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 Author's personal copy

Trends Trends in Analytical Chemistry, Vol. 32, 2012

Determination of volatile organic

compounds in drinking and
environmental waters
Nallanthigal Sridhara Chary, Amadeo R. Fernandez-Alba

Volatile organic compounds (VOCs) are of prime concern due to their toxicity and persistence in the environment.
We focus on sample-preparation methods, instruments used and concentrations reported in the determination of VOCs in
aquatic matrices (e.g., seawater, river water, groundwater and drinking water). We pay special attention to sample-enrichment
methods and mention the application of different detectors with respective sensitivities.
We note that, among the sample-pre-concentration methods, purge-and-trap and solid-phase microextraction were the most
chosen methods, which enabled excellent recoveries for a wide range of VOCs. Among the detectors, the mass-selective detector
was unchallenged, due to the remarkable sensitivity and detection based on mass. Tandem mass spectrometry is still emerging for
determining VOCs, since not many papers have been published on it.
The compounds detected most were the halogenated volatiles [e.g., dichloroethane, trichloroethane, bromodichloromethane
and dibromochloromethane (DBCM)], followed by benzene, toluene, ethylbenzene and xylene (BTEX). Trihalomethanes have also
been reported as a result of water-disinfection byproducts. Finally, the VOC levels detected most were the trihalo-alkanes
(trichloromethane: 1900 ng/L in estuary surface water; tribromomethane: 147–762 ng/L in drinking water; and, DBCM:92–399 ng/L
in drinking water), and among BTEX were benzene (3.9–141.7 ng/L in seawater) and xylene (4.3–332 ng/L in seawater).
We also note the need for quality assurance and mention the European Union Directive regarding VOCs.
ª 2011 Elsevier Ltd. All rights reserved.

Keywords: Benzene, Toluene, Ethylbenzene and xylene (BTEX); Drinking water; Environment; Environmental water; Gas chromatography;
Halogenated volatile; Method detection limit; Sample-enrichment method; Volatile organic compound; VOC Solvents Emissions Directive

Abbreviations: ACF, Activated carbon filter; AED, Atomic emission detector; BDCM, Bromodichloromethane; BTEX, Benzene toluene,
ethylbenzene, xylene; CLSA, Closed Loop Stripping Analysis; CMS, Capillary membrane sampler; CRM, Certified reference material; DAI, Direct
aqueous injection; DBCM, Dibromochloromethane; DBM, Dibromomethane; DCB, Dichlorobenzene; DCE, Dichloroethane; DCEY, Dichloroeth-
ylene; DCM, Dichloromethane; DELCD, Dry electrolytic conductivity detector; DVB, Divinylbenzene; EAQC, European Analytical Quality Control;
ECD, Electron capture detector; EI-PTR, Equilibrium inlet proton-transfer reaction; FIA, Flow-injection analyzer; FID, Flame-ionization detector; GC,
Gas chromatography; GIS, Geographical information system; HF-LPME, Hollow fiber-liquid-phase microextraction; HS, Headspace; IBMP,
2-Isobutyl 3-methoxy pyrazine; IMS, Ion-mobility spectrometry; INCAT, Inside needle capillary adsorption trap; IPMP, 2-Isopropyl 3-methoxy
pyrazine; IRMS, Isotope ratio mass spectrometry; IRMM, Institute for Reference Materials and Measurements; ITMS, Ion trap mass spectrometer;
LIMS, Laboratory information management system; LLE, Liquid-liquid extraction; LOD, Limit of detection; MI, Membrane introduction; MIMS,
Membrane-introduction mass spectrometer; 2-MIB, 2-Methyl isoborneol; MSD, Mass-selective detector; MRM, Multiple-reaction monitoring; MTBE,
Methyl tert-butyl ether; NIST, National Institute of Standards and Technology; NMIJ, National Metrology Institute of Japan; P&T, Purge and trap;
PDMS, Polydimethylsiloxane; PDPID, Pulsed discharge photoionization detector; PFBHA, 1,2,3,4,5-Pentafluorobenzylhydroxylamine; PID, Photo
ionization detector; PLOT, Porous layer open tubular; PT, Proficiency test; QA, Quality assurance; QC, Quality control; QUASIMEME, Quality
Assurance of Information in Marine Environmental Monitoring in Europe; RSD, Relative standard deviation; SBSE, Stir-bar sorptive extraction; SCMS,
Supported capillary membrane sampling; SIM, Selective ion monitoring; SPDE, Solid-phase dynamic extraction; SPME, Solid-phase microextraction;
TBE, Tetrabromoethylene; TBM, Tribromomethane; 2,4,6TCA, 2,4,6-Trichloroanisole; TCE, Trichloroethane; TCEY, Trichloroethylene; TCM,
Trichloromethane; THM, Trihalomethane; TLHS, Thin-layer headspace; TOF-MS, Time-of-flight mass spectrometry; USEPA, United States
Environmental Protection Agency; VOC, Volatile organic compound; WFD, Water Framework Directive; WISE, Water Information System of Europe

Nallanthigal Sridhara Chary, Amadeo R. Fernandez-Alba*

IM DEA-Agua (Madrid Institute of Advance Studies-Water), Punto Net, Edificio ZYE, Parque Cientifico Technologico de la Universidad de Alcala,
28805 Alcala de Henares, Madrid, Spain

* Amadeo R. Fernandez-Alba*
Corresponding author.
Pesticide Residue Research Group, University of Almeria, 04120 Almaria, Spain
E-mail: amadeo@ual.es

60 0165-9936/$ - see front matter ª 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2011.08.011
 Author's personal copy
Trends in Analytical Chemistry, Vol. 32, 2012
1. Introduction
Volatile organic compounds (VOCs) are one of the chief
issues in the environment and their wide distribution has
raised major concerns, in particular with environmental
sciences. VOCs correspond to a class of organics that are
characterized by their highly volatile nature under
existing environmental conditions. The chemical char-
acteristics (e.g., low water solubility, high lipid solubility,
semi-volatility and ability to pass through biological
membranes and accumulate in the fatty tissues) make
them of great concern in the environment.
Many definitions are available for VOCs {e.g., USEPA
defines VOCs as chemical compounds that contribute to
creation of photochemical ozone [1], and the EU Solvents
Directive defines VOCs as organic compounds having
vapor pressure of 10 Pa at 20C [2]}. There are other
definitions that characterize VOCs as compounds with
vapor pressure less than 13.3 Pa at 25C [3].
The main subgroups of VOCs include halogenated
organics, monocyclic aromatic hydrocarbons, organic
sulfides and sulfoxides, BTEXs, THMs, acetone, and
esters. VOCs may be of biogenic or anthropogenic origin.
Anthropogenic sources raise more concern than natural
sources. Major anthropogenic sources of VOCs to the
aquatic environment are paints and coatings, gasoline,
solvents, industrial and urban wastewaters, urban and
rural run-offs, and atmospheric depositions.
The analysis of VOCs is of growing interest due to their
impact on global environmental conditions and human
health. Apart from accumulating and persisting in the
environment, VOCs contribute to the increased green-
house effects and associated ozone depletion. Of total
dissolved organic carbon, 10% is VOCs in relatively
unpolluted waters and the concentrations are much
higher in raw waters from different anthropogenic
sources [4]. Once received in water, VOCs will behave in
ways influenced by their physicochemical properties (e.g.,
dilution, toxicological changes, and biodegradation will
play important roles in the stability and the concentra-
tions in water). Further, for halogenated VOCs, the sub-
stitution of halogens is known to affect the chemical and
toxicological properties in water. Hence, to get deep
insight into the occurrence and the behavior of VOCs,
analytical techniques at environmental background
levels (lg/L and ng/L) become crucial. Analysis of envi-
ronmental waters is not a simple issue, not only because
of the diversity of analytes and the range of their available
concentrations but also due to the complexity of the
matrix in which they are present. Hence, choosing
appropriate methods of sample enrichment, determina-
tion, isolation and quantification needs to depend on the
nature of the sample.
The highly volatile nature limits the analytical tech-
nique used for enrichment and quantification of a VOC,
so, when determining the concentrations of VOCs in
Trends
aqueous systems, their properties (e.g., low boiling point,
high vapor pressure and hydrophobicity) should be
taken into account.
Gas chromatography (GC) has been the first choice
and an efficient technique in determining and under-
standing the distribution and the occurrence of VOCs in
the environment. In most GC systems, performance in
the determination of VOCs was improved by combining
GC with classical detectors [e.g., flame-ionization detec-
tor (FID), electron-capture detector (ECD), and photo-
ionization detector (PID)] and modern detectors [e.g.,
mass-selective detector (MSD)], which have been widely
accepted for separation, identification and quantification
of VOCs at ng/L or lg/L levels.
All recent technical developments in GC have cer-
tainly contributed to the current analytical possibilities
for measuring VOCs in environmental matrices. The
purpose of this article is to present an overview of the
most efficient analysis of VOCs, emphasizing the methods
of sample preparation and separation, detection, the
range of concentrations of different VOCs reported in
different water sources, and the most frequently detected
compounds. We review research articles to understand
the best possible sample enrichment and detection
methods. Also, we present and discuss the limitations
and the advantages of each technique and methods to
facilitate fast, rapid analysis of VOCs.
2. Extraction and analysis of VOCs using GC
In aquatic samples, VOCs are reported in the range
ng/L–lg/L, hence determination of the truthful concen-
tration is typically achieved when large volumes are
injected. Alternatively, sample-enrichment techniques
can be applied to entrap a representative sample that can
be subjected to GC analysis. The sensitivity of the detector
used, appropriate sample preparation and pre-concen-
tration methods applied become significant for the trace
determination of VOCs. There have been research publi-
cations with reference to sampling, sampling prepara-
tion, method development and analysis of diverse VOCs
[4–12]. By contrast, in this section, we present a sum-
mary of sample-enrichment methods, chromatographic
separation, detectors used and LODs. Table 1 presents the
different sample-preparation methods in VOC analysis
and the most frequent detectors employed with GC. Also
included are LODs and limits of quantification (LOQs)
of sample-enrichment methods for different aquatic
matrices. Fig. 1 shows different sample-preparation and
direct sample-introduction methods along with detectors
available for GC.
2.1. Sample-introduction and enrichment techniques
In the analysis of environmental water matrices, sample
enrichment is a crucial, decisive step wherein the
http://www.elsevier.com/locate/trac 61
62
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Table 1. Main publications addressing analysis of volatile organic compounds in various aqueous matrices

