Journal of Chromatography A, 1592 (2019) 143–160

Contents lists available at ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Methods of assaying volatile oxygenated organic compounds in

effluent samples by gas chromatography—A review
Patrycja Makoś a , Andrzej Przyjazny b , Grzegorz Boczkaj a,∗
a
Gdansk University of Technology, Faculty of Chemistry, Department of Process Engineering and Chemical Technology, G. Narutowicza St. 11/12, 80 – 233
Gdansk, Poland
b
Kettering University, 1700 University Avenue, Department of Chemistry & Biochemistry, Kettering Flint, MI 48504, USA

a r t i c l e i n f o a b s t r a c t

Article history: The paper is a review of the procedures for the determination of volatile and semivolatile oxygenated
Received 31 October 2018 organic compounds (O-VOCs) in effluent samples by gas chromatography. Current trends and outlook for
Received in revised form 12 January 2019 individual steps of the procedure for the determination of O-VOCs in effluents are discussed. The available
Accepted 17 January 2019
sample preparation techniques and their limitations are described along with GC capillary columns used
Available online 18 January 2019
for O-VOCs separation and selective and universal detectors used for their determination. The results
of determination of O-VOC content in various types of real effluents are presented. The lack of legal
Keywords:
regulations regarding the presence of the majority of O-VOCs is pointed out as well as the availability of
Derivatization
Effluents
just a few procedures allowing a comprehensive evaluation of the O-VOC content in effluents.
Extraction © 2019 Elsevier B.V. All rights reserved.
Gas chromatography
Sample preparation
Volatile organic compounds

1. Introduction demand or total organic carbon. Among a wide variety of O-VOCs,

currently, the only regulation of many countries concerns volatile
Volatile and semivolatile oxygenated organic compounds, phenols determined as the phenol index whose allowed values are
which include the organic compounds containing at least one oxy- from 0.1 to 15 mg/L and from 5 to15 to mg/L for industrial effluents
gen atom, such as aldehydes, alcohols, phenols, esters, ethers, discharged to environmental waters or soil and sewage systems,
carboxylic acids and their derivatives are characterized by high respectively [20–24].
toxicity, carcinogenic and mutagenic properties and malodorous Due to their negative impact on the environment, oxygenated
character [1–5]. Oxygenated organic compounds commonly occur organic compounds have recently been an object of considerable
in municipal wastewater [6,7] as well as in various kinds of indus- interest among the scientists developing new methods of degrada-
trial effluents, including refinery [8–14], textile [15], coke [16], tion of O-VOCs in effluents and analytical procedures allowing their
chemical [17] and food [18] industries. All types of effluents have identification and determination at low concentration levels which
a very complex matrix, which hinders the determination of indi- is illustrated by the number of relevant papers published between
vidual O-VOCs, whose concentrations can vary from high to trace. 2004 and 2019 (Fig. 1). The importance of phenols in effluents is
Moreover, most O-VOCs are hydrophobic, highly reactive and low- reflected by the number of papers on the presence of O-VOCs in
molecular-weight compounds are highly volatile [19]. effluents, over 50% of which deals with phenolic compounds (Fig. 2).
Despite their noxiousness, the content of the majority of O-VOCs In order to assay the remaining groups of O-VOCs, the methods
in effluents is not regulated. The maximum allowed concentrations based on sensitive and selective techniques are needed, includ-
in industrial and municipal effluents involve primarily organochlo- ing gas chromatography, high-performance liquid chromatography
rine compounds, hydrocarbons, heavy metals as well as total [15,16,25,26], ion chromatography [27] or capillary electrophoresis
parameters, i.e., chemical oxygen demand, biochemical oxygen [28]. Owing to physicochemical properties of O-VOCs, gas chro-
matography is the preferred technique due to its lower cost of
a single analysis, very high resolution and the possibility of fine-
tuning selectivity of a procedure through the choice of a wealth of
∗ Corresponding author. stationary phases as well as the availability of both universal and
E-mail addresses: aprzyjaz@kettering.edu (A. Przyjazny), selective detection methods. However, in order to ensure sufficient
grzegorz.boczkaj@pg.edu.pl (G. Boczkaj).

https://doi.org/10.1016/j.chroma.2019.01.045
0021-9673/© 2019 Elsevier B.V. All rights reserved.
144 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

Fig. 1. Number of papers published during 2004–2019 on the presence of oxygenated organic compoundsin effluents - based on Scopus database(searched keywords:
aldehydes, ketones, ethers, esters, alcohols, phenols, carboxylic acids, wastewater or effluent; accessed on 04.01.2019).

Fig. 2. Percent of papers published during 2004–2019 dealing with the presence of oxygenated organic compounds in effluents - based on Scopus database (searched
keywords: aldehydes, ketones, ethers, esters, alcohols, phenols, carboxylic acids, wastewater or effluent; accessed on 04.01.2019).

sensitivity of a procedure, a sample preparation step providing iso- column such as an empty capillary column). Water is retained in
lation and enrichment of analytes is usually required. the initial segment of the column and the analytes, released by the
The paper provides a review of the procedures for the determi- flowing carrier gas, are retained as a narrow band further down
nation of content of volatile and semivolatile oxygenated organic the column. This is a simple technique which does not require any
compounds in samples of domestic, industrial and municipal special sample preparation. Thus, DAI can significantly reduce the
wastewater by means of gas chromatography. The available tech- time of analysis and decrease the loss of volatile analytes which
niques at each step of the analytical procedure are discussed along can take place during sample preparation. However, DAI is not
with the outlook and general problems resulting from the use recommended for samples of wastewater since it precludes deter-
of various sample preparation and final determination methods. mination of compounds present at low concentrations and can
Applications of the discussed procedures to the analysis of real cause contamination of a GC column with contaminants and inor-
effluents are also included. ganic salts thus shortening the column lifespan. There are just a few
reports on the application of DAI in the analysis of wastewater but
2. Sample preparation methods they only confirm the problems with peak tailing, the appearance of
ghost peaks, shifts of retention times, etc. [6,29]. Special problems
Among the available methods of introduction of liquid sam- due to very low sensitivity can be observed in the determination
ples with aqueous matrices into the GC injection port, a direct of acetic acid, which is a very important O-VOC, during monitor-
aqueous injection (DAI) technique has gained some popularity. In ing wastewater treatment in anaerobic reactors [30]. A somewhat
this approach, on-column injection is typically used, recently along better approach to the determination of carboxylic acids in wastew-
with programmed temperature vaporization (PTV). The syringe ater is thermal desorption (TD) due to an improved reproducibility
needle is introduced directly on-column (or into a deactivated pre- of the results and minimization of the problem of retention time
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 145

Fig. 3. Schematic diagram of the procedure for the determination of volatile oxygenated organic compounds in wastewater samples using gas chromatography (D – detectors
used for the determination of O-VOCs after derivatization).

shifts. Nevertheless, similarly to DAI, also thermal desorption does Fully automated autosamplers for SHS are commercially available.
not allow the determination of volatile fatty acids at sufficiently A schematic diagram of the SHS procedure is shown in Fig. S1. The
low concentrations [6]. use of static headspace analysis for the determination of O-VOC
Consequently, isolation and enrichment of analytes from content has a number of advantages, including universal applicabil-
wastewater samples is the required step in a procedure. Owing to ity, simplicity and the possibility of automation, which is important
environmental concerns and according to green chemistry prin- in the case of a large number of samples. Moreover, in comparison
ciples, sample preparation techniques should meet a number of with conventional extraction techniques, SHS does not cause losses
requirements, including possibility of automation, small sample of the most volatile organic compounds which are responsible for
volumes and being so-called solventless sample preparation tech- malodorous properties of wastewater due to their low odor thresh-
niques, i.e., the techniques that either do not use organic solvents at old of O-VOCs [33–36]. On the other hand, a serious disadvantage of
all or use only small volumes of them [31,32]. A standard procedure SHS is its insufficient sensitivity for compounds with higher boiling
for the determination of O-VOCs in wastewater samples is shown points and the problems related to variable composition of matri-
in Fig. 3. ces of wastewaters [37,38]. As a result of low sensitivity of SHS
for higher boiling O-VOCs, which are commonly present in various
kinds of wastewater, the technique is rarely used in the analytics
2.1. Gas extraction
of effluents [37].
One of the sample preparation techniques meeting all the
requirements of green chemistry is headspace analysis, which can
2.1.2. Dynamic headspace
be carried out either in static or dynamic mode.
The problem of relatively low sensitivity of SHS was partially
eliminated by using dynamic headspace analysis (DHS), which
2.1.1. Static headspace is often called purge-and-trap, in which analyte enrichment is
The procedure of headspace analysis involves placing a sam- achieved by a continuous shift of the equilibrium toward headspace
ple in a vial which is then tightly closed with a crimp or screw [39]. In this way, the detection limit for the same compounds can
cap equipped with a septum. In addition to the sample, the vial be lowered by as much as three orders of magnitude compared
must also contain some headspace. The sample is then thermostat- to SHS. The DHS procedure involves transfer of analytes from the
ted at a specific temperature until thermodynamic equilibrium aqueous phase to the headspace by purging the sample with an
between the sample and the headspace is reached. Next, the inert gas followed by trapping volatile components in a trap (using
headspace is sampled using a gas-tight syringe (which is also sorption or cryofocusing). The purge can take place in a tightly
thermostatted) and injected the GC injection port. The time and closed vial equipped with a stopper with a septum through which
temperature of equilibration depend on the rate of diffusion of a purge gas inlet is introduced. Alternatively, U-tube shaped con-
volatile sample components. As a rule, these parameters are deter- centrators equipped with sintered glass (for dispersion of the gas)
mined experimentally during the development of the procedure. just below the sample can be used. The purge gas outlet is typically
146 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

Table 1
Compilation of conditions for DHS extraction.

