Trends in Analytical Chemistry 80 (2016) 12–29

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Applications of solid-phase microextraction in food analysis

Chang-Hua Xu a,1, Guo-Sheng Chen b,1, Zhen-Hai Xiong a, Yu-Xia Fan a, Xi-Chang Wang a,
Yuan Liu a,*
a
College of Food Science and Technology, Shanghai Ocean University, Shanghai 201306, China
bMOE Key Laboratory of Aquatic Product Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen
University, Guangzhou 510275, China

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

Keywords:
Solid-phase microextraction (SPME), a solvent-free extraction technique, is an effective, cost-saving, ver-
SPME
satile, and easily automated assay for high sample throughput. This paper reviews the application of solid-
Food
Progress
phase microextraction (SPME) for the analysis of flavors/off-flavors in wine, fruits, meats, cereal products
Volatiles and non-volatile compounds such as pesticides, pharmaceuticals and personal care products, endog-
Non-volatiles enous substances and other contaminants in food samples. The future developments and potential
Contaminants applications of SPME methods in food analysis was looked ahead.
© 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 12
2. Solid-phase microextraction ............................................................................................................................................................................................................................ 13
2.1. SPME-fiber coating ................................................................................................................................................................................................................................ 13
2.2. SPME quantification in food analysis .............................................................................................................................................................................................. 13
3. Applications of SPME for food analysis ....................................................................................................................................................................................................... 13
3.1. Volatile compounds of food ............................................................................................................................................................................................................... 13
3.1.1. Flavors ....................................................................................................................................................................................................................................... 13
3.1.2. Off-flavors ................................................................................................................................................................................................................................. 18
3.2. Non-volatile compounds of food ...................................................................................................................................................................................................... 18
3.2.1. Pesticides and other agrochemicals ............................................................................................................................................................................... 18
3.2.2. Pharmaceuticals and personal care products ............................................................................................................................................................. 22
3.2.3. Endogenous substances ...................................................................................................................................................................................................... 23
3.2.4. Other contaminants ............................................................................................................................................................................................................. 24
4. Conclusions and perspectives ......................................................................................................................................................................................................................... 25
Acknowledgements ............................................................................................................................................................................................................................................. 25
References .............................................................................................................................................................................................................................................................. 25

1. Introduction eration process is the most important research and developmental

frontier in modern separation science.
Sample preparation, which is mainly used for analyte enrich- One of the most significant developments in sample prepara-
ment and removal of interfering matrix components, is the critical tion has been, without doubt, solid phase microextraction (SPME),
step in separation science and plays an important role in analyti- a technique first described by Arthur and Pawliszyn in 1990 [1]. SPME
cal chemistry. However, sample preparation process is usually tedious is a solvent-free sample preparation technique and combines sam-
and needs to consume large organic solvent. Developing a green pling, analyte isolation, and enrichment into one step. In this
sample preparation technique with high efficiency and simple op- approach, microquantities of the solid sorbent or liquid polymer in
appropriate format are exposed to the sample. Quantification is based
on the amount of analyte extracted at appropriate conditions [2].
Since its convenience and speed, SPME was implemented by re-
* Corresponding author. Tel: 86-21-61900380; Fax: 86-21-61900365.
E-mail address: yliu@shou.edu.cn (Y. Liu). searchers worldwide in food and drugs analysis, clinical chemistry,
1 These authors contributed equally to this work. biochemistry, forensic medicine and other fields.

