Trends in Analytical Chemistry, Vol.

35, 2012

Trends

Direct chromatographic methods

in the context of green analytical
chemistry
Marek Tobiszewski, Jacek Namiesnik
We review analytical protocols based on gas and liquid chromatography (GC and LC), but involving no sample preparation.
Green analytical chemistry seeks to minimize negative impacts of analytical chemistry. Direct analytical methods ideally fulfill
this requirement, as they preclude sample preparation the most polluting step of the analytical procedure.
We describe examples of GC methodologies for environmental and food analysis using on-column, programmed
temperature vaporizers and injectors with sorbent-packed liners.
Although LC methods are less amenable to eliminating sample pretreatment, we also present some successful applications
of direct LC methods in environmental and food analysis, and bioanalysis.
2012 Elsevier Ltd. All rights reserved.
Keywords: Analytical protocol; Direct chromatographic method; Direct injection; Environmental analysis; Food analysis; Gas chromatography;
Green analytical chemistry; Liquid chromatography; Vaporizer; Waste minimization
Abbreviations: APCI, Atmospheric pressure chemical ionization; BTEX, Benzene, toluene, ethylbenzene, xylenes; DAD, Diode-array detector; DAI,
Direct aqueous injection; ECD, Electron-capture detector; EPA, Environmental Protection Agency; ETBE, Ethyl tert-butyl ether; FID, Flame-ionization
detector; GAC, Green analytical chemistry; GC, Gas chromatography; LC, Liquid chromatography; LOD, Limit of detection; LVI, Large-volume injection;
MS, Mass spectrometry; MTBE, Methyl tert-butyl ether; PTV, Programmed temperature vaporization; RSD, Relative standard deviation; SPME, Solidphase microextraction; THMs, Trihalomethanes; VOX, Volatile organohalogen compounds; WHO, World Health Organization

1. Introduction
Marek Tobiszewski*,
Jacek Namiesnik

Department of Analytical
Chemistry, Chemical
Faculty, Gdansk University
of Technology (GUT), ul. G.
Narutowicza 11/12, 80-233
Gdansk, Poland

Corresponding author.
Tel.: +48 5 83472110; Email: marektobiszewski@
wp.pl

Green analytical chemistry (GAC) is an

aspect of green chemistry and of the concept of sustainable development. GAC
focuses on reducing the environmental
impact of analytical methodologies. There
are several approaches to achieve this goal
{e.g., green sample pretreatment [1],
application of environmentally benign
solvents and reagents [2], reducing the
impact of chromatographic analysis by
shortening chromatographic separation
times [3], miniaturization of analytical
devices [4], and management of analytical
wastes [5]}. The idea of GAC is spreading
in analytical laboratories and the need to
make analytical chemistry greener is
becoming more widely accepted.
Direct analytical techniques (i.e. with-out
sample preparation) are particularly
desirable from the GAC point of view. Such
techniques include ion-selective electrodes,
immunoassays, and some

0165-9936/$ - see front matter 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2012.02.006

coulometric and spectroscopic methods.

However, chromatography with various
detection systems is frequently applied to
environmental, industrial, biomedical and
food analysis of organic compounds.
Generally,
chromatographic
analysis
requires sample pretreatment for the preconcentration of analytes and the removal of
interferents. The great number of
chromatographic analyses carried out and
the potential to generate wastes during
sample preparation
make it desirable
to introduce
direct
chromatographic
methods.
We review direct
chromatographic
methodologies. We show that the samplepreparation step can be successfully omitted
when
performing
gas
or
liquid
chromatographic (GC or LC) analysis,
making this greener. We compare the results
obtained with direct chromato-graphic
methodologies with those of some
methodologies involving sample preparation.

67

Trends

Analyticalprocessstep
Samplecollection

Transportandstorage

Trends in Analytical Chemistry, Vol. 35, 2012

Avoidingthestep

Locationof
devicein
line,atline
oronline

Passivedosimetry
enablesanalyte
preconcentration
duringsample
collection
Introductionofdirecttechniques

Samplepreparation

Directinjectionmassspectrometryforvolatilecompoundsingas
samples

Chromatographicseparation

Detection

Figure 1. Steps in the determination of organic compounds and ways of avoiding particular steps of analysis.