Analytes Purge time Gas flow rate Purge Desorption Desorption Sorbent LOD RSD [%] R [%] Ref.
[min] [ml/min] temperature time [min] temperature
[◦ C] [◦ C]

Alcohols, phenols, 5 20 (H2 ) 20 4 250 Tenax TA 0.005–20 mg/L <5.0 – [12]

ketones, aldehydes,
esters, ethers (36
O-VOCs)
MTBE 10 – 40 10 220 Tenax TA 2.9 ng/L – 99.1 [44]
Alcohols, phenols, 10 100 (N2 ) – 10 220 Tenax TA – – – [45]
ketones, aldehydes
(28 O-VOCs)
Acetone 12 – 60 4 260 Carbopack 0.32–2.39 ␮g/L < 13.4 – [43]
B/Carbosieve III

made of a stainless steel or fused silica capillary. The purge gas An essential criterion for the selection of a sorbent is its water
(usually helium or hydrogen, less often nitrogen) flowing through sorption capacity and the effect of water on the trapping efficiency
the sample sweeps out volatile compounds and transfers them to of individual O-VOCs. Lowering the amount water vapor introduced
a trap packed with a sorbent. A different approach involves the use onto the sorbent can be accomplished by using either micro con-
of a short length of an empty deactivated capillary column made densers installed in the DHS-trap line or membrane dryers (usually
of fused silica and cooled with vapors of liquid nitrogen. The latter Nafion). In order to avoid introducing water collected in the trap
approach eliminates the problem of sorbent bed breakthrough and into the chromatographic system, an additional step, so-called dry
ensures narrower bands of analytes during the desorption step. The purge is added, during which water vapor having low retention on
limitations of DHS include more expensive equipment, the use of the sorbent bed is removed from the bed by purging with a dry gas
liquid nitrogen and the need for drying the gas to remove water in the same direction as that during the extraction step.
vapor carried from the sample. Volatile chemical compounds are Some examples of extraction conditions for extraction of O-
then released from the trap by thermal desorption and introduced VOCs are listed in Table 1. It is also possible to combine DHS-GC with
into the GC injection port. A schematic diagram of the procedure is an automated sampling device which allows performing wastew-
shown in Fig. S2. The main shortcomings of DHS other than the ones ater sample analysis in situ. Such an approach eliminates the
mentioned above include a relatively long time of extraction (as a possibility of analyte losses during transport of samples to the lab-
rule longer than 10 min) and the possibility of analyte losses due oratory and reduces the time of analysis [43]. The DHS technique
to sorbent breakthrough if the extraction time is too long and/or coupled with gas chromatography allows the determination of a
the flow rate of the purge gas is too high. Additionally, as was wide variety of O-VOCs, including alcohols, aldehydes, phenols,
the case with SHS, only volatile compounds with boiling points up ketones, esters and ethers present at low concentrations in sam-
to about 150 ◦ C can be extracted [40]. Another limitation of DHS ples having a complex matrix, i.e., effluents from the production of
involves the problem with extraction of samples containing surfac- petroleum bitumens [12], petrochemical effluents [45] or munic-
tants which require addition of a defoamer, such as 1-tetradecanol ipal effluents [43]. The detection limit values are typically in the
[41,42]. An important element of any DHS system is a sorbent trap order of single ppb. However, due to the problem with the deter-
which allows isolation of analytes from the gaseous phase. This step mination of compounds having medium or low volatility in order to
is necessary since volatile compounds in the gaseous phase occur ensure comprehensive analysis of organic compounds occurring in
at high concentrations. wastewater, other types of extraction should also be considered.
The dynamic headspace technique generally offers good repro-
ducibility with RSDs varying from 2 to 10% evaluated in one batch,
2.1.2.1. Enrichment/trapping of oxygenated volatile organic com- and from 3 to 15% related to batch-to-batch variation. Usually, the
pounds for dynamic headspace. To extract O-VOCs from wastewater linearity for quantitative analysis is over two orders of magnitude.
samples commercially available sorbents characterized by a high
specific surface area, such as carbon molecular sieves Carbosieve 2.2. Liquid extraction
S-III and S-II, Carboxen (300–1000 m2 /g) [43], a porous polymer
Tenax TA based on2,6-diphenyl-p-phenylene oxide(specific sur- 2.2.1. “Conventional” liquid-liquid extraction
face area 18 m2 /g [12,44,45] or a composite material containing 70% Classical liquid-liquid extraction (LLE) is still very much in use
Tenax TA and 30% graphite carbon (Tenax GR), are predominantly in analytical procedures for the analysis of water and wastew-
used. Carbosieve S-II is recommended only for the sorption of most ater due to its simplicity and lack of complex equipment. The
volatile compounds whereas the most universal sorbent which has extraction procedure involves placing a sample in a separatory fun-
found wide applicability in the analysis of wastewater is Tenax TA nel to which an extraction solvent immiscible with water is then
[12,44,45]. Another approach which is commercially available is added. Next, the separatory funnel is shaken and left in a stand
the use of multibed sorbent traps in which the weakest sorbent for the phase separation to take place. The extraction is usually
retaining only heavier O-VOCs is the first in series followed by other performed repeatedly to transfer a maximum amount of the ana-
sorbents ordered by increasing sorbent strength. Good results of lytes from the aqueous phase to the organic phase. The procedure
extraction of O-VOCs can also be obtained by using other sorbents, is depicted in Fig. S3. LLE is time-consuming and labor-intensive
such as a granular activated carbon obtained from macadamia nut- which limits its widespread use. Other limitations include the pos-
shells [46]. However, the alternative sorbents were only tested with sibility of emulsion formation and large volumes of very pure
standard mixtures. The extraction is also affected by the time and organic solvents used. Furthermore, the enrichment factor for O-
temperature of purge and desorption of analytes. Extraction con- VOC analytes when using LLE is considerably smaller compared
ditions should be selected depending on the kind and properties of with other sample preparation techniques available [47]. The most
analytes. Elution of analytes from sorbent traps should be carried important factor affecting the extraction yield is the selection of
out countercurrently to the extraction step. an appropriate solvent. The solvents used most commonly for the
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 147