Compounds Matrix Sample preparation/analysis LOD LOQ Ref.

Purge and trap technique
Halogenated organic compounds Waters (tap, mineral) P&T/GC-AED 0.05–0.5 lg/L 0.1–2.0 lg/L [16]
BTEX and other volatiles Wastewaters P&T/GC-FID 0.32–2.39 lg/L NR [20]
BTEX and halogenated organic Household and bottled waters P&T/GC-MS 0.06–0.11 lg/L NR [62]
compounds
Chlorinated hydrocarbons and aromatic Estuary waters P&T/GC-MS 0.79–28 ng/L NR [17]
hydrocarbons
Halomethanes and other volatiles Drinking waters P&T/SPME, GC-MS 0.002–0.2 lg/L NR [19]

http://www.elsevier.com/locate/trac
Hydrocarbons and halocarbons Tap water and groundwater Spray and trap/GC-FID-ECD 0.93–1.71 lg/L NR [18]

Headspace techniques
Chlorinated alkanes, alkenes, mono and Wastewaters, river waters HS-GC-MS 0.1 lg/L NR [25]
polycyclic aromatics
BTEX Drinking waters HS-GC-MS 0.01 lg/L NR [34]
Halogenated organic compounds Waters Microwave-assisted HS-HAPSITE GC-MS NR NR [37]
Halogenated organic compounds, Aqueous samples ITEX 2, HS/GC-MS 1–10 ng/L NR [24]
benzenes, xylenes, fuel oxygenates etc.
BTEX, chlorinated hydrocarbons Environmental aqueous matrix HS-GC-PID-FID 0.22–7.48 lg/L NR [42]
BTEX Spiked drinking waters HS-GC-MS NR NR [35]

HS-SPME/SPDE techniques
MTBE, BTEX Lake waters HS-SPME/GC-FID 0.01–1.0 lg/L 0.1–0.5 [26]
Chlorinated hydrocarbons waters HS -SPME/GC-MS 106–195 ng/L NR [30]
Chemical by-products (e.g., geosmin, 2- Tap waters HS- SPME/GC-ITMS 0.38–0.65 ng/L NR [58]
MIB, IBMP, IPMP
Chlorinated Hydrocarbons Waters and wastewaters HS-SPME, GC-ECD 0.08–23.8 ng/L 0.25–79.3 ng/L [29]
Chloroform, trichloro, tetrachloro Ground waters HS-SPME/GC-MS 0.0009–0.05 lg/L 0.001–0.1 lg/L [9]
Author's personal copy

ethylene, etc.
MTBE Water and gasoline HS-SPME/IMS 0.7–4.9 lg/L NR [38]
BTEX Drinking waters HS-SPME/GC-TOF-MS 0.015–0.477 lg/L NR [69]
Chlorinated toluenes River water and sewage HS-SPME/GC-MS-MS 0.03–0.33 pg/L 0.13–0.71 lg/L [39]
Taste and odorous compounds Lake and reservoir waters HS-SPME/GC-ITMS 5–140 ng/L NR [27]
BTEX Wastewaters HS-SPME/GC-lFID < 1.5 lg/L NR [28]
BTEX Drinking and Wastewaters INCAT-SPME/GC-FID 0.019–0.125 lg/L 0.052–0.341 lg/L [31]
Halogenated organics, BTEX and mono Seawater Purge with N2 gas SPME/GC-MS 25–49 pg/L NR [40]
aromatic compounds
BTEX Melted snow waters HS-SPDE/GC-MS 19–30 ng/L 53–89 ng/L [36]

LLE and LPME techniques

Geosmin and MIB Drinking waters LLE/GC-MS 1–5 ng/L NR [41]
Geosmin and MIB Tap waters HS-LPME/GC-MS 1.0–1.1 ng/L NR [44]
BTEX River waters and wastewaters HF-LPME/GC-FID 5–30 lg/L NR [43]
Other sample introduction and preparation techniques
THMs Drinking waters CMS/GC-ECD 0.3–0.7 lg/L 0.9–35 lg/L [48]
Trends in Analytical Chemistry, Vol. 32, 2012
 Author's personal copy

Trends in Analytical Chemistry, Vol. 32, 2012 Trends

sensitivity, the selectivity and the reliability of the ana-

AED, Atomic emission detector; BTEX, Benzene, toluene, ethylbenzene, xylene; CLSA, Closed loop stripping analysis; CMS, Capillary membrane sampler; DAI, Direct aqueous injection;
DMSO, Dimethyl sulfoxide; ECD, Electron-conductivity detector; FID, Flame-ionization detector; GC-MS, Gas chromatography-mass spectrometry; HF-LPME, Hollow-fiber liquid-phase

In-tube extraction device; ITMS, Ion-trap mass spectrometry; 2-MIB, 2-methylisoborneol; MTBE, Methyl tert-butyl ether; PID: Photoionization detector; P&T, Purge and trap; SCMS, Supported
capillary membrane sampling; SPDE, Solid-phase dynamic extraction; SPE, Solid-phase extraction; SPME, Solid-phase microextraction; THM, Trihalomethane; TOF: Time of flight; VOC,
microextraction; HS, Headspace; IBMP, 2-isobutyl-3-methoxy pyrazine; INCAT, Inside needle capillary adsorption trap; IPA, Isopropyl alcohol; IPMP, 2-isopropyl-3-methoxy pyrazine; ITEX 2,
[47]
[14]
[15]
[46]
[45]
[55]
[59] lytical method are improved. This step mainly helps in
partitioning the analyte of interest from the complex
aqueous matrix. Taking into account the time taken for
sample pre-concentration, cost, solvents or gas used,
0.81–20 lg/L

micro and miniature techniques are being developed and

widely used. Since the concept of ‘‘green chemistry’’ is
 1 ng/L

greatly encouraged, recycling of solvents used or, more

NR

NR
NR
NR
NR

correctly, sample enrichment without using solvents is

much preferred. Among sample-enrichment methods,
direct aqueous injection (DAI), purge and trap (P&T),
liquid-liquid extraction (LLE), headspace (HS), and
1.09–6.86 lg/L
0.07–2.8 lg/L

2–12 pmol/L
0.1–6.1 lg/L

membrane-based techniques (solid-phase microextrac-

 1 ng/L

tion, SPME) are practised. Information on sample-prep-

10 ng/L

aration methods with advances and preferences is

NR

available [9].

2.1.1. Direct aqueous injection. DAI for sample intro-

Online GC-MS with automatic sampling device

duction has been reported in a small number of studies.

This is the only technique to skip the sample-preparation
step in analyzing VOCs. It can be applied only when the
sample is clear or contains very small amounts of
organic matter.
In the determination of BTEX, Kubinec et al. [13]
employed Chromosorb P-NAW as absorbing material in
DAI with LiCl/GC-FID

the liner of the injection port to retain water and other

CLSA-SPME/GC-MS

non-volatiles while the BTEX stripped into the column.

SCMS/GC-ECD

This method was reported to perform better with a

CLSA/GC-MS
DAI/GC-MS

EI-PTR-MS

method LOD of 0.6–1.1 lg/L.

