Accepted Manuscript

Title: A critical review of the state of the art of solid-phase microextraction of

complex matrices I. Environmental analysis

Author: rica A. Souza-Silva, Ruifen Jiang, Angel Rodrguez-Lafuente,

Emanuela Gionfriddo, Janusz Pawliszyn

PII: S0165-9936(15)00162-4
DOI: http://dx.doi.org/doi:10.1016/j.trac.2015.04.016
Reference: TRAC 14464

To appear in: Trends in Analytical Chemistry

Please cite this article as: rica A. Souza-Silva, Ruifen Jiang, Angel Rodrguez-Lafuente,
Emanuela Gionfriddo, Janusz Pawliszyn, A critical review of the state of the art of solid-phase
microextraction of complex matrices I. Environmental analysis, Trends in Analytical Chemistry
(2015), http://dx.doi.org/doi:10.1016/j.trac.2015.04.016.

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 1 A critical review of the state of the art of solid-phase microextraction of complex
2 matrices I. Environmental analysis
3
4 rica A. Souza-Silva a, Ruifen Jiang b, Angel Rodrguez-Lafuente c, Emanuela Gionfriddo a, Janusz Pawliszyn a, *
5
a
6 Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada
b
7 School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, China
c
8 Maxxam Analytics, Mississauga, Ontario, Canada
9
10 HIGHLIGHTS
11
12 Recent developments in solid-phase microextraction (SPME) for complex matrices
13 Part I discusses critically practical SPME strategies in environmental matrices
14 There is special emphasis on the development of new devices for SPME
15 Quantification in complex matrices is related to calibration strategies
16
17 ABSTRACT
18
19 The present review, the first of a series of three, aims to describe recent developments in solid-phase microextraction (SPME)
20 technology in the fields of environmental analysis applied to complex environmental matrices. We offer the reader an introductory,
21 concise discussion of SPME fundamentals followed by a perspective on the most commonly used sample-preparation methods. We
22 give particular attention to a comparison of the more recent SPME developments. We especially emphasize the development of new
23 devices, such as cold fiber and thin films. We address quantitation in complex environmental matrices in this review with a concise
24 discussion on calibration strategies for SPME methods.
25
26 Keywords:
27 Cold fiber
28 Complex matrix
29 Environmental
30 High throughput
31 Pollutant
32 Soil
33 Solid-phase microextraction
34 SPME

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35 Thin-film microextraction
36 Wastewater
37
*
38 Corresponding author. Tel.: +1 (519) 888-4641; Fax: + 1 (519) 746-0435.
39 E-mail address: janusz@sciborg.uwaterloo.ca (J. Pawliszyn)
40
41 1. Introduction and fundamentals
42
43 Nowadays, extensive efforts towards modernization of analytical instrumentation have greatly simplified and at times even
44 eliminated the need for complex, laborious sample-preparation methods prior to analysis. However, in most cases, sample preparation
45 still represents the bottleneck in the pursuit of optimum analytical methodologies. In particular, the determination of trace-level
46 analytes in complex matrices often requires the employment of extensive sample-preparation protocols prior to analysis. Steps often
47 involved in sample preparation include extraction of analytes from the matrix, clean-up and pre-concentration, which are conducted in
48 order to achieve adequate sensitivity for a particular analytical method. As such, simpler sample-preparation regimens are sought not
49 only to decrease the time required to process samples, but also to diminish errors associated with each step of the procedure, as,
50 statistically, the amount of uncertainty in a method is directly related to the number of steps that it contains. Automation of the
51 complete workflow, including sample preparation, also improves reproducibility, while decreasing the labor required to prepare
52 samples.
53 Thus, one of the main goals of sample pre-treatment is to reduce the time and the labor involved in multistep sample-preparation
54 techniques. Introduced in the early 1990s, solid-phase microextraction (SPME) addresses several challenges in traditional sample
55 preparation, as it successfully integrates a number of analytical steps, such as sampling, extraction, pre-concentration, and, in case of
56 gas chromatography (GC) applications, sample introduction for instrumental analysis [1]. Additionally, SPME is a simple, sensitive,
57 time-efficient, cost-effective, reliable, easy-to-automate, portable sample-preparation technique that minimizes solvent consumption.
58 In contrast to conventional exhaustive extraction methods, such as SPE, SPME is a non-exhaustive technique based on the partition
59 equilibrium of the analytes between the sample matrix and the extraction phase. In SPME, the extraction phase can be exposed
60 directly to the sample media (direct immersion, DI) or to its headspace (HS). When the SPME coating is placed directly in contact
61 with the sample, the amount of analyte extracted at equilibrium (ne) can be described as [2]:
62
63 (1)
64 In Equation (1), ne is proportional to the distribution coefficient of the analyte between the coating and sample matrix (Kfs), the
65 volume of the extraction phase (Vf), the volume of the sample (Vs) and the analyte concentration in the sample matrix (Cs). Equation
66 (1) indicates that the amount of analyte extracted onto the coating (ne) is linearly proportional to the analyte concentration in the
67 sample (Cs), which is the analytical basis for quantitative analysis using SPME.

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68 When the sample volume is large enough (Vs >> KfsVf), Equation (1) can be simplified to:
69
70 (2)
71 Equation (2), in practice, denotes that the amount extracted by the coating is directly proportional to the concentration of the sample
72 and completely independent of sample volume. This implication is of the utmost importance, since it denotes the capability of SPME
73 to achieve quantitative results when directly exposed to flowing fluids that, from the environmental point of view, apply in on-site
74 sampling in rivers or lakes, for example, or air analysis.
75 As depicted in Figure 1, pre-equilibrium extraction can also be performed to shorten the time required for analysis. Although
76 extraction equilibrium is not reached, there is still a linear relationship between the amount of analyte extracted onto the fiber and the
77 concentration of analyte in the sample matrix. The time required to reach equilibrium is infinitely long; as such, equilibrium time is
78 assumed to be achieved when 95% of the equilibrium amount of an analyte is extracted from the sample [2,3].
79 The above explanation is a simplified overview on the fundamentals governing the SPME technique. A more comprehensive
80 discussion in terms of theoretical fundamentals of SPME is out of the scope of the present review; however, readers seeking further
81 SPME theory are strongly encouraged to consult the literature [27].
82 The extraction efficiency in SPME techniques can therefore be enhanced by increasing the magnitude of Kfs (chemistry of the
83 extraction phase) and/or by increasing the volume or active surface area of the extraction phase (geometry of the extraction phase).
84 Kfs values play a critical role in the recovery and the distribution of analytes when changing the geometry of the extraction phase is
85 not convenient. Equation (1) takes into account the extraction-phase amount that participates in the extraction process, the entire
86 coating volume (Vf) in liquid coatings [e.g., polydimethylsiloxane (PDMS) and polyacrylate (PA)] and the total surface area (Sa) in
87 solid, porous coatings. This implies that the amount of analytes extracted by solid porous coatings is limited by the number of active
88 sites available for extraction.
89 Although saturation is rarely encountered in most applications of SPME, readers should be aware of this possibility in order to
90 understand better possible bias in results obtained, and to correct their modus operandi accordingly. A direct consequence of coating
91 saturation is inter-analyte competitive adsorption. This phenomenon was first studied for a two-component system, and recently
92 deeply investigated to interpret analyte behavior in complex matrices[8,9].
93 In summary, a mathematical description of the phenomenon can be given by the following equation for a two-analyte system at
94 equilibrium conditions [8]:
95
96 (3)
97 where KA and KB are the adsorption equilibrium constants for the analytes A and B, and
98 represents the maximum concentration of active sites on the coating. and and represent
99 the equilibrium concentrations on the fiber and in the sample of the analyte A and B, respectively.

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100 Considering B as the analyte that induces coating saturation, it possible to notice that, when KB and are large enough to render the
101 term negligible, the amount of analyte A extracted at equilibrium will decrease when the concentration of saturating compound
102 B in the matrix is higher. Saturation of the coating, especially in complex mixtures, may eventually affect the HS-SPME mode more
103 than the DI-SPME mode [9]. This mainly relates to the mass-transfer resistance of the analytes at the interface of the HS/matrix and to
104 their Henrys law constants. Compounds characterized by higher affinities for the coating and high Henrys law constants readily
105 enrich the HS above the matrix and are extracted by the coating, consistently occupying its active sites. By contrast, semi-volatile and
106 hydrophilic analytes bearing higher solubilities in aqueous media display increased mass resistance at the interface between different
107 phases, thus enriching the HS at slower rate. DI extraction provides more balanced coverage in terms of analytes extracted compared
108 to HS sampling, even at pre-equilibrium conditions, because the kinetics of extraction is faster for hydrophilic compounds, while the
109 extraction of hydrophobic compounds will be more affected by their diffusion in the boundary layer surrounding the extraction phase.
110 SPME is available in different configurations, depicted in Figure 2. In its most known configuration, the SPME device consists of
111 an extraction phase coated onto a fused-silica rod. Fiber SPME allows for complete automation of the entire analytical workflow when
112 coupled to GC applications due to the commercialization of autosamplers dedicated to SPME, and its similarity to the common
113 injection syringe used in GC applications [2,10].
114 Automated coupling of SPME to liquid chromatography (LC) was first achieved through the development of in-tube SPME. In
115 contrast to fiber SPME, in-tube SPME consists of an extraction phase coated onto the inner walls of fused-silica tubing [11].
116 The simplified features of SPME contributed to its expanded applications, which, in turn, motivated the ever-growing set of novel
117 advances in SPME sorbents, configurations and applications to a broader scope of sample matrices and analytes.
118 In recent years, a number of review articles on SPME were published [10,1219], addressing topics including calibration [20],
119 environmental analysis [21] and novel devices [12,14,17,2225]. However, in spite of the numerous advantages presented by SPME
120 and the ever-increasing number of reports regarding applications of SPME, analyses of complex matrices impose substantial
121 challenges, especially when dealing with trace-level analytes. For example, the DI of the extraction phase in a complex sample matrix
122 can cause damage to the extraction phase. Fouling of the extraction phase by irreversible adsorption of macromolecules from the
123 sample matrix could not only lead to a substantial decrease in the coating lifetime, but also possibly change the extraction properties of
124 the coating. Carrying the matrix to the instrument may cause matrix effects, so the search for robust SPME coatings to improve the
125 performance of SPME in complex matrices is an active research topic. Additionally, since SPME is an equilibrium technique that
126 extracts free concentrations of analytes, when studying environmental matrices containing solid particulate, extensive binding of
127 analytes to the solid matter might occur, leading to diminished free concentrations of analytes, which, in turn, reduces method
128 sensitivity. In such cases, SPME advances have focused on developing highly-specific extraction phases and implementation of large
129 surface-area SPME devices capable of improved extraction efficiency.
130 We have made a focused effort to provide a critical overview of the most recent advances in terms of development of novel SPME
131 devices and applications within the complex matrices arena, including environmental (Part I), food (Part II) and bioanalysis (Part III).
132 Another topic broadly discussed in the present series of reviews is the concern frequently expressed regarding the ability of SPME to