extraction of O-VOCs are volatile so that they are eluted before which increases the rate of mass transfer between the headspace
analytes, i.e., diethyl ether [48], dichloromethane (DCM) [49] or and extraction solvent. This technique provided low LOD values for
methyl tert-butyl ether (MTBE) [49–52]. Several papers mention diethyl ether and ethyl acetate equal to 10 ␮g/L [62].
problems with quantitative extraction of acetic and propionic acid
by diethyl ether [48] whereas good results were obtained with 2.2.2.2. Dispersive liquid-liquid microextraction. A relatively new
MTBE for which the extraction yield was about five times higher mode of solvent microextraction is dispersive liquid-liquid
than for DCM [49]. Bisphenol A and B were best extracted with microextraction (DLLME) [63]. In this technique, an aqueous sam-
chloroform [53]. Extracting solvents with high boiling points could ple is placed in a conical centrifuge tube and a mixture of disperser
co-elute with analytes which is particularly troublesome when uni- and extraction solvent is added. Then the mixture is agitated and
versal GC detectors, such as FID, are used. The extraction efficiency centrifuged. Next, the sedimented organic phase is collected from
can be improved by decreasing the solubility of O-VOCs in water by the bottom of the tube (in some applications the extract is lighter
using the salting out effect (sometimes also used in SHS and DHS) than water and is collected from the top) and injected into the GC
[53] and/or by changing the pH of samples. However, despite such (Fig. S3). Owing to its simplicity, a very short extraction time (sev-
approaches, the detection limits of O-VOCs are often still too high. eral seconds) and often almost 100% analyte recovery DLLME has
In addition, salting-out effect might not be as effective as it can become one of the most common modes of liquid-liquid extrac-
be expected. Sometimes, the solubility is even increasing or minor tion [57]. DLLME was used, among others, in the determination of
changes are reported after the salt addition. carboxylic acids [64,65] and 43 volatile oxygenated organic com-
pounds in effluents from the production of petroleum bitumens,
2.2.2. Liquid-liquid microextraction techniques including alcohols, esters, ethers, ketones, aldehydes and phenols.
Due to disadvantages of LLE and general trends in sample prepa- Low LOD values ranging from 0.07 to 0.82 ␮g/mL were obtained
ration techniques, methods minimizing the volume of organic for all the analytes except for acetaldehyde for which LOD was
solvents used are becoming increasingly popular. Such techniques 2.06 ␮g/mL [11]. One of the drawbacks of DLLME is the possibility of
are generally called either liquid phase microextraction (LPME) or losses of the most volatile analytes during extraction; therefore, it
solvent microextraction (SME) [54]. The difference between LPME is recommended for the extraction of compounds with higher boil-
and classical LLE involves much smaller volumes of both samples ing points, such as phenols [66,67] or acrylates [68]. Until recently,
and extracting solvents. In the determination of phenols and car- a serious limitation of DLLME was the inability to automate it.
boxylic acids, 3 ␮L of organic solvents were sufficient to obtain a However, some recent papers describe automated DLLME, which
high extraction yield of the analytes with a good reproducibility of makes this sample preparation technique more efficient [69–75]. A
results. The procedures also offered low LOD values when using the comparison of parameters of various liquid-liquid extraction pro-
FID detector, ranging from 0.94 to 1.97 ␮g/L for phenols [55] and cedures is presented in Table 2.
0.0093 to 0.015 ␮g/L for carboxylic acids [56].
2.3. Sorbent extraction
2.2.2.1. Single-drop microextraction. One mode of solvent microex-
traction is single-drop microextraction (SDME), which requires 2.3.1. Solid-phase extraction
only 0.3–3 ␮L of the extractant. The sample is placed in a tightly In order to isolate and enrich of oxygenated organic compounds
closed vial with a cap equipped with a septum. The extractant is from wastewater, liquid-solid extraction is commonly used, includ-
drawn into a GC microsyringe, and the tip of the needle of the ing solid-phase extraction (SPE). The first step in any SPE procedure
microsyringe is placed either inside the sample. The extractant is involves conditioning of the sorbent bed using a solvent appro-
then extruded from the microsyringe forming a drop at the tip of priate for a particular sorbent. This step aims at solvation of the
the needle. The extraction is typically performed for 5–30 min. Fol- sorbent to increase its sorption capacity. Next, a sample of wastew-
lowing extraction, the drop is withdrawn into the microsyringe and ater is loaded onto the SPE column and the analytes are adsorbed
the extract is injected into the GC [57]. A schematic diagram of the onto the sorbent bed. The SPE cartridge is then washed with an
procedure is shown in Fig. S3. Advantages of SDME include a high aqueous solution to remove impurities, followed by elution of the
enrichment factor (mostly due to the phase ratio), simplicity and adsorbed analytes with an appropriate organic solvent. The proce-
the possibility of automation [58]. The technique was successfully dure for SPE extraction is depicted in Fig. S4. SPE technique provides
used in the determination of phenols in municipal wastewater with high selectivity due to a wide variety of sorbents available and the
low detection limits (0.45 – 1.5 ng/mL) and a good reproducibility of possibility of fractional elution with a series of solvents. For isola-
results [59]. However, a significant problem in SDME is drop insta- tion of phenols the sorbents used most commonly include silica gel
bility and a limited drop volume as well as the problem of solvent modified with octadecyl groups (C18) [76–80] as well as commer-
volatility. The problem of drop instability in SDME was partially cially available polymeric sorbents, such as styrene/divinylbenzene
solved by placing the drop in the headspace above the sample (Fig. co-polymer (S-DVB) [81] or divinylbenzene/N-vinylpyrrolidone
S3) (headspace single-drop microextraction, HS-SDME) [60] and (DVB/N-VP) [82–84], which have also been successfully used to
the use of mixtures of solvents with different densities, such as isolate fatty, benzoic and dicarboxylic acids [84]. For isolation
chloroform and 1-octanol (1:1 v/v), which improved the stability of of carboxylic, benzoic and hydroxybenzoic acids, a mixture of
the hanging drop [61] and, to a greater extent, by placing the solvent commercial SPE sorbents containing C18 and ethyl vinyl benzene-
in the lumen of a porous hollow fiber (hollow fiber-protected liq- divinyl benzene polymer was used (EVB-DVB/C18) (1:1) [85].
uid phase microextraction, HF-LPME). Selectivity of the extraction Compared to classical LLE extraction, SPE provides greater enrich-
is achieved by selecting the appropriate solvent and the fiber mate- ment factors; however, its main disadvantages are the need for
rial. The pores in the fiber preclude extraction of large molecules large sample volumes (100–500 mL) [76,77,82] and, sometimes, the
which in the case of wastewater facilitates subsequent GC anal- use of toxic organic solvents as well as a long extraction time which
ysis. An interesting approach is headspace knotted hollow fiber can exceed 2 h [82]. In standard SPE assemblies, the eluent flow is
microextraction (HS-K-HFME), in which the knot-shaped commer- driven by reduced pressure, which entails the risk of losses of most
cially available Q 3/2 Accurel polypropylene hollow fiber is filled volatile analytes. In order to shorten the extraction time to 20 min
with 25 ␮L of the extraction solvent (1-octanol). The excess sol- and reduce sample volume to 10 mL, magnetic solid phase extrac-
vent forms a large droplet (13 ␮L) which is held in the center of tion (MSPE) can be used. In this technique, either the sorbents have
the knot (Fig. S3). The knot-shaped fiber has a larger contact area magnetic properties or they are immobilized on magnetic cores.
 148
Table 2
Compilation of parameters of liquid-liquid extraction.

Extraction Analytes Extractant Derivatization Sample Extraction time Detector LOD RSD [%] R [%] Ref.
technique volume/
extractant
volume

Carboxylic Diethyl ether – 1 mL/1 mL 30 s FID – <2.7 – [48]

acids
Carboxylic MTBE/DCM – 10 mL/10 mL 10 min MS – – – [49]
LLE
acids
Carboxylic MTBE – 4 mL/2 mL – MS 0.1–0.5 mg/L <1.3 – [50]
acids
Carboxylic MTBE BSTFA, TMCS 4 mL/2 mL 2 min MS 0.03–0.2 ␮g/L <2.1 92–106 [51]
acids

P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

Carboxylic MTBE BSTFA, TMCS 4 mL/4 mL 2 min MS 0.8–4.2 ␮g/L <9 61–79 [52]
acids
BPA, BPF CHCl3 TMSA 500 mL/5 mL 1 min MS 0.006–0.02 ␮g/L <5.6 – [53]
HF-LPME Carboxylic 1-Octanol TBA-HSO4 3 mL/4␮L 10 min MS 0.0093–0.015 ␮g/L <11.5 – [56]
acids
Phenols Chloroform TBA-Br 5 mL/3 ␮L 20 min MS – <7.5 96–121 [59]
DI-SDME
Phenols Chloroform:1- TBA-Br 3 mL/3 ␮L 12 min FID, MS 0.2–0.7 ␮g/L <5.4 (GC-MS), – [61]
octanol (MS); <7.1 (GC-FID)
(1:1) 12–17.3 ␮g/L
(FID)
HS-SDME Phenols [C8 MIM][PF6 ] – 10 mL/1 ␮L 25 min FID 0.1–0.4 ␮g/L <9.5 81–111 [60]
HS-K-HFME Diethyl ether, 1-Octanol – 4 mL/25 ␮L 20 min MS 10 ␮g/L <11.6 96–104 [62]
ethyl acetate
Phenols, DCM, (ACN- – 10 mL/0.5 mL 60 s MS 0.07–0.82 mg/L <5 71–119 [11]
aldehydes, disperser)
ketones,
DLLME
alcohols, esters,
ethers
Phenols DCM, (IPA – 5 mL/0.2 mL – FID 0.32–0.34 ␮g/L <3.2 85–96 [66]
–disperser)
Phenols CTC/chlorobenzen – 5 mL/15 ␮L 2 min MS – <9.1 68–104 [67]
2:1 v/v (ACN -
disperser)
Acrylates Chlorobenzen – 5 mL/20 ␮L 5 min FID 0.071–0.13 ␮g/L <9.1 81–109 [68]
(AcCN-
disperser)
Carboxylic Chloroform TBA-HSO4 9 m L/300 ␮L 60 s MS 6.9–1120 ␮g/L <6.4 69–126 [64]
acids (IPA- disperser)
Carboxylic ChCl:4MPh ChCl:4MPh 9 m L/500 ␮L 10 min MS 1.7–8.3 ␮g/L <6.7 82–106 [65]
acids (1:2 molar (1:2 molar
ratio) (MeOH- ratio)
disperser)
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 149