http://dx.doi.org/10.1016/j.trac.2016.02.022
0165-9936/© 2016 Elsevier B.V. All rights reserved.
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
Food analyses are important for the evaluation of nutritional
value, the quality control of fresh and processed products, and the
monitoring of food additives and other toxic contaminants. For
example, flavor, being a combination of taste and olfaction, is a crucial
factor in consumer acceptance of foods [3]. However, food samples
are very complex, often containing proteins, fat, salts, acids, bases,
and numerous food additives with different chemical properties. A
large number of analytical tools, especially chromatography, have
been used to analyze the constituents of food in order to control
their quality. Beyond that, considering the complex constituents in
food samples, a novel sample preparation with enhanced efficien-
cy and highly selective extraction is needed to apply in pretreating
food matrices.
With increasing applications in food samples, SPME plays an im-
portant role in food sample pretreatments. Compared to traditional
extraction technology such as Head Space technique (HS), Nitro-
gen Purge and Trap method (NPT), Solid Phase Extraction method
(SPE), Continuous Steam Distillation Extraction method (SDE), and
Supercritical Fluid Extraction method (SFE), SPME has a serial of
aforementioned advantages. Moreover, owing to its unique format
and miniature device design, SPME is feasible to couple with gas
chromatograph (GC), high performance liquid chromatography
(HPLC) and capillary electrophoresis (CE), etc. and capable of full
automation. Therefore, it is feasible to realize fast and high-
throughput test in food sample.
In this article, we review the application of SPME in food anal-
ysis, which makes the whole analysis process more selective, more
sensitive and more environment friendly. These studies include vol-
atile, semi-volatile and non-volatile organic compounds
determination in diverse food samples (wine, juice, fruits, meats,
cereal products, other edible plants and animals). Emphasis is placed
on brief descriptions of the unique capabilities and advantages of
SPME and recently researches have been focused on using differ-
ent modern SPME technique to improve absorption and extraction
for a variety of analytes. Finally, we look ahead to future develop-
ments and potential applications of SPME methods in food analysis.
2. Solid-phase microextraction
Solid-phase microextraction is based on the partitioning of the
analyte between the extracting phase immobilized on a fused-
silica fiber or inner coating and the matrix (air, water, etc.). After
equilibrium is reached or a well-defined time, the absorbed com-
pounds are thermally desorbed by exposing the fiber into the
injection port of a GC or redissolved in an organic solvent for further
HPLC, GC or CE analysis.
2.1. SPME-fiber coating
SPME is an advanced sample pretreatment technique integrat-
ing sampling, extraction, concentration and sample introduction into
a single solvent-free step. The major advantages of SPME are its easy
miniaturization, automation of devices, and its convenience in cou-
pling with chromatographic instruments. The facilitation of high-
quality analytical methods based on SPME technique requires
optimization of the parameters that affect the extraction efficien-
cy, such as extraction-phase chemistry, extraction mode, agitation
method, sample modification (pH, ionic strength, organic solvent
content), sample temperature, extraction time and desorption con-
ditions [4]. Within these parameters, the fiber coating is one of the
most critical factors influencing the performance of SPME methods.
In the past, substantial state of the art technology were proposed
in the fabrication of the optimal SPME coating/fiber/device for food
analysis, such as sol-gel coating [5,6], polypyrrole/sol-gel coating
[7], ionic liquids [8], molecularly-imprinted polymer coating [9], etc.
The suitability of the fiber coating for a specific analyte of interest
13
is determined by the polarity of the coating and its selectivity
towards the analytes of interest in contrast to other matrix com-
ponent. Recently, the new SPME coating materials was summarized
by Xu et al [10].
Food matrix are very complex, often containing proteins, fat, salts,
acids, bases, and numerous food additives with different chemical
properties. Among all the coating materials, PDMS, as a liquid coating
with a smooth, homogeneous surface, suffers less from the irre-
versible fouling effect caused by the matrix components than solid
coatings [11]. This makes the PDMS coating the most robust option
for direct analysis of food sample. However, its sensitivity towards
the analytes of interest was a critical problem. It motivated the mod-
ification of existing commercial SPME-fiber coatings with a thin layer
of PDMS to create a new type of SPME-fiber coating, achieving matrix
compatibility while retaining the original coating sensitivity towards
the analytes of interest [12]. As shown in Fig. 1, The modified SPME-
fiber coating, such as PDMS/DVB, DVB/CAR/PDMS, PDMS/DVB/
PDMS, was demonstrated to possess extraction efficiency and
longevity when directly subjected to a complex matrix [12,13]. There-
fore, these PDMS modified coating were the favored tools for SPME
in food analysis. Beyond PDMS modified coating, other novel fab-
ricated SPME fiber coating will be discussed in the following section.
2.2. SPME quantification in food analysis
The amount extracted by SPME is proportional to the free con-
centration of the analytes in the samples due to the equilibrium
nature of the SPME technique [12],. This principle often causes mis-
conceptions regarding the quantification capabilities of SPME,
especially when dealing with complex matrices, where the abso-
lute recovery of analytes may lie within a small percentage of the
total amount. On this occasion, the choice of a proper calibration
technique is vital for the achievement of accurate quantification.
The most commonly employed calibration approach in food anal-
ysis, where complex matrices are present, is matrix matching to the
unknown sample. A recent review was summarized the SPME quan-
tification methods in food analysis [14,15], thus, the detail of SPME
quantification method was not discussed in this manuscript.
3. Applications of SPME for food analysis
3.1. Volatile compounds of food
3.1.1. Flavors
SPME has been successfully used in the extraction of many dif-
ferent volatile compounds in various foods for analytical purposes
[15–19]. However, there are not standard protocols that can be
adopted for the complex target analytes of various foods. There-
fore, many researchers devoted to investigating the optimum
conditions of SPME to achieve different research purposes.
3.1.1.1. Wine and alcoholic beverage. It can be noticed that SPME has
been more commonly used for the extraction of volatile organic com-
pounds from wine [20–22], liquor [23], brandy [24] and spirits [25].
Fan et al. [26] used an automatic headspace sampling system with
SPME with a 50/30 μm DVB/CAR/PDMS fiber for extraction of vol-
atile compounds of Chinese “Yanghe Daqu” liquors. Cheng et al. [27]
used SPME with a 50/30 μm DVB/CAR/PDMS fiber for aroma ex-
traction in Chinese liquors. According to the strong aroma type,
chemometric analysis methods, such as partial least squares (PLS)
regression and principal component regression (PCR) models de-
veloped to predict the quality grade of liquors, and principal
component analysis (PCA), partial least squares discriminant anal-
ysis (PLS-DA), and stepwise linear discriminant analysis (SLDA), were
used to classify the Chinese liquors from different geographic origins.
Another effort selected 75 μm CAR/PDMS as the fiber coating to
14 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
Fig. 1. (A) Micrograph of the commercial PDMS/DVB coating before extractions. (B) Micrograph of the PDMS/DVB/PDMS coating before extractions. (C) SEM images of the
PDMS/DVB coating after 20 extractions cycles in grape. (D) PDMS/DVB/PDMS coating after over 130 extractions cycles in grape. (SEM surface morphology using 580 × magnification).
Reprinted with permission from ref [13]. Copyright 2010 American Chemical Society.
perform the Headspace SPME for Chinese liquors analysis was re-
ported by Xiao et al. [28] and 86 aroma compounds were confirmed.
Moreover, Wang et al. [29] studied a homemade sol-gel DVB/OH-
TSO fiber to conduct the PMSE procedure, which provided the highest
analytical responses to the volatile compounds compared with com-
mercial fibers. 57 volatile aroma compounds were identified in
Chinese Daohuaxiang liquors. Castro et al. [30] compared rotatory
and continuous LLE and a SPME method using a 85 μm CW-DVB fiber
to determinate volatile compounds of “fino” sherry wine. Both meth-
odologies showed adequate detection and quantitation limits, and
linear ranges for correctly analysing these compounds. Neverthe-
less, the SPME method showed more advantages.
Fiber coating was the core of the SPME technique. Therefore, the
kinds of the selected fiber could influence the performance of SPME
method. Pena et al. [31] found that SPME with a 65 μm CW-DVB
fiber was better than ones with PDMB fiber for extraction of 22 vol-
atile compounds in orujo spirits from a defined geographical origin.
The results showed that the proposed method was more sensitive
(with detection limits between 0.0045 and 0.2399 mg/L), more
precise (with coefficients of variation in the range 0.99–8.18%), and
possessed wider linear range (over more than 1 order of magni-
tude). Sagratini et al. [32] used HP-SPME coupled with GC-MS to
identify 28 volatile chemicals in red wines from two different regions
of Italy. The performances of three different fibers were com-
pared. The results showed that PA fiber and PDMS fiber displayed
different sensitivity for some compounds, but DVB/CAR/PDMS fiber
showed a lower degree of reproducibility. Burin et al. [33] com-
pared six fibers used for SPME to extract heterocyclic compounds
in red wines. The 85 μm CAR/PDMS fiber was the best option for
all heterocyclic compounds. The method allowed the simultane-
ous determination of 24 heterocyclic compounds in the wine and
showed satisfactory repeatability (2.7%–12% of RSD), reproducibil-
ity (2.8%–12% of RSD) and accuracy. Slaghenaufi et al. [34] also
compared five different fibers for SPME to extract five
megastigmatrienone isomers in aged wine. However, the 65 μm
DVB–PDMS fiber resulted in the highest sum of the area of the five
isomers and was considered as the most efficient fiber for extrac-
tion. The research showed the megastigmatrienone content was
dependent on the wine age. Liu et al. [35] reported a homemade
SPME syringe with sol–gel-derived OH-TSO-BMA-DVB fiber used to
transfer the extracted sample to the GC injector for analysis. They
established HS-SPME-GC method to determine the content of the
volatile compounds in red wine. The recoveries obtained ranged from
85.87 to 104.2%, and the relative standard deviation values were
below 9%, which showed satisfactory linearity, precision, detec-
tion limits and accuracy. Fiorini et al. [36] compared three SPME
fibers (DVB/CAR/PDMS, 50/30 μm, gray fiber; PDMS 100 μm, red fiber
and PDMS/DVB 65 μm, blue fiber) for extraction of the volatile com-
pounds in the red wine Vernaccia di Serrapetrona. The gray fiber
was found to be the most efficient fiber for abundant volatiles ex-
traction. The research was in agreement with Riu-Aumatell et al.
[37] and the group [38] used SPME to extract volatiles from beers
and identified and quantified 59 volatile compounds in beers with
DVB/CAR/PDMS fiber. In addition, DVB/CAR/PDMS fiber was also
applied to oak compounds analysis in aged red wines and the de-
tection limits and reproducibility of the proposed method were
excellent [39]. Rebière et al. [40] investigated volatile compounds
within and between vintages of Semillon wines by SPME extrac-
tion. A 50/30 μm DVB/CAR/PDMS fiber was also considered as a
better choice. The research identified 21 volatile compounds and
3-methyl-1-butanol was quantified as the most concentrated vol-
atile compound with 83 and 66 mg L−1 for the 2006 and the 1996
wines, respectively. Beyond the DVB/CAR/PDMS fiber, PDMS fiber
was another widely used fiber. Li et al. [41] identified a total of 41
volatile compounds in Chardonnay dry white wines. However, in
this study, a 100 μm PDMS was adopted as the best fiber to extract
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
volatile compounds. The results indicated that 13 volatile com-
pounds were considered to be the powerful impact odorants of this
wine. The volatiles of German white wine was investigated to verify
botanical origin. Moreover, SPME with a PDMS fiber was used for
extraction and a partial least-squares discriminant analysis (PLS-
DA) model was validated based on the GS-MS data. External samples
were correctly classified for 97% Silvaner, 93% Riesling, 91% Pinot
Gris/Blanc and 80% Müller-Thurgau [42].
Several studies about fruit wine have been reported in recent
years. For example, Headspace (HS) and immersion (IM) SPME tech-
nique for extraction aroma compounds of strawberry wine were
compared [43]. The results found that esters were the major com-
pounds and a total of 17 volatile aroma compounds were identified
in the strawberry wine, including twelve esters, two acids, two ter-
penes and one higher alcohol. SPME with a 50/30 μm DVB/CAR/
PDMS fiber was employed for aroma extraction in apple ciders [44].
Compared with LLE-SAFE, HS-SPME was more sensitive for esters
