Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
A review: Total vaporization solid-phase microextraction
procedure in different matrixes
Yunes M. M. A. Alsayadi a,*, and Saahil Arorab
a University Institute of Pharmaceutical Sciences, Chandigarh University, Punjab-140413, India
b University Institute of Pharmaceutical Sciences, Chandigarh University, Punjab-140413, India
ABSTRACT
Total vaporization solid-phase microextraction (TV-SPME) is a type
of extraction technique in which a specic solvent dissolves the
analyte. Then a tiny amount of solvent is taken to the vial of SPME.
Then, the solvent vaporizes in the SPME vial, and sampling is carried
out on the headspace of the SPME ber. As a result, the partitioning
phase of the analyte between the headspace and liquid sample is
omitted. The equilibrium phase remains the analyte partitioning
between the headspace and SPME. TV-SPME was introduced in
2014 by Goodpaster to increase the recovery compared to the liquid
injection method. This review discusses different aspects of TV-
SPME, including its impact on sampling techniques, theoretical part,
sampling procedure, and method optimization. Special attention
was paid to its applications. A comprehensive literature study was
conducted in the relevant databases to summarize the research
work that has been done on this technique. In TV-SPME, the liquid
samples completely vaporized and had a less matrix effect and better
adsorption. This method needs no sample preparation, consumes less
supply, and can be done automatically. Also, TV-SPME enables a cost-
effective and efcient extraction for different matrixes. This review
summarizes aspects related to TV-SPME including its sampling
procedure, method optimization, and its preference for conventional
liquid methods. Special attention was paid to its applications of the
vacuum-assisted total vaporization solid-phase microextraction
procedure (VA-TV-SPME).
Keywords:
Solid-phase microextraction,
Headspace solid-phase microextraction,
Total vaporization solid-phase
microextraction,
Vacuum-assisted total vaporization
solid-phase microextraction,
Method optimization
ARTICLE INFO:
Received 21 May 2022
Revised form 2 Aug 2022
Accepted 28 Aug 2022
Available online 29 Sep 2022
*Corresponding Author: Yunes M. M. A. Alsayadi
Email: yunes20171@gmail.com
https://doi.org/10.24200/amecj.v5.i03.190
1. Introduction
Solid-phase microextraction technique (SPME) is
widely used for pre-concentration/separation of
analyte from the sample, analytes are absorbed on
a ber and then, it desorbed before determined by
analytical instrument such as GC-FID [1,2]. SPME
was introduced in 1989, and since then, it has been
used extensively in the eld of environmental
chemistry, with more than 1500 publications. SPME
is a technique with off-column pre-concentration
sampling that facilitates the trace analysis of the
occurring abundance of matrices and samples. This
technique depends on a polymer ber with surface
chemistry designed to increase targeted compounds’
adsorption [3, 4, 5]. SPME was initially presented as
a solvent-free technique combining the prepared
sample into one-step sampling, sample introduction
extraction, and concentration [1,6]. Two processes
are involved in the SPME extraction: (1) the
analytes partitioning between the ber coating and
the sample, and (2) the desorption process occurs
by the concentrated analytes from the coated ber
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A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
to the instrument to be used for the analysis. The
extraction is performed by placing a solid sample
containing volatile analytes and an aqueous sample
containing organic analytes into a vial, then closed
with a septum and cap [7]. The main advantages
of SPME are a simple extraction method, efcient,
selective, and fast. SPME followed with less amount
of sample volumes and no-solvent consumption.
For those advantages, it was implemented quickly
in many disciplines of analytical chemistry, like
bioanalysis, environmental science, and chemical
analysis [8,9,10]. In addition, SPME can be
coupled and automated with instruments like
gas chromatography, which easily estimates the
organic compound [11]. Direct analysis of complex
matrixes mostly cannot be performed in a manner
that attains the sensitivity and selectivity needed
for many trace analysis applications. To solve
this issue, SPME techniques were used so that
preconcentrating of analytes occurs selectively
before placing it into ion trap mass spectrometric/
gas chromatographic analysis. This approach was
introduced to be used in the trace analysis of the
metabolites of explosives in seawater [6]. The SPME
technique includes exposing a ber of fused silica
coated with a solid phase to an aqueous solution
containing organic compounds [12]. It involves
using a silica ber coated with a polymer lm to
adsorb compounds of interest from their matrices.
Such a technique is a solvent-free, reliable, and
inexpensive method that can be used practically
for aqueous sample analysis/headspace and shows
good sensitivity and excellent selectivity [13]. The
SPME technique is used for multiple sampling, and
sample preservation leads to minimizing the risk of
contamination of the sample because the technique
affords a simplied sample handling [14]. SPME is
mainly carried out in one of the two modes; either
headspace or immersion technique. In headspace
SPME mode, the extraction of analytes by bers
occurs from the headspace above a sample. While in
immersion SPME mode, the extraction of analytes
by the ber takes place directly from a liquid
sample [15]. In headspace SPME, the partition of
analytes occurs between the headspace above the
sample and the coating ber of SPME [16,17]. The
main criteria for applying headspace solid-phase
microextraction (HS-SPME) was to prevent the
ber of SPME coatings from being tricked by the
components of sample matrices [18]. In HS-SPME,
the ber is placed into the vial of the sample, the
volatile organic compounds that are available in
the headspace, are bound to the coating, and then
the ber is to be taken to the site of injection of
the Gas Chromatography (GC) for desorption and
further analysis [13] HS-SPME compounds having
analytes with low volatility from complex aqueous
samples can be used by the manner of increasing
the temperature of the sample. Still, some SPME
coatings made from some adsorbent substances
may face difculties due to their low stabilities,
particularly in a hot medium like a steam of hot
water. It is the preparation of super hydrophobic
metal-organic framework (MOF) that is obtained
from decoration nodes of the amino-functionalized
UiO-66(Zr) with phenyl silane was needed and then
successfully improved to be used in a novel ber
coating of SPME [15]. The scientists of food avors
have appreciated the ease of use and sensitivity
of the headspace technique mode by using it in
analyzing the volatile compounds in many food
products [19]. Headspace SPME sampling was
widely used in analyzing of some intact explosives
like triacetone triperoxide (TATP) which was
detected from headspace applying planar SPME
with the help of an ion mobility spectrometer[20].