Sorbent particles are added to a wastewater sample and left in extraction of BPA from wastewater [95,96]. For carboxylic acids
it until the analytes are adsorbed. Next, the sorbent particles are with a longer chain and for aldehydes and volatile phenols the
attracted by a magnet while the sample matrix is decanted. This is best results were obtained when using PDMS-CAR-DVB [90,97].
followed by analyte desorption using an appropriate organic sol- Other investigations demonstrated improved extraction efficiency
vent. The extract is then analyzed by GC. The MSPE procedure is for polyethylene glycol as a fiber coating. Selectivity of sorption
depicted in Fig. S4. Just 40 mg of Fe3 O4 @C@polyaniline magnetic of individual analytes present in the headspace, in addition to
microspheres were needed to obtain high recoveries (85.3–110.6%) elimination of analytical signal of undetermined VOCs in the
and low LOD values (0.89–7.58 ng/mL) for phenols extracted from chromatogram, also affects the sorption capacity of the fiber, since
10 mL of wastewater samples [86]. only the analytes of interest will be accumulated. Compared to the
fiber coated with PDMS-CAR, extraction using PEG provided lower
2.3.2. Stir bar sorptive extraction detection limits for the majority of carboxylic acids (C2 –C7 ) [98]
Another extraction technique that can be used for the determi- while LOD values for the same analytes extracted with CAR-DVB
nation of phenols and carboxylic acids is stir bar sorptive extraction were lower by a factor of 300 compared with direct aqueous injec-
(SBSE). SBSE procedure calls for transfer of analytes from the aque- tion. Only extraction of formic acid yielded a twofold increase in
ous phase to a sorbent layer (usually PDMS) coated onto a magnetic sensitivity compared to DAI [99]. Similar results were obtained in
stir bar. During extraction wastewater samples are stirred magnet- other investigations [88]. The use of fibers coated with polymeric
ically using the stir bar. Next, the adsorbed analytes are recovered materials has a number of disadvantages, including relatively
from the stir bar using either thermal desorption or extraction with low maximum desorption temperatures, which generally ranges
an appropriate organic solvent (Fig. S5). In SBSE the sorbent (PDMS) from 240 to 280 ◦ C, instability and too low polarity which limits
volume is 50 to 250 times greater than that in SPME, which results their usefulness for some compounds. High thermal stability is
in higher recoveries and enrichment factors for the majority of required for the thermal desorption step. Insufficient desorption
O-VOCs. However, because of long extraction times (as much as temperature will cause peak broadening and tailing as well as
240 min) and relatively low extraction efficiency (for example, 1% discrimination of higher boiling analytes.
for salicylic acid) disqualify SBSE as a sample preparation method
for routine analyses of wastewater [87].

2.3.3. Solid phase microextraction 2.3.3.1. Developments in solid-phase microextraction for oxygenated
Solid phase microextraction (SPME) is a miniaturized version volatile organic compounds analytics. Therefore, a number of novel
of SPE. In this technique, analytes are sorbed onto a layer of fiber coatings have recently appeared, such as carbon nano-
extracting phase coated onto a fused silica fiber which is placed tubes, including multiwalled carbon nanotubes [100–102], ionic
inside a needle held in a holder. After introduction of the needle liquids [103] or based on calixarenes, i.e. amide bridged-C[4]/OH-
into a sample the fiber is exposed to the sample. Next, the fiber TSO(25,27-dihydroxy-26,28-oxy(2 ,7 -dioxo-3 ,6 -diazaoctyl)oxy-
is retracted into the needle which is then inserted into the GC p-tert-butylcalix[4]arene/hydroxy-terminated silicone oil) [104],
injection port for thermal desorption of analytes. SPME can be per- which eliminate the problems mentioned above and can be
formed in the direct immersion mode (DI-SPME) in which the fiber successfully used for the determination of O-VOCs in wastew-
is immersed directly into an aqueous sample or in the headspace ater samples. An increase in volume of the extracting phase in
mode (HS-SPME) where in the fiber is placed in the headspace SPME results in lowering detection limits and extending a linear
above the sample (Fig. S6). The latter mode is more favorable for range; however, until now the increase in the amount of sorbent
analysis of wastewater as it protects the fiber from mechanical required modification not only of the SPME apparatus but also of
damage by solids present in the sample and prevents extraction of the thermal desorption module. The problem has recently been
analytes of low volatility or nonvolatile which could contaminate eliminated by the introduction of the PAL SPME Arrow system,
both the fiber and the chromatographic system [88]. However, DI which contains a stainless steel wire coated with a greater amount
mode allows the determination of less volatile O-VOCs in wastew- of a sorbent compared to a typical SPME fiber and ending with
ater samples, which cannot be determined using the HS mode. the arrow-shaped tip. This arrangement ensures compatibility
Regardless of SPME mode, the key role in extraction is played by with the commercially available thermal desorbers and liners. In
the kind of sorbent and shape of the fiber [89]. A number of fibers addition, the presence of a steel wire provides a much improved
of varying polarities are now available commercially for extraction fiber stability [105,106]. The SPME Arrow system has not yet been
of various groups of chemical compounds. In the determination of used for extraction of O-VOCs from wastewater samples. Another
volatile fatty acids numerous problems are posed by short-chain important parameter is extraction temperature. An increase in
acids, i.e., acetic and propionic acid [90–92]. Among five fibers, extraction temperature can accelerate adsorption of analytes on
including polyacrylate, Carbowax/Divinylbenzene (CAR-DVB), the fiber but too high a temperature can result in desorption and
Polydimethylsiloxane/Divinylbenzene(PDMS–DVB), Poly- losses of the most volatile sample components. Consequently, the
dimethylsiloxane/Carboxen/Divinylbenzene (PDMS–CAR–DVB) procedures for the determination of volatile fatty acids made use
and Polydimethylsiloxane–Carboxen (PDMS–CAR), only PDMS- of mostly room temperature and time ranging from 15 to 60 min
CAR sorbent provided satisfactory extraction of C2 and C3 acids [88–90,93,98,99] whereas extraction of phenols and aldehydes
[93]. The same sorbent was highly effective in the extraction of was carried out at substantially higher temperatures (from 50
phenols [94]. In the determination of bisphenol A (BPA), tert- to 100 ◦ C) [94–97,102,104]. SPME technique requires splitless
nonylphenol and formaldehyde in samples of wastewater the injection using narrow glass liners in order to create high carrier
highest extraction efficiency was achieved using PDMS/DVB; gas velocity around the fiber which allows rapid removal of
however, the use of such a fiber can introduce errors due to the desorbed analytes from the injection port [107]. However, some
presence of BPA in epoxy resin that is used to attach the fiber to papers report successful use of the split injection [104]. So far,
the holder. A decrease in the amount of released BPA is observed no formation of O-VOCs artifacts on the SPME fibers have been
after multiple extractions which results in the aging of the fiber reported in the literature although such problems are known
and deterioration of extraction efficiency. The fiber coated with for other groups of volatile organic compounds, i.e., organosulfur
PDMS/DVB is highly effective for about 100 extractions. Conse- compounds. This phenomenon should be taken into consideration
quently, fibers coated with polyacrylate are recommended for in the investigations of more reactive O-VOCs.
 150
Table 3
Compilation of various types of solid-phase extraction procedures in the determination of O-VOCs in wastewater samples.

Extraction Analytes Sorbent Derivatization Extraction Thermal Elution Detector LOD RSD [%] R [%] Ref.
technique temp./time desorption eluent/time
tempera-
ture/time

phenols C18 MTBSTFA RT – MeOH (5 mL), MS 0.6–3.16 ␮g/L – 93 [77,78]

hexane:ACN
(50:50,
SPE
v/v) (3.5 mL)/–
phenols C18 BSTFA/pyridine RT/80 min – DCM (4 mL), MS 0.03– 0.41 ␮g/L <13.9 >60 [79]
hexane (2 mL)
phenols DVB/N-VP AAA RT/over 2 h – ACN (3 mL) and MS/MS 0.03–2.5 ␮g/L <30 60–135 [82]
DCM (2 mL)
phenols C18 - BSTFA/TMCS RT – DCM MS 3.64–97.64 <13.6 – [83]
DVB/N-VP ng/L
esters, DSC-18 HMDS/TFA RT – Hexane (5mL), MS 0.92–600 ng/L <10 94 [84]
carboxylic ethyl acetate (5
acids, phenols mL), MeOH

P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

14mL)
carboxylic EVB-DVB/C18 BSTFA/TMCS RT – MeOH (200 ␮L) MS 0.6–15 ng/L <4.6 93–101 [85]
acids
MSPE phenols Fe3O4@C@PANI BSTFA/TMCS RT/20 min – Ethyl MS 0.89–7.58 ␮g/L <13.1 85–111 [86]
microspheres acetate/5min
SBSE Phenols and PDMS MTBSTFA RT/240 min – Ethyl acetate MS 1–800 ng/L <20 70 – 130 [87]
carboxylic (0.2 mL)/30
acids min
formaldehyde PDMS-DVB PFBHA 50 ◦ C/40 min 250 ◦ C/7 min – MS 10 mg/L <23 – [96]
carboxylic CAR-DVB – 25 ◦ C/20 min 250 ◦ C/3 min – MS 11.5 mM/L <16.7 77–114 [99]
acids
SPME
carboxylic Ionic liquid: – 35 ◦ C/10 min 170 ◦ C/4 min – MS – – – [103]
acids Poly
(1-Vinyl-3-
Hexylimidazolium)
Chloride
phenols MWCNTs – 70 ◦ C/50 min 280 ◦ C/5 min – FID 5–50 ␮g/L <6.5 88–112 [100,102]
phenols Polyamide – 30 ◦ C/60 min 280 ◦ C/3 min – MS 0.04–1 ␮g/L <10 – [95]
phenols MWCNTs – 50 ◦ C/40 min 250 ◦ C/3 min – FID 1.89–65.9 ng/L <12.4 88–112 [101]
phenols PDMS–CAR AAA 100 ◦ C/30 min 270 ◦ C/– – MS 0.001–0.04 <16.2 – [94]
␮g/L
phenols Amide bridged- – 50 ◦ C/15 min 260 ◦ C/3 min – FID 0.47–9.01 ␮g/L <9.1 90–103 [104]
HS- C[4]/OH-TSO
SPME phenols, PDMS-CAR- – 70 ◦ C/30 min 250 ◦ C/1 min – MS 0.003–0.6 ␮g/L <16 >70 [97]
aldehydes DVB
◦ ◦
carboxylic CAR-DVB – 25 C/20 min 250 C/3 min – FID 3–467 ␮g/L <10 85–117 [88]
acids
carboxylic PEG – 25 ◦ C/40 min 230 ◦ C/3 min – MS 0.017–0.064 – – [98]
acids mg/L
carboxylic PDMS-CAR – 25 ◦ C/20 min 300 ◦ C/5 min – FID 6–675 ␮g/L <13.3 – [90]
acids
FID, 6–675 ␮g/L
carboxylic 300 ◦ C/5 (FID), 2–6 ␮g/L
PDMS-CAR – 25 ◦ C/– – NCI-MS (NH3 ), <16 – [93]
acids min (NCI-MS),
PCI-MS (CH4 )
10–115 ␮g/L
(PCI- MS)

Solvent used for elution of fraction of interest.