Pettersson and Roeraade [14] proposed direct sample
analysis for polar VOCs using a precolumn packed with
lithium chloride. A capillary column was coupled in
series for the real separation of analytes. In the precol-
umn, the lithium chloride retained the entire water
WWTPs, rainfall waters, etc.

matrix leaving behind all polar and non-polar VOCs,

which were then transferred to the capillary column.
The LODs and the LOQs obtained by this direct analysis
Volatile organic compound; WWTP, Wastewater-treatment plant.
Drinking waters

Drinking waters

were 1 lg/L.
Groundwater
Wastewaters

River waters

Another study presented the analysis of 24 VOCs in

Seawater

groundwater. Volumes of 1–10 lL were directly injected

into the GC without any pre-concentration step and
the method LODs were reported to be 0.07 lg/L and
2.8 lg/L [15].
DAI looks to be a convenient method, but the GC
needs to be equipped with a deactivated guard column
between the injector and the analytical column. The
Acetone, acetaldehyde, propene,

guard column traps non-volatiles or high-molecular-

weight compounds, preventing them from collecting in
BTEX, MTBE, butyl alcohol

the analytical column.

The main limitations of DAI are possible interferences
DMSO, IPA, acetone
Chlorinated toluenes
Geosmin and MIB

NR: Not reported.