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133 provide reliable quantitation in complex samples due to its non-exhaustive nature. We classify the detailed discussion presented in this
134 series of reviews by matrix, including a critical discussion of novel fundamental findings, developments, and applications of SPME,
135 including their advantages and disadvantages, thus allowing the reader to make a decision over the most appropriate approaches.
136 In this first part, we discuss critically practical strategies when implementing SPME in complex environmental matrices. From the
137 viewpoint of environmental analysis, SPME has been successfully applied to sampling and analysis of volatile and semi-volatile
138 organic pollutants in environmental samples, including water, air, soil, sludge, and sediments [10,14,15,21,2628].
139 In light of the advantages presented by SPME, compared to traditional sample-preparation methods, especially that SPME can be
140 easily deployed for on-site analysis, the following sections present recent developments and special considerations regarding the
141 application of SPME methods to troublesome environmental matrices, such as wastewater and solid samples.
142
143 2. Soil and sediments
144
145 Soil and sediment are complex sample matrices containing minerals, organic matter, air and water. Organic matter as part of soil
146 composition can be strongly bound to minerals. Extraction from soil matrices is a process in which solutes desorb from the sample
147 matrix and then dissolve into a selected solvent. Traditional sample-preparation methods include Soxhlet extraction (EPA 3540),
148 automated Soxhlet extraction (EPA 3541), supercritical fluid extraction (SFE) (EPA 3560, 3561, 3562), accelerated solvent extraction
149 (ASE), ultrasonic extraction (EPA 3550C), and microwave-assisted extraction (MAE) (EPA 3556). Such methods are time-consuming
150 and tedious, and some of them require large quantities of organic solvents and/or additional devices. Expensive instrumentation, such
151 as microwave and ultrasonic devices, are sometimes required to facilitate desorption of analytes from the soil-matrix pores.
152 The development of SPME provides an alternative sampling tool for solid samples. In soil or sediment sampling, both DI and HS
153 sampling have been reported (Table 1). Two different SPME protocols have been reported for DI soil/sediment sampling. The simplest
154 one consists of directly exposing the coating into a solid matrix without any modifier [29,30]. Analytes present in the soil distribute
155 between the matrix and the fiber coating until equilibrium is reached. However, since the soil sample cannot be agitated and the
156 volume of the SPME fiber is very small, only the analytes located in the vicinity of the fiber coating can be extracted, and the
157 concentration determined may not be representative of the whole sample. Another approach often employed is therefore to prepare a
158 suspension of the solid sample in water. An appropriate amount of water is added into the solid sample to dissolve the analytes
159 contained in the sample before conducting the extraction by SPME fiber [31,32]. The water addition homogenizes the sample and
160 facilitates analyte release from the solid matrix. This procedure is quite effective when the analytes are not too strongly bonded to the
161 matrix. For cases when the analytes/matrix interactions are too strong, organic solvents [3335] or other pre-extraction solvents, such
162 as surfactants [36] or ionic liquid (IL) [37] should be used to facilitate the extraction. The extracted solution can be later diluted in
163 water prior to DI-SPME analysis. To improve further the unbinding of analytes from the solid sample, other techniques {e.g., MAE
164 [37,38] or ultrasonic-assisted extraction (UAE) [39]} were utilized as pre extraction techniques prior to SPME.

Page 5 of 26
165 The major limitation of DI-SPME sampling in soil analysis is the possibility of damaging the fiber coating during agitation due to
166 the high viscosity of the matrix. Conversely, in HS mode, matrix effects can be reduced and the lifetime of the fiber can be improved.
167 In HS sampling, the analytes should be released into the HS before being trapped by the fiber [4043]. Similar to DI-SPME, common
168 strategies used to facilitate the release of analytes from the matrices, so their transport through the HS includes adding modifiers, such
169 as water [4447], and utilizing microwaves [4851] and ultrasound [52] to facilitate the extraction.
170 The simplest way to facilitate the release of analytes from the solid matrix is to increase the sample temperature enough to
171 overcome the energy barrier of desorption of the analytes trapped in the soil pore. However, according to the fundamentals of SPME,
172 an increase in sample temperature results in a low distribution coefficient, leading to decreased sensitivity. In order to improve the HS
173 concentration and the distribution coefficient simultaneously, cold-fiber SPME was introduced (CF-SPME). In this approach the fiber
174 coating is cooled while the sample matrix is heated [53]. This strategy improves the mass-transfer rate of analytes due to the increase
175 in sample-matrix temperature, and, concomitantly, the distribution coefficient is enhanced as the coating temperature is kept low
176 (Figure 3).
177 CF-SPME has been applied to the determination of benzene, toluene, ethylbenzene and xylenes (BTEX), and polycyclic aromatic
178 hydrocarbons (PAHs) from the HS of soil and sediment samples [53]. Results showed that the extraction efficiency was significantly
179 improved with cooling, to the extent that exhaustive extraction was achieved in some cases.
180 Vacuum-assisted SPME is another simple method to improve the extraction kinetics of HS-SPME [5456]. Reported work has
181 shown that the sampling rate can be accelerated by reducing the total pressure of the sample container, especially for compounds with
182 low Henrys law constants. In addition, the equilibrium extracted amount was not affected by the pressure conditions inside the
183 sample container. Vacuum-assisted SPME has been applied for aqueous [5456] and solid samples as raw turkey-meat homogenates
184 [57], showing great potential for sensitive determination of contaminants in solid environmental sample (e.g., soil) in the future.
185 Regarding the choice of fiber coating, both commercially-available and home-made fibers have been reported for soil/sediment
186 sampling (Table 1). Amongst commercial fibers, the polydimethylsiloxane (PDMS) coating is the most commonly employed in such
187 studies, due to its high affinity towards semi-volatile hydrophobic compounds, such as PAHs and pesticides, and its non-porous
188 structure, less prone to matrix effects, caused by the complexity of the soil matrix [58]. However, polyacrylate (PA) is often the
189 coating of choice for relatively polar compounds, such as 2,4,6-trinitrotoluene [29], chlorophenols [48] and organophosphorus
190 pesticides [59]. But, when the sample matrix contains modifiers, such as surfactants, the extraction efficiency may be influenced by
191 the modifier.
192 Pino et al. [36] found that, in a sample matrix containing a micellar medium of polyoxyethylene-10-laurylether, the PA coating
193 provided better extraction efficiency to PAHs than the PDMS coating.
194 The Carboxen/PDMS coating is used for sampling volatile small molecules, such as N2O [30], and BTEX [43], while the
195 PDMS/DVB coating has been reported for global screening of organic pollutants from soil [33] and relatively polar compounds, such
196 as synthetic polycyclic musk [51]. In addition to commercially-available coatings, home-made coatings, such as

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197 diglycidyloxycalix[4]arene [60] and acrylate/ silicone co-polymer [61], were prepared to sample chlorobenzenes and 2-chloroethyl
198 ethyl sulfide in soil samples, respectively. Results showed higher extraction efficiencies compared to PDMS and PA fibers.
199 SPME was also applied to a variety of solid samples, as summarized in Table 1. The majority of applications involved the
200 determination of the widespread organic pollutant PAHs. HS-SPME proved to be an efficient method to extract the low-molecular-
201 weight PAHs [41], while the high-molecular-weight PAHs are difficult to extract due to their low volatility and strong adsorption to
202 particles [36]. However, most high molecular weight PAHs, such as benzo[a]pyrene and benzo[ghi]perylene, are highly toxic and
203 carry a higher risk of carcinogenesis and mutagenesis than low-molecular-weight PAHs [39]. In addition, heavier PAHs are prone to
204 accumulate in solid matrices due to their lipophilic character. Thus, it is imperative to provide reliable methods for the accurate
205 quantification of heavier PAHs in soil samples. For this purpose, DI-SPME has been commonly applied in combination with other
206 extraction methodologies, such as LLE [31,33], UAE [39] and MAE [36,38]. For example, with the help of micellar media and UAE
207 combined to SPME leaded to the simultaneous determination of 16 PAHs in soil sample [39]. SPME coupled with LLE was also
208 reported to be a reliable sample-preparation technique for a broad range of PAHs with different molecular weight [41].
209 The application of SPME for pesticide sampling in solid samples is relatively scarce, probably due to experimental limitations of
210 the technique in soil applications. First, the strong interaction between pesticide molecules and different constituents of sediments
211 requires other strategies to facilitate the desorption of analytes from the solid matrix. Similarly to the strategies used for extraction of
212 PAHs, LLE [32,46,59] and MAE [50] or UAE are usually applied to pre-extract pesticides from the soil and sediment before using
213 SPME. Another limitation of the technique involves calibration, which is difficult due to the complexity of soil matrices, limiting the
214 direct use of external calibration curves. Some authors investigated the effect of soil organic matter or clay content on the recovery of
215 pesticides present in soil; results indicated that the co-extractants from the analyzed media complicated evaporation and diffusion of
216 the pesticides to the SPME fiber during HS-SPME sampling, and the spiked standard calibration curve was found to not be
217 representative of the complex matrix [40,62].
218 Bioavailability of organic contaminants in soil is another popular research area. Exhaustive extraction of contaminants by strong
219 acids, chelating agents and solvents is commonly used. Despite the efficiency of these extraction methods, certain limitations may
220 persist due to destruction, alteration and swelling caused by these methods, adversely impacting the soil structure. Contaminant
221 bioavailability is therefore often overestimated because the exhaustively-extracted amounts are markedly higher than those that can be
222 available for biodegradation by microorganisms.
223 Many alternative non-exhaustive extraction methods have been increasingly adopted in the analysis of volatile and semi-volatile
224 contaminants. Several studies utilized SPME as a tool to predict the bioavailability of PAHs [35,63] organic micropollutants [64],
225 2,4,6-trinitrotoluene [29], and DDT [26] in different soil matrices. The authors determined the soil organic-water distribution
226 coefficients (Koc) and the bioaccumulation concentration (BAC) of organic pollutants on organisms, such as earthworms, and then
227 found the relationship between the Koc and the BAC. Most results demonstrated that SPME is a promising technique to predict the
228 bioavailability of organic compounds in sediment. Conversely, some researchers also questioned the flexibility of using SPME as a
229 surrogate for organisms [33,65]. Bergknut et al. compared the bioavailability of PAHs using different techniques, including SPME and