HS-SPME is a pre-sampling technique that does not
need complicated apparatus or solvents [21]. HS-
SPME can integrate the concentration, extraction,
and introduction in a single step. Combing HS-
SPME with GC–MS is employed to determine
the volatile components in different plants like tea
samples [22]. In the immersion SPME sampling
technique, the ber is directly placed into a liquid
sample and the compounds of interest absorb/
adsorb to the ber coating. After the absorption/
adsorption, the ber is then placed for desorption
in the inlet of a LC or GC for further analysis
[23]. Immersion SPME sampling has been utilized
practically in the applications of environmental
82 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
studies for extracting organic explosives that are
present in aqueous soil extracts and/or water to be
later analyzed by GC-MS and GC-electron capture
detection [6,16]. Some explosives examples that
have been detected and recognized in this method
like PETN, 2,6-dinitrotoluene, RDX (composition
C-4), TNT, and NG (dynamite) [24,25]. Both the
techniques either headspace or immersion SPME
cannot be smoothly applied to the detection and
identication of some explosive residues especially
those present on post-blast debris, regardless of
many previously reported descriptions of its unique
use, for example, the detection of a single particle
of smokeless powder [2] or the residue extraction
of the explosives that obtained from soil samples
collected from the blast site after an explosion
[25,26]. In fact, headspace and immersion SPME
methods have been used to analyze a various
analytes [27]. TV-SPME is almost a new technique
that is being utilized in analytical chemistry. It is
always in comparison with conventional techniques
including HS-SPME in the motive of determination
of the superior technique. That comparison is
highly appreciated as it plays a critical turn in the
superiority of the method that is to be adopted.
And in the case of TV-SPME and HS-SPME, it is
important to compare them to see if one is superior,
as it helps to choose a method with specic samples
[28]. These two methods are among the advanced
micro extraction methods as they require least to
almost no sample preparation compared to other
liquid methods which require a high amount of
the sample [29]. They involve placing the samples
directly into the headspace in place of placing them
to do individual extraction techniques to a sample
ahead of being directly injected into the GC. Table
.01 shows the differences between the HS-SPME
and TV-SPME [30]. The comparison concentrates
on the sample volumes, analysis time, and matrix
effects as these parameters are critical for analysis
samples.
Environmentally, TV-SPME has been used to
analyze drugs and their metabolites in saliva,
urine, and hair. This valuable simple technique
has also been used in analyzing lipids, fuel
samples, street drugs, lipids, and pollutants in
water and post-blast explosive residues [30],
[33], [36-38]. TV-SPME has been used to identify
illegal adulterants in tiny samples (microliter
quantities) of alcoholic beverages [39-40].
Both gamma-butyrolactone (GBL) and gamma-
hydroxybutyrate (GHB) were identied at levels
that would be found in spiked drinks [34]. There
were techniques being used, including Membrane
protected micro-solid-phase extraction (µ-SPE),
which was used for the rst time in 2006 with the
motive of replacing multistep SPE. The principle
of µ-SPE lies in taking a minimal amount of the
sorbent and packing it inside a porous membrane
paper having edges that are heat sealed for the
fabrication of a µ-SPE device. This device can
perform pre-concentration and extraction in a
single step. Such techniques seem to have the
best extracting method, especially for complex
Table 1. Differences between the HS-SPME and TV-SPME
Parameter HS-SPME TV-SPME
Sample volumes Sample utilization is at least 1mL.[29,31-33].**Almost 1 µl - 100 µl as TV-SPME vaporizes the
sample completely [31,34].
Matrix effect The effect of matrix is higher as it is between two
phases only [32, 33].
less matrix effects are there as it results in fully
vaporizing the analyte and its matrix[34].
Analysis time.
***HS-SPME and other liquid injection, need that
the analyte to be reacted with the derivatizing agent
in solution [33, 35].
As TVSPME allows for the analyte to be derivatized
during the extraction process which reduces analysis
time [27, 34].
**Almost 1 µl - 100 µl as TV-SPME vaporizes the sample completely, analyte partitioning will be there between the vapor and only
the ber, which lead forcing more amount of the sample to adsorb into the ber and large amount of the sample can be exposed to
the vapor. And that can cause minimizing the sample size [31,34].
***Other methods including HS-SPME and other liquid injections, need that the analyte to be reacted with the derivatizing agent
in solution prior to being injected into the GC. And that lead to minimize the time of analysis[33, 35].
83
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
samples, since extraneous matter does not adsorb
over the sorbent as it is protected effectively inside
the Membrane [39]. Direct Immersion-Solid
Phase Microextraction (DI-SPME) is preferred
for aqueous samples as the ber is introduced
directly to the sample solution. However, when
applied to a complex matrix, the sample must be
pretreated; otherwise, some interfering substances
from the matrix can bind irreversibly to the ber.
As a result, choosing the mode is not preferred in
the case of complex samples, including samples
arising from food, sludge, and biological origin
[39-40]. To overcome such issues, HS-SPME can
be used, although it has some limitations, including
it can work better only for volatile compounds and
that compounds having good volatility even with
almost moderate heat. Therefore, nonvolatile or
low volatile compounds cannot be extracted by
applying such an approach. So, something should
be developed for extracting compounds with less
or no volatility from complex samples by adopting
a mode of direct immersion [41]. Differences
between DI-SPME, HS-SPME, and Membrane
Protected SPME, are shown in Figures 1 (a and b).