and highly volatile compounds. Volatile compounds of pineapple
wine were analyzed and also used SPME method for extraction
[45]. In concluded that a 100 μm PDMS coating fiber was the good
choice for analysis of volatile compounds from several pineapple
wine. In this study, eighteen volatiles were identified, including
thirteen esters, four alcohols and one acid. Ethyl octanoate, ethyl
acetate, 3-methyl-1-butanol and ethyl decanoate were the major
constituents. Sun et al. [46] compared the influence of cultivars
on aromatic compounds and polyphenols in cherry wines by HS-
SPME coupled with GC–MS and HPLC. The results showed that
twenty-one aromatic compounds were identified and eleven poly-
phenols were quantified. The calculated results indicated that cherry
cultivars play a decisive role in wine aroma and polyphenol com-
positions. Xiao et al. [47] had extracted 75 volatiles of cherry wines
by HS-SPME with a DVB-CAR-PDMS fiber and analyzed by GC-MS.
They have successfully discriminated nine different cherry wines
based on their sensory properties and aromatic finger printing. Re-
cently, Xiao et al. [48] used SPME method coupled with GC-MS to
confirm and quantify a series of volatile compounds in cherry wines.
They optimized several parameters, including 50/30 μm DVB/CAR/
PDMS fiber, 45 min extraction time and 50°C extraction temperature
for extraction. The LODs, LOQs and precision of the method were
all within the acceptable range. Gallardo-Chacon et al. [49] re-
ported to describe the volatiles retained by lees during second
fermentation of sparkling wines. An optimized SPME with 50/
30 μm DVB/CAR/PDMS fiber was developed and applied to
obtain a wide qualitative profile of lees’ surface volatiles,
from a heterogeneous group of sparkling wines. 57 compounds
were identified or tentatively identified. Bueno et al. [50] develop
an analytical method for the simultaneous determination of free
and bonded forms of wine sensory relevant carbonyls. DVB/PDMS
was used as a SPME fiber and 14 carbonyls were successfully
captured.
The use of SPME for extraction of volatile flavor compounds from
alcoholic beverage was also reported. Khio et al. [51] selected an
85 μm CAR/PDMS fiber for SPME extraction due to its high sensi-
tivity and extraction efficacy. Li et al. [52] studied volatile components
of camel-naizi (CSCN) by SPME-GC/MS. The extraction perfor-
mances of three types of SPME fibers (75 μm CAR/PDMS, 65 μm
PDMS/DVB, and 50/30 μm DVB/CAR/PDMS) were studied and com-
pared. A total of 45 volatile compounds were identified by using
three fibers. Mo et al. [53].compared three types of fibers (PDMS,
CAR/PDMS, and DVB/CAR/PDMS) for the analysis of volatile com-
pounds in Chinese rice wine qu. The DVB/CAR/PDMS fiber was found
to be the most effective for all of the target molecules, whereas the
fewest compounds were extracted by PDMS fiber. Finally, the DVB/
CAR/PDMS fiber was selected for the extraction of the aroma
compounds in Qu, which was consistent with the previous results
[16,54].
15
3.1.1.2. Fruits and juices. Fruit is an important part of plant. It can
be used for food directly or applied in liquor production and candy
production. The flavor emitted from fruits, including alcohols, al-
dehydes, carboxylic esters and ketones, is an important attribute
of fruits quality. In addition, it influences the quality of relative
product such as wines, candy and essential oils. Therefore, study
on the volatile compounds profile of the fruits plays guiding roles
in agriculture, liquor production, candy production and essential oil
industry. Nowadays, SPME can successfully apply to flavors analy-
sis in fruits sample.
Ceva-Antunes et al. [54] compared 50/30 μm DVB/CAR/PDMS,
65 μm CW/DVB, 75 μm CAR/PDMS and 100 μm PDMS fiber for the
volatile composition of ripe siriguela fruits. DVB/CAR/PDMS turned
out to be the more efficient qualitatively and semi-quantitatively
fiber in trapping these compounds. Beaulieu et al. [55] also em-
ployed 50/30 μm DVB/CAR/PDMS fiber to identify volatile and semi-
volatile compounds in five seedless watermelon varieties through
coupling with GC-MS. Ong et al. [56] established SPME coupled with
gas chromatography-time-of-flight mass spectrometry (GC-TOFMS)
method for analysis of volatile compounds in five jackfruit. The 50/
30 μm DVB/CAR/PDMS fiber displayed the largest extraction
efficiency. Wang et al. [57] applied HS-SPME to study the charac-
teristic volatiles of peaches and nectarines at the germplasm level.
They selected 65 μm PDMS/DVB fiber for isolation the volatiles and
total 84 compounds were identified. The study indicated the amount
of total volatiles and certain individual compounds was influ-
enced by years and locations. To investigate the volatile metabolite
profile of Madeira island fruit species, Pereira et al. [58].evaluated
and compared five different commercialized fibers for HS-SPME pro-
cedure, including 85 μm PA, 100 μm PDMS, 65 μm PDMS/DVB, 70 μm
CW/DVB and 85 μm CAR/PDMS. The SPME fiber coated with CW/
DVB offered the highest extraction efficiency in kiwi and papaya
pulps, while the same performance was achieved with PMDS/DVB
fiber in lemon and plum. Gebara et al. [59] investigated volatile com-
pounds on fruits and leaves of Mangifera indica var. coquinho. The
HS-SPME technique was also evaluated by the comparative study
among three fibers: commercial PDMS, NiTi-ZrO2 and NiTi-ZrO2-
PDMS. The fiber NiTi-ZrO2-PDMS showed better sensitivity and
precision and was adopted for the extraction of volatile components.
After long-term natural evolution or artificial cultivation, most
plant species contain different varieties. Fruits from different cul-
tivated varieties vary in color, flavor, size and shape. Flavor, as one
of the most appreciated characteristics of fruit, can be used to dis-
tinguish different types of fruits or cultivars. Moreover, re-harvest
environment, harvest maturity, and post-harvest handling or storage
also affected overall flavor of fruits. Gokbulut et al. [60] deter-
mined the aroma compounds of Malatya apricots using SPME
coupled with GC-MS. Volatiles were extracted by the 75 μm CAR/
PDMS SPME fiber. They found volatiles of apricot cultivars composed
of mainly of aldehydes, alcohols, acetates, esters, terpenes and acids.
The volatile compounds in four selected African star apple fruit va-
rieties were isolated by HS-SPME using 50/30 μm DVB/CAR/PDMS
fiber and identified by GC–MS. A total of 59 compounds were iden-
tified. The result showed the relationship between the apple varieties
and the key volatile compounds [61]. Kraujalyte et al. [62] also used
HS-SPME with a 50/30 μm DVB/CAR/PDMS fiber to extract volatiles
of two berry fruits. Twenty two aroma-active compounds were de-
tected and characterized by the trained panelists in HS-SPME using
GC-O detection frequency analysis. HS-SPME with a 50/30 μm DVB/
CAR/PDMS fiber was also selected for analysis the volatile aroma
compounds in fresh melon fruits by Verzera et al. [63] and for ex-
traction flavor profiles of varieties of muskmelon by Lignou et al.
[64]. Beaulieu et al. [65] studied the aroma, astringency, and flavor
of rabbiteye blueberry. 53 volatile profiles were extracted by SPME
and obtained in five cultivars assayed at four maturities. Steingass
et al. [66] reported HS-SPME-GC/MS was used to detect volatiles
16 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
from pineapple fruits at four ripening stage. And 132 volatiles were
identified, which were extracted using a 65 μm DVB/PDMS fiber.
Multivariate data analysis was developed to assess the effect of dif-
ferent ripening stage and type-freighted. They also studied SPME
as extraction method extracted lactone profiles of pineapple fruits
and identified pineapple at different maturity stage. Five volatiles
were extracted by HS-SPME for 40 min at 50°C without pre-
incubation using a 95 μm Carbon WR/PDMS fiber [67]. The changes
of the volatiles in different Chinese bayberry fruit in different storage
conditions were observed and characterized by Cheng et al. [68] re-
ported that HS-SPME with a 50/30 μm DVB/CAR/PDMS was used
for the extraction and concentration of volatile compounds. 82 vol-
atile compounds (including aldehydes, alcohols, acids, esters,
terpenes and others) were identified and there were significant dif-
ferences in the composition of volatiles among different cultivars.
And the volatile profiles at different storage conditions can be used
for freshness evaluation during storage.
Juice is an important processed goods of fruits. Due to the very
complicated matrix in juice sample, a suitable sample preparation
method is of great concern. Schmutzer et al. [69] employed HS-
SPME-GC-MS to extract and characterize the volatile organic
compounds in apple juice. A 65 μm PDMS fiber was used for SPME
and more than seventy volatile organic compounds were deter-
mined from different chemical families. Llorente et al. [70] also
studied volatile compounds in Asturian apple juices by HS-SPME-
GC-MS method. Three different fiber coatings have been checked
(100 μm PDMS, 65 μm PDMS-DVB and 75 μm CAR-PDMS) and PDMS-
DVB has been presented to be the most suitable one. Fourteen
compounds (esters, aldehydes and alcohols) were determined in ap-
proximately 4 min. Wei et al. [71] compared SDE and SPME to isolate
volatile compounds in noni fruit juice. SPME was useful to recover
low boiling point and low molecular weight compounds; in con-
trast, SDE possessed higher extraction capacity and higher recovery
for polar compounds. SPME and SDE can provide complementary
information. Abdullah et al. [72] developed HS-SPME-GS-MS to
analyze the volatile compounds in starfruit juice. Different exper-
imental parameters were optimized to improve efficiency. A 65 μm
DVB/PDMS fiber was used for adsorption 30 min at 50°C.
Mahattanatawee et al. [73] developed HS-SPME-GS-MS to deter-
mine β-damascenone in orange juice and evaluated the effect of
thermal processing in orange juice. A 50/30 μm DVB/CAR/PDMS was
used for the extraction. The β-damascenone had been quantified
by HS-SPME and they found β-damascenone concentrations in-
creased with increased heat treatment.
3.1.1.3. Meat and meat products. Solid phase microextraction (SPME)
has been demonstrated to be a useful method to extract volatile com-
pounds from meat and meat products [74,75]. Moon et al. group
[76] detected volatile compounds in simulated beef flavor using HS-
SPME method. The four type of SPME fibers of 65 μm PDMS/DVB,
65 μm CW/DVB, 75 μm CAR/PDMS and 50/30 μm DVB/CAR/PDMS
were compared for optimization the SPME condition. The selected
extraction conditions for SPME were as the following: 50/30 μm DVB/
CAR/PDMS fiber; 60 min extraction time and 60°C extraction
temperature. Based upon the established method, they applied the
SPME technique to investigate the volatile components of simu-
lated beef flavor, boiled beef and roasted beef samples. A total of
70 aroma compounds were identified in the simulated beef favor
by combined use of HS-SPME coupled with GC-FID and GC-MS.
While the absence of various aldehydes and ketones resulted in the
subtle difference between the simulated beef favor and cooked beef
[77]. Giuffrida et al. [78] developed the SPME-GC-MS method to
quantify low amounts (μg/g range) of hexanal in beef bouillons. Three
different fibers were compared, including 50/30 μm DVB/CAR/
PDMS, 50/30 μm DVB/CAR and 65 μm PDMS/DVB. The best results
were observed for the DVB/CAR/PDMS fiber (37°C; 40 min).
Watanabe et al. [79] also selected a stable-flex SPME fiber coated
with 50/30 μm DVB/CAR/PDMS for analysis of volatile compounds
in beef fat by SPME-GC-MS. Fifty-three compounds were identi-
fied from only 0.20 g of rendered beef fat, and 76% of these showed
reliable peak size repeatability.
Similar to fruit, the flavors emitted from meats were influ-
enced by types, cultivars, slaughter age and storage, etc. This unique
characteristic facilitates the widely applications of SPME on the eval-
uation of VOCs composition of meats in different cultivars, slaughter
stage or during storage to get more economic benefits. Bhattacharjee
et al. [80] investigated the volatile compounds produced by Sal-
monella typhimurium in the repackaged beef samples (aged and fresh)
using HS-SPME coupled with GC-MS. A 75 μm CAR-PDMS fiber was
used for SPME extraction. The study indicated that Salmonella
typhimurium affected several volatile compounds in fresh and aged
beef. Santander et al. [81] detected 6 volatile organic compounds
in beef, which were extracted by SPME method with a 75 μm CAR-
PDMS fiber. These volatiles data was modeled by using PLS and SVM
classifiers for recognizing age at slaughter of cattle. Argyri et al. [82]
evaluated meat spoilage through the evolution of volatile com-
pounds in the spoilage of minced beef. The volatile compounds of
meat were isolated HS-SPME with a 50/30 μm DVB/CAR/PDMS fiber.
They found that the HS-SPME-GC/MS analysis provided useful in-
formation about a great number of volatile metabolic compounds
detected during meat storage. Rivas-Canedo et al. [83] compared
dynamic headspace (DHS) and solid-phase microextraction (SPME)
as extraction methods for analysis the volatile profile in cooked beef.
SPME with a 50/30 μm DVB/CAR/PDMS fiber was more efficient in
extracting substances such as 1-alcanols, ethyl esters and acids. They
also compared DHE and SPME extraction methods to assess the effect
of the effect of high-pressure treatment on the volatile com-
pounds of low-acid fermented sausage “espetec” and sliced cooked
pork shoulder. SPME extracted more efficiently a large number of