due to matrix effects and incompatibility of the station-

ary films of capillary columns with FID detectors [13].
Polar VOCs

Another sample-introduction method, but not so

isoprene

popular, is membrane-introduction mass spectrometry

THMs

(MIMS), where the analytes are introduced directly into

the mass spectrometer without chromatographic

http://www.elsevier.com/locate/trac 63
 Author's personal copy
Trends
Figure 1. Sample extraction and analysis scheme for VOCs in environmental and drinking waters.
separation. Before introduction, the sample is passed
through a thin membrane where the extraction occurs,
so analytes on the membrane diffuse and evaporate
directly into the mass spectrometer where ionization
takes place. MIMS has advantages because of its cost
effectiveness, short analysis time, exclusion of solvents,
high sample throughput and real-time monitoring and
sampling of VOCs, but it lacks sensitivity at ultra-trace
levels [4,5,7,8,10].
2.1.2. Purge and trap methods. Due to the high
sensitivity and recoveries, P&T still remains the most
frequently used pre-concentration method for the
analysis of VOCs in water. Apart from sensitivity, P&T
has the advantages of precision and possibility of auto-
mation. The drawbacks of P&T are its complexity and
the interference of water vapor generated in the purge
stage.
64 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 32, 2012
Campillo et al. [16] used capillary trap and thermally
desorbed P&T for the determination of volatile halogens
and trihalo-methanes in drinking waters. A purge-gas
flow rate of 40 mL/min, a desorption time of 4 min and
temperature up to 200C were reported to achieve im-
proved extraction efficiencies with the highest peak areas
for all the THMs analyzed.
P&T extraction was applied to study 25 VOCs,
including monocyclic hydrocarbons, chlorinated hydro-
carbons in the southern North Sea [17]. A sample ali-
quot of 60 mL was purged for 20 min at a flow rate of
50 mL/min, and the compounds were trapped using a
water trap at 15C and thermally desorbed at 275C
for 15 min. Sample recoveries were 106 ± 29%,
92 ± 34% and 82 ± 24% for TCM, toluene and chloro-
benzene, respectively. This method was reported to be
sensitive with good precision for the extraction of VOCs
from seawater.
 Author's personal copy
Trends in Analytical Chemistry, Vol. 32, 2012
A spray and trap device was successfully developed
and used in a pre-concentration method for on-line
monitoring of dissolved VOCs in tap water and ground-
water [18]. Extraction of BTEX was conducted using the
spray and trap and was compared with a P&T system.
The recovery values were inconsistent and clearly indi-
cated poor sensitivity of the spray and trap system
compared with P&T at different sample concentrations
when extraction of BTEX was exhaustive.
Studies were conducted using SPME and P&T to select
an appropriate sample-preparation method for analysis
of VOCs in drinking waters using GC-MS. Results
revealed that signals were overlapped when SPME was
used for extraction of DBCM and tetrabromoethylene
(TBE). By contrast, P&T was reported to have better
performance for extraction of halogenated VOCs with R2
values greater than 0.998 and LODs of 0.002–0.2 lg/L
with recoveries of 81–117%, fulfilling the sensitivity
requirements [19].
P&T sample preparation was predominant in many of
the studies for analyzing monocyclic hydrocarbons, hal-
ogenated organics, BTEX, and halomethanes in drinking
waters and other environmental waters [20–22].
Zoccolillo et al. [22] used P&T injection to extract halo-
genated hydrocarbons from waters. The samples were
purged and cold trapped ( 100C) using liquid nitrogen
for enrichment of chlorinated hydrocarbons and THMs in
tap waters, mineral waters and snow. This modification
resulted in high accuracy and reproducibility, and
achieved sensitivity (1 ng/L) in order to make this
method suitable for slightly contaminated waters [e.g.,
found in remote areas in environmental monitoring
(concentrations 0.5–100 ng/L)]. This work also reported
that, by changing the cold-trap temperature, the inter-
ference of carbon dioxide during the cryo-concentration
can be avoided.
Development of a P&T continuous flow system
(PATCY) for the analysis of halogenated organics in
waters allowing stable carbon isotope analysis was
demonstrated by Auer et al. [23]. The PATCY system is
designed to adapt sample size, depending on sample
concentration, to meet GC LODs of ng/L. This was
mainly designed for high-volume sampling for haloge-
nated VOCs in waters to allow stable carbon-isotope
analysis. The ultrasonic nebulizer combined ultrasonic
and spray extraction to make it successful in determi-
nation of the carbon-isotope ratio of halogenated VOCs.
The PATCY was regulated and compared with the
available P&T systems and showed throughput higher
than that of regular P&T in analyzing contaminated
groundwaters with LODs of 0.5 ng carbon absolute. This
system can be applied successfully to the stable carbon
isotope of halogenated VOCs with boiling points of
32–187C.
Recently, a novel in-tube extraction device (ITEX 2)
was developed and successfully evaluated for analyzing
Trends
20 compounds in water samples [24]. The functioning of
ITEX 2 was similar to that of P&T, which is much sim-
pler and affordable, and requires very low volumes of
sample. ITEX 2 was reported to be a sound alternative to
the P&T technique with method LODs of 1–10 ng/L.
P&T provides reliable analytical information, but it is
time consuming, needs complex instrumentation and is
labor intensive, particularly when many samples need to
be analyzed, so making it unsuitable for on-line, real-
time monitoring of VOCs.
2.1.3. Headspace and HS-SPME methods. The next most
popular sample-enrichment methods used for VOC
determination in water are HS and HS-SPME. HS anal-
ysis is a technique to separate and to collect VOCs (in the
gas phase) from aqueous samples. HS techniques have
been very popular and widely used in the analysis of
VOCs in diverse waters. The advantage of HS techniques
is that the VOCs of the sample can be analyzed directly
without any interference so as to reduce the possibility of
matrix effects. Since the entire analysis occurs in a closed
system, reproducibility can be high.
The applicability of HS alone was demonstrated for the
analysis of 53 chloroorganics in wastewaters, treated
waters and river waters from Russia [25]. A low-volume,
highly inert, heated volatile interface was optimized and
the results showed good consistency and confirmed
anthropogenic pollution sources in river waters. The HS
pre-concentration method was found to possess good
recovery values at the lg/L level (LOD, 0.1 lg/L).
For occurrence and fate modeling studies of BTEX and
methyl tert-butyl ether (MTBE) in Swiss lake waters,
Schmidt et al. [26] applied HS-SPME with a Combi-PAL
auto sampler to the pre-concentration of waters to
obtain good reproducibility. These values were reported
to be much better than HS alone. The method of HS
followed by SPME had sample-recovery values of
105–110% with good sensitivity and reproducibility.
Taste and odorous compounds in lake and reservoir
waters were quantified by Furtula et al. [27] by applying
an HS-SPME method using a 65-lm polydimethylsilox-
ane/divinylbenzene (PDMS/DVB) fiber. The sample
recoveries were 84–113% with geosmin and 100% for
2-methylisoborneol (MIB).
A PDMS/DVB-membrane fiber with HS-SPME was also
reported to have good recovery (98.4–111.4%) and
consistency in the determination of BTEXs in waste-
waters with method LODs of <1.5 lg/L [28].
The HS-SPME method was successfully applied for the
analysis of chlorinated volatiles in drinking waters and
effluents of a water-treatment plant [29]. All the
extraction parameters were studied. For SPME, four dif-
ferent fibers were tested and 85-lm CAR/PDMS was
reported to give best extraction efficiency. It was also
stated that this fiber used in SPME can be used for 60
cycles for the enrichment of water samples. The HS
http://www.elsevier.com/locate/trac 65
 Author's personal copy
Trends
volume was also optimized and a 15-mL volume was
found to yield the best recoveries. Along with the above,
an extraction time of 30 min at a temperature of 35C
resulted the best sample preparation [29].
Sun et al. [30] investigated the use of an activated
carbon filter (ACF) in SPME for the extraction of chlori-
nated hydrocarbons in water. The ACF was also evalu-
ated for various parameters, including scanning electron
microscopy, which was found to be suitable to use along
with HS for analyzing VOCs in waters. The ACF was
preferred due to its resistance to organic solvents,
endurance at high temperatures and recycling capacity.
HS with inside needle capillary adsorption trap
(INCAT) using Porapak Q and wet alumina as sorption
material was a viable option for the analysis of BTEX in
water samples. Application of INCAT increased extrac-
tion capacity over regular SPME with LOD and LOQ
below 0.5 lg/L [31]. Concentrations of MTBE in urban
and non-urban groundwaters in Germany were quan-
tified and HS-SPME was found to be an appropriate
sample-enrichment method for complete extraction of
MTBE in groundwaters [32]. The spiked reagent waters
with concentration of 0.01 lg/L gave recoveries of
83–118% and the spike concentration of 0.02 lg/L gave
a recovery rate of 96–125% with relative standard
deviation (RSD) of <11% with an LOD of 10 ng/L.
Determination of acetone in seawater was conducted by
derivatization using 1,2,3,4,5-pentafluorobenzylhydr-
oxylamine (PFBHA) followed by SPME [33]. An LOD of
3.0 nM was reported in the analysis of Nordic seawaters
with good recovery (at an optimum pH of 3.7).
Kavcar et al. [34] applied an automated HS sampler
attached to GC-MSD to study the risk associated with
VOCs in the drinking waters of residents of Izmir,
Turkey. The analyte recovery using automated HS
technique was good with LODs of 0.01 lg/L. Coupling of
HS to MS has also been found to reduce sample-extrac-
tion time dramatically with good, reproducible recovery
values during the determination of BTEX and corre-
sponding mixtures in polluted waters [35]. The HS-MS
data were used to develop an associated three-parameter
Gaussian curve. This was used for standard multilogistic
regression model for VOCs in drinking-water samples
and showed maximum abundance.
HS with solid-phase dynamic extraction (HS-SPDE)
was verified for the quantitative determination of BTEX
and aldehydes in melted snow waters [36]. A cooling
device (down to 15C) to control temperature of the
SPDE needle during extraction showed positive impact as
the GC response improved by cooling the SPDE needle
and the sensitivity remained similar even after 60 cycles.
For all the compounds, the highest GC response was
observed at a desorption volume of 500 lL with a
desorption flow rate of 50 lL/sec [36].
Microwave energy as a heating source instead of
conventional resistive-based heating was tested for
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field-based HS sampling. This showed a significant in-
crease in sensitivity and reduced time, even though it is
not widely accepted due to the associated risk of sub-
jecting VOCs to microwave energy [37].
In HS-SPME, a cooled SPME fiber coated with a film of
dodecylsulfate-doped polypyrrole coupled to ion-mobility
spectrometry (IMS) equipped with corona-discharge
ionization was suggested for the determination of MTBE
in waters. These results were compared with literature
values of SPME and found to be at the same level as
commercially-available SPME membranes [38]. Studies
reporting usage of commercially-available SPE, SPME
alone for the pre-concentration of drinking waters, tap
waters, river waters and sewage and sea water samples
have also been successful in quantification of VOCs [38–
40].
Overall, we can infer that application of HS-SPME is
advantageous due to it taking less time for sample pre-
concentration and having the desired sensitivity.
2.1.4. Liquid-liquid extraction and liquid-phase microextrac-