Fig. 1b. DI-SPME, HS-SPME and membrane protected SPME
Fig. 1a. DI-SPME, HS-SPME and membrane protected SPME
84 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
SPME and its derivative techniques are a well-
recognized method of extraction which utilize zero
solvents and has a wide scope and applications,
including biomedical, food, forensic, and
environment [35,41]. Moreover, they can be applied
in organic contaminants extraction like; pesticides,
Pharmaceutical compounds, emerging pollutants,
and persistent organic pollutants [42-53]. Total
vaporization (TV) is a technique that can be
practically utilized in conjunction fused with
headspace sampling. The residual solvents will
be released from the matrix by applying TV to a
solid sample. Furthermore, applying it to the liquid
samples allows the whole sample to be vaporized
before the headspace sampling [54]. TV technique
applies to many samples like solid samples (e.g.,
residual solvents), [55], aqueous solutions (e.g.,
odor compounds) [56] and fermentation liquor
(e.g. ethanol) [57]. The approach of coupling TV
and SPME (TV-SPME) offered great sensitivity
and even low detection limits for compounds
present in the hair of some users of tobacco such as
nicotine and cotinine. In the TV-SPME technique,
a sample extract needs to be heated until it gets
vaporized and ber of SPME is utilized for pre-
concentrating analytes from the produced vapor
[53]. In TV-SPME, a complete vaporing of the
liquid samples gives a fewer matrix effect and
better adsorption. This method does not need
any sample preparation, utilizes less supplies
and can be done automatically, enabling it to be
both a cost-effective and efcient method [58].
SPME is a sensitive technique where the liquid
portion is totality vaporized before being placed
for sampling, easing to attain equilibria inside the
sample vial and increasing the analyte’s availability
in the headspace, leading to making the analyte
quantity more [53,59]. TV-SPME is an effective
technique that does not require derivatization while
being used to analyze controlled substances, either
with or without on-ber. Total vaporization is a
technique that has been utilized in simple headspace
sampling. Still, matrix effects that result between
two phases in headspace sampling are a matter of
concern. One important method to remove matrix
effects is completely evaporating the analyte
and its matrix. Total vaporization headspace is
applicable in determining ethanol in fermentation
liquor, methanol in wood pulp, odor compounds in
aqueous samples, and volatile organic compounds
in biological samples [56,60-62]. The matrix
effects in SPME can be eliminated by extracting
analytes (quantitatively) from complex matrixes.
This method is known as cooled ber SPME, and it
has been applied for extracting polycyclic aromatic
hydrocarbons (PAHs) from heated soil samples
[3]. Also, the urine extracts in solvent and have
been evaporated in a headspace vial. The residue
was heated until analytes derivatize, vaporize, and
absorb to a SPME ber [63].
2. Experimental
2.1. TV-SPME sampling procedure and practical TIPs
SPME ber format was one of the most commonly
used forms of the technique for many years [64]. In
SPME ber format, a small amount of the extracted
phase is coated by a thin and short fused-silica rod,
which is revealed for a specic time directly to the
headspace above the sample or to the sample itself.
Analytes of interest were taken from the sample to
be analyzed in the SPME ber coating, and then
the sample was extracted till the point when the
quantity of analyte extracted by the ber remained
constant even if the sampling time increased i.e., the
analyte concentration attained partition equilibrium
state between the ber coating and sample [65].
Generally, the time needed to attain equilibrium
relies on the characteristics of the ber coating,
matrix, and target analyte, and its range varies
from a few minutes to many hours [66]. SPME
sampling includes two stages of the equilibrium
mechanism, which occur between the headspace/
sample (first stage) and the fiber coating/
headspace (second stage). In the TV-SPME
technique, the equilibrium process between the
sample/headspace is no longer needed since the
analytes can be directly partitioned from the fiber
coating and headspace [67]. Figure 2 shows the
sample preparation of HS-SPME and TV-SPME.
For HS-SPME, the extraction of volatile analytes
85
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
is noticed to happen faster than analytes with
semi volatiles nature [15]. For that, the longer
equilibration times could be less in various ways,
including agitating the sample, heating the sample,
maximizing the headspace/sample interface, and
implementing the cold ber HS-SPME proposal
to cool the ber coating and heating the sample
matrix occurs simultaneously [13]. The effects
of the matrix that can be produced between two
phases while sampling in the headspace technique
is a matter of concern. An important method to
remove such effects from the matrix is applying
heat to evaporate the analyte and its matrix fully. An
excellent example of the use of total vaporization
headspace involves estimation of volatile organic
compounds in biological samples, methanol in
wood pulp, odor compounds in aqueous samples,
and ethanol in fermentation liquor [27]. In TV-
SPME, the extracted aliquot of the sample is
sentenced for heating till the point where both the
analytes and solvent are completely vaporized; after
that, the analytes partition between the SPME ber
and the vapor phase [16]. TV-SPME extraction of
analytes from a sample of interest was performed by
applying a specic solvent in this approach. Then,
a small part of this extract is fully vaporized inside
a headspace vial inserted into an SPME ber. Also,
the VOCs in water samples based on ber coating
on the needle were determined after HS-SPME and
TV-SPME were coupled to the GC-MS (Fig.3).
Fig. 2. Samples preparation of HS-SPME and TV-SPME
Fig.3. Determination VOCs in water samples based on ber coating on needle
after HS-SPME and TV-SPME coupled to the GC-MS
86 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
These results are a simple two-phase system.
In particular, patterns occur when the analytes
partition between the extract and the headspace is
removed and when the analyte partitioning occurs
directly between the vapor phase and the SPME
ber. In general, combining the total vaporization
technique with SPME increase preconcentrating
analytes onto the ber. For example, the estimation
of an organic analyte in an organic solvent is not
accessible by either immersion or headspace
SPME. For that, the solvent should get vaporized
and the analyte absorbed into the ber of SPME.