 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 151

A compilation of solid-phase extraction procedures used for the 4. Separation proces - stationary phases
determination of O-VOCs is shown in Table 3.
The selection of a proper chromatographic column has a deci-
sive effect on the results of both qualitative and quantitative
analysis. Efficient separation of analytes is required for correct
3. Derivatization identification, accurate determination and thus applicability of an
analytical procedure. A number of commercial capillary columns
Derivatization is carried out in order to improve physicochemi- with various types of stationary phases are now available, which
cal properties of analytes, including change in polarity, lowering are recommended for the analysis of individual groups of chemical
of boiling point and improvement of thermal stability. Further- compounds in order to ensure the best selectivity and resolution.
more, by introducing a functional group containing for example
a halogen, the sensitivity of the determination can be improved 4.1. Polydimethylsiloxane based stationary phases
by using the selective electron capture detector (ECD) [108,109].
On the other hand, derivatization of wastewater samples having For direct injection of aqueous solutions without prior removal
a very complex matrix can result in unwanted chemical reactions of the water matrix, a polar stationary phase, such as a wax-based
in the sample. In addition, introduction of a derivatizing agent can sol-gel phase [118] or, alternatively, a stationary phase of low
contaminate a sample and extend the time of sample preparation. polarity, i.e., polydimethylsiloxane or 5% phenyl 95% polydimethyl-
Consequently, derivatization of analytes should be considered as a siloxane should be used. These stationary phase practically do not
last resort used only for the analytes for which direct determination interact with water so they are not damaged by aqueous samples
at low concentrations is very difficult or impossible, including com- [119]. Another option is to use apolar-deactivated guard column,
pounds containing carboxyl or hydroxyl groups. Depending on the which enables complete evaporation of water prior to introduction
group of analytes investigated, various types of derivatization reac- of analytes onto the column [119,120].
tions are carried out, including silylation, esterification, alkylation The use of PDMS as a stationary phase is recommended for the
or acylation. separation of phenols due to strong dispersive forces which leads
Derivatization methods have been described in a number of to elution of the majority of analytes according to their boiling
papers [47,110–114]. The most common reagents used for deriva- point, thus facilitating identification [100,109]. The most common
tization of O-VOCs, which block polar groups being proton donors stationary phases used for the separation of volatile oxygenated
(i.e., −OH and −COOH), include alkylsilanes, such as N,O-bis- organic compounds, except for carboxylic acids, from wastewater
(trimethylsilyl)trifluoroacetamide (BSTFA) [51,52,79,83,85,86] samples are 5% phenyl 95% dimethylpolysiloxane and 5% phenyl
N-trimethylsilylimidazole (TMSIM), trimethylchlorosilane 95% dimethylarylenesiloxane, which have low polarity.
(TMCS) [51,52], N,O-bis(trimethylsilyl) acetamide (TMSA)
[53], hexamethyldisilazane (HMDS) [84] and N-methyl-N-(tert- 4.2. Polyethylene glycol based stationary phases
butyldimethylsilyl)trifluoroacetamide (MTBSTFA) [76,77,87]. They
allow introduction of the trimethylsilyl group (TMS) to analyte Some carboxylic acids (C2 – C8 ) are sufficiently volatile and
molecules thus increasing volatility of the analytes, improving thermally stable to be determined by GC without derivatization.
separation of isomers and enhancing sensitivity of detection when However, their high polarity and ability to form hydrogen bonds
using a mass spectrometer operated in the positive chemical precludes obtaining symmetrical peaks with most popular sta-
ionization mode. However, despite numerous advantages, silyl tionary phases of low and medium polarity. Consequently, polar
derivatives are very unstable and the analysis must be carried out stationary phases based on polyethylene glycol (PEG) are rec-
within 12–24 h, which limits the use of these reagents in routine ommended for the separation of volatile fatty acids [120–124].
determinations of a large number of samples [51]. Alkane monocarboxylic acids tend to adsorb in the injection
Carboxylic acids can undergo direct 100% reaction yield in port or on the column, therefore, many reports recommend
2–3 min is diazomethane; however, it is not recommended due the use of PEG modified with 2-nitroterephthalic acid (called
to its irritating, carcinogenic and explosive properties [47,113]. free fatty acid phase – FFAP), which deactivates its basic sites
Consequently, diazomethane is often replaced with less hazardous [43,49,88–90,93,98,99,103,125]. FFAP was also successfully used
reagents, such as pentafluorobenzyl bromide (PFBBr), which pro- for the separation of phenols [60]. Another interesting approach is
vides much lower yields and the reaction takes several hours to connect several capillary columns in series, including a column
[113,115]. The method of derivatization of carboxylic acids that is with a polar stationary phase connected to a short deactivated col-
not time consuming and enables automation is the formation of umn, followed by a PDMS column and another deactivated column.
ion pairs through the reaction of carboxyl or hydroxyl groups with The use of such a sequence allows complete separation of carboxylic
tetraalkylammonium salts in the sample solution. The ion pairs acids C2 - C8. Furthermore, using a polar stationary phase in the first
formed after being injected into the hot (>280 ◦ C) GC injection port column resulted in obtaining narrow and symmetrical peaks [126].
are converted into alkyl (often butyl) esters. The most common A significant disadvantage of polar stationary phases is their rela-
ion pairing reagents include tetrabutylammonium hydrogensul- tively low maximum operating temperature (<260 ◦ C) which makes
fate (TBA-HSO4 ) [56,64], tetrabutylammonium chloride (TBA-Cl) them unsuitable for the analysis of higher boiling compounds, such
and tetrabutylammonium bromide (TBA-Br) [56,59,61]. The butyl as long-chain carboxylic acids or dicarboxylic acids [127].
esters formed have greater mass-to-charge (m/z) ratio compared The most recent (and most expensive) approach is the coupling
to methyl esters which improves selectivity in GC MS analysis of time-of-flight mass spectrometer (TOF-MS) with comprehensive
[56,68,116]. Another interesting approach is the procedure based two-dimensional gas chromatography (GCxGC). Two-dimensional
on the use of inexpensive and simple to synthesize deep eutectic GC separation of analytes greatly improves peak capacity and
solvent composed of choline chloride and 4-methyl phenol in 1:2 M enables a very effective separation. Typically, analytes are sepa-
ratio (ChCh:4MPh1:2) for both the extraction of the analytes and rated on a column with the stationary phase of a low polarity in
their ion pair derivatization [65].Another class of reagents allowing the first dimension, followed by the separation of each fraction on
derivatization of carboxylic acids to alkyl esters in aqueous are alkyl a more polar stationary phase in the second dimension. However, a
chloroformates. The alkyl esters formed can be readily extracted reverse order of polarity of the stationary phases is sometimes used.
into nontoxic organic solvents [117]. The technique GC x GC-ToF-MS was used to determine isomers of
152 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

Table 4
A list of the most popular commercially available stationary phases for the separation of selected groups of O-VOCs.