chemical families, especially fatty acids [84]. Watkins et al. [85] used
DHE and SPME techniques to extract volatile compounds in heated
beef and sheep fats. A 50/30 μm DVB/CAR/PDMS fiber was used for
extraction compounds. Around 100 compounds were character-
ized in the volatile profiles using SDE and SPME, which were
observed differences in the volatiles by each extraction technique.
Volatile organic compounds of bovine fresh meat samples were mea-
sured by GC/MS–SPME using four SPME fibers. The result revealed
that the 65 μm PDMS/DVB and 50/30 μm DVB/CAR/PDMS were the
most suitable for extraction of volatile compounds from beef [86].
Some researchers demonstrated that HS-SPME, as a quick, inex-
pensive, solvent-free technique, coupled with GC/MS analysis, was
a method that allows to detect 2-dodecylcyclobutanone (DCB) in
order to distinguish irradiated ground beef from nonirradiated one
[87] or quantify DCB [88]. They both selected PDMS fiber for SPME
extraction. Miks-Krajnik et al. [89] detected chicken breast spoil-
age based on analysis volatile organic compounds using HS-SPME-
GC/MS-FASST. The fibers including 100 μm PDMS, 85 μm PA, 50/
30 μm DVB/CAR/PDMS, and 85 μm CAR/PDMS were compared. The
largest number of volatile peaks and the largest total peak areas were
obtained using DVB/CAR/PDMS fiber and the most promising vol-
atile spoilage markers for chicken breast were EtOH and 3-methyl-
1-butanol, followed by acetic acid (C2) and sulfides. Volatile
compounds of traditional Chinese Nanjing water-boiled salted duck
(NJWSD) during its stages of processing were investigated by HS-
SPME coupled with GC-MS [90]. A 75 μm CAR-PDMS SPME fiber was
selected for extraction according to the previous research [91]. The
results showed that the major volatiles identified were degrada-
tion products of fatty acids, which were considered to account for
the typical flavor of duck meat. Moreover, three different extrac-
tion techniques were compared for determining the flavor profiles
of traditional Chinese Nanjing marinated duck (NJMD), which were
solid phase microextraction (SPME) with a Carb/PDMS fiber, purge
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
and trap (P&T) using Tenax-TA absorbent and simultaneous
distillation–extraction (SDE) in 2007 [92]. Results indicated that SPME
method was better than P&T method, and SPME with SDE method
may well complement each other.
Processed meats, such as hams and salami, are widely con-
sumed around the world. To evaluate the flavors emitted from
processed meats was an important application of SPME. A 75 μm
CAR-PDMS SPME fiber was also selected for extraction of volatile
flavor compounds from Jinhua ham. They studied the changes of
volatile flavor and compounds were studied during the traditional
ageing process of Jinhua ham [93]. Del Pulgar et al. [94] used the
SPME technique with a CAR/DVB/PDMS fiber to extract volatile com-
pounds and the most odor-active compounds of dry-cured Iberian
hams. Jerkovic et al. [95] developed a HS-SPME-GC-MS method for
the analysis of 54 volatile compounds in Istrian dry-cured hams.
PDMS/DVB fiber was used to extract volatiles. Wagner et al. [96]
reported the extraction of volatile compounds in salami by SPME.
The optimal conditions were determined to be an extraction period
of 45 min at 50°C for the extraction of volatile compounds by HS-
SPME with a CAR/PDMS fiber. Lorenzo et al. [97] studied the effect
of fiber coating and extraction time on the volatile profile of dry-
cured loin analyzed by SPME in order to determine the most suitable
conditions for extraction. Two SPME fibers of 75 μm CAR/PDMS and
50/30 μm DVB/CAR/PDMS and three extraction time (15, 30 and
45 min) were compared. Two fibers provide a similar volatile com-
pound profile for dry-cured foal loin and the extraction time
significantly affected DVB/CAR/PDMS fiber. Benet et al. [98] also used
SPME with a 50/30 μm DVB/CAR/PDMS fiber to extract volatile com-
pounds from cooked cured pork ham and analyzed the influence
of the IMF content and the fatty acid saturation profile on cooked
cured pork ham volatiles.
Some researchers reported SPME methods applied to determin-
ing volatile compounds in fish and seafood. The volatile compounds
were evaluated during storage for different sample. Edirisinghe et al.
[99] developed a SPME-GC-MS method to study the changes of
volatiles in fresh yellowfin tuna during storage. SPME was used for
extraction the volatiles coated with a 100 μm PDMS fiber. Xu et al.
[100] also developed HS-SPME-GC-MS method for the study of the
volatile profile characteristics of turbot during refrigerated storage
at 4°C for 20 days in order to find possible markers of freshness or
spoilage. Four fibers of 100 μm PDMS, 75 μm CAR/PDMS, 65 μm
PDMS/DVB and 50/30 μm DVB/CAR/PDMS were compared. DVB/
CAR/PDMS fiber was found to give a good result in terms of relatively
high total peak area in GC-MS chromatogram and extract 61 vol-
atile compounds. The volatile profile characteristics of turbot were
changed at different storage periods. Tuckey et al. [101] reported
on monitoring the changes of volatile organic compounds in
Greenshell™ mussels during chilled storage using HS-SPME-GC-
MS. 65 μm PDMS/DVB fiber was used to extract target volatiles and
9 volatile compounds were found to change in relative concentra-
tion in homogenised mussel meat. Duflos et al. [102] also monitored
the changes of volatile compounds in whiting (Merlangius merlangus),
cod (Gadus morhua) and mackerel (Scomber scombrus) and related
to spoilage by HS-SPME-GC-MS. They selected a 75 μm CAR/
PDMS fiber for SPME extraction and SPME/GC/MS identified 86
compounds, 20 of which could perhaps be used to characterize fresh-
ness. Soncin et al. [103] also selected a 75 μm CAR/PDMS fiber for
SPME extraction volatile compounds of precooked prawn (Penaeus
vannamei) and cultured gilthead sea bream (Sparus aurata) stored
in ice to monitor fish freshness. Chan et al. [104] developed a HS-
SPME-GC-MS method for monitoring the change of the alkylamines
in two chilled and frozen fish species and dimethylamine (DMA)
and trimethylamine (TMA) were opined to be effective chemical in-
dicators for monitoring the freshness of fish.
Analogously, both qualitative and quantitative information are
desired in order to monitor flavor quality and provide quality control
17
for fresh and processed sea food. SPME also shows prominent su-
periority in this field. Iglesias et al. [105] used a 50/30 μm DVB/
CAR/PDMS fiber for the extraction of volatile compounds by HS-
SPME and analyzed volatile compounds by GC-MS, which were
characterized the fresh and frozen-thawed Italian and Spanish cul-
tured gilthead sea bream fish. Iglesias et al. [106] determined
carbonyl compounds in fish by HS-SPME-GC-MS, but selected a
65 μm PDMS-DVB fiber for extraction because linear aldehydes
PDMS-DVB produced higher responses than CAR-PDMS-DVB. They
applied the HS-SPME-GC-MS method to the determination of vol-
atile compounds associated with oxidation of fish muscle. The
different fibers were also compared and a 75 μm CAR/PDMS fiber
was selected for extracting the volatiles. Analysis of volatile com-
pounds could be successfully applied to indicate the oxidative
deterioration in fish muscle [107]. O’Dwyer et al. [108] also used
SPME-GC/MS to determinate volatile compound in order to eval-
uate the oxidative stability of tuna fat. Souza et al. [109] established
a HS−SPME−GC−MS method to quantify the volatile lipid oxida-
tion products (VLOPs) in shrimp during the salting and drying
process. A 50/30 μm DVB/CAR/PDMS fiber was the most adequate
for the extraction of the VLOPs after evaluation four fibers. The salting
and drying negatively affected shrimp quality, reducing the fatty acid
content and increasing the VLOPs, especially hexanal. In addition,
HS-SPME was applied to the extraction volatile compounds in
seafood, such as smoked fish [110], sardine [111], Chinese mitten
crab [112], Alaska Pollock [113], puffer [114] and shrimp head [115].
Different fibers were always compared for optimization of the ex-
traction condition and the selection was different because of the
sample and the target analytes.
3.1.1.4. Cereal products. More than 500 wheat bread volatile com-
pounds have been reported in the literature, which belong to different
chemical classes such as alcohols, aldehydes, ketones, pyrazines and
other N-heterocycles, acids, furans, esters, sulphides and others
[116,117]. Wheat bread volatile compounds have been deter-
mined and extracted with SPME. However, these reports neglected
several important bread odorants or a poor precision in the deter-
mination of some important odorants has been observed [118–123].
An improved method was developed for the analysis of wheat
bread volatile compounds to provide a more complete volatile pro-
files and give more precise information. A 50/30 μm DVB/CAR/
PDMS fiber was used for HP-SPME to extract volatiles from the
headspace of a bread powdered sample. The research concluded that
134 kinds of volatiles were identified [124]. SPME as a fast, solvent-
free technique was also used for analyzing cereal or flour volatile
composition, such as oat [125], barley flour [126], pea flour [127],
kama flour [128], noodle [129] and bread oils [121,125].
Most researchers were focused on volatile compounds in oils
sample. Tu et al. [130].used HS-SPME technique to extract volatile
compounds and analyzed with GC-MS. Based on the data with mul-
tivariate analysis techniques, Edible Oils and Waste Cooking Oil were
classified on the basis of different volatile compounds. Wei et al.
[131] developed a HS-SPME method with a 50/30 μm DVB/CAR/
PDMS fiber combined with GC-MS to identify aroma-active
compounds in flaxseed oils. A total of 60 compounds were tenta-
tively identified and six aroma-active compounds were considered
major contributors to the characteristic flaxseed oils odor. Cecchi
et al. [132] applied HS-SPME-GC-MS to identifying volatile pro-
files of Italian monovarietal extra virgin olive oils. They also selected
a 50/30 μm DVB/CAR/PDMS fiber for SPME extraction and forty-
eight compounds were characterized by GC-MS. Kwon et al. [133]
established a HS-SPME-GC-MS method for the simultaneous char-
acterization and quantitation of pyrazines in perilla seed oils. For
the optimal extraction of pyrazines, a HS-SPME conditions was set
for the absorption time of 20 min at 70°C with a CAR/PDMS fiber.
Fourteen pyrazine compounds were isolated, identified, and quan-
18 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
titated in perilla seed oils. Petersen et al. [134] reported that HS-
SPME-GC-MS was used to identify in total 74 volatile lipid oxidation
compounds altogether in thermally stressed conventional and high-
oleic sunflower oil samples. A 50/30 μm DVB/CAR/PDMS fiber was
used for volatile extraction. Sanchez-Cabrera et al. [135] analyzed
volatile compounds in nine spices by HS-SPME combined with GC-
MS and GC-FID. Four fibers were compared and a 100 μm PDMS fiber
was used because of its stability. They found the evaluation of the
analytical parameters indicating that the method had a high pre-
cision for the analysis of the spices volatile compounds in dry
flavoring. Park et al. [136] analyzed volatiles using SPME with a
65 μm DVB /PDMS fiber in sesame oils at different roasting condi-
tions. Pyrazines were major volatiles in sesame oils and furans,
thiazoles, aldehydes, and alcohols were also detected. Koprivnjak
et al. [137] used HS-SPME with DVB/CAR/PDMS fiber to extract vol-
atile compounds determined by GC-FID in virgin olive oils. Influence
of free fatty acids, sterols and phospholipids on volatile com-
pounds were evaluated, which did not significantly influence the
determination of virgin olive oils volatiles in concentration ranges
considered. Aroma compounds in olive oil were determined by HS-
SPME-GC and two fibers of 100 μm PDMS and 85 μm PA were
compared. They observed that PDMS fiber was capable of extract-
ing the olive oil aroma compounds faster than PA fiber, but PA fiber
was found to be the adequate fiber to perform relative quantifica-
tion of aroma compounds in a non-equilibriumstate in a non-
aqueous sample like olive oil [138]. Volatile compounds in virgin
olive oils from five new cultivars were also analyzed by SPME with
a 100 μm PDMS fiber. Forty five compounds were isolated and char-
acterized by GC-MS and the results indicating the profiles of oleaster
oils were distinctly different from those of European and Tunisian
oil [139]. Kalua et al. [140] developed a HS-SPME-GC method to
monitor volatile compounds in extended time-course experi-
ments of olive oil. A 50/30 μm DVB/CAR/PDMS fiber was used for
extraction volatile compounds. The results demonstrated that the
method could applied to monitor the change in concentration of
selected C6 volatile compound. HS-SPME technique was also re-
ported for analysis and characterization of volatile lipid oxidation
products present in oil-in-water emulsions [141] and fish oil [142].
3.1.2. Off-flavors
Jelen et al. [143] reported the SPME applied to analysis of food
taints and off-flavors in a review. He introduced compounds causing
the taints and off-flavors in food and the application of SPME. Re-
cently, López et al. [144] isolated and evaluated the volatile sulfur
off-flavor compounds in wine by HS-SPME with a 85 μm CAR/
PDMS fiber combined with GC-PFPD. Gomez-Ariza et al. [145]
developed multiple headspace solid-phase microextraction (MHS-
SPME) coupled with GC/MS to determine off-flavors in wine. 100 μm
PDMS fiber and 50/30 μm DVB/CAR/PDMS fiber were compared and