So, when the analyte gets distributed (in TV-
SPME) at a solid/vapor interface, it has been found
that the extraction time is less important than the
sample volume and extraction temperature for the
analytes to be recovered efciently. In TV-SPME,
extracts of the sample do not have to get ltered,
which gives it a signicant advantage compared
to liquid injection. Nonvolatile compounds or
solids that may have the chance to be laid within
an extract of the sample will stay on the surface
of the vial. That may lead to minimize extensively
the contamination and the quantity of buildup that
may take place in the inlet and the column of GC.
Furthermore, the boiling point of the analytes plays
an essential role in the selectivity of the GC inlet
in liquid injection. TV-SPME can add a level of
chemical selectivity because of the advantage of
the ber that can enable it to select the targeted
analyte specically. Finally, the volumes for the
liquid injection are almost 1 to 2 μL; thus, only
a tiny portion of the sample extract is needed for
the injection. The Large-volume injection (LVI)
techniques have thus been developed to be used
in the GC. However, LVI needs some changes
to meet the requirements for the instrument and
other analysis parameters. So, TV-SPME needs no
modication in instruments and other parameters,
enabling the use of large volumes of the sample for
the analysis in GC, which ultimately concluded
in great sensitivity over the liquid injection [27].
The idea of combining total vaporization with
SPME is almost similar to that of LVI techniques
in those large volumes of the sample (e.g., 200
mL) which lead to an increase the sensitivity.
However, TV-SPME is an essential technique
because it does not require any modication in the
GC instrument, such as exits for solvent vapor or
adding retention gaps.
Additionally, the sample extracts require no
ltration as any non-volatile or volatile components
oat above and within the surface of the vial. A
critical feature of TV-SPME is that although it
evaporates the liquid sample completely, resulting
in a much larger volume, it plays a vital role in pre-
concentrating the analytes more than compensates
for this dilution. In addition, a clear choice of
ber chemistry used in SPME can add remarkable
selectivity to the analysis [16].
2.2. TV-SPME method optimization
HS-SPME is a process of multi-stage equilibrium
[68] where the extracted analytes in the headspace
partition with the adsorptive surface on the ber
after the compounds get extracted from the matrix
to the sample headspace by the help of some
external force, including ultrasound, agitation
and rising the temperature. These strategies
shorten the time needed to attain equilibrium.
In 2014, a novel separation technique was
introduced by Goodpaster in which sampling
was to be performed only in the headspace [53].
In this technique, the extraction of the analyte
occurs by a solvent. Then a tiny amount of
the solvent is taken to the SPME vial by total
vaporization of the transferred solvent in the vial
used in SPME, and sample processing is taken
place on the SPME ber from the headspace [23].
Therefore, the phase of partitioning the analyte
extracts between the headspace and liquid sample
is omitted, and the only equilibrium phase that
remains is the partitioning of the analyte between
the headspace and SPME [69]. Reecting that
the partitioning process of the analyte is to occur
between the vapor and solid, it was noticed that
in comparison with extraction temperature and
sample volume, the extraction time parameter has
less signicance [67]. In addition, all non-volatile
and solid compounds stay on the surface of the
87
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
SPME vial and are not taken to the injection
portion or the GC column. Therefore, it reduces
contamination in GC, and the sample extracts
require no ltration [16]. Also, the evaporation
of the sample is almost more, and a proper ber
of SPME is used for the preconcentration of
the analytes to enable the TV-SPME technique
to have a greater sensitivity compared to the
traditional SPME [69]. The TV-SPME method
depended on the vaporization of the total portions
of the sample, containing volatile, non-volatile,
and semi-volatile components. Therefore, it
is noticed that semi-volatile and non-volatile
compounds require more heat, and the sample
volume needed is a more signicant amount.
Consequently, it was reported that the SPME ber
is heated and that heat does not cause any fault
in the absorption of the analytes on the SPME
ber [67]. Maybe this is one of the limitation
factors, but it is considered to be among the main
reasons why this valuable technique is not more
widely used. As a result, few publications based
on TV-SPME have been written [70]. The TV-
SPME technique should be coupled with another
method to ease the vaporization; surpassing the
preparation steps and minimizing the required
heat would be helpful [71]. Various factors
must be investigated and optimized, such as the
desorption temperature, the extraction time and
temperature, and the salt concentration. Such
factors signicantly affect thermal desorption
and extraction efciencies [15]. For controlled
substances that are not thermally stable and
not sufciently volatile while being analyzed
by GC-MS, derivatization is used to improve
their characteristics to match the required
conditions in the method optimization in GC-
MS. The performance of GC-MS is signicantly
improved by the use of such derivatizing
compounds [71]. Although derivatization has
many benets, techniques of the conventional
solution phase work are time-consuming and
intensive. However, derivatization was adapted
to a sampling technique that is called TV-SPME
to automate and simplify the process. SPME is
a technique in which the analytes of interest are
placed for pre-concentration onto a ber coated
in adsorptive or absorptive material. TV-SPME
is a unique and novel technique in which a tiny
amount of solution is poured into a vial and heated
until complete vaporization occurs [53]. A ber
of SPME is then introduced, and the adsorption
of the sample onto the ber coating takes place.
TV-SPME belongs to immersion SPME in that
both are two-phase systems which differ from
headspace SPME, which is a three-phase system
[69]. Calculating the maximum volume for total
vaporization of a given solvent can be easily
obtained by the vial volume, molecular weight,
solvent vapor pressure, and temperature [53].
For example, the calculated maximum volume of
methanol for total vaporization in a 20-mL vial at
60°C is 24 μL [53].
When TV-SPME is used for sampling, it can
be streamlined the process of derivatization by
enabling it to be taken place simultaneously with
the extraction step in a process called on-ber
derivatization (Fig.4). This On-ber derivatization
was used before in conjunction with immersion
or headspace SPME [72]. However, it could be
desirable to use the advantages brought by TV-
SPME to bear for on-ber derivatization. In the
process of derivatization on-ber with TV-SPME,
an SPME ber is introduced to the headspace
of a vial that contains a small aliquot of liquid
derivatization agent. The ber is then taken to the
heated headspace of a vial that contains the sample.