Polarity Stationary phase Analytes

Non-polar Dimethylpolysiloxane phenols, aldehydes, ketones, alcohols, esters, ethers

5% Phenyl 95% dimethylpolysiloxane phenols, aldehydes, ketones, alcohols
Intermediate polarity 5% Phenyl 95% dimethyl arylene siloxane phenols, aldehydes
6% Cyanopropyl-phenyl, 94% dimethyl polysiloxane phenols, aldehydes, ketones, alcohols, esters, ethers
Polyethylene glycol carboxylic acids
Polar
Polyethylene glycol modified with 2-nitroterephthalic acid carboxylic acids, phenols
Highly polar (1,5-di(2,3-dimethylimidazolium)pentane bis(tri fluoromethylsulfonyl)imide) phenols, aldehydes, ketones, alcohols, esters, ethers

nonylphenol. This approach allowed to minimize co-elution of ana- [139]. Such high LOD values disqualify this detector for determi-
lytes and to identify a larger number of isomers which could not be nation of volatile oxygenates in wastewater samples, in which the
separated in the SIM mode by GC MS [128,129]. analytes occur at concentrations in the order of ppb and ppm. Thus
far, no procedures for the determination of O-VOCs in wastewa-
4.3. Ionic liquids ter making use of analyte enrichment and derivatization combined
with GC-O-FID have been reported.
An alternative to stationary phases based on polyethylene gly-
col are novel stationary phases based on ionic liquids which, due to 5.2. Mass spectrometry
unique properties of ionic liquids, are polar or extremely polar. At
the same time, columns with ionic liquids as the stationary phase At present, a mass spectrometer is the detector most commonly
can operate at higher temperatures compared to conventional polar used in the determination of volatile oxygenated organic com-
columns [130–132]. When separating a model mixture contain- pounds in wastewater. When using selected ion monitoring (SIM)
ing 36 O-VOC compounds, the highest selectivity was obtained mode, the MS can selectively detect analytes in the presence of co-
with an ionic liquid (1,5-di(2,3-dimethylimidazolium)pentane eluting matrix components. Moreover, when used with an analyte
bis(trifluoromethylsulfonyl)imide) as the stationary phase com- isolation and enrichment procedure, GC–MS allows determination
pared to traditional stationary phases of low and medium polarity. of analytes at a ␮g/L or even ng/L level [51–53,56,62,85]. A major
Co-elution was observed only for several compounds with substan- advantage of a mass spectrometer over the other GC detectors is its
tially different mass spectra due to occurrence of specific fragment ability to identify unknown compounds in the SCAN mode based on
ions, which did not interfere with quantitative analysis. Moreover, comparison of the obtained spectra with vast mass spectral libraries
the use of the column with the ionic liquid resulted in elution of when the electron ionization (EI) is used. On the other hand, in the
C5 to C8 n-alkanes in dead time which reduced matrix interference SIM mode identification of analytes is carried out by comparison of
since these alkanes are commonly present in petroleum refinery their retention times with those of standards, taking a confidence
effluents [9,11,12,133]. interval of ± 0.2% tR [min], as well as on the basis of selected char-
Oxygenated organic compounds are also separated on station- acteristic values of mass-to-charge ratios and comparison of their
ary phases based on carbon nanotubes whose properties can be intensities. As a rule, several characteristic ions are selected for each
modified by binding various functional groups improving their compound in a given interval of retention time. It should be noted,
selectivity toward alcohols and esters and reducing the time of however, that the detector sensitivity decreases with an increase
analysis. However, most of the papers published report the use in number of monitored ions. Therefore, a reasonable approach is
of such stationary phases for the separation of model mixtures to select two characteristic mass-to-charge values, of which one is
[134–136]. used for integration of the peak while the other is used to con-
A list of the most popular commercially available stationary firm the peak identity based on the ratio of intensities with an
phases for separating selected groups of O-VOC is compiled in assumed confidence interval of 15–30 %. Such an approach consti-
Table 4. tutes a sufficient confirmation of peak identification while allowing
the determination of analytes at suitably low concentration levels
5. Detection [11,12].
The second type of ionization commonly used in a mass spec-
A popular detector used in the analyses of wastewater is the trometer is positive or negative chemical ionization (CI), which
universal flame ionization detector (FID) [55,60,61,66,68,85,93]. does not ensure such a high reproducibility of ionization as was the
However, due to its lack of selectivity toward oxygenated organic case with EI, which results in the absence of commercially available
compounds and a considerably lower sensitivity, it is not recom- mass spectral libraries and identification is carried out on the basis
mended for the determination of O-VOCs in samples with very of an intense molecular ion which is possible due to soft ionization.
complex matrices, such as wastewater [85,93]. The studies in which two modes of ionization, EI and positive CI in
which ammonia was used as a reagent gas, were compared revealed
5.1. Oxygenate selective flame ionization detector only slight differences in reproducibility of the results obtained in
the SIM mode for 22 carboxylic acids, LOD values lower by a factor of
The only GC detector selective exclusively to oxygenated com- ca. 25 and a wider linear range for EI-MS [85]. A comparison of pos-
pounds is oxygenate selective flame ionization detector (O-FID) itive(reaction gas CH4 ) and negative (reaction gas NH3 ) chemical
[137]. The detector includes a cracking reactor which converts ionization in the determination of volatile fatty acids demonstrated
any oxygenated compounds to carbon monoxide and a special lower detection limits when negative chemical ionization was used
FID with a microreactor for the catalytic hydrogenation of CO and [93].
detection of methane Hydrocarbons give no signal. Peaks in the A complex matrix composition of wastewater sample often pre-
chromatogram represent solely oxygenated organic compounds cludes direct identification due to co-elution of many analytes.
and the peak areas depend upon the analyte content and the num- To accomplish peak resolution and obtain pure spectra, chemo-
ber of oxygen atoms in a molecule [137,138]. GC-O-FID enables the metric models such as Parallel Factorial Analysis (PARAFAC) [140]
determination of O-VOCs at concentration levels 0.17–15% (m/m) or Multivariate Curve Resolution Alternating Least Squares (MCR-
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 153

Fig. 4. The advantages and disadvantages of universal and selective detectors for the determination of O-VOCs in wastewater samples.

ALS) [141,142] can be used. A different approach involves the All compounds absorption in this region have unique absorp-
use of a time-of-flight mass spectrometer which offers a much tion spectra, especially low-molar-mass oxygenates, including
improved resolution and the determination of m/z with an accuracy esters, aldehydes, ketones and short-chain volatile fatty acids.
of 0.1 m Da [143]. So far, this technique was applied to study the compounds
exhaled with human breath [146]. Additionally, GC-VUV has
5.3. Detectors based on ultraviolet light found use in the analysis of fatty acid methyl esters in edi-
ble oils [147], hydrocarbons in diesel fuels [148], pesticides
Theoretically, oxygenated organic compounds could also be [149], polychlorinated biphenyls [150] and investigation of iso-
determined without derivatization by a photoionization detector mers whose separation is difficult by other standard procedures
(PID). However, this method has not found a wide use in process [151]. Thus far, however, GC-VUV has not been used for the
analysis of wastewater. determination of O-VOCs in wastewater samples although due
Another universal detector allowing both qualitative and to its specific properties and the possibility of determination
quantitative determinations is a vacuum ultraviolet detector of oxygenated compounds at low concentrations it could be
(VUV) introduced in 2014. Detector VUV allows the measure- utilized for routine analyses of O-VOCs in samples of wastewa-
ment of absorption spectra in the 125–240 nm range [144,145]. ter.
154 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

5.4. Other detectors Table 5

List of internal standards used in quantitative analysis of O-VOCs.

Electron capture detector (ECD), which is based on absorption Analytes Internal standards
of electrons by electrophilic molecules, is highly selective toward Alcohols 4-chloro-2-butanol
compounds having a high electron affinity, such as organochlorine [11],4-chlorophenol
compounds for which ECD is specific. ECD is selective to O-VOCs; [11],1,1,3,3-tetramethoxypropane [29],
however, this selectivity is insufficient for analysis of samples hav- N,N-diisopropylformamide [29]
Aldehydes 4-chloro-2-butanol [11],
ing a very complex matrix. The presence of water in extracts, even
3-chloro-2-butanone [11],
at trace levels, is also a problem due to a large ECD response to 4-chlorophenol [11],acetone-d6 [96]
water. Therefore, analytes should be converted into derivatives Ketones 3-chloro-2-butanone [11],
containing atoms of chlorine, bromine [152] or fluorine [153] to 4-chlorophenol
[11],1,1,3,3-tetramethoxypropane [29],
obtain high sensitivity of detection. However, this approach has not
N,N-diisopropylformamide [29]
found a widespread use in the analysis of wastewater. Theoretically, Esters 4-chloro-2-butanol [11]
other selective detectors, such as a nitrogen-phosphorus detec- Ethers 4-chloro-2-butanol [11],
tor (NPD), chemiluminescence detector (CLD), flame photometric 1,1,3,3-tetramethoxypropane [29],
detector (FPD) or a pulsed flame photometric detector (PFPD) and N,N-diisopropylformamide [29],
MTBE-d16 [44]
sulfur chemiluminescence detector (SCD), could be used for the
Phenols 4-chlorophenol [11], n-pentadecane
determination of O-VOCs in wastewater samples after conversion [59,61], 1,1,3,3-tetramethoxypropane
of analytes into suitable derivatives. Nonetheless, despite their high [29], N,N-diisopropylformamide [29],
sensitivity these detectors have not found use in routine analyses bisphenol-d16 [79],
[13 C6 ]-pentachlorophenol [82],
of wastewater samples.
phenol-d5 [87], 2-chlorophenol-d4
Research is continuing on the development of novel types of [87], 2,4-dimethylphenol-d3 [87],
GC detectors, such as an amperometric detector based on a sil- 4-chloro-3-methylphenol-d2 [87],
ica sol-gel solid electrolyte. This detector is not selective toward 2,4-dichlorophenol-d3 [87],
hydrocarbons but it enables identification of compounds such as 2-nitrophenol-d4 [87],
2,4,6-trichlorophenol-d2 [87],
phenol or p-cresol at low concentrations. Thus, it could be success-
4-nitrophenol-d4 [87],
fully used for the analysis of O-VOCs in among others, petroleum 2,4-dinitrophenol-d3 [87],
refinery effluents which have a matrix rich in hydrocarbons [154]. pentachlorophenol-13 C6 [87],
The list of detectors along with their advantages and disadvan- 2-methyl-4,6-dinitrophenol-d2 [87]
Carboxylic acids 2-ethylbutyric acid [37,90,93],
tages is depicted in Fig. 4.
margaric acid [51], heneicosanoic acid
[52], anthracene-d10 [53],
2-chlorobenzoic acid [64,65],
6. Quantitative analysis triphenylphosphate [85]