better results were obtained with the latter for haloanisoles deter-
mination. Fan et al. [146] developed a SPME-GC-MS method to
quantify 2-aminoacetophenone (2-AAP) in white wines, which causes
an “atypical aging” or “untypical aging” (UTA) off-flavor. A 50/
30 μm DVB/CAR/PDMS fiber was used for the extraction of 2-AAP
and the distinct off-flavor associated with 2-AAP could be de-
tected when the concentration of 2-AAP reaches 0.5 μg/L. HS-SPME-
GC-MS applied to determinate (E)-2-nonenal in beer was reported
by Scherer et al. [147]. The extractions were carried out in 75 μm
CAR-PDMS fiber and showed a good response to (E)-2-Nonenal. The
method proved to be simple to carry out and could be used in routine
analysis for (E)-2-nonenal for quality control of beer. Campillo et al.
[148] reported that HS-SPME with a 75 μm CAR-PDMS fiber was used
for the determination of volatile organic sulphur and selenium com-
pounds in beers, wines and spirits. Shim et al. [149] developed
method to identified and quantified trimethylamine (TMA) in
spinach, cabbage, and lettuce at alkaline pH by HS-SPME. Six fiber
were compared for a good extraction efficiency and a 65 μm PDMS/
DVB fiber was selected. The results showed that the amount of TMA
formed was dependent on pH. The amount of TMA formed in-
creased dramatically at a pH greater than 9 and was not formed at
a pH lower than 7. Tian et al. [150] developed HS-SPME-GC-MS
method for determination of volatile off-flavor compounds in citral
emulsion. Three types of SPME fibers (65 μm PDMS/DVB, 100 μm
PDMS and 75 μm CAR/PDMS) were compared and 65 μm PDMS/
DVB was chosen as the optimum fiber to obtain the highest
extraction efficiency for seven off-flavor compounds. Bai et al. [151]
reported an in vivo SPME method applied to monitoring the con-
centration of off-flavor compounds (geosmin and 2-methylisoborneol
(2-MIB)) in living fish. The detection limit of in vivo SPME in fish
muscle was 0.12 ng/g for geosmin and 0.21 ng/g for 2-MIB, which
are both below the human sensory thresholds. The HS-SPME-GC-
MS technique was applied to the analysis of the off-flavor compounds
in milk. Vazquez-Landaverd et al. [152] used a 50/30 μm DVB/CAR/
PDMS fiber for extraction the volatile compound. The results
concluded that 2, 3-butanedione, 2-heptanone, 2-nonanone,
2-methylpropanal, 3-methylbutanal, nonanal, decanal, and di-
methyl sulfide could be important contributors to the off-flavor of
UHT milk. Vazquez-Landaverd et al. [153] also determined the vol-
atile sulfur compounds in Milk, which were extracted by HS-
SPME with a 85 μm CAR/PDMS fiber, and analyzed by GC. Seven
sulfur compounds were accurately quantified and Jimenez-Alvarez
et al. [154] characterized and quantified volatile compounds in a
food matrix supplemented with fish oil. The primary oxidation prod-
ucts of long-chain polyunsaturated fatty acids in fish oil degraded
and promoted some volatile compounds. HS-SPME-GC/MS could
monitor lipid oxidation in early stage and c-4-heptenal as a possi-
ble oxidation marker gave rise to off-flavors in a milk.
3.2. Non-volatile compounds of food
3.2.1. Pesticides and other agrochemicals
Pesticides, mainly including organochlorine pesticides (OCP),
organophosphorous pesticides (OPP), carbamate pesticides (CP),
phenyl urea pesticides (PUP) and pyrethroid pesticides (PP) have
been used effectively to control pests, fungi and weeds. Use of pes-
ticides plays a beneficial role in providing large quantities of a low-
cost supply of fruits, vegetables and etc. [155,156], but also be along
with side effects. Pesticides and other agrochemicals may pene-
trate the tissues of fruits, vegetables, etc., where they remain as
residues, result in the contamination of foods, and pose both acute
and chronic health effects to human health due to their toxicity.
Therefore, there is a need to strike a balance between their ex-
pected benefits and possible risks [157]. Hence, their concentration
must always be minimal in fruits and vegetables and must be below
the maximum residue limits. Today, the monitoring of pesticide resi-
dues in food is an objective of high priority in agrochemical research
in order to allow extensive evaluation of food quality and contam-
ination. Therefore, the analysis of pesticide and other agrochemical
residues in food is essential for monitoring and safety purposes.
The sample preparation step is commonly believed to be a most
critical step in the qualitative and quantitative analysis of pesti-
cide and other agrochemical residues in complex food matrices. The
SPME extraction technique has also been adequately applied for the
extraction of pesticides and other contaminants from food matri-
ces with numerous of advantages, including no toxic solvents
involved, short sample preparation time, compatibility with analyte
separation and detection with chromatographic instruments and
amenable to automation, feasibility for the extraction of diverse pes-
ticides and other food contaminants from sample matrices in solid,
liquid, or gaseous state, and linear results for a wide range of analytes,
better consistency and highly quantifiable results from very low
analyte concentrations, small volumes of sample required,
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
relatively low cost and ruggedness, a small size viable for design-
ing portable field-sampling devices. The technique is frequently
chosen for the qualitative and quantitative sample preparation
method for chromatographic (GC, LC) and hyphenated
chromatographic-mass spectrometry analysis (GC-MS, LC-MS, GC-
MS/MS, LC-MS/MS) (Table 1).
Beverages, generally divided into alcoholic beverages and soft
drinks, are very popular with consumers all over the world. There-
fore, to control the quality in beverage sample is vital. Cortes et al.
[178] developed a vanguard-rearguard SPME analytical method
coupled to GC-MS and GC-MS/MS for determining 54 pesticide resi-
dues in natural and commercial orange, peach and pineapple juices.
A fast screening (vanguard) method was firstly implemented for de-
tecting juicy samples containing pesticides at concentrations above
a pre-established cut-off value. The samples were secondly re-
analyzed by a conventional pesticide residue (rearguard) method
to confirm and quantify the pre-detected pesticides. The extrac-
tion process was very simple, fast and semiautomatic and required
only 1 ml of juice sample. The screening step only required 10 min
of SPME extraction and the confirming/quantifying step required
55 min of SPME extraction. The combination of single solvent based
on SPME extractions and GC-MS/MS provided an excellent selec-
tivity and sensitivity with a proven reduction of false positive and
negative cases. Using vanguard-rearguard strategy reduced 50% of
the total time required for determining common juices in a labo-
ratory by a conventional analytical approach. A simple and
environmentally friendly HS-SPME-GC-MS/MS method using a fiber
of polyacrylate (PA) has been proposed by Robles-Molina et al. [171]
for the simultaneous quantification of 32 pesticides in fruit-based
soft-drinks. The proposed method applied a triple quadrupole ana-
lyzer to the multiple reaction monitoring (MRM) acquisition mode
in MS/MS analysis and was successfully applied to the analysis of
26 market purchased fruit-based soft drink samples from Spain and
some other countries. The data presented indicated that the method
yielded good recoveries in the range 75–113% with RSD (%) along
with LODs varied in the ranges of 0.1–180 ng/L for spiked samples
and 1.5–320.8 ng/L for commercial samples.
SPME using PDMS/DVB fibers in combination with sample stack-
ing micellar electrokinetic chromatography (MEKC) was proposed
by Ravelo-Pérez and coworkers [177] for the simultaneous deter-
mination of 11 multi-class pesticides residues (pyrimethanil,
procyrniclone, pirimicarb, metalaxyl, nuarimol, tebufenozide,
fenarimol, azoxystrobin, benalaxyl, penconazole and tetradifon) in
red wines. The combination of two preconcentration procedures
(SPME and reversed-electrode polarity stacking mode (REPSM))
allowed the determination of 10 pesticides in red wines at con-
centrations between 0.049 and 1.69 mg/L (except for pirimicarb) with
recovery values in the range of 90–107%. Multiple homemade red
wine samples from the Canary Islands and two commercial samples
were used to demonstrate the promising potential of the pro-
posed method. Martins et al. [172,173] reported a SPME-GC-MS/
MS method to quantify multi-class pesticides in fortified white wine
and fortified red wine. The proposed method showed good linear-
ity with R2 ≥0.989 for all pesticides, and good limits of detection
(LOD, 0.05–72.35 μg/L) and quantitation (LOQ, 0.16–219.23 μg/L),
much lower than the maximum residue levels (MRL) set by Euro-
pean Regulation for grapes.
Wang et al. [176] applied a home-made sol-gel-derived co-
poly (hydroxy-terminated silicone divinylbenzene) (OH-TSO/DVB)
coating fiber for HS-SPME coupled with GC-NPD to determine 5 or-
ganophosphorus pesticides (OPPs) in pakchoi samples. Compared
with commercial available fibers and OH-TSO SPME fiber, OH-TSO/
DVB fiber showed statistically better enrichment capability for the
5 pesticides. The developed HS-SPME-GC method offers the limits
of detection (LOD) ranging from 0.007 to 0.07 ng/g with recover-
ies of spiked pakchoi samples ranged from 80.74 to 101.47% for every
19
pesticide at each investigated concentration. Analytical methods
(SPME-GC-mu-ECD and SPME-GC-NPD) for the residues of fungi-
cide (boscalid, cyprodinil and fludioxonil) in blueberries were
developed by Munitz [179,180]. The effect of pH values and fiber
coatings were studied. The SPME fiber coating selected was 100 μm
PDMS. Degradation of boscalid, cyprodinil and fludioxonil were
studied in a blueberry field located in Concordia, Argentina, with
fruits from Emerald and Jewel varieties. The degradation of these
fungicides in both blueberry varieties studied followed first-order
rate kinetics for all fungicides, and the half-life for boscalid was 5.3
and 6.3 d for Emerald and Jewel cultivars, respectively, for cyprodinil
was 2.2 and 3.4 d, respectively, and for fludioxonil was 12.7 and 16.3
d, respectively. Saraji et al. [7] prepared a SPME fiber coated with
polypyrrole/sol-gel composite through electrochemical deposi-
tion. Organophosphorus pesticides (OPPs) in cucumber and lettuce
were analyzed to evaluate the SPME composite coating, having
porous surface structure, stable performance in high temperature
and good preparation reproducibility, followed by GC-NPD detec-
tion. The coating exhibited better extraction efficiency than
polypyrrole and commercial SPME fibers, and had LODs of ppb level
and excellent precision and recoveries (80–109%). Wang et al. [163]
applied a sol-gel technique for preparing water-compatible mo-
lecularly imprinted polymer (MIP) for SPME using diazinon as
template and polyethylene glycol as functional monomer. The MIP-
coated fiber demonstrated much larger extraction capability than
the non-imprinted polymer and commercial fibers, and excellent
thermal and chemical stability due to its specific adsorption to
diazinon, rough and porous surface. Excellent capability (LODs,
0.017–0.77 μg/kg; recoveries, 81.2–113.5%) for evaluating OPPs in
spiked cucumber, green pepper, Chinese cabbage, eggplant and
lettuce samples had been proved by developing a MIP-SPME-GC-
NPD approach.
As water and soil pollution have become a global environmen-
tal issues, the vegetation, which could directly contact with polluted
water and soil, may threat human health through the food chain.
Recently, SPME was widely used for contamination monitor in edible
vegetation sample. Chai et al. [175] reported a HS-SPME-GC-ECD
method using 100 μm PDMS fiber for the determination of pesti-
cide residues in fruits (strawberry, star fruit and guava) and
vegetables (cucumber, tomato and pakchoi). The developed HS-
SPME procedure gave a good linear range, accuracy, precision,
detection and quantification limits and was adequate for analysing
pesticide residues in fruits and vegetables. Specifically, the LOD (0.01–
1 μg/L) and the limits of quantification (LOQ, 0.05–5 μg/L) of these
pesticides were far below the maximum residue levels (MRL) regu-
lated in Malaysia. The obtained recoveries for each pesticide ranged
from 71% to 98% at three fortification levels with the RSD less than
5%. Chai et al. [174] also applied the developed HS-SPME-GC-ECD
method to examining the organophosphorus (diazinon, mala-
thion, chloropyrifos, quinalphos, profenofos) and organochlorine
(chlorothalonil, alpha-endosulfan and beta-endosulfan) pesticide resi-
dues in cucumber and strawberry before and after being washed
by different solutions. Compared to sodium carbonate, sodium chlo-
ride and tap water, the results demonstrated that acetic acid was
the most effective solution in removing the residues of the inves-
tigated pesticides from cucumber and strawberry. The effectiveness
of pesticides removal by solution washing was related to water sol-
ubility and vapor pressure properties of pesticides as well. A DI-
SPME-GC-ECD method using a 100 μm PDMS fiber was developed
by Mariani [167] for trace determination of 19 chlorinated pesti-
cides in tomato samples. The LODs ranged from 0.5 to 8 μg/kg, and
the LOQs from 5 to 30 μg/kg with good linearity ranging from 0.97
to 0.9985. Organochlorine pesticides (lindane, heptachlor, aldrin, diel-
drin and endrin) from milk samples were investigated by Merib [159]
using HS-SPME-GC-ECD. A fiber coating DVB/Car/PDMS exhibited
the best extraction efficiency towards the target pesticides. A
Table 1