The reaction between the derivatization agent
and analyte takes place directly in the headspace
surrounding the ber or on the SPME ber. After
sufcient time for adsorption and reaction, the
ber is taken to the inlet of the GC for desorption.
The use of an autosampler can make this a fully
automated process wherein the only sample prep
necessary is to dissolve the sample in a suitable
solvent and place an aliquot into the vial [73].
Several parameters are in direct touch with TV-
SPME method, involving desorption time, SPME
ber type, extraction time, sample volume and
desorption temperature [16,69].
88 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
2.3. TV-SPME based on liquid method
Although Gas Chromatography – Mass
Spectrometry (GC-MS) is considered to be
one of the most frequently used techniques in
the laboratories, it has some limitations since
compounds need to be volatile as well as thermally
stable. Without these two characteristics, GC-MS
cannot be used for regular routine analysis. For that
some compounds have to undergo derivatization
before injecting them into the gas chromatograph
(GC) to meet and satisfy these requirements of
thermostability and volatility. In SPME technique,
a sample is taken into a vial and then heat is applied
on the vial to initiate a site of the analyte to get
vaporized into the headspace. A polymeric material
such like polydimethylsiloxane-divinylbenzene
(PDMS/DVB) used to coat SPME ber, the coated
SPME ber is placed into the headspace of the
sample or immerged graphene-Fe3SO4–SPME
Fiber in water samples and the analyte is adsorbed
onto the ber concluding that the formation of a
thin coating of the analyte on the ber (Fig.5). The
ber is then introduced to the inlet of the GC for
desorption [74]. TV-SPME technique is almost
similar to that of headspace SPME but it differs by
the complete vaporization of a liquid sample prior
getting adsorbed onto the ber. Such adsorption
permits the occurrence of partitioning of the analyte
between only the coating of the ber and the vapor.
By this technique, more portion of the sample is
exposed for the adsorption onto the ber lead to
minimize the sizes of the sample (e.g., 1 – 200 μL)
can be utilized [75-76].
TV-SPME showed its ability to be an efcient
technique especially when used for the analysis
of controlled substances in both the ways
either with or without on-ber derivatization.
A summarized table for the results is presented
below: Table 2. Brief of results for TV-SPME and
liquid injection methods. + denotes that a single
chromatographic peak is formed. 0 denotes that
multiple chromatographic peaks are formed, and
– denotes that no any chromatographic peak is
formed [72,77].
even it could not be applied for all analytes, TV-
SPME with on-ber derivatization can serve
as a powerful technique for amine, GHB and
hydroxylamine-controlled substances [78]. The
technique can increase the efciency of the analyst
by minimizing the time required for preparation of
the sample for these types of analytes. Since GHB
cannot be analyzed directly in its native state by
GC/MS, this method is particularly well-suited to
overcome such limitation [72,79].
Fig. 4. Derivatization on-ber in TV-SPME
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A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
Table 2. liquid injection methods based on V-SPME
Drug TV-SPME Liquid Injection
Methamphetamine + +
Amphetamine + +
Methamphetamine + TFAA + +
25I-NBOH 0 -
Gabapentin + +
Psilocin + +
25I-NBOH + TFAA + +
Pregabalin + -
Ephedrine + +
Ephedrine + TFAA 0 +
Lorazepam + +
Vigabatrin - -
GHB - -
Gabapentin + DMF-DMA 0 +
GHB + BSTFA + 1% TMCS + +
Vigabatrin + DMF-DMA - +
Pregabalin + DMF-DMA - 0
Fig.5. Immerged (graphene-Fe3SO4 –SPME Fiber) in water
and adsorbed the BTEX from water onto the ber
90 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
2.4. Application of TV-SPME procedure
2.4.1.Ascertainments of lipid proles of Phormia
regina
Pupae of Phormia regina was the sample used in
this study which basically belongs to a kind of blow
y species; while doing the inquiries of death, the
forensic entomologists commonly found this type.
which is commonly found by forensic entomologists
during the investigations of death. Conventionally,
the insect species analysis in a forensic backdrop has
been falling within the prospect of biologists along
with entomologists. Nevertheless, considerable
effect has been done by the chemistry domain for
the evaluation of these specimens by LC-MS, GC-
MS and likely analytical techniques [80]. Studies
that rely on liquid extraction are more commonly
used for such analysis. Usually, the pest is placed
in a non-polar solvent by the mean immersion for
a particular time, allowing the extraction process
of the cuticular and internal lipids. Derivatization
is a kind of needful for these excerpts to improve
performance and sensitivity within subsequent
separation steps [81-82]. Unavoidably, single or
multifold rounds of chromatography follows: liquid
chromatography (LC), gas chromatography (GC)
and thin layer chromatography (TLC) are some
of the techniques that have been used. This wide-
ranging method has been applied to the analysis of
pupae [83-86].
Some experiments have been sought for the evaluation
of the Volatile Organic Compounds (VOCs) that
emitted by pupae using HS-SPME at elevated
temperatures, unfortunately, the experiments were
unsuccessful. For that, attentions have been exerted
towards developing a new technique for the liquid
extraction of pupae in order for the isolation of any
hydrocarbons and lipids subsequent to TV-SPME
analysis. The derivatization by trimethlysilyl was
also performed internally within the sample vial
immediately before GC-MS analysis took place,
such derivatization would come very handy and
with potential advantage to future analysts in order
to rundown on blow y pupae [23].
A new-fangled technique has been developed
for the evaluation of sterols, fatty acids and
other naturally occurring lipids within pupae
of the blow y Phormia regina. Such method
counted on liquid extraction in a solvent (non-
polar), followed by derivatization using N,O-
bis(trimethylsilyl)triuoroacetamide (BSTFA)
w/ 1% trimethylchlorsilane (TMCS) carried out
inside the sample vial. The facilitation of this
rundown was done by total vaporization solid-
phase microextraction (TV-SPME), along with
gas chromatography-mass spectrometry (GC-MS)
which served as the instrumentation for analysis.