2. The analytical process in the light of green

chemistry
The analytical process usually comprises sample collection, transportation and storage, and then sample
preparation and final analysis (see Fig. 1). Its role is to
obtain reliable results from measurements of a given
chemical species in a sample. During chemical analysis,
some analytical wastes are produced [5]. It is the analytical chemist s responsibility to manage these wastes, or,
following the principles of green chemistry, to pre-vent
their production [6]. For example, by placing an analytical
device in in-line, on-line, or at-line modes [4], the analysis
can be performed without sample collection. With directinjection mass spectrometry (MS), virtually all steps,
except the final determination, can be omitted when
volatile organics are determined in gaseous sam-ples [7].
Determination of trace volatile analytes in complex
gaseous mixtures is possible due to the high sensitivity and
selectivity of recent mass spectrometers. Various systems
have been developed for specific appli-cations in
environmental (particularly atmospheric) chemistry, plant
chemistry, and food and industrial analysis.
The sample-preparation step is considered the most
polluting in the analytical procedure [8], as it may in-volve
the use of toxic chemicals and/or volatile solvents during
operations mentioned in Fig. 2. Solvents used in analytical
chemistry are high purity, and their manu-facture requires
more material and higher energy input than technical-grade
solvents. Recently, much attention has been given to
reducing the environmental hazards of sample-preparation
techniques. Various extraction systems, based on
miniaturized liquid-liquid extraction (LLE) [9], solid-phase
extraction (SPE) and solid-phase

68

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microextraction (SPME) [10], headspace (HS) analysis,

membrane techniques [11] or the use of alternative solvents
[12], have been introduced. The National Environmental
Methods Index (NEMI) defines the method as green if
chemicals used in the procedure are not listed in the Toxic
Release Inventory list as being persistent, bioaccumulative
and toxic or being hazard-ous, the pH during analysis is
within the 212 range and the amount of waste produced is
less than 50 g [13]. According to this definition, the
methods that we present are green. The application of
direct chromatographic techniques is a step forward in
reducing the environ-mental impact of chromatographic
analyses.
3. Gas-chromatography techniques
The introduction of the sample (usually water but also
water-ethanol mixture) directly into the chromato-graphic
capillary column used not to be recommended. Water is
considered to cause increased column bleeding, especially
when polar stationary phases are applied, so a dense, nonpolar column stationary phase and dense, polar, crosslinked phases are used. Recent developments in the quality
of column stationary phases and novel methods of crosslinking have improved resistance to deterioration caused by
water. The on-column intro-duction of environmental water
may cause problems with column performance, especially
when the water has high salt content, and may decrease
detector sensi-tivity. Deactivated precolumns therefore
have to be in-stalled in front of the analytical column to
prevent inorganic salts and organic non-volatile compounds
from entering the column. The deactivated column also
serves as a retention gap, which provides space for the

Trends in Analytical Chemistry, Vol. 35, 2012

Trends

Analyticalmethodologiesforthedeterminationofanalytesinacomplex
matrixsample

Modeofmeasurement
Directtechniques
Nosamplepreparationisrequired

Potentiometry
Graphitefurnaceatomic
absorptionspectrometry
Inductivelycoupledplasma
techniques
Neutronactivationanalysis
Xrayfluorescence
Immunoanalysis

Indirecttechniques
Thesampleisanalyzedfollowing
itspretreatment
Extraction
(nowadaysoftensolventless)
Mineralization
Derivatization
Homogenization
Cleanup
Drying

Directsampleinjectioninto
chromatographiccolumn
Figure 2. Classification of analytical techniques with respect to the sample-preparation step.

solvent to evaporate. The sensitivity of methods based on

on-column injection depends on the volume of sample
injected.
The alternative approach to injecting a liquid sample into
the column is to prevent solvent from reaching it by
removing the most or all of the solvent in the injector [14].
Programmed temperature vaporization (PTV) causes the
solvent to evaporate before the sample reaches the column.
The device used is similar to a split/ splitless injector but is
equipped with an efficient heating and cooling system.
After introducing sample into the injector, the solvent is
slowly evaporated and vented at relatively low
temperature, below its boiling point in the split mode of the
injector. This causes enrichment of analytes in the injector.
The analytes are then intro-duced into the column by
rapidly increasing the injector temperature in splitless
mode. PTV is suitable only for analytes with boiling points
considerably higher than that of the solvent involved.
Another approach to preventing the solvent from
reaching the column is to use a liner filled with sorbent
[15]. Proper sorbent selection is required to retain sol-vent
and thus enable the analytes to be introduced into the
column. Applying organic sorbent (i.e. Tenax) retains nonpolar analytes, while venting polar solvent.