20
Typical application of SPME to determination of pesticides in food samples

Pesticide class Food matrix Fiber type Mode of Extraction Extraction Chromatographic LOD LOQ Linearity Ref
application time/min temp/°C
type

14 pesticides (multi- Apple, tomatoes, cucumber PDMS, 100 um HS-SPME 34 62 GC-MS 0.35–8.33 μg/kg 1.15–27.76 μg/kg 1 to 500 μg/kg [158]
class) and cabbage ( > 0.99)
OCPs Bovine milk DVB/CAR/PDMS HS-SPME 90 80 GC-ECD 0.5 to 1.2 μg/L [159]
2 OPPs (diazinon and Cucumber, lettuce, apple Polypyrrole/ DI-SPME 30 45 GC–CD–IMS 0.020 and 0.035 g/L 0.05–10 and [160]
fenthion) montmorillonite 0.08–10 g/ L
nanocomposite
4 OCPs Cocoa powder 100 lam HS-SPME GC-MS 2.5 to 500 μg/kg [161]
polydimethylsiloxane
fibers
8 OCPs Water convolvulus and MOF-199/GO fibers HS-SPME 40 80 GC-ECD 2.3–6.9 ng/L [162]
longan
OPPs Cucumber, green pepper, Sol–gel molecularly HS-SPME 30 70 GC-NPD 0.017–0.77 μg/kg [163]
Chinese cabbage, eggplant, imprinted polymer
lettuce

C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29

CPs Apple Carbon nanotubes- DI-SPME 40–60 HPLC-DAD 0.09–6.00 ng/g 0.25- 11.00 ng/g [164]
reinforced hollow fibre
OPPs Cucumber and lettuce Polypyrrole/sol–gel DI-SPME 30 45 GC-NPD 1.5–10 ng/L [7]
composite
OPPs Turnip, green cabbage, PDMS, 100 um HS-SPME 45 70 GC–MS 0.01–2.5 μg/L [165]
French beans, eggplant,
apple, nectarine and grapes
OCPs Asparagus africanus, 100 μm PDMS QuEChERS/ 20 60 GC-ECD 0.102 −1.693 μg /L [166]
Cleome hirta and HS-SPME GC-TOF-MS
Nymphaea nouchali
19 chlorinated Tomatoes PDMS, 100 um DI-SPME GC-ECD 0.5–8 μg/kg 5–30 μg/kg [167]
pesticides
4 pesticides Apple PDMS, 100 um HS-SPME 30 60 GC-MS 0.01–0.2 μg/kg 0.05–1 μg/kg 0.5–50 μg/kg [168]
(Fenobucarb,
diazinon,
chlorothalonil and
chlorpyrifos)
10 pesticides Lettuce Carbowax/ templated DI-SPME 30 22 ± 3 HPLC-DAD 0.8–25.6 μg/kg [169]
(multi-class) resin (CW/TPR)
8 pesticides Tea PDMS, 100 um HS-SPME 70 70 GC-IDMS 1.2–19.6 ng/g [170]
(Multi-class)
32 pesticides Fruit-based soft drinks PA DI-SPME GC-MS/MS 0.1–180 ng/L [171]
(Multi-class)
31 pesticides Fortified white wine and PDMS, 100 um DI-SPME 60 35 GC-MS/MS 0.05–72.35 μg/L 0.16–219.23 μg/L [172,173]
(Multi-class) fortified red wine
OPPs and OCPs Cucumber and strawberry PDMS, 100 um HS-SPME 30 60 GC-ECD 0.01–1 μg/L 0.05–5 μg/L [174]
OPPs and OCPs Strawberry, star fruit and PDMS, 100 um HS-SPME 30 60 GC-ECD 0.01–1 μg/L 0.05–5 μg/L [175]
guava; cucumber, tomato
and pakchoi
OPPs Pakchoi OH-TSO/DVB (Co-poly HS-SPME 50 75 GC-NPD 0.007- 0.07 ng /g [176]
(hydroxy-terminated
silicone
divinylbenzene)
coating)
11 pesticides Red wine PDMS/DVB DI-SPME 143 ambient MEKC 0.049–1.69 μg/L [177]
(multi-class) temperature
54 pesticides Orange, peach and DVB DI-SPME 10 ambient GC-MS/MS 0.6–19.6 μg/L [178]
(Multi-class) pineapple juices temperature