The TV-SPME delivery technique was considered to
be sensitive and effective approximately ve times
more than traditional liquid injection, this higher
sensitivity may ease the reconstitution requirement,
rotary evaporation, and collection of high-
performance liquid chromatography fractions, and
many of the other pre-concentration steps that are
commonplace in the current literature. In addition
to that, the ability of this method to derivatize the
liquid extract in just single step while ensuring
good sensitivity represents an improvement over
present derivatization method. Various saturated
and unsaturated fatty acids were the lipids present
by and large in y pupae, ranging from lauric
acid (12:0) to arachinoic acid (20:4), as well as
cholesterol. The concentrations of myristic acid
(14:0), palmitelaidic acid (16:2), and palmitoleic
acid (16:1) emerged as the most reliable indicators
of the age of the pupae [23, 87-88].
2.4.2.Detection of ɣ-butyrolactone (GBL) and
ɣ-hydroxybutyric acid (GHB) in alcoholic
beverages via TV-SPME and GC-MS
ɣ-butyrolactone (GBL) and ɣ-Hydroxybutyric
acid (GHB) are important drugs since the can
be spiked into a victim’s beverage to facilitate
sexual assault(surreptitiously). These drugs may
cause sedation, memory loss, and are difcult to
be detected especially in plasma and biological
samples. The challenge related to their analysis
of these drugs lies on that they may be prone to
readily interconvert in aqueous samples, which
was showed in samples that required longer time
to stand at room temperature. A volume required
91
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
for the study of GBL in water was performed with
volumes that ranged from 1µl to 10mg as compared
to the efcacy of headspace SPME, immersion
SPME and TV-SPME. Lastly, water, liquor, wine
beer, and mixed drinks were spiked with either
GBL or GHB along with realistic concentrations
(mg/ml) and microliter quantities were analysed
using a combination of the TV-SPME and GC/
MS method. The volume study of GBL exhibited a
great sensitivity in the detection of GBL when TV-
SPME was used. In addition to that, GBL and GHB
were recognized in many beverages at realistic
concentrations. Overall, TV-SPME is a method of
benets since it does not require sample preparation
and uses lesser sample volume as compared to the
immersion and headspace SPME [73].
2.4.3.Detection of both cotinine and nicotine in
hair
TV-SPME can be used in detection of both cotinine
and nicotine in hair as biomarkers of tobacco users
whereas the cotinine detection was not possible
in the past by using conventional SPME [89].
Only few research papers have published in using
headspace SPME in the detection of nicotine
in human hair by using. It was reported for rst
time that both cotinine and nicotine are efciently
detected using TV-SPME from a hair sample
collected from a tobacco user. Incidentally, full
scan data detect many other important compounds
relied on a library search [53]. These involves
phenacetin (an analgesic), squalene (a hair lipid
that occurs naturally), 1,4-benzenediamine (a
precursor of hair dye), and homosalate (type UV
lter seen in shampoos). The hair taken from a
two more smokers had nicotine concentrations
of 21 and 29 ng mg-1 hair, which is almost same
as that the concentrations reported from other
studies [24,25]. A detailed studies of validating
the TV-SPME for the use of hair analysis showed
its ability to detect both the cotinine and nicotine
even in a small portion of the hair from the tobacco
users which could serve as a good method for
the researchers of toxicology and other medical
backgrounds [53].
2.4.4.Tracking explosive residues on the places
of bombing
The detection of the residues seen on bombing
places and that arising from a debris of post-blast has
a great role for the explosive’s investigators. This can
be used on the determining of explosive type, which
may be used to catch a link about some suspect. To
solve the issue of not nding a particle of explosives,
some standard methodology can be used including
the extraction of some pieces of debris with specic
solvent (i.e., acetone and/ or dichloromethane) and
then the extract(s) is to be analyzed via liquid injection
GC/MS and/or infrared spectroscopy [16,90]. A TV-
SPME method for the analysis of explosive residues
on pipe bomb fragments has been designed and
optimized. Optimization of this method was done
by the following parameters incubation temperature,
extraction time, and sample volume of the TV-SPME
method. For the nitroglycerin, method optimization
parameters were a 70 mL sample volume, a
30-minute extraction time and a 65 C incubation
temperature. In addition to that, TV-SPME showed
great sensitivity as compared to conventional liquid
extraction methods as it was found to be 13-fold more
sensitive and it has a very low detection limit (i.e.,
less than 10 ng mL-1). When this developed method
was used to actual pipe bombs, the recovery of the
estimated NG mean mass was 1.0 mg and the mean
concentration of NG on the fragments of steel was
almost 0.26 ppm (w/w). It was noticed that end caps
fragments yielded higher amount of NG and DPA.
These ndings could contribute to understand how
IEDs functioning and it help the analysts regarding
the required sensitivity for the analysis smokeless
powder from post-blast fragments.
Fragments from the end caps yielded the highest
amount of DPA and NG. These results of this study
contributed by the meaning of understanding of
how small IEDs function as well as inform analysts
regarding the sensitivity that is required for post-
blast analysis of smokeless powder. It is expected
that many other types of smokeless powder could
be analyzed by this technique. This technique also
can be used for the analysis of some other types of
containers like PVC [16].
92 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
2.4.5.Identication and Automated
Derivatization of Controlled Substances via
TV-SPME and Gas Chromatography/Mass
Spectrometry (GC/MS)
Due to polarity, many compounds that present in
biological and environmental samples are not suitable
to be analyzed by GC. In addition to that, some
compounds have the tendency to have decomposing
and adsorbing properties on the injector or columns
and to show non-reproducible peak areas, shapes
and heights [91]. To overcome such issues, the need
of introducing derivatization reactions arises [92].