tion. LLE is a commonly used sample-extraction tech-
nique, which uses relatively large volumes of solvents,
and, because of this, researchers have shifted to alter-
native extraction methods. In the past few years, there
have been some studies using LLE for extractions of
VOCs. Hexane LLE was performed for the detection of
geosmin and MIB in drinking waters of Shanghai to
understand the serious odor problem of waters. The
sample recoveries were found to be >50% for MIB and
80% for geosmin with method LODs of 1.0 ng/L and
5.0 ng/L for geosmin and MIB, respectively [41].
Kistemann et al. [42] conducted a long-term investi-
gation to assess groundwater contamination by VOCs in
Germany and their associated public-health issues. LLE
was applied for sample extraction using pentane as sol-
vent and the quantities of VOCs determined were
transferred to a geographic information system (GIS) for
spatial analysis. A sample-extraction method based on
polypropylene hollow-fiber liquid-phase microextraction
(HF-LPME) was applied as an alternative for the
extraction of VOCs from water. In this extraction, a
hydrophobic membrane made of polypropylene sepa-
rates the sample and the organic phase. The amount of
organic solvent inside the HF and in the pores is much
less than the LLE method [43]. Four different organic
solvents were tested, and N-octanol was chosen. Good
reproducibility was obtained with RSD values of 2.02–
4.61%.
HF-LPME is supposed to be directly compatible with
GC [43]. Recently, geosmin and MIB were extracted
using solvent microdrop HS-LPME from tap waters with
average recoveries of 95.4–113.7%. Under optimized
detection and extraction conditions, the LODs were
1.1 ng/L and 1.0 ng/L for geosmin and MIB, respectively
[44].
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LLE is mainly used because it is easy and does not
require any additional equipment. LLE is not a preferred
sample pre-concentration method due to its limitation of
needing large volumes of solvent and the availability of
alternative extraction techniques.
2.1.5. Closed loop stripping analysis. In closed loop
stripping analysis (CLSA), VOCs in the liquid phase are
trapped on a multichannel sorbent trap by pumping the
purge gas in a closed circuit via aqueous phase and the
trap. The trap retains the VOCs that are then extracted
from the trap using small amounts of appropriate sol-
vent. Very few authors have reported use of this sample-
enrichment method for the determination of VOCs in
aqueous systems.
An occurrence study of chlorinated toluene in Llob-
regat River, Spain, was reported by Marti et al. [45], who
applied CLSA with activated carbon filters as sorbents to
trap the analytes. The sample recoveries were 99–104%
with an RSD <10%.
Coupling SPME and CLSA was proposed for the anal-
ysis of MIB and geosmin in drinking waters [46]. An
LOD of 10 ng/L of MIB and geosmin was achieved using
CLSA/SPME with a polyacrylate phase and analysis by
GC-MS. Further, it was concluded that CLSA/SPME
provided a faster, solvent-free and less labor-intensive
method than CLSA alone. In spite of these positive
factors, this method has not appeared popular for the
extraction of VOCs in water.
2.1.6. Thin-layer headspace. In thin-layer HS (TLHS),
the aqueous sample to be analyzed is continuously
pumped into a special TLHS column. The sample runs
down a spiral thermostatic glass tube and a stream of
clean purging gas is run in a counter-current system.
The VOCs in the aqueous sample are released into the
purged gas. The water vapor and the volatile analytes
then enter a second column, where the water vapor and
analyte condense together. The condensed water vapor
thus becomes a stream of liquid sorbent and the analytes
partition between the gas and the condensing water.
This condensate from the TLHS column is collected and
further analyzed by DAI-GC.
For TLHS, the samples should not be too volatile
because they will form two-phase mixtures that will be
difficult for DAI in GC. Application of TLHS preconcen-
tration is predominantly seen in the analysis of biological
fluids [6,7]. Application of TLHS to preconcentration of
environmental and drinking waters is limited to one or
two studies [47], as observed from the publications after
the year 2000.
2.1.7. Stir-bar sorptive extraction. In SBSE, the stir bars
are coated with PDMS, typically to 0.5–1-mm thickness.
For the extraction, the stir bars are introduced into
the flask containing the sample being analyzed. Stirring
Trends
the sample results in the division of analytes between the
matrix and the stationary phase (PDMS). After extrac-
tion, the deposited analytes are thermally desorbed or
extracted using appropriate solvent and analyzed using
GC. Since there is no need to dry the stir bar before
analysis, the loss of VOCs at this stage is negligible,
making this extraction technique advantageous.
SBSE uses single-step extraction with recoveries much
higher than SPME. SBSE is easy to apply and to auto-
mate, and it can be used for heterogeneous aqueous
medias. Its robust nature, high sensitivity, and repeat-
ability are its main advantages. Its chief limitations are
its single apolar polymer (PDMS), which can be applied
to medium-high volatility and medium-high thermo-
stability analytes when thermal desorption is employed.
Solvents that are compatible with PDMS can only be
adopted if liquid desorption is applied. SBSE is currently
used in food, biomedical and environmental analysis
[48,49].
2.1.8. Other miscellaneous methods. Supported capillary
membrane sampling (SCMS) was evaluated for the
analysis of THMs in drinking waters. A metal body with
helical shaped groves along a 90-cm silicone membrane
with a length exposed to sample of 75 cm was used for
sample pre-concentration. The sample recoveries were
> 100% for three of the four THMs analyzed with LODs
of 0.1–6.1 lg/L [50].
A needle-trap device with Carbopack X as a sorbent
material with modified metal liner to desorb analytes
trapped in the needle-trap device was proposed to ana-
lyze BTEX in water samples [51]. This sample pre-con-
centration method showed good repeatability with RSDs
of 0.5–11.6% for five different concentrations studied
with LODs of 0.05–0.07 lg/L. The merits of this method
are its cost-effectiveness, rapidity in analysis and
mechanical robustness. Drawbacks include limited
amount of sample, limited desorption temperature
compared to injection port and eluted zones that are
somewhat depressed.
Extraction of VOCs from aqueous phase to gas phase
was demonstrated using a microdialysis membrane that
was interfaced with GC. With this system, the recoveries
were well within the matching ranges of other extrac-
tion methods. The lowest detectable concentrations with
microdialysis membrane were 5 mM without any pre-
concentration and 0.01 mM for volatile hydrophobic
analytes [52]. A single instrument was presented for the
selective analysis of THMs.
An improved version of capillary membrane
sampler-flow-injection analyzer (CMS-FIA) was based on
the fluorescence reaction between nicotinamide and
basic solution of THM. The products formed by this
reaction will be excited at 370 nm and will emit in
450 nm range, the intensity at 450 nm being
proportional to the concentration of THMs. This selective
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analysis showed a recovery of 108% with LODs of
2.5 lg/L. This method was further compared with
USEPA methods 502.2 and 552.3 in chloraminated
distribution system, exhibiting reproducible results in the
range 0.2–5 lg/L [53].
2.2. Chromatographic separation
While the separation of VOCs mainly relies on interac-
tion with the stationary phase, since interaction with
mobile phase is negligible, the choice of column chosen
in combination with passable temperature programs for
separation is crucial. A good basis for selection of a
column involves differences in intermolecular interac-
tions, as an aid to develop a reliable method for the
separation of VOCs.
A wide range of columns have been used for the sep-
aration of VOCs in aqueous samples [54]. Among these,
fused silica capillary columns coated with a liquid phase
used to be popular. Most of them have a polysiloxane
stationary phase that is combined with different phenyl,
cyanopropylphenyl groups to obtain different degrees of
polarity.
Silicone-based columns are commercially available
and frequently reported in VOC analysis of waters (e.g.,
AT-502.2, Sil5CB, DB-5, SPE-1, HP-1, CP select 624,
VF-5, VF-624, Rtx-5M5, OV-624, OV-1701, and WCOT
– all with 100% poly dimethysiloxane).
The DB 1701 column is also frequently used in the
separation of VOCs. Made of 14%-cyanopropyl-phenyl)-
methyl polysiloxane, it is known to provide desired sep-
arations and can be rinsed with solvent. Some columns
(e.g., VOCOL, RTX-VGC, DB-VRX, DB-624, DB-608,
RTx-502, RTx-volatile, and AT-624) are a series of
specially synthesized stationary phases of unique selec-
tivity, due to the presence of cyanopropyl and phenyl
groups that are configured for different environmental
analyses with good thermal stability. Among these, the
most frequently used and reported is the DB-624 capil-
lary column.
Apart from the above, there are some multipurpose
columns especially designed for analysis of VOCs, keep-
ing in view the USEPA-specified method. Capillary
column with methylsilicone gum as stationary phase has
been successfully applied for the separation of chlori-
nated hydrocarbons in snow waters and tap waters [22].
With the methylsilicone column, the temperature pro-
gram of 40C/min to 120C and holding for 1.5 min at
final temperature with a total run time of 5.50 min
yielded best resolution.
For analyzing different VOCs in wastewaters, treated
waters, rainfall waters and river waters, different col-
umns were applied to achieve suitable separation. A
porous layer open tubular (PLOT) column was applied
for light carbon number C2–C4 VOCs (alkanes, alkenes
and aromatics), and heavier species C4–C10 VOCs were
separated by DB-1 column [55]. The peak separation
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Trends in Analytical Chemistry, Vol. 32, 2012
was very good in both columns with notable retention
times.
Application of a PLOT divinylbenzene GC capillary
column as a part of DAI-GC was found to be successful in
separating polar and non-polar VOCs in groundwaters
[15]. This column was preceded by a deactivated guard
column for filtering non-volatiles before entering the
analytical column. The PLOT column showed good
performance when held at 200C for 15 min.
Yazdi et al. [43] demonstrated separation using a
CP-Sil 24CB (50% phenyl, 50% dimethylsiloxane) cap-
illary column, WCOT Fused silica, for analyzing BTEX in
water matrices. This column was shown to produce
superior peak separation for BTEX in river water
resulting in different retention times.
Dimethysiloxane stationary phase columns were
found to be most preferred choice for separation of a
variety of water samples.
2.3. Detectors and method detection limits
The detectors most widely used for identification and
quantification of VOCs in aquatic matrices include MSDs,
electron-capture detectors (ECDs), flame-ionization
detectors (FIDs) and photo-ionization detectors (PIDs)
sensitive for aromatic hydrocarbons. Among these, the
MSD is very potent and highly preferred, since it rapidly
identifies target and non-target analytes by comparing
them with the library of spectra of known compounds.
For qualitative analysis and identification of VOCs in
highly complex matrices (e.g., contaminated waters),
this detection method can be decisive in exact quantifi-
cation of the compound.
2.3.1. Classical detectors. Applications of FID for
hydrocarbons and ECD for halocarbons are well dem-
onstrated.
The ECD, which is known to be highly specific for
detection of halogenated VOCs, is reported to achieve
good LODs (0.93–1.71 lg/L) in various aqueous matri-
ces [20]. By switching the water sources between tap
water and groundwater, the sensitivity of ECD detected