Note: OCP, organochlorine pesticides; OPP, organophosphorous pesticides; CP, carbamate pesticides; phenyl urea pesticides (PUP) and pyrethroid pesticides (PP); PDMS, polydimethylsiloxane; PA, polyacrylate; CAR, Carboxen;
CW, Carbowax; DVB, divinylbenzene; MOF, Metal-organic framework; GO, graphite oxide; HS, headspace; DI, direct immersion; GC, gas chromatography; MS, mass spectrometry; ECD, electron capture detection; TOF, time-of-
flight; NPD, nitrogen-phosphorus detector; IDMS, isotope dilution mass spectrometry; MEKC, micellar electrokinetic chromatography.
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
Doehlert design was used to condition optimization, and an ex-
traction temperature of 80°C and an extraction time of 90 min were
found to be the best conditions to afford satisfactory LODs (0.5 to
1.2 μg/L) and recoveries (>75%). The fiber was tough as a single fiber
was used throughout the study and no damage on coating was
observed.
A headspace solid-phase microextraction/gas chromatography-
isotope dilution mass spectrometry (HS-SPME/GC-IDMS) method
was developed by Feng et al. [170] for determination of
8 pesticides in tea samples. The isotopic labels spiked in
incurred samples were equilibrated for 15 min followed by HS-
SPME, and analytes were absorbed by a 100 μm PDMS fiber for
70 min at 70°C. Compared with the conventional sample prepara-
tion methods, the proposed method has the advantage of being
quick, easy to operate, highly sensitive and also solvent saving. Com-
pared to the traditional external standard method, the optimized
HS-SPME/GC-IDMS method offered improve RSD, good recoveries
(86.7–112.8%) and LODs (1.2–22.1 ng/g), demonstrating its appli-
cability for qualitative and quantitative analysis of pesticides in
tea.
SPME methods coupled to HPLC-DAD were increasingly applied
to determining pesticides in fruits and vegetables. Melo et al. [169]
developed a SPME method coupled to HPLC-DAD for the determi-
nation of 10 pesticides frequently used in lettuce production
(acetamiprid, azoxystrobin, cyprodinil, fenhexamid, fludioxonil, folpet,
iprodione, metalaxyl, pirimicarb, and tolyfluanid). CW/TPR fiber was
selected and response surface methodology based on central com-
posite design was applied to investigating interactions between three
key variables (pH, NaCl% and extraction time) and their optimal
levels. The method was applicable for the quantification of
fludioxonil, folpet, iprodione, azoxystrobin, cyprodinil, fenehexamid,
and tolyfluanid in lettuce at concentrations from 0.8 to 25.6 mg/
kg. The dissipation behavior during days to harvest of folpet and
fenehexamid were investigated after Lettuce samples suffered treat-
ments of the two pesticides. It was found that concentration of the
two pesticides was reducing continuously till not detected at 64 days.
A carbon nanotubes (CNTs)-reinforced hollow fiber (HF) was pre-
pared and applied in SPME-HPLC-DAD approach for determining
five carbamate pesticides in apples [164]. Through adding surfac-
tant, the CNTs were dispersed in water and then held in the HF pores
supported by capillary forces and sonication. The SPME device was
incubated with 1-octanol before being immersed in a stirred apple
samples to extract pesticides. The results obtained under the op-
timized extraction conditions demonstrated that the described
method was efficient for the determination of trace carbamate pes-
ticides in apples.
Obuseng et al. [166] developed dispersive solid phase extrac-
tion in the form of the quick, easy, cheap, effective, rugged and
safe (QuEChERS) method and solid phase microextraction (SPME)
for the cleanup of pesticides in plant samples from the Okavango
Delta (Botswana). Concentration levels of aldrin, 1,1-dichloro-2,4-
bis[chlorophenyl]ethane (DDD), 1,1-dichloro-2,2-bis[p-chlorophenyl]-
ethylene(DDE),1,1-trichloro-2,2-bis[p-chlorophenyl]ethane (DDT),
dieldrin, endosulfan and endrin were investigated using GC-ECD
and confirmed with GC-TOFMS. Recoveries for both QuEChERS and
SPME were in the range 61–95 %. The calibration plots were repro-
ducible and linear (R2 > 0.995) with LODs between 0.102 and
1.693 μg/L for all the pesticides. The optimized QuEChERS and SPME
method were successfully applied to the extraction of pesticides
residues from the edible parts (leaves, roots and/or stems)
of Asparagus africanus, Cleome hirta and Nymphaea nouchali
plants.
A new hybrid material of a copper-based metal-organic frame-
work (MOF-199) and graphite oxide (GO) was used as SPME coating
[162]. The MOF-199/GO fibers with 10% (wt%) GO contents showed
enhanced adsorption affinity to organochlorine pesticides (OCPs)
21
compared to MOF or GO individually and commercial PDMS and
PDMS/DVB fibers. The new fiber was used for HS-SPME-GC-ECD
analysis of eight OCPs in water convolvulus and longan rendering
satisfactory results. A new SPME fiber, polypyrrole/montmorillonite
nanocomposite, was prepared and coupled with gas chromatogra-
phy corona discharge ion mobility spectrometry (GC-CD-IMS) for
the determination of diazinon and fenthion (as model compounds)
in cucumber, lettuce and apple [160]. The fiber exhibited a rather
porous and homogenous surface, and good thermal stability. The
satisfactory LODs of low ppb level and recoveries demonstrated the
capability of the two-dimensional separation technique (reten-
tion time in GC and drift time in IMS) for the analysis of complex
matrices based on SPME extraction.
A HS-SPME-GC-MS method was developed for eleven dedi-
cated OPs assessment in turnip, green cabbage, French beans,
eggplant, apple, nectarine and grapes [165]. Based on range-
specific evaluation, each OP in extracts was characterized by sub-
ppb level sensitivity with a wide 0.01–2.5 mg/L dynamic range.
Effective sample clean-up afforded precise quantification (0.5–
10.9% RSD) within a 70–120% recovery range and the developed
method could be a promising way to deliver international stan-
dards in OP screening routines. Abdulra’uf et al. [168] applied
multivariate strategy to determining the significance of the factors
affecting HS-SPME of pesticide residues (fenobucarb, diazinon,
chlorothalonil and chlorpyrifos) in apples using a randomized fac-
torial design (23 factorial designs). Analytes were extracted with
100 μm PDMS fibers according to the factorial design matrix and
desorbed into a GC-MS detector. The developed method offered
LODs between 0.01 and 0.2 μg/kg and RSD between 0.1% and 13.37%
with average recoveries of 80–105%. Chlorpyrifos, fenitrothion, endo-
sulfan I, and endosulfan II pesticide residues in cocoa powder were
analyzed by Abdulra’uf [161] using HS-SPME-GC-MS based on mul-
tivariate strategy and central composite design and the applied
analytical methodology exhibited good figures of merit. A new
chemometric approach (Plackett-Burman (P-B) design combined
with central composite design (CCD) was employed for the opti-
mization of HS-SPME-GC-MS for the determination of multiclass
pesticide residues in apple, tomatoes, cucumber and cabbage [158].
P-B design was used to estimate/identify the significance of each
factor and CCD was applied to optimizing the significant factors,
for the identification of significant factors. Compared to the con-
ventional HS-SPME-GC-MS method, the chemometric approach
helped to reduce optimization time and improved analytical
throughput.
Since the in vivo sampling-rate calibration was proposed by
Ouyang et al. [181], the in vivo SPME technique was demonstrated
and considered to be an efficient method for contaminants detec-
tion and monitoring in biota [182]. Recently, in vivo SPME was
proposed for contaminants analysis in fish and vegetable samples.
In a recent study, in vivo SPME with 44 PDMS fiber was applied to
studying the impact of nanoparticle on the accumulation/depuration
behaviors of contaminants in crop, mustard (Brassica juncea) (Fig. 2).
The uptake and depuration kinetics of 8 contaminants, including
organochlorine pesticides, organophosphorus pesticides, pyre-
throid insecticides, pharmaceuticals, and personal care products
(PPCPs), were long-time traced the living mustard. The results
showed that an enhancement of contaminant accumulation in living
plants exposed to nanoparticle was observed. Combination with a
series of characterizations, they concluded that nanoparticle can act
as contaminant carriers and be transported to the edible parts of
mustard [183]. Meanwhile, Xu et al. introduced in vivo SPME with
PDMS fiber to trace the uptake and elimination processes of pes-
ticides in living fish. Moreover, the metabolism of fenthion was also
traced with in vivo SPME. Importantly, the method was time-
efficient and laborsaving. Much fewer experimental animals were
sacrificed during the tracing [184].
22 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
Fig. 2. The schematic diagram of in vivo SPME in mustard plant leaf. a) The petiole of mustard plants was pierced with a 26 gauge hypodermic needle to a depth of ap-
proximately 1.4 cm, b) two parallel samplings in both sides of the petiole were conducted at each sampling point, c) the custom-made 44 μm PDMS fiber. Reprinted with
permission from ref [183]. Copyright 2015 Nature Publish Group.
3.2.2. Pharmaceuticals and personal care products
Pharmaceuticals and personal care products (PPCPs) are com-
pounds with special physical and chemical properties that address
the care of animal and human health. Interest in these emerging
contaminants as environmental pollutants has increased rapidly.
Milk, including its related commercial products, is one of the most
popular foods in daily life but sometimes polluted by chemical con-
taminants, such as PPCPs. For example, antibiotics have been widely
used in animal rearing and veterinary practice for therapeutic and
prophylactic purposes [185], which have induced their contami-
nation of milk products. Tylosin in different milk samples was
determined by functionalized TiO2 hollow fiber solid/liquid-phase
microextraction method [186]. The absorbent phase was
functionalized with TiO2 nanoparticles dispersed in organic solvent
and held in the pores and lumen of a porous polypropylene hollow
fiber membrane. Compared with conventional hollow fiber liquid-
phase microextraction, the extraction method showed excellent
extraction efficiency and a high enrichment factor (540.2) for the
isolation and determination of tylosin in milk samples with good
linearity (0.51–7000 mg/L (R2 = 0.991) and LOD (0.21 mg/L). Zhao,
T. et al. [187] recently reported a new SPME technique based on a
new temperature sensitive molecularly imprinted polymer (MIP)
with ofloxacin (OFL) as template. OFL in milk was effiectively ex-
tracted and determined by the proposed SPME coated with the MIP
fiber coupled with HPLC. A new SPME method using crosslinked
polymeric ionic liquid (PIL)-based sorbent coatings was applied to
the extraction of 21 polychlorinated biphenyls (PCBs) from bovine
milk. Due to the incorporation of benzyl moieties of PCBs into the
PIL structures, PIL-based fibers showed higher sensitivities for PCBS
than a commercial 7 mm PDMS fiber using GC-ECD and GC-MS as
detectors. A nanocomposite composed of graphene, cetyl
trimethylammonium bromide (CTAB), and polyaniline was pre-
pared and applied by Abedi [188] to HS-SPME of three tricyclic
antidepressant drugs (TCAs), imipramine, desipramine and clomip-
ramine. The nanocomposite coating had large specific surface
resulting in good mechanical and thermal stability and high ex-
traction efficiency. The develop SPME-GC method was successfully
applied to the extraction and determination of TCAs in milk samples.
PPCPs and their metabolites are typically introduced to the en-
vironment through wastewater treatment plant (WWTP) effluent.
As a result, PPCPs and their metabolites have been measured in
surface waters, sediments, and groundwater at ng/L to μg/L levels.
Inevitably, aquatic products and vegetation have been threaten by
these pollutants. In the last decade, application of SPME for PPCPs
determination in aquatic products and vegetation has increased
rapidly. Wu et al. [189] used one-step microwave-assisted headspace
solid-phase microextraction (MA-HS-SPME) coupled with gas
chromatography-mass spectrometry (GC-MS) to analyze synthet-
ic polycyclic musks, galaxolide (HHCB) and tonalide (AHTN), in oyster
samples. The good precision and accuracy of the developed method
for analyzing trace level of AHTN in oyster samples was demon-
strated as well. Wu et al. [190] also applied MA-HS-SPME-GC-MS
to successfully analyzing synthetic polycyclic and nitro-aromatic
musks with the total concentrations ranged from 2.1 to 23.1 ng/g
in various fish samples. Xu et al. [191] reported a SPME technique
using graphitic carbon nitride (g-C3N4) as a coating material for the
extraction of amphetamine, deltamethrin, nerolidol, dodecane,
ametryn and acrylamide. By GC analysis, g-C3N4 coating showed
superior extraction ability and durability than commercial fibers
(100 mm PDMS and 85 mm CAR/PDMS) due to its loose structure
and unique physicochemical properties. Acrylamide in potato chips
was effectively analyzed by the g-C3N4 SPME fiber coated SPME
coupled to GC-ECD.
Some researchers developed in vivo SPME for PPCPs monitor-
ing in living fishes [192]. For example, Zhang et al. [193] summarized
recent challenges and solutions associated with the application of
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
Fig. 3. Analysis of fluoxetine and its metabolite norfluoxetine in fish by using a novel solid-phase microextraction fiber. Reprinted with permission from ref [198]. Copy-
right 2015 American Chemical Society.
in vivo SPME in freely moving fish, including questions of invasive-
ness, sequential sampling of individual fish, calibration methods,
and interpretation of data and their ecotoxicological relevance. They
also examined spatial and temporal resolution and associated tech-
nical parameters, such as sampling time and dimensions of the SPME
probe. Finally, the application of in vivo SPME for PPCPs monitor-
ing in living fish was evaluated. Relative to other in vivo sampling
techniques, such as microdialysis, in vivo tissue collection or
biosensors. SPME has distinct advantages in its simplicity and its
ability to sample simultaneously various tissues and locations in a
single fish in a relatively non-invasive, timely and cost-effective
manner. In a study by Togunde et al. [194], a new thin film
microextraction (TFME) configuration based on C18 thin film was
optimized to improve SPME sensitivity and extraction kinetics for
in vivo determinations of trace pharmaceuticals in fish tissue, and
C18 TFME phase successfully quantified fluoxetine, venlafaxine,
sertraline, paroxetine, and carbamazapine in muscle of living fish
at concentrations ranging from 1.7 to 259 ng/g. Reproducibility of
the method in spiked fish muscle was 9–18% RSD with limits of de-
tection and quantification ranging from 0.08 to 0.21 ng/g and 0.09
to 0.64 ng/g (respectively) for the analytes examined. The complex-
ity of matrix effects (ME) in food sample, such as fish tissues, is an
issue needing to be considered. An isotopic internal standard (IIS)
method was developed, with the strengths and limitations of the
approach discussed. This study provides a framework for applying
SPME within complex sample systems where the influences of ME
are inevitable, thus ensuring more accurate quantitation of PPCPs
during fish tissues samples [195]. Moreover, Space-Resolved SPME
(SR-SPME) technique utilized miniaturized segmented fibers was
proposed by Zhang et al., and then was simultaneously applied to
PPCPs analysis [196] and relative bioaccumulations [197] in adipose
and muscle tissue of fish. Systematic testing over increasing levels
of in vitro and in vivo complexity demonstrated the feasibility, ac-
curacy, and efficiency of this approach. The segmented design of
the SPME fibers and stepwise successive esorption procedure offer
not only high spatial and temporal resolution but also increased ca-
pability for high-throughput parallel sampling with a single probe,
which suggests the potential for depth-profiling studies in compli-
cated biological systems. Very recently, direct detection of fluoxetine
and its metabolite norfluoxetine in living fish brains was also re-
23
alized for the first time by using a novel solid-phase microextraction
fiber, which was prepared by mixing the polyelectrolyte in the oligo-
mer of silicone rubber and followed by in-mold heat-curing [198].
The polyelectrolyte was finally encased in microcapsules dis-
persed in the cured silicone rubber (Fig. 3). The fiber exhibited
excellent interfiber reproducibility (5.4–7.1%, n = 6), intrafiber re-
producibility (3.7–4.6%, n = 6), and matrix effect-resistant capacity.
Due to the capacity of simultaneously extracting the neutral and
the protonated species of the analytes at physiological pH, the fiber
exhibited high extraction efficiencies to fluoxetine and norfluoxetine.
Beside the fish sample, in vivo SPME was recently expanded for
PPCPs evaluation in vegetable samples. Chen et al. [199], used in
vivo SPME with PDMS fiber to investigate the environmental fates
of synthetic musks in fish and aloes. The validation of the pro-
posed SPME was demonstrated through comparing the extraction
results with liquid extraction method. In this work, the uptake and
elimination behaviors, as well as the transferable capacities, of SMs
in living fish and aloe were revealed. Fish muscle was approximate-
ly 100–2000 times more efficient in accumulating SMs than was
aloe leaf, and nitro musks showed a higher bioaccumulation po-
tential than polycyclic musks in biota. In addition, the transferable
capabilities of SMs by root uptake in aloe were poor. This investi-
gation also showed that both nitro musks and polycyclic musks that
accumulated in biota exhibited excellent elimination rates in clean
water.
3.2.3. Endogenous substances
Except for contaminants analysis, endogenous substances of food
sample, mainly focused on edible plant, were successfully de-
tected by SPME recently, but the relative studies were few. For
instance, a multilayer interparticle linking hybrid MOF-199 SPME
fiber was prepared for plant hormone ethylene analysis in grapes,
wampees, blueberries and durian husks [200]. Furthermore, a new
poly(acrylamide-co-ethylene glycol dimethacrylate) (poly(AM-co-
EGDMA)) coating was prepared for the preconcentration of 24-
epibrassinolide (24-epiBL), which represents a new sixth class of
plant hormones with wide occurrence in plant samples, from pollen
samples [201].
Importantly, the novel SPME probe based on phenylboronic acid
functionalized carbon nanotubes was proposed or ultrasensitive car-
24 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29