The importance of derivatization comes from its
ability to decrease the polarity of the compounds
of interest and increase the volatility and improve
the analytes thermo stability. The derivatization
also can improve the process of selecting of
compounds behavior towards selective detectors,
such as the spectrometry (MS) and electron capture
detector (ECD). One of the main purposes from the
formation of derivatives is to enhance the selectivity
of the compounds, limit of detection (LOD) or
both [93]. Before applying the analytical method,
the targeted compounds placed for a procedure of
sample preparation that involves a derivatization,
concentration, or clean-up step procedures[26].
Combining extraction technique with derivatization
result in enhancing the separation characteristics,
detectability, and analyte recovery [94]. Generally,
derivatization has been performed to promote
the extractability of the analytes, reduce polarity,
improve the GC characteristics of compounds,
and make them compatible with the analytical
system and/or to increase the detection sensitivity
[91]. In forensic science laboratories, controlled
substances units are placed under pressure for
analyzing samples adapting methods that can show
cost-effectiveness and high throughput. Additional
to that, it is recommended in the eld of analytical
chemistry that that new chemical compounds
appear in forensic chemists and exhibits must
react to this by developing instrumental methods
have great selectivity and high specicity [95].
It was observed that TV-SPME offering greater
sensitivity for controlled substances as compared
to traditional liquid injection. Additionally, TV-
SPME technique was easily applied to involve
either a post-extraction or a pre-extraction on-ber
derivatization step species with thermally labile.
Promising results were obtained for almost all
categories of drugs that were analyzed successfully
by the meaning of on-ber derivatization as
solutions. This important discovery may increase
the use of this novel technique, because controlled
substances are existed mostly in their solid forms
in the laboratories of forensic science. This
technique can be applied in the determination of
solid drug powders and beverage sample, since
these applications include a signicant decrease
in the amount of sample preparation. Although not
applicable ideally for all analytes, TV-SPME with
on-ber derivatization could serve as an important
technique for the determination of hydroxylamine
and amine, controlled substances, and GHB. Thus,
this work results in a set of optimized derivatization
methods that can serve in TV-SPME and even in
liquid injection. This approach presents a possible
method for automated derivatization and sampling
for a wide variety of thermally labile compounds
and for analyzing compounds that need no
derivatization [72,74,96]. Many applications exist
for extraction analyte by the TV-SPME which was
shown in Figure 6.
2.4.6.VA-TV-SPME procedure
Considering that SPME is that method depended
on vaporizing the whole portion of the sample of
interest, including volatile, nonvolatile and semi-
volatile components. However semi-volatile and
non-volatile compounds needs more heat, for that
more amount of the sample volume is required. As a
resultant of that, the SPME ber get heated and that
ber has not affected the absorption of the analytes
on the SPME ber [53]. It could be a limiting factor,
and considered to be the main reason behind this
important extraction technique is not more used
widely. For that reason, publication studies based on
TV-SPME technique are less [23,69,70]. To solve
such limitations, TV-SPME is coupled with another
technique to encourage the analytes vaporization
93
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
and the preparation steps are omitted lead to a great
reduction in the required heat which would assist
a great benet. In 2001, Brontun explained that
when there is inhibition of the vessel pressure, it
will lead to effect positively on the sampling [19].
One more explanation revealed that by decreasing
the pressure, the analytes gets released from the
matrix of the sample. Additional to that, decreased
pressure reduces the boundary layer that attached
to the ber and strengthens the analyte absorption
on the surface of the absorbent [49]. Recently, new
extraction technique was introduced by Psillakis
called Vac-HS-SPME as a new method depends
on reduction of the pressure of the vessel used for
sampling [76]. They revealed that when the vacuum
conditions are applied, HS-SPME the extraction
rate of analyte will be increased be speeding up
the conversion from the aqueous matrix to the
headspace. As a result of that, the vaporization
of the analytes increased attributed to vacuum
removal and faster equilibrium of the air from the
headspace. This technique could not be able to
extract analytes from the sample in solid phase and
soil without preparation [77]. The sample may be
lost due to the direct contact between the vacuum
and the sample while evacuation period occurring.
To overcome such risk, the need of using a novel
setup for the sampling vessel, Vacuum Assisted
HS-SPME (VA-HS-SPME) was introduced to
be used in the extraction of Polycyclic Aromatic
Hydrocarbons (PAHs) from polluted soil without
the need of preparation and the risk of analytes
loss is less [52]. In that proposed technique, for
the rst time, a low-cost, sample, reliable and fast
setup was developed by using both VA-HS-SPME
(low pressure) [78] and TV-SPME techniques.
One of the main advantages of VA-TV-SPME,
more temperature can be applied for the extraction
of analyte from the matrix of the sample without
increasing the ber temperature, which results
in the increasing the of analyte extraction, as
compare to conventional TV-SPME. One more
advantage is that the time of sample vaporization
is shorter. Also, when vacuum-assistance and
total vaporization are simultaneously used, it
maximizes the rate of analyte extraction in a
complex matrix, with no need of any preparation.
To evaluate the PAHs extraction from polluted
water samples, a PDMS ber is used, then the
determination is done by GC-FID [67]. The main
purpose of coupling TV-SPME with the VA-TV-
SPME system (Fig.7) was to increase the sensitivities
Fig. 6. Some applications of TV-SPME
94 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
in shorter times, which lead to lower extraction time
and temperature, as compared to the conventional
TV-SPME technique [67]. Such technique offers a
new method to solve the warm of the SPME ber
caused by the heating process needed for separating
the analyte from the matrix avoiding the use of
complicated equipment and the sample is vaporized
totally with lower duration as well as low heat energy.
Additional to that, the total vaporization of the sample
presents highly efciency due to the increasing of the
mass transfer in just one step. In addition to that, it is
possible to use of homemade and commercial SPME
ber, and there is potential for coupling with other
SPME techniques and automation, such as an inside
needle capillary adsorption trap (INCAT) or a needle
trap device (NTD [79].