Page 7 of 26
230 semi-permeable membrane devices, leaching with various solvent mixtures, and found distinct differences between the techniques
231 evaluated. They concluded that it may be difficult to develop a chemical method that is capable of mimicking biological uptake.
232 New developments aiming to improve the sensitivity of SPME in soil sampling include CF-SPME, thin-film microextraction
233 (TFME), and stir-bar sorptive extraction (SBSE). CF-SPME proved to be a promising technique for solid-sample preparation due to
234 utilization of high sample temperatures. Both fundamental and experimental results demonstrated that the extraction efficiency of CF-
235 SPME improved as the sample-matrix temperature increased [66]. In addition, the CF-SPME sampling device has been coupled to
236 autosamplers to achieve full automation and high-throughput analysis.
237 TFME utilizes a piece of membrane with a large surface area-to-volume ratio as extraction phase, which enhances the sensitivity
238 without sacrificing the sampling time [15]. TFME has been used to study the bioavailability or fugacity of hydrophobic compounds in
239 sediments [67,68]; a thin layer of ethylene/vinyl film was coated onto the inner wall of a vial, and sediment sample was directly added
240 into the vial for extraction. After sampling, the analytes absorbed on the thin film were desorbed in hexane before quantification in the
241 analytical instrument.
242 In SBSE, commercially known as Twister, the extraction phase was coated on a magnet stir bar, rendering a volume ~50250 times
243 larger than a typical SPME fiber. Due to the large volume of the extraction phase, the SBSE device has better capacity than SPME
244 coating thus can provide more sensitive determinations of trace-level pollutants in water. SBSE was also reported for sampling
245 organic pesticides and phenolic organic pollutants in soil samples. Since solid samples are difficult to agitate, SBSE was usually
246 coupled with other techniques, such as solvent desorption [32], ultrasonic desorption [69] or pressurized subcritical water extraction
247 [70] as a means to extract compounds from the soil matrices in the solution prior to SBSE.
248
249 2.1. Quantification in soils and sediments
250
251 The concentration of analytes in soil samples can be quantified by traditional calibration methods, including external calibration,
252 standard addition and internal calibration.
253 External calibration involves the preparation of a calibration curve by spiking the standards into an aqueous solution, which can be
254 pure water, the extracted solution, or a simulative solution. By using this method, it is assumed that pre-extraction of organic
255 compounds from the soil matrix is exhaustive. Another method used to prepare external calibration involves the preparation of several
256 standard samples using matrix-matched blank samples, such as uncontaminated soil or certified reference soil. However, despite the
257 straightforward approach of matrix-matched calibration, differences in soil composition can significantly influence the slope of the
258 calibration curves [40], demonstrating that the selection of matrix-match samples is very important in the external calibration method.
259 Where blank matrices of standardized composition are not available, standard addition is the traditional calibration method of
260 choice. The standard-addition method is accomplished by spiking a series of known concentrations of target analytes in the solid
261 sample [51,60] or in its extracts [50] containing the unknown amount of analytes that needs to be quantified. Compared to external

Page 8 of 26
262 calibration, this approach is able to compensate for matrix effects to some extent. The limitation of this method is the relatively large
263 amount of sample at unknown concentration required to prepare the calibration curves.
264 The internal standard (IS) approach involves adding a known concentration of an analyte that is not expected to be present in the
265 matrix to be analyzed. This analyte must mimic the behavior of the investigated analytes during extraction and analysis in order to
266 correct for any possible variation in the matrix composition. Calibration is then done by comparing the ratio of the analyte signals to
267 the IS with a known concentration [39]. This method shows significant advantages, as it takes into account possible matrix variations,
268 such as loss of target analytes during the sample preparation. However, it is difficult to determine suitable compounds to use as ISs;
269 isotopically-labeled ISs are preferable, but they are not usually available for any type of target analyte and are generally expensive.
270 Besides traditional calibration methods, equilibrium calibration and exhaustive calibration methods were also reported for soil-
271 sample quantification [31,33].
272 Equilibrium calibration is based on the relationship between the amount of analyte extracted at equilibrium conditions and the
273 sample-matrix concentration [Equation (1)]. When the distribution coefficient and the sample volume are known, the concentration of
274 analytes in the sample matrix can be calculated by determining the equilibrium extracted amount. The limitations of this method are
275 the long extraction time needed to achieve equilibrium conditions and the difficulties in obtaining accurate distribution coefficients.
276 Exhaustive extraction occurs when more than 95% of the analytes present in the sample matrix has been extracted onto the fiber
277 coating. For fiber SPME, due to the small volume of the extraction phase, exhaustive extraction is unusual. CF-SPME has been
278 reported for exhaustive sampling of BTEX from spiked sediment [72], where the concentration of the sample was determined by
279 dividing the extracted amount by the total amount present in the sample.
280 In addition to using proper calibration methods, a quantitative SPME method must be validated in order to prove its suitability for
281 its intended use. Validation of the method might include comparison of quantitation results with certified values obtained for reference
282 materials. For example, Guerra-Abreu et al. used focused MAE followed by SPME-GC-MS to extract successfully seven PAHs from
283 certified reference sediment BCR-535. Average recoveries for six of the seven certified PAHs were 85101% [38].
284 Similarly, Pino and co-workers developed and validated a method for the determination of PAHs in marine sediments using MAE
285 with a micellar medium combined with SPME and GCMS. The method performed well when analyzing a certified marine sediment
286 (SRM 1941a), obtaining recoveries of 59112% [36].
287
288 3. Wastewater
289
290 Wastewater samples comprise variable amounts of natural dissolved organic matter, non-aqueous phase liquids, solid particles,
291 suspended sediments, inorganic ions and dissolved gases, among others, that make their analysis very challenging. The complexity of
292 wastewater is closely linked to its origin (e.g., industrial, municipal or agricultural) and level of treatment (raw, or primarily or
293 secondarily treated). Sample-preparation techniques such as liquid-liquid extraction (LLE) and solid-phase extraction (SPE) have been
294 routinely used to extract and isolate target compounds from their matrices [75].

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295 LLE is very simple and does not require complex apparatus; it is also frequently used as a sample-preparation technique in many
296 official methods for wastewater analysis. For example, most EPA methods for wastewater samples are based on LLE procedures.
297 Significant efforts towards miniaturization and automation have been made during the past few years in order to overcome traditional
298 LLE disadvantages, but the LLE approaches described in official methods are still laborious, use relatively large quantities of organic
299 solvents and very often need additional steps, such as back-extraction, evaporation, or clean-up procedures. Nevertheless, the main
300 drawback of LLE when applied to the analysis of wastewater samples is the formation of emulsions due to the occurrence of
301 surfactants [75].
302 SPE is replacing LLE in some official methods for drinking-water analysis due to its low consumption of solvents, clean-up, broad
303 selectivity, easy automation (on-line and off-line), and high throughput. SPE disadvantages include carryover in automated systems,
304 and the need for sample pre-treatments, such as filtration or centrifugation, when dealing with matrices with high levels of suspended
305 solids and particulate matter, such as untreated wastewater samples, due to the possibility of cartridge clogging. Moreover, in some
306 cases, SPE-sorption efficiency may not be enough to achieve the required sensitivity [76].
307 SPME, coupled to GC or LC, has also been widely used in wastewater analysis; however, like other sample-preparation techniques,
308 the occurrence of matrix effects still remains a challenge to be addressed. Many intrinsic characteristic of wastewater matrices can
309 influence the extraction efficiency of the SPME process, such as organic content, solid particulate, sediments, pH and ionic strength.
310 As such, the HS mode could be used instead of the DI mode: by avoiding contact between fiber coating and sample, the risk of fiber
311 damage or fouling is eliminated. However, the applicability of HS-SPME is limited to volatile analytes with high Henrys Law
312 constants. In addition, HS-SPME can still lead to relative matrix effects when used in very complex samples, such as non-treated
313 wastewater, due to the binding of organic matter and sample-to-sample variations in pH, ionic strength or soluble organic content.
314 Another major concern in wastewater analysis is sensitivity: one reason is that many target analytes, such as emerging
315 contaminants, are present at very low concentrations; the second reason is the presence of interfering organic compounds. Some
316 efforts have focused on enhancement of SPME efficiency and its application to wastewater samples.
317 TFME, introduced for the first time by Cudjoe and co-workers, is an SPME technology that uses a flat geometry to increase
318 extraction-phase volume and the surface area-sample ratio, which ultimately results in better extraction efficiency and accelerates
319 extraction rate [77]. A mix-mode of C18 and benzenesulfonic acid (SCX) phases for TFME, coupled with desorption electrospray
320 ionization (DESI-MS), was successfully used in the analysis of pharmaceuticals in effluent wastewater samples. The proposed method
321 was faster than the current SPE-LC-MS techniques, but required external calibration with isotopically-labeled ISs [78]. Good
322 sensitivity was obtained, within the ng/L range, despite the serious ion suppression found in wastewater (5090%) compared to pure
323 water. The TFME/DESI-MS method developed was compared to SPE/LC-MS for the analysis of spiked wastewater samples, and the
324 results were found to be slightly different between methods, especially at low spiking levels.
325 In turn, Togunde et al. reported the determination of trace levels of pharmaceuticals in municipal wastewater using an automated
326 C18 TFME and LC-MS/MS analysis. In this case, extraction was performed in a 96-well plate format, and the use of a robotic station
327 allowed a high-degree of automation and high throughput [79].