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69

Making the wrong decisions about sorbent selection may

cause analytes to degrade or may strengthen their retention.
The solvent is vented at increased tempera-tures.
There are review papers on the large-volume injection
(LVI) of samples into GC columns that discuss technical
solutions and modification modes in detail [14,15].
However, not all LVI methods are direct as the injected
sample may be an extract (then the method is not direct). It
is debatable whether PTV sample introduction is a direct
analytical method or on-line sample prepara-tion to be
applied before chromatographic analysis. We include
examples of PTV applications without off-line sample
preparation in the discussion. Table 1 summa-rizes some
examples of application of direct GC methods.
3.1. GC-ECD
The first direct aqueous injection-GC-electron-capture
detection (DAI-GC-ECD) system was introduced by Grob
and Habish [16]. ECD, which is extremely sensitive
towards compounds containing halogen atoms, enables
these compounds to be determined at sufficient levels
without the need for their isolation and enrichment. The
limits of detection (LODs) for halogenated volatile
organics are at low-lg/L levels; a significant

Trends

Trends in Analytical Chemistry, Vol. 35, 2012

Table 1. Applications of direct gas chromatographic methods, their limits of detection (LODs) and relative standard deviations (RSDs)
Matrix
GC-ECD
Water
Water
Water

Analytes

Injection mode

Sample
volume [lL]

LOD [lg/L]

RSD [%]

Ref.

On-column 60LC
On-column
Cold on-column

1
4
2

110
0.30.8
0.021.6

2.15.7
2.13
1.222

[18]
[19]
[20]

Rainwater and snow (after melting)

Water and wastewater

11 VOX
6 VOX
12 VOX including
chlorobenzenes
7 VOX
26 VOX

Cold on-column
Cold on-column

2
2

0.010.2
0.0153.9

Not specified
1.712

[41]
[22]

GC-FID
Water

BTEX

250

0.61.1

Not specified

[24]

Wine, whisky, other beverages

Methanol

Injector liner filled

with sorbent
Splitless

0.1

1000

1.31.7 for wine

2.83.7 for whisky

[27]

Cold on-column
Cold on-column
PTV-PTV

110
110
12

0.16
0.0531
1000

1.843
223
Not specified

[30]
[29]
[33]

Splitless
PTV

1
50

Not specified
Not specified

0.73.3
4.525

[34]
[36]

Sorbent-packed liner

not specified

1.926

[38]

GC-MS
Surface and groundwater
Surface and groundwater
Wastewater
Gasoline
Wine
Whisky

24 VOCs
13 VOCs
170 VOCs and semiVOCs
MTBE
13 Carboxylic acids
and alcohols
21 Compounds

improvement may be obtained when the cooling system is

applied to the on-column injector.
DAI-GC-ECD is frequently applied in the determination
of trihalomethanes (THMs) and/or other disinfection byproducts in drinking water [17]. Compared to the purgeand-trap (P&T) method, LLE and HS analysis, DAI, as
applied to the determination of THMs in water, is the
simplest, least labor-intensive procedure, involving no
sophisticated equipment, reagents or solvents. However,
the LODs are high (110 lg/L), compared to HS analysis
(0.050.6 lg/L), P&T (0.020.05 lg/L) or even LLE (0.81
lg/L). But, the precision is also usually better than that of
other methods, as relative standard devia-tions (RSDs) are
in the 15% range for both DAI and LLE and up to 50%
for HS and P&T methods. The DAI method was
characterized by good recoveries, within the 84108%
range, while ranges for HS analysis were 34 128%, 85
124% for P&T, and 95111% for LLE [18]. Another study
showed that the LODs obtained with DAI (0.30.8 lg/L)
were comparable with those of the P&T technique (0.61.5
lg/L) but higher than those of LLE (0.020.07 lg/L) when
analytes were extracted with 1 mL of hexane from 10 mL
of water. DAI showed good precision (RSDs 2.13%)
similar to P&T (RSDs 1.24%) but better than LLE (RSDs
47.3%) [19].
The value of 80 lg/L (the sum of four THMs) is the
maximum permissible concentration (MPC) of THMs in
drinking water, as laid down by the US Environmental
Protection Agency (EPA). The values stipulated by the
World Health Organization (WHO) are 300 lg/L, 60 lg/L,