the range in concentrations (10.14–54.20 lg/L) and
maintained its stability throughout the operation.
LODs of ng/L were obtained in the determination of
trihaloalkanes in drinking waters and chlorinated sec-
ondary effluents. Method LODs of 0.08–23.8 ng/L and
LOQs of 0.25–79.3 ng/L with good correlation coeffi-
cients were reported [e.g., for BTEX, isopropyl alcohol,
dimethyl sulfide, and acetone in complex matrices (e.g.,
wastewaters)].
Wu et al. [55] demonstrated use of GC-FID for ana-
lyzing various VOCs in untreated and treated waste-
waters, rainfall waters and river water known to be
contaminated with wastewaters. The method LOD was
0.14–1.02 lg/L for determining VOCs in wastewaters
and river waters. FID, which is said to be sensitive for
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Trends in Analytical Chemistry, Vol. 32, 2012
non-aromatic compounds, was successfully used for the
quantification of BTEX in environmental waters (river
and wastewater) with LODs of 5–30 lg/L. Further, the
RSDs obtained for BTEX were in agreement with previ-
ously reported studies using FID [43].
The fate and the occurrence of MTBE and BTEX in
Swiss lake waters were quantified using FID, where the
lower LOD of 0.05 lg/L was reported [26]. Some 17
different VOCs were quantified in real-time monitoring of
wastewaters using GC-FID with LODs of 0.32–2.39 lg/L.
This system is reported to be reliable, rugged and
excellent for continuous monitoring of wastewaters from
treatment plants with accuracies of 0.3–23.5% [20].
An analytical protocol was developed to study the
diversity of VOCs on the Fortaleza coast, Brazil, using
GC-PID-FID in series [56]. The studies revealed that,
except for carbon tetrachloride, all other VOCs showed
higher sensitivity with PID than FID, with LODs of
0.22–7.48 lg/L.
Application of an induced plasma atomic emission
spectrometry detector (AED) was demonstrated by
Campillo et al. [16] for the determination of halogenated
organics in drinking waters. This detector was reported
to be sensitive for the determination of THMs with LODs
0.05–0.5 lg/L, and it was proposed for regular moni-
toring of VOCs in waters. There are not many studies
reporting use of AED for comparison, as this detector has
become outdated.
Recently, an online membrane-introduction (MI)
interface coupled with FID/ECD was demonstrated for
online determination of VOCs in water samples at sub-
lg/L levels. This instrument was said to be effective for
online screening and real-time monitoring analysis of
varied water samples. The LODs of MI-FID and MI-ECD
were reported to be 0.4–118 lg/L and 0.2–10 lg/L,
respectively. These results were further compared with
MIMS, and it was found that both detection methods
were compatible [57].
2.3.2. Mass-selective detector. Irrespective of the VOC
and the sample matrix to be analyzed, the MSD remained
dominant among detection methods for the determina-
tion of VOCs in aqueous matrices. MSDs are becoming
more popular because of the excellent selectivity they
provide based on molecular masses.
Although the ECD can offer selectivity and low LODs,
it has limited dynamic range and finds application
mostly for halogenated compounds, but the interferences
frequently observed make MSD more accepted in ana-
lyzing halogenated compounds. The ranges of LOD differ
from matrix to matrix, depending on the compounds
being analyzed. For analyzing chlorinated hydrocarbons
in melted snow waters and tap waters, the LOD of the
MSD was 0.1–0.04 lg/L for tap waters [22] and
19–30 ng/L for BTEX in melted snow waters [36]. For
the same chlorinated hydrocarbons and monocyclic
Trends
aromatic hydrocarbons in estuary surface waters, LODs
were 0.79–28 ng/L [17], in contrast with similar types
of seawater with reported LODs of 25–49 pg/L for hal-
ogenated compounds, monoaromatics and BTEX [40].
In all the above, selective ion monitoring (SIM) mode
was employed for analysis to achieve much lower LODs.
LODs at the lg/L level were obtained for BTEX
(LOD, 0.01 lg/L), THMs (LOD, 4–20 lg/L) and MTBE
(LOD, 0.01 lg/L) in drinking waters [19,32–34], which
were supposed to have very much lower matrix inter-
ference than seawaters.
A low-resolution ion trap mass spectrometer (ITMS)
was employed for the determination of taste and odorous
compounds. Compounds (viz hexanal, heptanal,
2t,4t-heptadienal, 2t,4t-octadienal, 2t,6t-nonadienal,
2t,6c-nonadienal, MIB, 2t,4t-nonadienal, b-cyclocitral,
2t,4t-decadienal, geosmin and b-ionone) were quantified
in several lake and reservoir water samples from British
Columbia, Canada. The LODs were reported to be at ng/L
levels and the quantification of the analytes was carried
out in both full-scan and SIM mode [27].
Application of ITMS was reported in the analysis of
MIB, 2-isobutyl-3-methoxy pyrazine (IBMP), 2-isopro-
pyl-3-methoxy pyrazine (IPMP) and 2,4,6-trichloroani-
sole (2,4,6-TCA) in order to determine musty odors of
water samples. The ITMS was used in SIM mode with
LODs of 0.38–0.65 ng/L for spiked tap waters and
0.32–0.66 ng/L for spiked lake waters [58].
Regueiro et al. [39] analyzed the concentrations of
chlorinated toluene in river waters and sewage with GC-
ITMS. GC-MS/MS was operated in full-scan mode with
mass ranges of 80–500 m/z, and targets were identified
comparing their mass spectra and retention times with
those of standard solutions. LODs were 270–330 pg/L
for monochloro toluene and 30–47 pg/L for polychloro
toluene.
An HS-SPME device coupled with IMS was reported for
the first time for the analysis of MTBE in waters. In IMS,
the analytes are thermally desorbed and transferred to
the measuring cell. The ionization takes place by irra-
diation with 63Ni source on the way to the collision cell,
and IMS is a gas-phase electrophoretic technique, where
the ions are separated based on their mass, charge and
collision cross section. The LODs were reported to be
0.7–4.9 lg/L. IMS offers portability and high sensitivity
with short analysis time, which can be effective for VOC
analysis [38].
Recently a study was published for measuring iso-
prene, propene, acetone, acetaldehyde, and methanol in
seawater using the bubbling-type equilibrator for equil-
ibration between seawater and air. The equilibrator
inlet-proton-transfer-reaction (EI-PTR-MS) system was
designed by combining the bubbling-type equilibrator
with a (PTR)-MS instrument. This method is mainly for
measuring the concentration of dissolved VOC on the
open ocean surface and will be useful in quantifying the
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production and consumption of VOCs in biological
activity. This study demonstrated that the EI-PTR-MS
system can be a viable tool in understanding global
production of VOCs [59].
The use of a pulsed-discharge photoionization detector
(PDPID) was proposed by Emmert et al. [60] for the
detection of THMs in drinking waters with an LOD of
0.5 lg/L.
Another possibility of the dry electrolytic conductivity
detector (DELCD) was recommended for monitoring
THMs in drinking water with LODs of <1.0 lg/L [61].
In the review by Dewulf and co-workers [7], pertain-
ing to volatile halogenated compounds, two emerging
MS-based detectors were reported; the first one is the
plasma-based MS microwave-induced plasma-AED; and,
the second is isotope ratio MS (IRMS). Application of
these two detectors in the detection of halogenated VOCs
was mentioned with examples. From the above reports,
it is evident that MSD remains the detector of choice and
the MS-MS detector can achieve excellent resolutions
and sensitivities for quantifying VOCs in waters.
A very limited number of published articles reported
use of tandem MS for identification and quantification of
VOCs. One article published in 2003 reported application
of tandem MS, but this report covered the analysis of
semi-VOCs in drinking waters. We could practically
identify and locate only one publication reporting the
application of tandem MS for the quantification of VOCs
[39]. This gives more insight into the application of
tandem MS studies in the analysis of VOCs in aquatic
matrices.
3. Frequently reported compounds and ranges
detected
This section encompasses the most frequently detected
VOCs in different aquatic media. Table 2 presents the
ranges of compounds along with the concentrations
reported in various publications in water matrices (e.g.,
tap waters, groundwaters, drinking waters, seawaters,
and wastewaters). Compounds that have most fre-
quently been determined include halogenated hydro-
carbons, aromatic hydrocarbons, VOCs, MTBE, BTEX
and chlorinated toluenes. Amongst these, the dominant
compounds were the halogenated compounds. In most
of the studies, it was observed that compounds identified
and detected as volatiles mostly have at least one of the
halogens.
3.1. Drinking waters
This section covers concentrations of VOCs in tap waters,
bottled waters and other drinking waters. Some 10 dif-
ferent tap waters were studied for concentrations of
THMs that were often reported. The concentrations of
THMs were reported to be 1–40.8 lg/L (TCM),
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Trends in Analytical Chemistry, Vol. 32, 2012
1.8–24.7 lg/L (TBM), 3.1–55.3 lg/L (BDCM) and
2–66.5 lg/L (DBCM) [16]. Studies conducted on the
occurrence and the risk assessment of VOCs revealed
high amounts of THMs along with BTEX, wherein the
overall concentrations were below LODs to 35 lg/L. The
concentrations of THMs were found to be high in tap
waters and concentrations of BTEXs were high in non-
tap waters. These concentrations were reported after
studying the demographics of drinking-water consump-
tion rates and household sample collection from almost
100 houses [25]. The presence of THMs in drinking
waters is well documented in some studies {1.28–
762 ng/L [29]}, as a result of reaction between chlorine
and organic matter in waters.
Kolb and Puttmann [32] studied drinking-water
samples from 50 cities of Germany for MTBE concen-
trations. MTBE was reported to be 17–712 ng/L, and
attributed to the contamination of groundwaters that
were used for as a source of drinking water.
Al-Mudhaf et al. [62] conducted a survey of volatile
contaminants in household drinking waters and branded
bottled waters, and reported 12 VOCs in 93% of samples
analyzed. BTEX and styrene were detected most in these
samples, and the concentrations were increasing in line
with the storage time. Except for styrene, all other con-
centrations were found to be below 20 lg/L, a guideline
set by WHO.
Different drinking water types from tap waters and
bottled water sources were tested and quantified for the
presence of VOCs. Among the samples analyzed, 97%
were shown to contain VOCs below the WHO-designated
levels. Except for two water samples that contained
60 lg/L of BDCM, the total quantities of THMs were 0–
322 lg/L with tap water (0.1–0.3 lg/L), spring waters
(0–7.6 lg/L), distilled waters (0.1–18.1 lg/L), and fla-
vored waters (0–5.7 lg/L) [21].
3.2. Other environmental waters
Here, we report the concentrations of VOCs in surface
waters, seawater, rain water, and snow. Occurrence of
25 VOCs was studied in surface waters over a period of
three years in the southern part of North Sea [17]. This
study reported that TCM and TCE were frequently found
at concentrations of 1900 ng/L and 270 ng/L, respec-
tively, and that concentrations of chlorinated hydro-
carbons were below 10 ng/L and the monocyclic
aromatics were 2.8–18 ng/L.
VOCs (viz chlorinated alkanes, and aromatic hydro-
carbons) were determined in treated wastewaters and
river waters that receive the treated wastewaters, and
the concentrations in the river waters were found to be
below 0.1 lg/L [25].
Simultaneous sampling of six chlorinated hydrocar-
bons and five monocyclic hydrocarbons was reported in
Yokohama, Japan. This study indicated that DCM and
TCEY were abundant among chlorinated hydrocarbons,
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Table 2. Ranges and concentrations of frequently detected volatile organic compounds reported in various aquatic matrices