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328 One of the main areas of SPME research in recent years was the development of new coatings. Novel extraction phases based on
329 nanomaterials, ILs, molecularly-imprinted polymers (MIPs) and single- or multi-walled carbon nanotubes (SWCNTs/MWCNTs) were
330 applied in wastewater analysis (see Table 2). Different techniques, such as dipping, microwave-assisted, electrochemical deposition, or
331 immobilization with epoxy glue, have been proposed to prepare the coatings; however, sol-gel preparation has been the technique of
332 choice for most of the new coatings reported in the literature [8092].
333 Apart from enhanced extraction efficiency and selectivity for the target analytes, the main advantage of novel coatings for
334 wastewater analysis is increased stability in very dirty, complex matrices. Liu and co-workers reported a method for preparation of
335 MWCNTs in fused-silica fibers by strong covalent bonding. The coating showed stability to matrices with high organic content and
336 extreme pH conditions, making it suitable for raw wastewater analysis [90].
337 Similarly, a very selective, stable, solvent-resistant IL-based coating was developed for extraction of polar phenolic environmental
338 estrogens (PEEs) and aromatic amines. It was prepared by the sol-gel technique, allowing for chemical bonding of the IL with the
339 substrate. The performance of this coating was evaluated by analyzing PEEs in sewage waters [82].
340 The efficiency of SPME for acidic or basic compounds strictly depends on the pH of the sample. In wastewater analysis, it is not
341 unusual to deal with these types of compounds, as happens with the analysis of certain emerging contaminants. To address this issue,
342 some new approaches were proposed. Suchara et al. developed a method to change the pH of residual wastewater during extraction of
343 acidic and basic pharmaceuticals. The sample pH was modified during extraction, without pauses, by injecting 900 L of a 0.4 M
344 Na2HPO4 solution with a microsyringe [93]. However, some authors reported that acidic pharmaceuticals could be desorbed when the
345 pH of the sample was made alkali. To overcome this problem, Unceta et al. introduced a new procedure, dual solid-phase
346 microextraction (dSPME), which involved use of two fibers for the extraction of acidic and basic pharmaceuticals on two different
347 aliquots from the same wastewater sample, each aliquot being adjusted at different pH values. After extraction, both fibers were
348 consecutively desorbed in the same desorption solvent and analyzed by LC-MS. Nevertheless, surrogate standards were needed to
349 compensate for absolute matrix effects [94].
350 If sensitive enough, SPME may be performed in pre-equilibrium, shortening the extraction time considerably [4]. Still, the
351 extraction rate can be accelerated by applying microwave radiation, which is a more efficient system than the conventional heat
352 sources. Microwave-assisted HS-SPME was applied for analysis of synthetic musk in domestic and industrial wastewater and for the
353 determination of organophosphate esters in wastewater treatment plant (WWTP)-influent samples [95,96]. In both cases, standard-
354 addition calibration was necessary to compensate for the matrix effect of real samples.
355 Another issue when working with untreated wastewater samples is the risk of fiber damage, with the subsequent loss of extraction
356 efficiency over time caused by solid particles, sediments, or high amounts of organic matter. Very recently, Valls-Cantenys et al.
357 reported the analysis of flame retardants in wastewater samples from different origins by using disposable PDMS rods. These
358 disposable devices allowed the extraction of the samples without previous filtration or centrifugation steps, thus avoiding
359 unintentional loss of analytes. In spite of the simplicity in extraction, the final procedure included desorption in an organic solvent,
360 evaporation to dryness, and reconstitution steps [97].

Page 11 of 26
361
362 3.2. Quantitative SPME in wastewater analysis
363
364 External calibration is not generally advised for SPME analysis of complex, untreated wastewater samples due to occurrence of
365 relative matrix effects. Its applicability should be evaluated by performing recovery studies with spiked real samples. The most
366 successful strategies proposed to overcome matrix-effect issues include, but are not limited to, the use of ISs, standard-addition
367 calibration and matrix normalization.
368 Matrix-matched calibration is often used in order to account for matrix effects when sampling complex matrices; however, its
369 implementation is cumbersome due to the inherent matrix complexity and the variability of wastewater samples. Within the past few
370 years, some novel SPME calibration techniques were developed to overcome the matrix-effect issue, and some of them were
371 successfully used on wastewater applications [20,21].
372 Zhang et al. proposed a kinetic calibration based on the symmetry between the extraction and desorption profiles for the analysis of
373 pharmaceuticals in municipal wastewater effluents [98]. As the matrix was the same for both extraction and desorption, no matrix
374 effects were observed and the analysis of wastewater samples was rapid and accurate. The main advantage of this technique is that it
375 did not require the use of isotopically-labeled standards, as it employed two different fibers for extraction and desorption. By contrast,
376 its main drawback was that it was unsuitable for very heterogeneous matrices because it required that both extractive segments be
377 exposed to exactly the same matrix.
378 A new approach presented by Gil-Garca et al. combined standard-addition calibration with a standardization technique based on a
379 multivariate curve resolution-alternating least-squares algorithm (MCR-ALS) [99]. This combination allowed elimination of a
380 significant matrix effect found in the determination of drugs in wastewater by SPME-LC-DAD and, at the same time, could be used to
381 correct the baseline and to perform the analysis in the presence of interfering compounds.
382 Overviews of the applications of SPME technologies in quantitative and qualitative wastewater analysis can be found in Chapter 8 of
383 Handbook of Solid Phase Microextraction [2] and in the Handbook of Water Analysis [75]. It is also worth mentioning the existence of an official
384 method approved by the US Environmental Protection Agency (USEPA) regarding the use of SPME for determination of PAHs in sediment pore
385 water (Method 8272)[100].
386 The unique properties of SPME have allowed its use in other types of application. For example, SPME has been used to determine
387 partition coefficients and the fraction of contaminants bonded to dissolved organic matter [101,102]. This type of information is
388 important both to study bioavailability of contaminants and to improve wastewater treatments, as contaminants bonded to organic
389 matter are not easily eliminated.
390 Additionally, SPME was also used to evaluate the solute-solute interaction between a steroidal contaminant, estradiol, and organic
391 matter at different pH values [103]. Similarly, Gomes et al. determined the total and free fractions of PAHs in oily wastewater from a
392 fuel station [104]. In these studies, the determination of the free fraction was done by negligible-depletion SPME, which is based on
393 the assumption that the equilibrium between the fiber and the matrix does not significantly change if the amount of analyte extracted is
394 less than 1% of the initial amount in the sample [105].

Page 12 of 26
395 An indirect method for detection of emerging contaminants in surface waters under the influence of wastewater effluents is the
396 application of in vivo SPME. In the first report, a 20-min pre-equilibrium extraction was performed by inserting the SPME fiber into
397 fish muscle [106]. The free and total concentrations of pharmaceuticals were determined in rainbow trout exposed to various
398 concentrations of pharmaceuticals. The method was shown to be robust and was successfully tested on-field, with no harm to the
399 studied animals. Although labeled ISs were not required, pre-equilibrium extractions and desorption in two different animals were
400 necessary for calibration. A second in vivo SPME procedure for detection of various emerging contaminants in wastewater-exposed
401 fish was developed by Wang et al. [107]. In this case, SPME was also used for direct analysis of wastewater samples, and kinetic
402 calibration with pre-loaded deuterated standards was shown to reduce the matrix effect.
403 SPME developments for applications in wastewater analysis have seen substantial growth in the past decade, and we expect efforts
404 will continue towards improving methods and devices. Novel coatings could be developed to increase SPME specificity when used in
405 complex wastewater matrices. We also expect increased interest in coupling SPME with ambient mass spectrometry techniques, such
406 as direct analysis in real time (DART) or desorption electrospray ionization (DESI).
407 The use of SPME devices together with portable instrumentation is an interesting alternative for on-site wastewater analysis. As
408 TFME may also be coupled off-line to GC instrumentation using flexible membranes that are directly desorbed in a thermal
409 desorption unit, their suitability for on-site wastewater analysis could also be explored in the future [15]. In applications, SPME
410 coupled with Orbitrap, time-of-flight (TOF) or similar high-performance MS instrumentation is a powerful tool that can be used in
411 environmental metabolomics and in identification of emerging contaminant by-products in wastewater.
412
413 4. Conclusions
414
415 Environmental analysis is one of the most demanding areas in terms of sensitivity requirements.
416 The overall demand for improvement in analytical methods for environmental analysis has led to the introduction of a new
417 generation of highly-sensitive analytical devices and development of new sample-preparation procedures. Given the great complexity
418 of soil, sediments and wastewater matrices, sample preparation is quite an arduous task.
419 In this context, SPME provides an alternative method for this solid-sample preparation. The fundamental understanding of SPME
420 principles resulted in evolution of the technique towards the development of new extracting materials, configurations and calibration
421 approaches.
422 Despite the fact that some developments are in their infancy, we can see that automation is constantly pushing forward the scope of
423 applications of such devices in environmental analysis in academic and industrial settings.
424 Another important conclusion of this review is that taking advantage of the miniaturized size and the portability of SPME devices
425 greatly facilitates implementation of on-site sampling and eventually on-site analysis when coupled to portable analytical instruments,
426 with the advantage of substantial reduction of errors associated with sample transportation and possible alterations during storage.
427