70

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100 lg/L and 100 lg/L for chloroform, bromodichloromethane, dibromochloromethane and bromoform,
respectively. The LODs obtained by DAI methods are
lower than the MPCs, making DAI an efficient, rapid
technique for routine THM determination in drinking
water.
DAI-GC-ECD was also applied to determine halomethanes, chloroethanes and chlorobenzenes in surface-water
samples [20]. Chlorobenzenes had higher LODs (0.091.6
lg/L) and higher RSDs (2.95%) than ali-phatic
compounds (0.020.09 lg/L LODs and 1.13% RSDs).
The application of DAI-GC-ECD to determine volatile
organohalogen compounds (VOX) in surface water is
limited by the presence of suspended matter in water. The
problem of suspended matter is limited when VOX are
determined in rainwater samples. Seven VOX have been
successfully determined in precipitation samples collected
in urban areas at sub-lg/L concentrations [21]. The
technique was also applied to determine VOX in process
water and oiled wastewater [22]. The aqueous phase of the
oiled sample is introduced into a column. Light
hydrocarbons pass through the column and give no signal
in ECD, whereas heavy hydrocarbons are hardly soluble in
water and any traces are captured in the precolumn.

3.2. GC-FID
Direct on-column injection can be applied to determine
hydrocarbons, alcohols or carbonyl compounds in clean

Trends in Analytical Chemistry, Vol. 35, 2012

environmental waters (e.g., rainwater) [23]. The LOD for

ethanol by direct on-column injection of 2-lL sample was
46 lg/L, while, with P&T and SPME, the LODs were 0.9
lg/L and 1000 lg/L, respectively.
Application of the sorbent Chromosorb P NAW in the
liner enables the direct LVI of the water sample. As 250-lL
water sample is slowly introduced into the liner, the nonpolar analytes are transferred to the capillary col-umn,
while the water is trapped by the sorbent. At the next stage,
water is removed from the liner via the split flow [24]. The
LODs were satisfactory, in the 23.6-lg/L range, although
some problems with real sample anal-ysis cropped up.
DAI was used in an investigation of VOX degradation in
batch and column studies [25]. DAI seems to be convenient
for periodic sampling and analysis during such
experiments. Direct sample injection ensures that no
further degradation occurs during sample pretreat-ment.
The technique was also used to calculate the kinetics of
MTBE and ETBE adsorption on activated carbon [26].
A chromatographic technique, involving no sample
pretreatment, was developed to determine methanol and
other alcohols in whisky, and red and white wines at mg/L
levels [27]. The method was suitable even for colored
samples with complex matrix composition. The short
analysis time of 9 min is a big advantage when routine
samples are analyzed. The method is useful for monitoring
the methanol content during fruit fermen-tation.
A similar method was used to determine eight compounds in Canary Islands wines. Having been spiked with
an internal standard, sample volumes of 1 lL were injected
with no sample preparation into the chro-matographic
column with split injector with 1:60 split ratio [28].
3.3. GC-MS
MS is a powerful tool in environmental and food anal-ysis,
which is why it is also frequently chosen in direct
chromatographic methods. The problem with MS detection
is that a large amount of water injected on-column affects
the stability of the ion source. Pressure increases are
observed, resulting in slightly lowered sensitivity and
worse recoveries of analytes co-eluting with water [29].
Applying internal standards also co-eluting with water and
injection of rather small volumes of water help to
overcome these problems. The initial conditions in the ion
source are re-established within 5 10 min (depending on
the volume of water injected) after water passes through
the detector. Despite these difficulties, the on-column
injection of a groundwater sample without pre-treatment
allowed BTEX, fuel oxy-genates and chlorinated solvents
to be determined at sub-lg/L levels [30]. These compounds
are typical groundwater pollutants, so this fast, accurate
and robust

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71

Trends

method seems to be good choice for their determination.