2.5. Estimation of BTEX Compounds present
in Polluted water using GO-APTES Fiber and
Novel VA-TV-SPME Method
Isomers of benzene, toluene, ethylbenzene and
xylene, all together known as BTEX (Fig.8),
are highly volatile aromatic hydrocarbons and
considered to be among the most serious human
health and environmental risk issues.[32,97-98].
When these organic compounds are exposed
in higher concentrations, they cause a harmful
effects on central nervous systems, respiratory and
skin [89-100]. Leakage of oil pipelines may be
resulted by accidental fuel spills, and the disposal
contamination of oil companies efuents and
petrochemical, such pollutants have been released
into groundwater and other water sources [97].
As a result of that, many analytical methods were
developed such as a consequence, a wide variety
of analytical methods, such as narrow-bore tube
DLLME [38], ultrasound-assisted emulsication
microextraction [101] and in syringe dispersive
liquid–liquid microextraction (IS-DLLME). These
methods have been developed with motive of
extracting and determining of BTEX compounds
from water [102]. For the determination of BTEX
from contaminated water without using ant
additional steps for the extraction and the preparation
of the aqueous samples, microextraction techniques
were used. VA-SPME removed one of the most
partitioning steps in the conventional HS-SPME and
that can increase the speed and the sensitivity of the
method [102]. A novel and reliable microextraction
technique was used for the fast determination of
Fig. 7. Diagram of the VA-TV-SPME Assembly: in [A.] the cap of the sample is
caped in close system while in [B.] the cape of the system is opened
95
A review: Total vaporization solid-phase microextraction Yunes M. M. A. Alsayadi et al
benzene, toluene, ethylbenzene and xylenes (BTEX)
from contaminated water without any extra steps
for the preparation or extraction of the aqueous
sample. Vacuum-assisted-total vaporization-solid-
phase microextraction (SPME) eliminated one of the
partitioning steps in conventional headspace SPME
and caused an increase in the sensitivity and speed
of the method. A special nanocomposite SPME
bre made of grapheme oxide/3-aminopropyl-
triethoxysilane ber was utilize as the extraction
phase to attain an efcient extraction. Numerous
parameters were considered for the optimization,
the extraction time, temperature, and desorption
conditions. The optimized method exposed
acceptable a good validity aspects according to
the ICH guidelines with acceptable range. In this
study, BTEX that present in aqueous samples were
determined by the use of VA-TV-SPME method.
It was observed that effect of adsorption time is
less in the extraction efciency of VA-TV-SPME
[102]. Additional to that, in order to preconcentrate
and extract the analytes, an affordable and home-
made GO-APTES SPME ber was utilized and
it was observed that it has reliable and a powerful
sorbent, compared with that bres obtained from the
market commercially. For achieve a précised analyte
determination, this method was hyphenated with a
GC-FID instrument. According the outcomes of
this method, an analytical parameters such as LDR,
LOD and RSD were within the acceptable range,
and it was observed this method is suitable for the
determination of BTEX in polluted water[32,47,59].
3. Conclusion
The coupling TV with SPME arises from the need
for a technique where a complete vaporing of the
liquid samples gives a fewer matrix effect and better
adsorption. Such a method requires less sample
preparation, utilizes the least supplies, and can be
done automatically, enabling it to be both a cost-
effective and efcient method. TV-SPME is a sensitive
technique where the liquid aliquot is totality vaporized
prior to sampling, easing to attain the equilibria inside
the sample vial and increasing the quantity of analyte
available in the headspace. TV-SPME is an effective
technique for analyzing controlled substances with
and without on-ber derivatization. The approach of
coupling TV and SPME (TV-SPME) offered great
sensitivity and even low detection limits for compounds
present in the hair of tobacco users, such as nicotine
and cotinine. A sample extract needs to be heated until
it gets vaporized, and ber of SPME is utilized for pre-
concentrating analytes from the matrix.
4. Acknowledgement
The authors are heartily thankful to management of
Chandigarh University for constant encouragement,
support and motivation.
Fig. 8. Structures of BTEX
96 Anal. Methods Environ. Chem. J. 5 (3) (2022) 80-102
5. List of abbreviation
TV-SPME: Total Vaporization Solid Phase
microextraction
SPME: Solid Phase Microextraction
GC: Gas Chromatography
HS-SPME: Headspace Solid Phase Microextraction
MOF: Metal-Organic Framework
TATP: triacetone triperoxide
I-SPME: Immersion Solid Phase Microextraction
LC: Liquid Chromatography
IR: Infrared Spectroscopy
UV: Ultraviolet Spectroscopy
TV: Total Vaporization
PAHs: Polycyclic Aromatic Hydrocarbons
LVI: Large-Volume Injection
MS: Mass spectrometry
GC/MS: Gas Chromatography/ Mass Spectrometry
PDMS/DVB: Polydimethylsiloxane-divinylbenzene
LC-MS: Liquid Chromatography- Mass
Spectrometry
TLC: Thin Layer Chromatography
VOCs: Volatile Organic Compounds
BSTFA: Bis(trimethylsilyl)triuoroacetamide
TMCS: Trimethylchlorosilane
GLB: ɣ-butyrolactone
GHB: ɣ-hydroxybutyric acid
DPA: Diphenylamine
NG: Nitroglycerin
ECD: Electron Capture Detector
LOD: Limit of Detection
VA-TV-SPME: Vacuum Assisted Total Vaporization
Solid Phase Microextraction
VA-HS-SPME: Vacuum Assisted Headspace Solid
Phase Microextraction
PDMS: Polydimethylsiloxane
GC-FID: Gas Chromatography Flame Ionization
Detector
CAT: Capillary Adsorption Trap
INCAT: Inside Needle Capillary Adsorption Trap
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