Quantitative analysis of O-VOCs in wastewater samples is usu-

ally carried out by a calibration curve (external standard) method. as FID, due to very complex matrix composition and the difficulty
However, when using some GC detectors, including mass spec- of selecting an internal standard which would not co-elute with
trometer, the detector sensitivity can gradually deteriorate after the matrix components. Another common method of quantitative
a dozen or so analyses. Thus, to ensure reliability of the results, cal- analysis is the standard addition method which involves addition
ibration should be often repeated which makes application of the to a sample known amounts of the analyte, followed by chromato-
developed procedures to routine analyses more challenging. The graphic analysis. This method has not found widespread use in the
problem can be minimized by using the internal standard method quantitative analysis of wastewater since it is tedious and time-
which allows a much longer stability period of the procedure pro- consuming but it useful during the development of new analytical
vided that the detector response changes to the same extent for procedures because it allows a comparison of the agreement of the
analytes and the standard. An internal standard is selected on the results obtained by the procedure being developed for real sam-
basis of similarity of its physicochemical properties to those of ples with other methods. In such a case the results obtained by the
analytes, such as boiling point, volatility, octanol-water partition standard addition method are accepted as the expected value.
coefficient, etc. It must also be absent from real samples, be sep-
arated on the chromatogram from analytes, be chemically stable 7. Oxygenated volatile organic compounds content in
and the detector response to the internal standard must be simi- various kinds of wastewater
lar to those of analytes. Examples of internal standards selected for
the determination of specific groups of compounds are compiled The presence of various groups of O-VOCs and their content is
in Table 5. The internal standard method works best for complex, closely related to the kind of wastewater. Chemical plants typically
multistep procedures, since it corrects for analyte losses which take generate high volumes of wastewater containing chemicals being
place at every step of an analytical procedure and also accounts the main products as well byproducts [43]. For example, wastewa-
for variations in sample volume during the injection step. Another ter from coke manufacturing plants contains considerable amounts
approach is to use isotope dilution which is a version of internal of phenol whose concentration can be as high as 213.23 mg/L
standard method wherein the internal standard differs from the and large amounts of cresols [55,67,104]. These values signifi-
analyte solely in its isotope composition (deuterated derivatives of cantly exceed the maximum allowed concentrations in industrial
analytes are used most often). Using the internal standard method effluents discharged to the environment [20–24]. Phenols also com-
introduces an additional step to the analytical procedure (addition monly occur in the effluents from the petroleum industry, including
of an internal standard/standards to the sample) but current com- refineries [68,155], effluents from the production of bitumens
mercial automated equipment, such as an P&T extraction module, [11,12] and petrochemical wastewater [45,78,156]. The content of
allow automatic addition of internal standards [106]. However, the phenolic compounds is lower compared to coke wastewater but
internal standard method may not find application in the analy- petroleum wastewater also contain other kinds of toxic O-VOCs,
ses of wastewater samples making use of universal detectors, such including alcohols, benzoic acids, acrylates, aldehydes, ketones
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 155

and ethers at concentrations in the order of ␮g/mL [11,12,68] or Consequently, there is a continuing need to develop novel, effec-
␮g/L in the case of MTBE [155]. On the other hand, wastewa- tive procedures for the determination of low concentrations of
ter from the paper industry contains mostly palmitic and stearic O-VOCs in wastewater samples. A necessary step of each such
acids [51,52]. The same compounds are also present in wastewa- procedure is extraction of analytes since direct analysis of such
ter from the production of antibiotics at concentrations equal to complex matrices can contaminate the GC system. Among the
80 ␮g/L and 95.8 ␮g/L for palmitic and stearic acid, respectively existing procedures for isolation of analytes from the aqueous
[56]. Oxygenated organic compounds, including phenols, benzoic matrix, headspace techniques are not the best choice despite full
acids, ketones and esters were detected in wastewater from the automation due to discrimination of compounds having a medium
textile industry, with 2,6-di-tert-butyl-4-ethylphenol and butyl- or low volatility. Classical LLE, which enables enrichment of both
tetramethylphenol having the highest concentrations (1.23 ␮g/L volatile and semivolatile analytes, is being gradually replaced by
and 0.58 ␮g/L, respectively) [156] whereas the tannery wastew- microextraction techniques as a result of consumption of large vol-
ater contained alcohols, phenols, carboxylic acids and ketones at umes of solvents and toxicity of some of them. At present, the
concentrations ranging from 0.01 to 0.03 ␮g/L [156,157]. technique most often used during the development of new proce-
Strongly contaminated industrial effluents have to undergo pre- dures is DLLME due to its simplicity, short time and small volumes
liminary treatment before being sent to municipal or industrial of organic solvents used. However, DLLME is difficult to automate
wastewater treatment plants (WWTP) in order to meet the required which constitutes its main disadvantage. Literature search revealed
specifications. The limits set pertain mostly to total parameters several attempts at automation of DLLME, however, these designs
and not individual compounds; thus, the concentrations of partic- are still at a development stage aiming at improvements in repro-
ular analytes are relatively high. In WWTP industrial wastewater is ducibility, recovery and an increase in the number of samples
combined with domestic wastewater, rain water and snowmelt, processed. Hopefully, new and improved automated DLLME sys-
forming so-called municipal wastewater, wherein both typical tems will become available in the near future. Other types of solvent
compounds found in domestic wastewater and compounds orig- microextraction, including SDME, HS-K-HFME, and LPME were also
inating from industrial wastewater can be identified. Common discussed in this review but all these modes are characterized by a
components of municipal and sanitary wastewater are phenols, long extraction time which is a significant disadvantage if a large
whose concentrations can be as high as 433 ␮g/mL and carboxylic number of samples has to be analyzed.
acids at concentrations up to 275 ␮g/mL [43,49,90,98]. In addition, Among liquid-solid extraction techniques, similarly to LLE, the
municipal wastewater also contained MTBE at 25 ␮g/mL [158] and most common solid-phase extraction is being replaced by minia-
acetone at 0.62 ␮g/mL [43]. turized versions which consume less sample and organic solvents.
Examples of various kinds of wastewater along with concentra- There is considerable interest in new stationary phases for SPME
tions of main O-VOC components are compiled in Table 6. which is likely to be continued, especially in the area of polar sor-
The majority of procedures described in this review pertain to bents which will have improved selectivity toward, for example,
the determination of carboxylic acids and phenols in wastewater. carboxylic acids.
There are just a few reports dealing with the presence and concen- In general, derivatization is not recommended in the analy-
trations of other O-VOC compounds in various types of wastewater. sis of wastewater due to complex sample matrix and a likelihood
There exist no procedures that would allow a comprehensive of unwanted chemical reactions. Furthermore, in most cases the
evaluation of content of various kinds of O-VOCs in wastewater derivatization procedure is complex and time-consuming. Never-
samples. The conclusions from reviews discussing investigations of theless, the determination of some compounds, such as carboxylic
advanced oxidation processes [159,160] used for chemical degra- acids with more than 9 carbon atoms or dicarboxylic acids at low
dation of organic pollutants in industrial effluents reveal that due concentrations in wastewater samples is very difficult. Therefore, in
to the lack of recent procedures for detailed characterization of such cases a good approach is to use tetrabutylammonium reagents
the effluents, the research is often based solely on changes in total which results in formation of derivatives in the GC injection port.
parameters, i.e., biochemical oxygen demand and chemical oxygen This approach is not labor-intensive and be automated which lim-
demand or total organic carbon. Dissemination of chromatographic its the activity of the analyst during the sample preparation step
procedures based on gas chromatographs commonly available in thus eliminating a number of errors and improving repeatability of
the laboratories of industrial facilities and sample preparation tech- results.
niques not requiring special equipment should result in an increase The availability of a variety of analytical procedures for the
in the scope and degree of detail of the results of analyses. determination of individual groups of O-VOCs in wastewater
The described analytical methods can also be used for the deter- samples requires performance of a number of time-consuming
mination of O-VOCs in other aqueous samples which have a very analyses. Consequently, the approach involving combination of
complex matrix. One of the examples are leachates from landfills gas chromatography with MS in electron impact ionization mode
which contain large amounts of toxic organic compounds including is becoming increasingly more popular. This approach allows not
phenols [129,161,162], dioxanes [163] and carboxylic acids [164]. only quantitative analysis in the SIM mode but also identification
The methods could also be used for the determination of contam- of unknown analytes based on matching their mass spectra with
inations in different types of environmental samples, i.e. airport those present in comprehensive spectral libraries. However, a com-
runoff water containing glycols [165], groundwater [166], rivers plex matrix often precludes correct identification of analytes due to
[167] and lakes located near factories [168] as well as for the deter- numerous co-elutions. An improved resolution can be obtained by
mination of O-VOCs in process water for evaluating and controlling using GC-TOF-MS but the high cost still hinders its widespread use.
the process such as production of biogas [169]. Therefore, chemometric models combined with GC MS in the EI
mode constitute a viable alternative, which allows obtaining a com-
plete resolution of chromatographic peaks and pure mass spectra.
8. Summary and outlook With the comprehensive two-dimensional gas chromatography
(GCxGC) instrumentation becoming more available, new proce-
Industrial, domestic and municipal wastewater contains a dures for the determination of O-VOCs making use of this technique
number of toxic volatile and semivolatile oxygenated organic are likely to appear. Orthogonality of the stationary phases used in
compounds with widely varying concentrations in very complex the two dimensions should allow a simplification of sample prepa-
matrices which makes their determination a serious challenge. ration steps. In addition, the VUV detector has found increased use
156 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160

Table 6
Compilation of O-VOCs occurring in various types of wastewater.