The method meets the requirements set by EPA and
European Union regulations. It is also suitable for
investigating in-situ transformation rates of compounds
[31].
DAI was applied in on-line wastewater-quality monitoring before reaching the wastewater-treatment plant
(WWTP) to ensure its proper functioning. The method is
advantageous because of the short time during which
analytical results are obtained, which enables waste-water
to be sent to a storage tank and not the WWTP. Heavy
loads of organics may affect biological treatment and
contaminate water, so fast analytical response is crucial to
assure chemical safety. Suspended matter was removed inline before sample collection, and samples were diluted
with ultrapure water. Samples were ana-lyzed by means of
two GC-MS systems to shorten the time delay between
sample collection and obtaining analytical result. Both
were equipped with PTV-PTV injection systems and 170
volatile and semi-volatile or-ganic compounds were
determined at mg/L concentra-tions [32]. These compounds
belonged to different chemical classes. The method can
deal with wastewater with a heavily polluted matrix [33].
Contrary to single PTV, the double PTV system also allows
analysis of volatile analytes. The first PTV is heated to
evaporate solvent, together with analytes. The second PTV,
packed with sorbent, retains analytes, even those that are
vol-atile, while solvent is vented. At the next stage, the
direction of gas flow is reversed in the second PTV and it
is heated. The trapped analytes are then released and
transferred into the chromatographic column.
Direct gasoline injection was used to determine MTBE
in fuels in a 1.5-min chromatographic run [34]. The method
parameters were comparable to those obtained with HS
analysis (RSD > 5% for both methods) but in a shorter time
(HS analysis takes 6 min). Direct injection of a gas sample
with a gas-tight syringe was reported to be suitable for the
determination of polar and non-polar VOX in industrial air
[35]. Compared to SPME, the di-rect-injection method was
rugged to bias. The difference in results obtained with these
two methods was up to 70%, explained by great differences
in adsorptivity and competitive adsorption of the analytes
in SPME.
Direct-injection methods based on a PTV injector were
used to analyze aroma compounds from wine. The analysis
time was twice as short as distillation and 10 times shorter
than for LLE. The precisions of all three methods were
comparable [36].
Bitrex, the compound added to alcohol for denaturing,
was determined by direct injection of alcohol. The precision expressed as RSD was below 4%. The method was
faster and less laborious than alternative methods based on
thin-layer chromatography and liquid chromatogra-phy
(LC) [37]. The quality of whisky can be assessed by directinjection chromatography. 21 trace components

Trends

Trends in Analytical Chemistry, Vol. 35, 2012

Table 2. Applications of direct liquid-chromatographic methods, their limits of detection (LODs) and relative standard deviations (RSDs)
Matrix
Water
Water
Wastewater
Wine
Wine
Olive oil
Serum

Analytes
12 Herbicides
4-Chloro-2-methylphenoxyacetic
acid and metabolite
4 Fatty acids and 10 resin acids
trans-Resveratrol
trans-Resveratrol
5 Phenols and phospholipids
Barbiturates

Analytical technique
2

Ref.

0.05
0.2

4.515
211

[41]
[42]

LC-APCI-MS
LC-DAD
LC-chemiluminescence detection
LC-UV/Vis
LC-UV/Vis

100
100
50
50
20

0.53
25
0.17
0.020.15
3070

27
1.45
1.16
122
0.31.8

[44]
[46]
[46]
[47]
[48]

