo
phthalate, di-

iso-butyl

pr
phthalate,
Polypyrrole/G
Fiber Boiling water benzyl butyl 9 60 0.1-245 0.042-0.26 GC-FID 83-120 [62]
O

e-
phthalate and

di-(2-

Pr
ethylhexyl)

phthalate

2-hydroxy-4-
l
na
methoxybenzop
River water henone, 2-
Zn-ZnO
Fiber and ethylhexyl 4- 15 40 0.1-200 0.052-0.084 HPLC-UV 85.8-105.3 [64]
ur

nanosheets
wastewater methoxycinnam
Jo

ate and 2-

ethylhexyl 4-

78
 f
(N,N-

oo
dimethylamino)

benzoate

pr
Lake water,
on-line Mn, Co, Ni, Cu, 0.00039-
GO-silica well water and 1 - 0.03-50 ICP-MS 85-119 [65]

e-
HF-SPME Cd and Pb 0.028
pond water

Pr
2-Ethylhexyl

salicylate; 2-

ethylhexyl 4-

l methoxycinnam
na
River water,
TiO2/NiOCNS ate; 2-hydroxy-
Fiber lake water and 15 45 0.1-300 0.03-0.064 HPLC-UV 87.3-104 [66]
s 4-methoxy-
wastewater
ur

benzophenone

and 2-
Jo

ethylhexyl4-

(N,N-

79
 f
dimethylamino)

oo
benzoate

Copper 1,4- Naphthalene,

pr
benzenedicarb acenaphthene,
Tap water and 0.00011-
oxylate – Fiber phenanthrene, 9 70 0.02-5.0 GC-MS 81.7-116 [67]

e-
river water 0.0021
MOF fluoranthene

nanosheet and pyrene

Pr
2,4,4´-

tribromodiphen
Bamboo
l
na
Tap water, yl ether;
charcoals
river water 2,2´,4,4´- 0.00025-
modified Fiber 10 20 0.001-1.0 GC-MS 78.5-101.5 [68]
and tetrabromodiphe 0.00062
ur

Fe3O4
wastewater nyl
nanosheets
Jo

ether;

2,2´,4,4´,5-

80
 f
pentabromodiph

oo
enyl ether;

2,2´,4,4´,6-

pr
pentabromodiph

enyl ether;

e-
2,2´,4,4´,5,5´-

hexabromodiph

Pr
enyl ether;

2,2´,4,4´,5,6´-

hexabromodiph
l
na
enyl ether and

2,2´,3,4,4´,5´,6-

hexabromodiph
ur

enyl ether
Jo

81
 f
Toluene,

oo
ethylbenzene,

m-Xylene, 2- 0.00014-
Lake water

pr
ZnO/carbon Chlorophenol, 0.00056;
Nanocubes Fiber and river - 12 0.002-2.0 GC-MS 95.3-105.8 [69]
nanocubes 2,4- 0.0011-
water

e-
Dichlorophenol 0.00284

and 2,4,6-

Pr
Trichlorophenol

Naphthalene,

acenaphthene,
l
na
fluorene,
Environmental phenanthrene, 0.00003-
MOF-HCNCs Fiber 10 30 0.005-2.0 GC-MS 91.2-116.3 [70]
water fluoranthene, 0.0007
ur

pyrene,
Jo

dimethyl

phthalate,

82
 f
diethyl phthalate

oo
and o-xylene

pr
Hexachlorobenz

e-
ene, heptachlor,

aldrin, trans-

Pr
chlordance, cis-

chlordance,
River water
endrin, o,p- 0.0001- 81-120,
Nanospheres MMCNSs Fiber and coking - 60 0.01-8.0 GC-MS [72]
l DDT, p,p-DDT, 0.0055 72.8-118
na
wastewater
Pyrene, Mirex,

Benzo[a]anthrac
ur

ene and

Benzo[ghi]peryl
Jo

ene

83
 f
Naphthalene,

oo
acenaphthylene,

acenaphthene,

pr
Nanospherical Rainwater and fluorene,
81.7-112,
MOF Fiber lake phenanthrene, 10 40 0.03-50 0.01-0.03 GC-FID [71]
83.8-113

e-
UiO-66 water anthracene,

fluoranthene,

Pr
pyrene and

chrysene

l
na
MMIP based

Polymer-based on Well water

MDSPME Diazinon 5 15 0.07-30 0.02 HPLC-UV 96-104 [73]
ur

NMs Fe3O4@SiO2 and tap water

NPs
Jo

84
 f
Imazameth,

oo
imazamox,
Imazethapyr Soil, rice and
Fiber imazapyr acid, 0.1 40 0.5-50 0.07-0.29 HPLC 61.3-116 [74]
MIP peanuts

pr
imazethapyr and

imazaquin acid

e-
l Pr
na
ur
Jo

85