Matrix Compounds Ranges detected Most detected concentrations Ref.

Tap waters TCM, TBM, BDCM, DBCM Tap waters: 1.0–66.5 lg/L Tap waters [16]
TCM 1–40.8 lg/L
TBM 1.8–24.7 lg/L
BDCM 3.1–55.3 lg/L
DBCM 2–66.5 lg/L
Surface waters MTBE, BTEX MTBE 0.29–1.4 lg/L – [26]
BTEX 0.39–2.05 lg/L
Snow and tap Chlorinated hydrocarbons Overall ranges: 1.7–394 ng/L Tap waters: TCM 44.9 ng/L [22]
waters TCM, TCE, TCEY, BDCM and TCM 13–236 ng/L TCE 130 ng/L
DBCM TCE 1.6–130 ng/L TCEY 95.3 ng/L
TCM 2.7–53 ng/L Tetrachloroethylene 40.4 ng/L
BDCM 0–249 ng/L Snow:
DBCM 0–57 ng/L TCM 12.8 ng/L
Tetrachloroethylene 3.8 ng/L
Estuary surface DCE, TCM, TCE, DCP, PCE, Chlorinated hydrocarbons DCE 13 ng/L [17]
waters HCB, TOL, XYL, DCB and TCB <LOD–1900 ng/L CHCL3 1900 ng/L
Monocyclic aromatics: 2.8– TCE 270 ng/L
18 ng/L PCE 280 ng/L
TOL 680 ng/L
XYL 170 ng/L
DCB 210 ng/L
Wastewater- TOL, MTBE, acetone 20 ppb–<1 mg/L Acetone 400 lg/L [55]
treatment plant DMSO and IPA DMSO 23 lg/L
IPA 641 lg/L
Seawater Halogenated organics 10–150 pmol/L BDCM 12.9 pmol/L [23]
16 of 24 compounds were 1-Bromo-2-chloroethane 3.3 nmol/L
identified and detected
Drinking waters TCM (71%), BDCM (46%), Levels: <LOD–35 lg/L. TCM 34.58 lg/L [34]
DBCM (47%), TBM (45%) BDCM 21.23 lg/L
BTEXs BEN (47%), TOL (96%), TOL 1.60 lg/L
XYL (74%), and NAP (70%), NAP 0.90 lg/L
Drinking waters TCM, TBM, BDCM, DBCM, TCE, Drinking waters: Drinking waters: [29]
and secondary DCAN and TCP 1.28–762 ng/L TCM 6–32 ng/L
effluents Wastewaters: TBM 147–762 ng/L
9–838 ng/L BDCM 16–97 ng/L
DBCM 92–399 ng/L
Effluents:
TCM 202–771 ng/L
BDCM 99–283 ng/L
DBCM 32–220 ng/L
DCAN 198–838 ng/L
TCP 211–556 ng/L
Seawater TCM, ethyliodide, DCBM, Halogenated: 0.2–1400 ng/L BEN 3.9–141.7 ng/L [40]
DBCM, BEN, TOL, EB, XYL and BTEX and mono-aromatics: 1.5– TOL 3.6–172 ng/L
Others 2900 ng/L XYL 4.3–332 ng/L
C5, C8, C9, C10, aliphatic Aliphatic hydrocarbons and EB 2.5–119 ng/L
hydrocarbons others:0.6–15,800 ng/L EI 30.5 ng/L
DBCM 2.90 ng/L
Melted snow BTEXs BTEXs: <DL – 0.236 lg/L TOL 0.236 lg/L [36]
waters EB 0.112 lg/L
Wastewater Acetone, TCM, TCE, TOL, NAP Total VOCs 200–1200 lg/L – [20]
and DCB
River waters and Chlorinated TolueneÕs Only 2,4-DCT was reported – [39]
sewage 38.3 ± 1.1 pg/L
Seawater CTC, TOL, BEN, TCE, EB, XYL Average concentration TOL 1.63 lg/L [56]
0.18–6.8 lg/L XYL 1.15 lg/L
TCE 1.08 lg/L
Seawater Isoprene, propene, acetone, Propene 84.9–286.4 pmol/L Propene 287 pmol/L [59]
acetaldehyde, and methanol Isopropene 36.9–118.7 pmol/L Methanol 325 nmol/L
Methanol 77.9–325 nmol/L
Acetone 4.4–41.3 nmol/L
(continued on next page)

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Trends Trends in Analytical Chemistry, Vol. 32, 2012

Table 2. continued

Matrix Compounds Ranges detected Most detected concentrations Ref.

Bottled and tap TCM, TBM, BDCM and DBCM Tap water: 0–322 lg/L TCM 0.12–0.73 lg/L [21]
water samples Spring water: 0–7.6 lg/L TBM 0.01–0.24 lg/L
Flavored: 0–5.7 lg/L DBCM 0.59–0.64 lg/L
BDCM 0.07–6.25 lg/L
Lake and BTEXs and Geosmin Lake waters: 0.044–2.16 lg/L Geosmin 26 ng/L [27]
reservoir waters BEN 2.165 lg/L

BDCM, Bromodichloromethane; BEN, Benzene; BTEX, Benzene toluene, ethylbenzene, xylene; CDBM, Chlorodibromomethane; CDS,
Carbon disulfide COS, Carbonyl sulfide; CTC, Carbon tetrachloride; DBCM, Dibromochloromethane; DBCP, 1,2-dibrome-3-chloropropane;
DBM, Dibromomethane; DCAN, Dichloroacetonitrile; DCB, Dichlorobenzene; DCE, Dichloroethane; DCEY, Dichloroethylene; DCM,
Dichloromethane; DCP, Dichloropropane; DCT, Dichlorotoluene; DMSO, Dimethyl sulfoxide; EB, Ethylbenzene; EI, Ethyliodide; HCB,
Hexachloro 1,3, butadiene; IPA, Isopropyl alcohol; MTBE, Methyl tert-butyl ether; PCE, Petrachloroethane; TBE, Tetrabromoethylene; TBM,
Tribromomethane; 2,4,6TCA, 2,4,6 trichloro anisole; TCB, Trichlorobenzene; TCE, Trichloroethane; TCEY, Trichloroethylene; TCNM, Tri-
chloronitromethane; TCM, Trichloromethane; TCP, 1,1,1 trichloro 2, propanone; TOL, Toluene; WWTP, Wastewater-treatment plant; XYL,
Xylene.

and toluene and DCB were abundant in aromatic
hydrocarbons, respectively. It was further reported that
the concentrations were several hundred times higher in
dew water than rain water, indicating more hydrophobic
volatiles tend to accumulate in dew waters. Mild con-
centrations of 10–150 pmol/L halogenated volatiles
were also found in sewage waters, which were analyzed
using the stable carbon-isotope method and attributed to
atmospheric depositions [23].
Surface seawater collected from the Irish Sea was
reported to have halogenated volatiles, BTEX and
aliphatic hydrocarbons in the ranges 0.2–1400 ng/L,
1.5–2900 ng/L and 0.6–15,800 ng/L, respectively [40].
Among the detected halogenated volatiles, the concen-
trations of brominated compounds were attributed to
biogenic sources, while the chlorinated compounds were
due to anthropogenic sources coming from rivers.
After halogenated organics, the most frequently re-
ported volatiles are BTEX. Schmidt et al. [26] reported
BTEX in the range 0.39–2.05 lg/L in a Swiss lake,
which was used as a drinking-water source, and the
likely source of these compounds were the discharges
from boating activity on the lake.
Sieg et al. [36] observed BTEX in melted snow waters
in the range 3.9–15.3%.
In seawater, concentrations of toluene and xylene
(680 ng/L and170 ng/L, respectively) in estuary waters
were determined by Huybrechts et al. [17].
MTBE (17–712 ng/L) was also reported in drinking
waters [32].
Other recent studies have reported toluene and xylene
concentrations in seawater matrices in the range 1.15–
1.63 lg/L [53].
Some of the recent studies have also reported con-
centrations of halogenated organics and BTEX in sea-
water [53]. One of the popular VOCs reported in different
environmental water matrices is MTBE, which was
found to be 0.29–1.4 lg/L in surface waters [26].
Apart from those above, a few other VOCs were
reported, including acetone, dimethyl sulfide, isopropyl
alcohol, and naphthalene [20,52].
4. Most detected compounds and concentrations
In spite of their relatively high air-water partition coef-
ficient, VOCs are ubiquitous in water matrices. In this
section, we emphasize the concentrations of compounds
quantified and chiefly detected in various waters. In
Table 2, we present the concentrations of each com-
pound said to be most commonly detected. These VOCs
levels are reported in the range pg/L to lg/L in aquatic
matrices.
In tap waters, the most detected compounds were the
halomethanes, among which the commonly reported
concentrations were TCM, TBM, BDCM and DBCM, which
comprised disinfection byproducts. TCM was reported
to be 1–40.8 lg/L, 44.9 ng/L, and 0.12–0.73 lg/L,
respectively, in various tap waters, followed by BDCM
3.1–55.3 lg/L and 0.07–6.25 lg/L [16,21,22].
Zoccolillo et al. [22] detected TCE, TCEY and tetra-
chloro-ethylene at 130 ng/L, 95.3 ng/L and 40.4 ng/L,
respectively, in tap waters.
In drinking waters, TCM and TBM were most widely
reported with concentrations for TCM of 34.58 lg/L [34]
and 6–32 ng/L [29], and concentrations for TBM of
147–762 ng/L [29] and 20.1 lg/L [61].
In seawater, TCM (1900 ng/L), DCE (13 ng/L), TCE
(270 ng/L), and tetrachloro ethane (280 ng/L) were
detected [17]. DBCM (2.9 ng/L) was also reported in
seawater along with ethyliodide (30.5 ng/L) [40].
Cavlcante et al. [56] determined TCE (1.08 lg/L) with
trace concentrations of toluene (1.63 lg/L) and xylene
(1.15 lg/L) in the coastal waters of Brazil. Recently,
while studying the air-sea exchange of VOCs, propene
and methanol concentrations were detected during