Matrix Analytes Method of Concentration range Compounds occurring at highest Ref.

determination concentration

Sanitary phenols SPME-GC-FID 1210–3480 ␮g/mL o-ethylphenol (2750 ␮g/mL), [88]

wastewater 2,3-dimethylphenol (3480 ␮g/mL)
phenols SPME-GC-FID 1240–22,900 ␮g/mL o-ethylphenol (1240 ␮g/mL), [90]
p-ethylphenol (22,900 ␮g/mL)
Municipal, animal farm carboxylic acids LLE-GC-MS 0.18–726 ␮g/mL acetic acid (726 ␮g/mL), propionic acid [50]
and landfill wastewater (58.2 ␮g/mL)
MTBE DHS-GC-MS 3–25 ␮g/mL methyl tert-butyl ether (3–25 ␮g/mL) [44]
acetone DHS-GC-FID 0.25–0.62 ␮g/mL acetone (0.25–0.62 ␮g/mL) [43]
phenols SDE-GCxGC-ToF-MS 820–12,950 ␮g/mL 4-tert-octylphenol (10,780 ␮g/mL), [129]
4-tert-nonylphenol (12,950 ␮g/mL)
phenols SPE-GC-MS 37.6–555 ␮g/mL nonylphenol (555 ␮g/mL), octylphenol [80]
(182 ␮g/mL), bisphenol A (38.8 ␮g/mL)
phenols SPE-GC-MS 43–433 ␮g/L phenol (433 ␮g/L), 2,4-dimethylphenol [77]
Municipal (240 ␮g/L)
wastewater phenols SPE-GC-MS 115–235 ␮g/L phenol (235 ␮g/L) [76]
phenols SPE-GC-MS 0.1–348 ␮g/L 2-sec-butylphenol (348 ␮g/L), phenol (34.6 [83]
␮g/L), m-cresol (31.0 ␮g/L)
phenols MSPE-GC-MS 7.94–8.15 ␮g/L phenol (8.15 ␮g/L), bisphenol A (7.94 ␮g/L) [86]
phenols, aldehydes HS-SPME- GC-MS 0.5–151 ␮g/L phenol (39.3 ␮g/L), m-cresol (151 ␮g/L) [97]
carboxylic acids HS-SPME-GC-MS 0.065–102 ␮g/mL acetic acid (102 ␮g/mL), propionic acid [98]
(19.6 ␮g/mL)
carboxylic acids HS-SPME-GC-NCI/MS 45–19,611 ␮g/L acetic acid (19,611 ␮g/L), propionic acid [90]
(NH3 ) (7812 ␮g/L), butyric acid (1338 ␮g/L)
phenols HS-SPME-GC-MS 0.073–2.1 ng/mL p-cresol (2.1 ng/mL), 3,4-dimethylphenol [94]
(2.1 ng/mL)
phenols DI-SDME-GC-MS – o-cresol, 2,3,5-trimethylphenol [59]
phenols LLE-GC-MS 0.046–0.245 ␮g/L bisphenol A (0.245 ␮g/L), bisphenol F [53]
(0.057 ␮g/L)
phenols SPE-GC-MS/MS 0.04–0.16 ␮g/L 4-tert-octylphenol (0.16 ␮g/L), [82]
4-n-nonylphenol (0.08 ␮g/L),
2,4-dimethylphenol (0.06 ␮g/L)
MTBE SPE-GC-MS 25–300 ng/L methyl tert-butyl ether (25 -300 ng/L) [158]
Paper mill process carboxylic acids LLE-GC-MS 49–275 ␮g/mL palmitic acid (49–275 ␮g/mL) [51]
water
Paper-recycling carboxylic acids LLE-GC-MS 0.8–4.2 ␮g/mL palmitic acid (4.2 ␮g/mL), stearic acid (3.4 [52]
process water ␮g/mL)
Wastewater from carboxylic acids LPME-GC-MS 35.2–95.8 ␮g/mL palmitic acid (80 ␮g/mL), stearic acid (95.8 [56]
antibiotics ␮g/mL)
manufacturing factory
Effluent from textile phenols, benzoic acids, HT-GC-MS 0.01–1.23 ␮g/L 2,6-di-tert-butyl-4-ethylphenol (1.23 ␮g/L) [156]
industry ketones and esters butyltetramethylphenol (0.34 ␮g/L)
Tannery phenols, carboxylic SPE-GC-MS – p-cresol, 4-methylbenzoic acid [157]
effluent acids
phenols, carboxylic HT-GC-MS 0.01–0.03 ␮g/L 2,6-di-tert-butyl-4- methoxymethylphenol [156]
acids, alcohols, ketones (0.03 ␮g/L), tetra-ethoxynonylphenol (0.03
␮g/L)
Coking phenols HS-SPME-GC-FID 4.4–131.8 ␮g/mL phenol (131.8 ␮g/mL), p-cresol (51.2 [104]
plant ␮g/mL)
wastewater phenols LPME-GC-FID 1.51–213.23 mg/L phenol (213.23 mg/L), o-cresol (23.05 [55]
mg/L), m-cresol (59.11 mg/L)
phenols DLLME-GC-MS 0.4–13.4 ␮g/mL phenol (13.4 ␮g/mL), m-cresol (9.4 ␮g/mL) [67]
aldehydes, ketones, DHS-GC-MS 0.5–21.55 ␮g/mL 2-butenal (21.55 ␮g/mL), phenol (19.9 [45]
Petrochemical
alcohols, phenols ␮g/mL)
wastewater
alcohols, ketones, SPE-GC-MS – phenol, 2-ethylhexyl alcohol, [78]
phenols acetophenone
alcohols, ketones, HT-GC-MS 0.01–0.05 ng/mL trimethylbenzoic acid (0.05 ␮g/mL), [156]
phenols, esters 2,5-dimethylbenzoic acid (0.03 ␮g/mL)
Effluents phenols, ketones, DHS-GC-MS 0.18–39.16 ␮g/mL furfural (39.16 ␮g/mL), cyklohexanol [12]
from alcohols, aldehydes, (19.28 ␮g/mL), 2-pentanone (18.7 ␮g/mL),
production of esters, ethers 2-butanol (14.75 ␮g/mL)
petroleum phenols, ketones, DLLME-GC-MS 0.37–27.43 ␮g/mL phenol (27.43 ␮g/mL), m-cresol (13.7 [11]
bitumens alcohols, aldehydes, ␮g/mL), 1-propanol (24.88 ␮g/mL)
esters, ethers
carboxylic acids DLLME-GC-MS 0.13–15.06 ␮g/mL heptanoic acid (15.06 ␮g/mL), benzoic acid [64]
(7.52 ␮g/mL)
carboxylic acids USA-DLLME-GC-MS 0.33–43.3 ␮g/mL benzoic acid (43.3␮g/mL), octanoic acid [65]
(30.1 ␮g/mL), nonanoic acid (21.9 ␮g/mL)
Effluents from MTBE HS-SPME/GC-MS 34.3–1877.5 ng/mL methyl tert-butyl ether (34.3–1877.5 [155]
crude oil ␮g/mL)
refinery acrylates DLLME-GC-FID 54.08–68.42 ␮g/mL methyl acrylate (68.42 ␮g/mL), methyl [68]
methacrylate (64.72 ␮g/mL)
 P. Makoś et al. / J. Chromatogr. A 1592 (2019) 143–160 157

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Acknowledgements Conditions to Be Met for the Introduction of Sewage Into Waters or to Land
and on Substances Particularly Harmful to the Aquatic Environment (Dz. U.
The authors gratefully acknowledge the financial support from Z Dnia 31 Lipca 2006 r.), 2019,
http://brasil.cel.agh.edu.pl/0̃9skmolfa/file/Dz.U.2006.137.984.R4.pdf
the National Science Center, Warsaw, Poland – decision no. DEC- (Accessed on 13.10.2016).
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Appendix A. Supplementary data [23] Estonian Governmental Regulation no. 269 from the 21st of July 2001.
Effluent guidelines for wastewater discharges to reservoirs and surface
Supplementary material related to this article can be found, in waters.
[24] Regulation of the Minister of Construction of 14 July 2006 on how to fulfill
the online version, at doi:https://doi.org/10.1016/j.chroma.2019. the obligation of industrial wastewater providers and the conditions for
01.045. introducing sewage into sewerage equipment (Dz. U. z dnia 28 lipca 2006 r.)
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