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428 Acknowledgments
429
430 The authors thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for the financial support.
431
432 References
433
434 [1] C.L. Arthur, J. Pawliszyn, Solid phase microextraction with thermal desorption using fused silica optical fibers, Anal. Chem. 62
435 (1990) 21452148.
436 [2] J. Pawliszyn, Handbook of Solid Phase Microextraction, Chemical Industry Press, Beijing, 2009.
437 [3] J. Ai, Solid Phase Microextraction for Quantitative Analysis in Nonequilibrium Situations, Anal. Chem. 69 (1997) 12301236..
438 [4] C.L. Arthur, L.M. Killam, K.D. Buchholz, J. Pawliszyn, J.R. Berg, Automation and optimization of solid-phase
439 microextraction, Anal. Chem. 64 (1992) 19601966..
440 [5] J. Pawliszyn, Solid Phase Microextraction: Theory and Practice, Wiley-VCH, New York, USA, 1997.
441 [6] J. Pawliszyn, Applications of Solid Phase Microextraction, Cambridge: Royal Society of Chemistry, Cambridge, UK, 1999.
442 [7] J. Ai, Headspace Solid Phase Microextraction. Dynamics and Quantitative Analysis before Reaching a Partition Equilibrium,
443 Anal. Chem. 69 (1997) 32603266..
444 [8] T. Grecki, X. Yu, J. Pawliszyn, Theory of analyte extraction by selected porous polymer SPME fibres, Analyst. 124 (1999)
445 643649..
446 [9] E. Gionfriddo, .A. Souza-Silva, J. Pawliszyn, Headspace versus direct immersion solid phase microex-traction in complex
447 matrices: investigation of analyte behav-ior in multicomponent mixtures-Manuscript in preparation, (2015).
448 [10] S. Risticevic, V.H. Niri, D. Vuckovic, J. Pawliszyn, Recent developments in solid-phase microextraction., Anal. Bioanal.
449 Chem. 393 (2009) 78195..
450 [11] H. Kataoka, Automated sample preparation using in-tube solid-phase microextraction and its application -- a review., Anal.
451 Bioanal. Chem. 373 (2002) 3145..
452 [12] L.B. Abdulrauf, W.A. Hammed, G.H. Tan, SPME Fibers for the Analysis of Pesticide Residues in Fruits and Vegetables: A
453 Review, Crit. Rev. Anal. Chem. 42 (2012) 152161..
454 [13] B. Bojko, E. Cudjoe, G.A. Gomez-Rios, K. Gorynski, R. Jiang, N. Reyes-Garces, et al., SPME - Quo vadis?, Anal. Chim. Acta.
455 750 (2012) 132151..
456 [14] E.A. Souza Silva, S. Risticevic, J. Pawliszyn, Recent trends in SPME concerning sorbent materials, configurations and in vivo
457 applications, TrAC Trends Anal. Chem. 43 (2013) 2436..
458 [15] G. Ouyang, R. Jiang, J. Pawliszyn, Thin-film microextraction offers another geometry for solid-phase microextraction, TrAC
459 Trends Anal. Chem. 39 (2012) 245253.

Page 14 of 26
460 [16] F.S. Mirnaghi, D. Hein, J. Pawliszyn, Thin-Film Microextraction Coupled with Mass Spectrometry and Liquid
461 ChromatographyMass Spectrometry, Chromatographia. 76 (2013) 12151223..
462 [17] A. Spietelun, . Marcinkowski, M. de la Guardia, J. Namienik, Recent developments and future trends in solid phase
463 microextraction techniques towards green analytical chemistry, J. Chromatogr. A. (2013).
464 [18] A. Spietelun, A. Kloskowski, W. Chrzanowski, J. Namienik, Understanding solid-phase microextraction: key factors
465 influencing the extraction process and trends in improving the technique., Chem. Rev. 113 (2013) 166785..
466 [19] F. Zhu, J. Xu, Y. Ke, S. Huang, F. Zeng, T. Luan, et al., Applications of in vivo and in vitro solid-phase microextraction
467 techniques in plant analysis: A review, Anal. Chim. Acta. 794 (2013) 114..
468 [20] G. Ouyang, J. Pawliszyn, A critical review in calibration methods for solid-phase microextraction., Anal. Chim. Acta. 627
469 (2008) 18497..
470 [21] G. Ouyang, J. Pawliszyn, SPME in environmental analysis., Anal. Bioanal. Chem. 386 (2006) 10591073..
471 [22] H. Bagheri, H. Piri-Moghadam, M. Naderi, Towards greater mechanical, thermal and chemical stability in solid-phase
472 microextraction, TrAC Trends Anal. Chem. 34 (2012) 126139..
473 [23] B. Bojko, D. Vuckovic, E. Cudjoe, M.E. Hoque, F. Mirnaghi, M. Wsowicz, et al., Determination of tranexamic acid
474 concentration by solid phase microextraction and liquid chromatographytandem mass spectrometry: First step to in vivo
475 analysis, J. Chromatogr. B. 879 (2011) 37813787.
476 [24] H. Yu, T.D. Ho, J.L. Anderson, Ionic liquid and polymeric ionic liquid coatings in solid-phase microextraction, TrAC Trends
477 Anal. Chem. 45 (2013) 219232..
478 [25] J. Xu, J. Zheng, J. Tian, F. Zhu, F. Zeng, C. Su, et al., New materials in solid-phase microextraction, TrAC Trends Anal. Chem.
479 47 (2013) 6883..
480 [26] H. Fang, X. Chu, X. Wang, G. Pang, Y. Yu, Using matrix solid-phase microextraction (matrix-SPME) to estimate
481 bioavailability of DDTs in soil to both earthworm and vegetables., Arch. Environ. Contam. Toxicol. 58 (2010) 6270..
482 [27] G. Ouyang, K.D. Oakes, L. Bragg, S. Wang, H. Liu, S. Cui, et al., Sampling-rate calibration for rapid and nonlethal monitoring
483 of organic contaminants in fish muscle by solid-phase microextraction., Environ. Sci. Technol. 45 (2011) 77928..
484 [28] J. Liu, H. Wang, N.E. Manicke, J.-M. Lin, R.G. Cooks, Z. Ouyang, Development, characterization, and application of paper
485 spray ionization., Anal. Chem. 82 (2010) 246371..
486 [29] J.M. Conder, T.W. La Point, Solid-phase microextraction for predicting the bioavailability of 2,4,6-trinitrotoluene and its
487 primary transformation products in sediment and water., Environ. Toxicol. Chem. 24 (2005) 105966.
488 [30] S.R. Drescher, S.D. Brown, Solid phase microextraction-gas chromatographic-mass spectrometric determination of nitrous
489 oxide evolution to measure denitrification in estuarine soils and sediments., J. Chromatogr. A. 1133 (2006) 3004..
490 [31] M.T.O. Jonker, S. a Van der Heijden, J.P. Kreitinger, S.B. Hawthorne, Predicting PAH bioaccumulation and toxicity in
491 earthworms exposed to manufactured gas plant soils with solid-phase microextraction., Environ. Sci. Technol. 41 (2007) 7472
492 8.

Page 15 of 26
493 [32] R. Zhao, X. Wang, J. Yuan, T. Jiang, S. Fu, X. Xu, A novel headspace solid-phase microextraction method for the exact
494 determination of organochlorine pesticides in environmental soil samples., Anal. Bioanal. Chem. 384 (2006) 15849..
495 [33] M. Bergknut, E. Sehlin, S. Lundstedt, P.L. Andersson, P. Haglund, M. Tysklind, Comparison of techniques for estimating PAH
496 bioavailability: uptake in Eisenia fetida, passive samplers and leaching using various solvents and additives., Environ. Pollut.
497 145 (2007) 15460..
498 [34] H.-C. Liu, C.-S. Hwu, C.-J. Lu, Effect of surfactant on the estimation by solid phase microextraction of bioavailable pyrene in
499 soil samples, World J. Microbiol. Biotechnol. 27 (2010) 10711076..
500 [35] H.-C. Liu, C.-S. Hwu, K.-C. Chu, C.-J. Lu, Estimation of bioavailability and potential risks of naphthalene in soils with solid
501 phase microextraction, World J. Microbiol. Biotechnol. 26 (2010) 13111316..
502 [36] V. Pino, J.H. Ayala, A.M. Afonso, V. Gonzlez, Micellar microwave-assisted extraction combined with solid-phase
503 microextraction for the determination of polycyclic aromatic hydrocarbons in a certified marine sediment, Anal. Chim. Acta.
504 477 (2003) 8191..
505 [37] V. Pino, J.H. Ayala, V. Gonzlez, A.M. Afonso, Determination of the alkyl- and methoxy-phenolic content in wood extractives
506 by micellar solid-phase microextraction and gas chromatography-mass spectrometry., Talanta. 73 (2007) 50513..
507 [38] L. Guerra-Abreu, V. Pino, J.L. Anderson, A.M. Afonso, Coupling the extraction efficiency of imidazolium-based ionic liquid
508 aggregates with solid-phase microextraction-gas chromatography-mass spectrometry. Application to polycyclic aromatic
509 hydrocarbons in a certified reference sediment., J. Chromatogr. A. 1214 (2008) 239..
510 [39] Y. Wang, J. Zhang, Y. Ding, J. Zhou, L. Ni, C. Sun, Quantitative determination of 16 polycyclic aromatic hydrocarbons in soil
511 samples using solid-phase microextraction., J. Sep. Sci. 32 (2009) 39517..
512 [40] R.D. urovi, T.M. orevi, Effects of soil composition on solid phase microextraction determination of triazine and
513 organophosphorus pesticides, J. Environ. Sci. Heal. Part B. 47 (2012) 851857..
514 [41] G. Orzechowska, R. Kidd, Analysis of Mars analogue soil samples using solid-phase microextraction, organic solvent
515 extraction and gas chromatography/mass spectrometry, Int. J. Astrobiol. 10 (2011) 209219..
516 [42] P. Rearden, P.B. Harrington, Rapid screening of precursor and degradation products of chemical warfare agents in soil by solid-
517 phase microextraction ion mobility spectrometry (SPMEIMS), Anal. Chim. Acta. 545 (2005) 1320..
518 [43] . Ezquerro, G. Ortiz, B. Pons, M.T. Tena, Determination of benzene, toluene, ethylbenzene and xylenes in soils by multiple
519 headspace solid-phase microextraction, J. Chromatogr. A. 1035 (2004) 1722..
520 [44] C. Salgado-Petinal, M. Garcia-Chao, M. Llompart, C. Garcia-Jares, R. Cela, Headspace solid-phase microextraction gas
521 chromatography tandem mass spectrometry for the determination of brominated flame retardants in environmental solid
522 samples., Anal. Bioanal. Chem. 385 (2006) 63744..
523 [45] M. Banar, A. Ozkan, C. Vardar, Characterization of an urban landfill soil by using physicochemical analysis and solid phase
524 microextraction (SPME)-GC/MS., Environ. Monit. Assess. 127 (2007) 33751..