Fig. 4. (A) The in vivo sampling procedure in plant tissues with the probe based on phenylboronic acid functionalized carbon nanotubes; (B) biological macromolecules
analysis in the eluent with MALDI-TOF MS; (C) carbohydrate assay in the stem of Malabar spinach and leaf of aloe; (D) in vivo continuous carbohydrate monitoring in aloe
leaf using the proposed probe. Reprinted with permission from ref [202]. Copyright 2016 Royal Society of Chemistry.

bohydrate determination in living aloe leaf without any expensive
enzymes or tedious pretreatment procedure [202] (Fig. 4). The
coating of the proposed probe possessed a 3D interconnected porous
architecture formed by the stacking of CNTs. As a result, the binding
capacity toward carbohydrates was excellent. The proposed ap-
proach was demonstrated to be much superior for most carbohydrate
sensors, including higher sensitivity, wider linear range, and ex-
cellent qualitative ability in multi-carbohydrate systems. Thus, this
approach opens up new avenues for the facile and efficient recog-
nition of carbohydrates in food sample as well as for important
applications such as glycomics.
3.2.4. Other contaminants
Foods can sometimes be contaminated with other pollutants
mainly originating from two aspects: naturally occurring and man-
made hazardous chemicals [185].These contaminants cause threats
to human health in diverse extent, hence it is essential to monitor
them in foods to reduce human health risks.
Polycyclic aromatic hydrocarbons (PAHs), carcinogenic to humans,
can be produced from food processing, packaging materials and other
environmental sources. Robles-Molina et al. [171] applied HS-
SPME method to extracting PAHs in fruit-based soft-drinks. Thirteen
PAHs, extracted in polyacrylate (PA) fiber, were selectively identi-
fied and quantified low to ng/L level by GC-MS/MS) using a triple
quadrupole analyzer in the multiple reaction monitoring (MRM) ac-
quisition mode. Recently, Menezes et al. [203] developed a cold fiber
(CF) SPME sampling method with GC/MS to identify 16 PAHs in
artisanal cachaca. Compared with conventional approaches, the pro-
posed method extracted higher amounts of PAHs in a single
extraction procedure. PAHs in 29 artisanal cachaca samples col-
lected in Brazil were analyzed by this method and the health risks
associated with PAR exposure were assessed by the benzo[a]pyrene
equivalent (BaPeq) value calculation. Finally, different sources of con-
tamination in cachaca were rapidly discriminated by Principal
component analysis (PCA).
Banned dyes have been attracting much attention from food sci-
entists and other related communities due to increasing food safety
occurrences. Banned dyes in food samples can arise from environ-
mental pollutants or illegal adulteration. Tian et al. [204] developed
a two-step SPME technique using a coacervation phase of the anionic
surfactant sodium dodecyl benzene sulfonate and diatomite bonded
Fe3O4 magnetic nanoparticles (DBMNPs) for preconcentration and
extraction of trace amounts of malachite green (MG) in flesh of fish.
The extracted surfactant-rich phase could be readily separated in
a magnetic field and then diluted with ethanol before measuring
its absorbance by spectrophotometer at 624 nm with a linear range
from 2 ng/mL to 180 ng/mL. A new SPME coating with carboxy
graphene (G-COOH) on a stainless steel wire was prepared by Wang
et al. [205] for the determination of methylene blue (MB). This SPME
was coupled to electrochemiluminescence detection of MB to offer
a low LOD of around 45 pM in original samples. Wang et al. [206]
designed a method, ionic liquid-based matrix solid-phase disper-
sion homogeneous liquid-liquid microextraction (IL-based MSPD-
HLLME), specifically for the extraction of four banned dyes (safranine
O, auramine O, chrysoidin and rhodamine B) in condiment samples.
HPLC was applied to separating and selectively determining the four
analytes with LODs between 6.7 and 26.8 mg/kg and LOQs between
15.99 and 58.48 mg/kg. Recently, Wang et al. [207] used new
 C.-H. Xu et al. / Trends in Analytical Chemistry 80 (2016) 12–29
monolithic fibers based on dual functional monomers (octadecyl
methacrylate and vinylimidazole copolymerized with DVB) for the
SPME extraction and determination of sudan dyes (I, II, III and IV)
in tomato sauce and egg yolk samples by coupling with HPLC.
4. Conclusions and perspectives
Solid-phase microextraction, combines sampling, isolation, con-
centration, and enrichment in one step, is a simple and effective
sample preparation technique. It possessed advantages over con-
ventional procedures, such as simple operation, low cost, low solvent
consumption, speed, high enrichment and ease to realize automa-
tion. Owing to the high flexibility, SPME is widely used in the analysis
of volatile/no-volatile compounds in complex matrix, especially in
food sample. As microextraction is one of the most important re-
search and development frontiers in modern sample pretreatment,
it could expect that the applications of SPME technique on food anal-
ysis will be extended to more and more endogenous as well as
exogenous substances in the further.
As well known, the researches on SPME technique are mainly
focused on two aspects. One is the fabrication of novel SPME coating.
Coating material is the core of SPME technique and could directly
determine the sensitivity and selectivity of the method. Novel sorbent
materials such as carbon materials, mesoporous nanomaterials, nano
inorganic oxides, ionic liquids, molecular imprinting polymers, and
mesoporous organicinorganic hybrid materials are usually pos-
sessed of larger specific surface area or controllable pore size, and
there are some interesting nanoscale materials being explored for
applications in fabricating SPME coating. We concluded that the use
of new types of materials or new strategies with novel sorbents for
coating preparation will still be the research hotspot in the further.
Another aspect is expanding the application of SPME tech-
nique. As mentioned above, volatile flavor compounds and some
contaminants are the main analysis objects in food sample. However,
the applications of SPME technique on endogenous non-volatile sub-
stances analysis are relatively rare and less works on the deep
analysis of contaminants behaviors in food sample were reported.
It is remarkable that the sensitivity, selectivity and accuracy of SPME
are the always important tasks to extend the application for en-
dogenous non-volatile substances, especially for the high polar
compounds. The sensitivity and selectivity may be improved by the
novel extraction phase, while the accuracy should be determined
by calibration method. With the increasing concern on food safety
as well as the successful applications of SPME in vitro or in vivo sam-
pling technique on animal studies, it could be expected that the
applications of SPME technique on food analysis will be extended
to the research on the real-time monitoring the accumulation, trans-
portation and metabolism of contaminants.
Acknowledgements
This work was funded by National Natural Science Foundation
of China (Grant No. 30901125, 31540087, 31401571), European
Union project “Sustaining Ethical Aquaculture Trade” (Grant agree-
ment No. 222889), Shanghai Engineering Research Center of Aquatic-
Product Processing & Preservation (Grant No. 11DZ2280300).
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