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Trends in Analytical Chemistry, Vol. 32, 2012
continuous measurement studies of VOCs in seawater
[59].
Next to halogenated compounds are BTEX, which are
most frequently detected in aquatic matrices. Of BTEX, the
most commonly detected and reported singly are toluene
and xylene. Toluene was detected in dew waters
(9.69 nM), estuary water (680 ng/L), drinking water
(1.6 lg/L), seawater (4.3–332 ng/L), melted snow water
(0.236 lg/L) and groundwater (0.04 lg/L) [17,34,36,
40,56]. By contrast, xylene concentrations were reported
mostly in estuary waters as 170 ng/L, and 4.3–332 ng/L
and 1.15 lg/L in seawater, respectively [17,40,56].
Benzene (3.9–141.7 ng/L), DCB (210 ng/L) and ethyl
benzene (2.5–119 ng/L) were also quantified in seawater
[17,40].
The occurrence of VOCs in seawater was attributed to
atmospheric deposition, while halogenated VOCs (e.g., in
estuaries, groundwater, and lake waters) are mostly
correlated with anthropogenic activities. The haloge-
nated compounds detected in drinking waters result
from the byproducts of disinfection processes.
5. Quality assurance and EU quality standards
Analytical reliability and accuracy are very significant
aspects to be considered when any data related to
monitoring of environmental contaminant are reported.
Advanced quality assurance (QA) and quality control
(QC) measures have to be employed (e.g., standard-
addition tests, addition of surrogates, internal standards
or isotope tagging should be implemented for more
accurate determination of aquatic environmental con-
centrations).
Spiking known amounts of recovery standards or
surrogates can facilitate losses during storage, trans-
portation and sample preparation. Addition of certified
reference materials (CRMs) to assess the analytical per-
formance is preferred over laboratory reference materi-
als. Nevertheless, currently no CRMs are available for
VOCs in waters, as verified from Institute for Reference
Materials and Measurements (IRMM), Europe, and
National Institute of Standards and Technology (NIST),
USA. CRMs for VOCs are available for air and food
samples [63,64].
Shimizu and co-workers [65] from the National
Metrology Institute of Japan (NMIJ) have reported
development of high-purity CRMs for VOCs in water
samples. One of the highly recommended, broadly
approved methods to validate analytical data is by par-
ticipation in inter-laboratory testing using GC methods
with the same detection techniques. Comparison of the
results within different laboratories and conducting
performance audits for various VOCs, including haloge-
nated compounds, BTEX, MTBE and other frequently
reported compounds, have to be considered for more
Trends
accurate presentation of the concentrations in different
waters.
It was also reported that the Quality Assurance of
Information in Marine Environmental Monitoring in
Europe (QUASIMEME) working group was established to
conduct inter-laboratory testing studies on volatile
organochlorine and trichlorobenzene in seawater [5]. On
the equivalent lines to QUASIMEME, QA information
centers for monitoring and inter-laboratory analysis of
VOCs in various environmental waters should be incor-
porated to report more accurate concentrations of VOCs.
Such programs can translate into a reference database
center for continual studies on VOCs.
Recently, European Analytical Quality Control in
association with Water Information System of Europe
(EAQC-WISE) created a network of proficiency-test (PT)
providers to support the implementation of the Water
Framework Directive (WFD) [66]. This network is
expected to implement the WFD by providing PT
schemes for effective implementation and evaluation in a
synchronized manner. Further, we anticipate that this
network will promote coordinated performance evalua-
tion of all European laboratories involved in WFD
monitoring and analysis program. In the first year, the
network organized two rounds of PTs in October/
November 2009, of which one concerned VOCs. More
than 100 analytical laboratories from across Europe
participated in this program, and details of this network
program are reported elsewhere [66].
Another addition would be application of statistical
data analysis using different statistical models that can
aid proper elucidation of results and provide improved
understanding of environmental distribution of VOCs.
For analytical QC, one of the studies has reported the
statistical analysis of matrix-spike and laboratory-con-
trol samples for analyzing VOCs in groundwaters. All the
analytical information was loaded to a laboratory
information management system (LIMS) database for
evaluation. This statistical analysis revealed that mean
recovery values of all analytes studied from matrix-spike
samples and laboratory-control samples were almost
same [67]. Also, the development of statistical models
can become an effective support for giving a hypothetical
projection of concentrations of VOCs in waters, keeping
in view the various environmental changes that can
affect the quantities of VOCs over a period of time. This
would also help establish plausible connections between
the sources of VOCs and the concentrations determined.
In the Directive of the European Parliament and
Council (2008/105/EC) [68], the maximum allowable
limits of benzene (50 lg/L) and chloroalkanes (1.4 lg/L)
are the only VOCs present. Even though the environ-
mental quality standards list comprises dichlorometh-
ane, trichloromethane and naphthalene, maximum
permissible limits have not been mentioned for these
compounds. Hence, this warrants the need for accurate
http://www.elsevier.com/locate/trac 73
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Trends
determination of different VOCs in a wide range of
aquatic matrices based on which the permissible limits
can be set for the remaining set of VOCs.
6. Conclusions
Since this review focused more on VOC concentrations in
aqueous environmental matrices, we stress publications
pertaining to sample preparation and analysis of VOCs in
different waters. Among the aquatic matrices were sea-
water, river waters, lake waters, groundwater, drinking
water, wastewater, bottled water, and melted snow
water.
Analysis of VOCs still requires research in sample
preparation to simplify the analysis and make it more
selective. From this reported information, we recorded
that HS techniques and SPME remain the methods of
choice.
New sample-preparation methods (e.g., spray and
trap, modified P&T, SCMS, CMS, use of carbon isotope)
have also been studied and recommended, but have yet
to be applied by many researchers due to the simplicity
and handy preparation of SPME and HS. This implies
that more insight is still needed into sample-preparation
processes for extraction of selected VOCs.
For the detection of VOCs, MSD obviously remains the
most popular technique for a variety of compounds, due
to its sensitive quantification based on mass.
We also presented use of ITMS and TOF-MS with good
sensitivity and detection at ng/L levels. Detectors (e.g.,
ECD) are still preferred, but determination and quantifi-
cation are limited to halogenated organics with this
detector.
Determinations of VOCs using PID and FID have also
been reported, but the LODs cannot be comparable to
that of MSD.
Use of tandem MS was reported in one publication for
the determination of chlorinated toluene, which is more
challenging and can achieve pg/L-level sensitivities [39].
Interestingly, the use of positive-mode electron impact
as source was observed in almost all reference papers.
Use of a chemical-ionization source was limited to one
or two publications.
Among the most detected and reported compounds,
halogenated organics were dominant followed by BTEX.
In drinking water, disinfection byproducts, mainly
THMs, were more frequently identified, with the most
reported compound being TCM.
From the information in this review, we understand
that, research is indeed essential to explore simpler, more
robust sample-preconcentration methods. For the
detection of VOCs, tandem MS detectors with multiple-
reaction monitoring (MRM) mode will be useful for
deeper understanding of VOC concentrations in envi-
ronmental waters.
74 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 32, 2012
Acknowledgments
N. Sridhara Chary thankfully acknowledges Marie-Curie
Actions for providing an AMAROUT Fellowship.
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