Page 16 of 26
525 [46] S.-M. Chang, R.-A. Doong, Concentration and fate of persistent organochlorine pesticides in estuarine sediments using
526 headspace solid-phase microextraction., Chemosphere. 62 (2006) 186978..
527 [47] C.D. de Souza Silveira, E. Martendal, V. Soldi, E. Carasek, Application of solid-phase microextraction and gas
528 chromatography-mass spectrometry for the determination of chlorophenols in leather., J. Sep. Sci. 35 (2012) 6027..
529 [48] M. Wei, J. Jen, Determination of chlorophenols in soil samples by microwave- assisted extraction coupled to headspace solid-
530 phase microextraction and gas chromatography electron-capture detection, 1012 (2003) 111118.
531 [49] P. Herbert, A.L. Silva, M.J. Joo, L. Santos, A. Alves, Determination of semi-volatile priority pollutants in landfill leachates
532 and sediments using microwave-assisted headspace solid-phase microextraction., Anal. Bioanal. Chem. 386 (2006) 32431..
533 [50] P.N. Carvalho, P.N.R. Rodrigues, F. Alves, R. Evangelista, M.C.P. Basto, M.T.S.D. Vasconcelos, An expeditious method for
534 the determination of organochlorine pesticides residues in estuarine sediments using microwave assisted pre-extraction and
535 automated headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry., Talanta. 76 (2008)
536 11249..
537 [51] S.-F. Wu, W.-H. Ding, Fast determination of synthetic polycyclic musks in sewage sludge and sediments by microwave-
538 assisted headspace solid-phase microextraction and gas chromatography-mass spectrometry., J. Chromatogr. A. 1217 (2010)
539 277681..
540 [52] B. Zygmunt, J. Namiesnik, Solid-phase microextraction-gas chromatographic determination of volatile monoaromatic
541 hydrocarbons in soil., Fresenius. J. Anal. Chem. 370 (2001) 10969.
542 [53] Z. Zhang, J. Pawliszyn, Quantitative Extraction Using an Internally Cooled Solid Phase Microextraction Device, Anal. Chem.
543 67 (1995) 3443..
544 [54] E. Psillakis, A. Mousouraki, E. Yiantzi, N. Kalogerakis, Effect of Henry s law constant and operating parameters on vacuum-
545 assisted headspace solid phase microextraction, J. Chromatogr. A. 1244 (2012) 5560..
546 [55] E. Psillakis, E. Yiantzi, L. Sanchez-prado, N. Kalogerakis, Analytica Chimica Acta Vacuum-assisted headspace solid phase
547 microextraction: Improved extraction of semivolatiles by non-equilibrium headspace sampling under reduced pressure
548 conditions, Anal. Chim. Acta. 742 (2012) 3036. doi:10.1016/j.aca.2012.01.019.
549 [56] E. Psillakis, E. Yiantzi, N. Kalogerakis, Downsizing vacuum-assisted headspace solid phase microextraction, J. Chromatogr. A.
550 1300 (2013) 119126..
551 [57] N.P. Brunton, D.A. Cronin, F.J. Monahan, The effects of temperature and pressure on the performance of Carboxen/PDMS
552 fibres during solid phase microextraction (SPME) of headspace volatiles from cooked and raw turkey breast, Flavour Fragr. J.
553 16 (2001) 294302..
554 [58] A. Jahnke, P. Mayer, Do complex matrices modify the sorptive properties of polydimethylsiloxane (PDMS) for non-polar
555 organic chemicals?, J. Chromatogr. A. 1217 (2010) 476570..
556 [59] F. Zhu, W. Ruan, M. He, F. Zeng, T. Luan, Y. Tong, et al., Application of solid-phase microextraction for the determination of
557 organophosphorus pesticides in textiles by gas chromatography with mass spectrometry., Anal. Chim. Acta. 650 (2009) 2026..

Page 17 of 26
558 [60] X. Li, Z. Zeng, Y. Xu, A solid-phase microextraction fiber coated with diglycidyloxycalix[4]arene yields very high extraction
559 selectivity and sensitivity during the analysis of chlorobenzenes in soil., Anal. Bioanal. Chem. 384 (2006) 142837..
560 [61] M. Liu, Z. Zeng, H. Fang, Preparation and application of the solgel-derived acrylate/silicone co-polymer coatings for
561 headspace solid-phase microextraction of 2-chloroethyl ethyl sulfide in soil, J. Chromatogr. A. 1076 (2005) 1626. .
562 [62] T. Zuliani, G. Lespes, R. Milacic, J. Scancar, M. Potin-Gautier, Influence of the soil matrices on the analytical performance of
563 headspace solid-phase microextraction for organotin analysis by gas chromatography-pulsed flame photometric detection., J.
564 Chromatogr. A. 1132 (2006) 23440. .
565 [63] B. Styrishave, M. Mortensen, P.H. Krogh, O. Andersen, J. Jensen, Solid-phase microextraction (SPME) as a tool to predict the
566 bioavailability and toxicity of pyrene to the springtail, Folsomia candida, under various soil conditions., Environ. Sci. Technol.
567 42 (2008) 13326.
568 [64] L. van der Wal, T. Jager, R.H.L.J. Fleuren, A. Barendregt, T.L. Sinnige, C. a M. Van Gestel, et al., Solid-phase microextraction
569 to predict bioavailability and accumulation of organic micropollutants in terrestrial organisms after exposure to a field-
570 contaminated soil., Environ. Sci. Technol. 38 (2004) 48428.
571 [65] H. a Leslie, T.L. Ter Laak, F.J.M. Busser, M.H.S. Kraak, J.L.M. Hermens, Bioconcentration of organic chemicals: is a solid-
572 phase microextraction fiber a good surrogate for biota?, Environ. Sci. Technol. 36 (2002) 5399404.
573 [66] H.K. Lee, J. Pawliszyn, R. Jiang, E. Carasek, S. Risticevic, E. Cudjoe, et al., Evaluation of a completely automated cold fiber
574 device using compounds with varying volatility and polarity, Anal. Chim. Acta. 742 (2012) 2229. .
575 [67] C.J. Golding, F. a P.C. Gobas, G.E. Birch, Characterization of polycyclic aromatic hydrocarbon bioavailability in estuarine
576 sediments using thin-film extraction., Environ. Toxicol. Chem. 26 (2007) 82936.
577 [68] L.M. Meloche, A.M.H. DeBruyn, S.V. Otton, M.G. Ikonomou, F. a P.C. Gobas, Assessing exposure of sediment biota to
578 organic contaminants by thin-film solid phase extraction., Environ. Toxicol. Chem. 28 (2009) 24753. .
579 [69] J. Llorca-Prcel, M. Martnez-Parreo, E. Martnez-Soriano, I. Valor, Analysis of chlorophenols, bisphenol-A, 4-tert-
580 octylphenol and 4-nonylphenols in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction with in situ
581 derivatisation., J. Chromatogr. A. 1216 (2009) 595561. .
582 [70] R. Rodil, P. Popp, Development of pressurized subcritical water extraction combined with stir bar sorptive extraction for the
583 analysis of organochlorine pesticides and chlorobenzenes in soils., J. Chromatogr. A. 1124 (2006) 8290. .
584 [71] F. Monteil-Rivera, C. Beaulieu, J. Hawari, Use of solid-phase microextraction/gas chromatographyelectron capture detection
585 for the determination of energetic chemicals in marine samples, J. Chromatogr. A. 1066 (2005) 177187.
586 doi:10.1016/j.chroma.2005.01.049.
587 [72] A.R. Ghiasvand, S. Hosseinzadeh, J. Pawliszyn, New cold-fiber headspace solid-phase microextraction device for quantitative
588 extraction of polycyclic aromatic hydrocarbons in sediment., J. Chromatogr. A. 1124 (2006) 3542. .