In reversed-phase LC, the trend nowadays is to use greener

solvents (i.e. water or ethanol) as mobile phases [3]. Their
application enables the direct injection of samples that
often have polar matrices (e.g., water in environmental
analysis and bioanalysis, or a water-alcohol mixture in the
analysis of beverages). LC requires the injected sample to
be absolutely clean, so there are hardly any absolutely
direct LC methods. Some are al-most direct because they
require simple filtration or dilution of the sample, but
without needing other oper-ations. Methodologies
involving sample dilution or fil-tration are included in the
discussion: these operations are good practice, as they
assure protection of the ana-lytical column and prevent its
contamination. Table 2 summarizes examples of successful
applications of direct methods based on LC.
DAI-LC with electrospray ionization tandem MS (ESI2
MS ) has been developed for the determination of herbicides in water samples [41]. The recoveries for treated
water, surface water and groundwater were in the 82
109% range [42]. Herbicide 4-chloro-2-methylphenoxyacetic acid and its metabolite could be determined in
groundwater and surface water (with recommended simple
filtration) at sub-lg/L levels. The analysis time of 14 min
made the method suitable for monitoring envi-ronmental
waters [43].
The traditional approach for determining fatty and resin
acids in wastewater involves extraction with MTBE,
derivatization and GC-FID or GC-MS analysis.
Alternatively, a direct method (filtration applied to

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RSD [%]

50
100

4. Liquid-chromatography techniques

Trends in Analytical Chemistry, Vol. 35, 2012

LOD [lg/L]

LC-ESI-MS
2
LC-ESI-MS

in whisky were assessed using direct sample injection to a

PTV or via a split injector with 1:20 split ratio. Split
injection was characterized by much greater precision with
RSDs of 0.63.4%, while PTV method had lower precision
with RSDs 1.329% [38]. The disadvantage was the need
to change the liner after several analyses to avoid
overloading with non-volatile material. Frequent cleaning
of the injector was needed to maintain the reproducibility
of the results [39].

72

Sample
volume [lL]

wastewater samples) based on LC with atmospheric

pressure chemical ionization MS (LC-APCI-MS) was
developed [44]. The advantage of LC-APCI-MS compared
to GC-MS was its greater reproducibility, precision and
robustness. However, its sensitivity, selectivity and linear
range were slightly worse. The LODs for LC-APCI-MS
were 0.53 lg/L of water, while those for GC-MS were
0.0040.2 lg/L.
The problem with beverage analysis by direct injection is
that the matrix composition is quite complex. The quality
of the chromatogram obtained depended on the amounts of
interfering compounds, which might have been be
colorants, antioxidants, preservatives or sweet-eners [45].
Trans-resveratrol could be determined in red wine with a
diode-array detector (LC-DAD) after 0.22-lm filtration or
chemiluminescence detector after filtration and dilu-tion
with a mobile phase [46]. With the chemilumines-cence
detector, quantification at sub-lg/L levels was possible
without analyte enrichment and the recoveries were better
than those obtained with DAD.
Food samples with a dirtier matrix can be analyzed
directly with LC. Dilution of olive oil with 2-propanol
enabled phenols and phospholipids to be determined
without further sample treatment [47]. Micellar LC enabled the direct injection of oil and simultaneous determination of phenols and phospholipids.
Analytical methods based on micellar LC were developed for the determination of barbiturates in serum [48]
and urine [49] after sample filtration and dilution with a
mobile phase. Although the matrices were complex, the
retention times remained stable for several hundred
analyses; the methods were fast, making them suitable for
routine serum analysis.
5. Conclusions
Direct chromatographic methods relate to green chem-istry
in two ways. By avoiding the sample-preparation step, they
comply with the principles of waste prevention and
reduced use of solvents, auxiliaries and energy. However,
the shorter time of analysis and the possibility

Trends

of locating the chromatograph on-line or at-line is a step

towards fulfilling the need for the real-time monitoring of
chemical processes, as stated in one of the principles of
green chemistry. This feature may be utilized at production plants, WWTPs, water-disinfection systems or in
environmental analysis. As sample pretreatment is
unnecessary, the possibilities of sample contamination or
loss of volatile compounds are minimized. The risk
associated with handling hazardous chemicals is also
avoided.
The examples described show that some wastes generated during time-consuming sample treatment can be
avoided without detriment to analytical parameters (e.g.,
precision, accuracy or LOD). However, better understanding of the environmental impact of individual
analytical methodologies requires detailed life-cycle
assessment studies of them. Such studies can assess if the
impact of cleaning or other operations on liners and
columns prevails over the amount of solvents saved by
applying direct methods.
Acknowledgements
Marek Tobiszewski expresses his gratitude for the financial
support that he received from the Human Capital Program
(POKL.04.01.01-00-368/09) and for financial support in
the form of a grant awarded by the Polish Ministry of
Science and Higher Education (NN 523 562838).

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