Page 18 of 26
589 [73] A. Mohammadi, A. Ameli, N. Alizadeh, Headspace solid-phase microextraction using a dodecylsulfate-doped polypyrrole film
590 coupled to ion mobility spectrometry for the simultaneous determination of atrazine and ametryn in soil and water samples.,
591 Talanta. 78 (2009) 110714. .
592 [74] B. Santos, B.M. Simonet, A. Ros, M. Valcrcel, On-line coupling of solid-phase microextraction to commercial CE-MS
593 equipment., Electrophoresis. 28 (2007) 13128. .
594 [75] L.M.L. Nollet, L.S.P. De Gelder, Handbook of Water Analysis, CRC Press, CRC Press: Boca Raton, Florida, 2007.
595 [76] J. Radjenovi, M. Petrovi, D. Barcel, Advanced mass spectrometric methods applied to the study of fate and removal of
596 pharmaceuticals in wastewater treatment, TrAC Trends Anal. Chem. 26 (2007) 11321144.
597 [77] E. Cudjoe, D. Vuckovic, D. Hein, J. Pawliszyn, Investigation of the Effect of the Extraction Phase Geometry on the
598 Performance of Automated Solid-Phase Microextraction, 81 (2009) 42264232..
599 [78] N. Strittmatter, R.-A. Dring, Z. Takts, Analysis of wastewater samples by direct combination of thin-film microextraction
600 and desorption electrospray ionization mass spectrometry., Analyst. 137 (2012) 403744..
601 [79] O.P. Togunde, E. Cudjoe, K.D. Oakes, F.S. Mirnaghi, M.R. Servos, J. Pawliszyn, Determination of selected pharmaceutical
602 residues in wastewater using an automated open bed solid phase microextraction system, J. Chromatogr. A. 1262 (2012) 3442.
603 [80] P. Hashemi, M. Shamizadeh, A. Badiei, P.Z. Poor, A.R. Ghiasvand, A. Yarahmadi, Amino ethyl-functionalized nanoporous
604 silica as a novel fiber coating for solid-phase microextraction, Anal. Chim. Acta. 646 (2009) 15.
605 [81] Z. Gao, W. Li, B. Liu, F. Liang, H. He, S. Yang, et al., Nano-structured polyaniline-ionic liquid composite film coated steel
606 wire for headspace solid-phase microextraction of organochlorine pesticides in water, J. Chromatogr. A. 1218 (2011) 6285
607 6291.
608 [82] M. Liu, X. Zhou, Y. Chen, H. Liu, X. Feng, G. Qiu, et al., Innovative chemically bonded ionic liquids-based solgel coatings as
609 highly porous, stable and selective stationary phases for solid phase microextraction, Anal. Chim. Acta. 683 (2010) 96106.
610 [83] T.-T. Ho, C.-Y. Chen, Z.-G. Li, T.C.-C. Yang, M.-R. Lee, Determination of chlorophenols in landfill leachate using headspace
611 sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatographymass spectrometry,
612 Anal. Chim. Acta. 712 (2012) 7277.
613 [84] M.K.-Y. Li, N.-Y. Lei, C. Gong, Y. Yu, K.-H. Lam, M.H.-W. Lam, et al., An organically modified silicate molecularly
614 imprinted solid-phase microextraction device for the determination of polybrominated diphenyl ethers, Anal. Chim. Acta. 633
615 (2009) 197203.
616 [85] J. Huang, Y. Hu, Y. Hu, G. Li, Development of metal complex imprinted solid-phase microextraction fiber for 2,2-dipyridine
617 recognition in aqueous medium, Talanta. 83 (2011) 17211729.
618 [86] S. Xu, X. Zhang, Y. Sun, D. Yu, Microwave-assisted preparation of monolithic molecularly imprinted polymeric fibers for
619 solid phase microextraction., Analyst. 138 (2013) 29827..
620 [87] A. Sarafraz-Yazdi, Z.R. Dizavandi, A. Amiri, Determination of phenolic compounds in water and urine samples using solid-
621 phase microextraction based on solgel technique prior to GC-FID, Anal. Methods. 4 (2012) 4316. doi:10.1039/c2ay25970b.

Page 19 of 26
622 [88] Z. Eshaghi, Z. Rezaeifar, G.-H. Rounaghi, Z.A. Nezhadi, M.A. Golsefidi, Synthesis and application of a novel solid-phase
623 microextraction adsorbent: Hollow fiber supported carbon nanotube reinforced solgel for determination of phenobarbital,
624 Anal. Chim. Acta. 689 (2011) 122128.
625 [89] Q. Li, X. Ma, D. Yuan, J. Chen, Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes
626 for the determination of benzene, toluene, ethylbenzene, xylenes in aqueous samples, J. Chromatogr. A. 1217 (2010) 2191
627 2196.
628 [90] H. Liu, J. Li, X. Liu, S. Jiang, A novel multiwalled carbon nanotubes bonded fused-silica fiber for solid phase microextraction
629 gas chromatographic analysis of phenols in water samples, Talanta. 78 (2009) 929935.
630 [91] W. Zhang, Y. Sun, C. Wu, J. Xing, J. Li, Polymer-functionalized single-walled carbon nanotubes as a novel sol-gel solid-phase
631 micro-extraction coated fiber for determination of poly-brominated diphenyl ethers in water samples with gas chromatography-
632 electron capture detection., Anal. Chem. 81 (2009) 291220..
633 [92] K. Farhadi, R. Tahmasebi, R. Maleki, Preparation and application of the titania solgel coated anodized aluminum fibers for
634 headspace solid phase microextraction of aromatic hydrocarbons from water samples, Talanta. 77 (2009) 12851289.
635 [93] E.A. Suchara, D. Budziak, E. Martendal, L.L.F. Costa, E. Carasek, A combination of statistical and analytical evaluation
636 methods as a new optimization strategy for the quantification of pharmaceutical residues in sewage effluent, Anal. Chim. Acta.
637 613 (2008) 169176.
638 [94] N. Unceta, M.C. Sampedro, N.K.A. Bakar, A. Gmez-Caballero, M.A. Goicolea, R.J. Barrio, Multi-residue analysis of
639 pharmaceutical compounds in wastewaters by dual solid-phase microextraction coupled to liquid chromatography electrospray
640 ionization ion trap mass spectrometry, J. Chromatogr. A. 1217 (2010) 33923399.
641 [95] Y.-C. Wang, W.-H. Ding, Determination of synthetic polycyclic musks in water by microwave-assisted headspace solid-phase
642 microextraction and gas chromatography-mass spectrometry, J. Chromatogr. A. 1216 (2009) 68586863.
643 [96] Y.-C. Tsao, Y.-C. Wang, S.-F. Wu, W.-H. Ding, Microwave-assisted headspace solid-phase microextraction for the rapid
644 determination of organophosphate esters in aqueous samples by gas chromatography-mass spectrometry, Talanta. 84 (2011)
645 406410.
646 [97] C. Valls-Cantenys, E. Villaverde-de-Sa, R. Rodil, J.B. Quintana, M. Iglesias, V. Salvad, et al., Application of
647 polydimethylsiloxane rod extraction to the determination of sixteen halogenated flame retardants in water samples, Anal. Chim.
648 Acta. 770 (2013) 8593.
649 [98] X. Zhang, K.D. Oakes, D. Luong, C.D. Metcalfe, J. Pawliszyn, M.R. Servos, Kinetically-calibrated solid-phase microextraction
650 using label-free standards and its application for pharmaceutical analysis., Anal. Chem. 83 (2011) 23717..
651 [99] M.D.G. Garca, F.C. Caada, M.J. Culzoni, L. Vera-Candioti, G.G. Siano, H.C. Goicoechea, et al., Chemometric tools
652 improving the determination of anti-inflammatory and antiepileptic drugs in river and wastewater by solid-phase
653 microextraction and liquid chromatography diode array detection, J. Chromatogr. A. 1216 (2009) 54895496.

Page 20 of 26
654 [100] EPA Method 8272, Parent and alkyl polyclic aromatics in sediment pore water by solid-phase microextraction and gas
655 chromatography/ mass spectrometry in selected ion monitoring mode, US Environmental Protection Agency: Washington, DC,
656 1994.
657 [101] J. Prschmann, F.-D. Kopinke, J. Pawliszyn, Solid-phase microextraction for determining the binding state of organic pollutants
658 in contaminated water rich in humic organic matter, J. Chromatogr. A. 816 (1998) 159167.
659 [102] E. Urrestarazu Ramos, S.N. Meijer, W.H.J. Vaes, H.J.M. Verhaar, J.L.M. Hermens, Using Solid-Phase Microextraction To
660 Determine Partition Coefficients to Humic Acids and Bioavailable Concentrations of Hydrophobic Chemicals, Environ. Sci.
661 Technol. 32 (1998) 34303435.
662 [103] P.A. Neale, B.I. Escher, A.I. Schfer, Quantification of SoluteSolute Interactions Using Negligible-Depletion Solid-Phase
663 Microextraction: Measuring the Affinity of Estradiol to Bulk Organic Matter, Environ. Sci. Technol. 42 (2008) 28862892.
664 [104] R.B. Gomes, R. Nogueira, J.M. Oliveira, J. Peixoto, A.G. Brito, Determination of total and available fractions of PAHs by
665 SPME in oily wastewaters: overcoming interference from NAPL and NOM., Environ. Sci. Pollut. Res. Int. 16 (2009) 6718.
666 [105] T. Grecki, Effect of Sample Volume on Quantitative Analysis by Solid-phase MicroextractionPart 1. Theoretical
667 Considerations, Analyst. 122 (1997) 10791086.
668 [106] S.N. Zhou, K.D. Oakes, M.R. Servos, J. Pawliszyn, Application of Solid-Phase Microextraction for In Vivo Laboratory and
669 Field Sampling of Pharmaceuticals in Fish, Environ. Sci. Technol. 42 (2008) 60736079.
670 [107] S. Wang, K.D. Oakes, L.M. Bragg, J. Pawliszyn, G. Dixon, M.R. Servos, Validation and use of in vivo solid phase micro-
671 extraction (SPME) for the detection of emerging contaminants in fish., Chemosphere. 85 (2011) 147280.
672
673 Captions
674 Figure 1 - SPME Extraction Time Profile.
675 Figure 2 - Various SPME configurations: (A) fiber; (B) in-tube; (C) thin-film; (D) magnetic ; (E) in-tip; and (F) stir-bar.
676 Figure 3: Schematic of cold-fiber strategy for enhanced extraction efficiency from solid samples. Reprinted with permission from
677 [66], Elsevier 2012.

678

679

680
681 Table 1.

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682 SPME method features for selected applications to soil and sludge analysis
683
Matrix Analytes Coatings Extraction Mode Calibration methods LOD Refs

Sediment 2,4,6-trinitrotoluene PA DI-SPME External (spiked in n/a [29]

soil)
Estuarine soils and Nitrous oxides Car/PDMS DI-SPME External (standard gas) 4.1 nM [30]
sediments
Soils PAHs PDMS Water-DI-SPME Equilibrium n/a [31]
calibration
Soil Pyrene PDMS OS/Water-DI-SPME External (spiked in n/a [63]
soil)
Soil Naphthalene PDMS OS/Water-DI-SPME None n/a [35]
Soil PAHs PDMS OS/Water-DI-SPME Equilibrium n/a [33]
calibration
Marine sample Energetic chemicals CW/DVB OS-water-DI-SPME External (spiked in 0.05-0.08 g/L (water) [71]
water) 1-9 g/kg (dry sediment)
Certified marine PAHs PA MWA-Micellar-DI- external (spiked in 0.28-7.66 ng/mL [36]
sediment SPME micellar solutions)
Certified reference PAHs PDMS MWA-ionic liquid-DI- External (spiked in 0.05-0.14 mg/kg [38]
sediment SPME ionic liquid extracted
solution)
Soil 16 PAHs PDMS USA-OS-water-DI- External + Internal 2-20 ng/g [39]
SPME Standard (spiked in the
soil sample)
Soil Triazine and PDMS HS-SPME External (spiked in 0.05-3.64 g/kg [40]
Organophosphorus soil)
Mars analogue soil PAHs PDMS HS-SPME External (Certified n/a [41]
reference material)
Soil Degradation products of PDMS HS-SPME External (spiked in 6.3-7.6 mg/kg [42]
chemical warfare agent soil)
Soil BTEX CAR/PDMS Multiple HS-SPME External (spiked in 0.2-1 ng [43]
water)
Sediment PAHs PDMS (CF-SPME) HS-SPME Exhaustive extraction 0.3-3 pg/g [72]
Soil and sediment Brominated flame retardants PDMS Water-HS-SPME External (spiked in 14-625 pg/g (soil) [44]
soil) 5.2-214 pg/g (sediment)
Urban landfill soil Global screening PDMS/DVB NaCl/Water-HS-SPME None n/a [45]
Estuarine sediment OCPs PDMS Water-HS-SPME External (spiked in 0.029-0.301 ng/g [46]
water)
Textiles 18 organophosphorus PA Simulative sweat External (spiked in 0.01-55 g/L [59]

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 Matrix Analytes Coatings Extraction Mode Calibration methods LOD Refs

pesticides (OPPs) solution-DI-SPME simulative sweat

solution)
Soil BTEX and cumene PDMS USA-Water-HS-SPME External (spiked in the c.a. 1ng/g [52]
extracted solution)
Sewage sludge Synthetic polycyclic musk DVB/PDMS MEA-Water-HS-SPME Standard addition 0.04-0.1 ng/g [51]
sediment (spiked in soil)
Estuarine OCPs PDMS MEA-OS-water-HS- External (spiked in 0.005-0.11 ng/g (GC-MS) [50]
sediments SPME soil) 0.01-0.26 ng/g (GC-ECD)
Landfill leachates PAHs and PCBs PDMS MEA-water-HS-SPME External (spiked in 0.1-0.7 ng/L (PCBs) [49]
and sediments leachates) 5-926 ng/L (PAHs)
Soil Chlorophenols PA MEA-Water-HS-SPME External 0.1-2 g/kg [48]
Soil Atrazine and ametryn Dodecyl sulfate-doped Water-cooled-HS- External (spiked in Water: 10 ng/mL [73]
polypyrrole fiber (PPy) SPME soil) (ametryn)
Water: 15 ng/mL
(atrazine)
Soil: 23 ng/g (ametryn)
Soil: 37 ng/g (atrazine)
Soils Tetracycline antibiotic CW-DVB Water-hollow External 2.9-3.2 g/kg [74]
residues membrane protect-
SPME
Soil & Sediment Organotin compounds PDMS OS-buffer-HS-SPME Standard addition (IS Clay: 2.35-387 ng Sn/g [62]
for peak area Soil: 2.85-17.74 ng Sn/g
calibration and
standard addition for
concentration
quantification)
Soil & Sediment Chlorobenzene Diglycidyloxycalix[4]aren OS-water-HS-SPME Standard addition Soil: 0.11-3.85 ng/g [60]
e (spiked in soil) Clay: 0.011-0.2 ng/g
Soil 2-chloroethyl ethyl sulfide Acrylate/silicone co- Water-HS-SPME External (spiked in 2.7 ng/g [61]
polymer soil)
684
685 n/a: not available

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686

687 Table 2.
688 SPME method features for selected applications to wastewater analysis
Matrix Analytes Coating-configuration Mode Calibration method Separation & LOD Ref.
detection
method
Municipal effluents Pharmaceuticals Homemade PDMS fiber DKinetic calibration HPLC-MS 0.2-0.5 ng/mL [98]
I with IS (LOQ)
WWTP effluent Drugs 65 m PDMS/DVB fiber DStandard addition LC-DAD n/a [99]
I
WWTP influent and Pharmaceuticals and C18/SCX thin-film blade DInternal standards DESI n/a [78]
effluent streams personal care products I
Treated municipal Pharmaceuticals C18 thin-film blade (96-well DEquilibrium LC-MS/MS 2-13 ng/L [79]
wastewater plate format) I calibration method
Sewage samples BTEX and phenolic Functionalized nanoporous HExternal calibration GC-MS 0.001-0.013 g/mL [80]
compounds silica (HTPES-SBA-15) fiber S
Wastewater and sewage Organochlorine pesticides Nano-structured polyaniline- HExternal calibration GC-ECD 0.12-0.31 ng/L [81]
treatment plant effluent ionic liquid fiber S
Leachate from sewage Chlorophenols Ionic liquid fiber HExternal calibration GC-MS 1.1-1.4 g/L [83]
farm S
WWTPs effluents Polybrominated diphenyl Molecularly imprinted DExternal calibration GC-NCI-MS GC-NCI-MS: [84]
ethers (PBDEs) organically modified silicate I GC-ECD 0.2-3.6 pg/mL
fiber GC-ECD:
1-8.8 pg/mL
Laboratory wastewater 2,2-dipyridine Metal complex imprinted DExternal calibration HPLC-UV 2 g/L [85]
polymer fiber I
Sewage samples BPA and analogues Monolithic molecularly DExternal calibration HPLC-UV 2-5.1 ng/mL [86]
imprinted fiber I
Laboratory & industrial Phenolic compounds Polyethylene glycol reinforced HExternal calibration GC-FID 0.005-0.5 ng/mL [87]
effluents with MWCNTs fiber S
Hospital wastewater Phenobarbital MWCNTs hollow fiber DExternal calibration HPLC-UV 0.32 ng/mL [88]
I
Paint plant effluent BTEX SWCNTs fiber HExternal calibration GC-FID 0.005-0.026 g/L [89]
S
Untreated sanitary Phenolic compounds MWCNTs/fused-silica fiber DExternal calibration GC-FID 0.005-0.05 g/L [90]
wastewater I
Wastewater from a water PBDEs Functionalized Single-walled HExternal calibration GC-ECD 0.08-0.8 ng/L [91]
institution carbon nanotubes (SWCNTs) S
Page 24 of 26
 Matrix Analytes Coating-configuration Mode Calibration method Separation & LOD Ref.
detection
method
fiber

Petrochemical wastewater BTEX Titania sol-gel anodized HExternal calibration GC-FID 5.4-14.8 g/L [92]
aluminum fiber S
Untreated wastewater & Pharmaceuticals 50/30 m DVB/CAR/PDMS DExternal calibration GC-MS (ion 0.02-0.43 g/L [93]
sewage plant treatment fiber I trap)
effluent
WWTP influent & effluent Pharmaceuticals CW/TPR fibers (x2) DInternal standards LC-MS/MS 0.005-0.05 g/L [94]
streams I (surrogates) (LOQ)
Detergent plant effluent & Synthetic polycyclic 65 m PDMS/DVB fiber HStandard addition GC-MS 0.05-0.1 ng/L [95]
domestic wastewater musks S
WWTP influent Organophosphate esters 65 m PDMS/DVB fiber HStandard addition GC-MS 0.5-4 ng/L [96]
S (LOQ)
WWTP influent and Halogenated flame Disposable PDMS rods DInternal standards GC-MS 0.4-10 ng/L [97]
effluents, textile industry retardants I (surrogates)
effluent & landfill leachate
Surrogate aqueous Estradiol (radiolabeled) - 34.5 m Polyacrylate fiber DNegligible depletion Scintillation n/a [103]
solutions of wastewater organic matter solute- I (nd-SPME) counter
solute interaction
Oily wastewater from fuel PAHs (free and total 100 m PDMS fiber HNegligible depletion GC-MS n/a [104]
station fractions) S (nd-SPME)
Wild fish in wastewater Pharmaceuticals Custom made 165 m PDMS I Pre-equilibrium LC-MS/MS 0.2-50.4 pg/g [106]
effluents fiber n vivo calibration
Municipal wastewater Various emerging 165 m PDMS fiber I Kinetic calibration LC-MS/MS n/a [107]
effluents & exposed fish contaminants n vivo with preloaded IS
&
DI
689 n/a: not available

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26

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