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, Solid-phase microextraction; THMs, Trihalomethanes; VOX, Volatile organohalogen compounds; WHO, World Health Organization

1. Introduction coulometric and spectroscopic methods.

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;
E-mail: marektobiszewski@
wp.pl
Green analytical chemistry (GAC) is an
aspect of green chemistry and of the con-
cept 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
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 pre-
concentration 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 sample-
preparation 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 prepara-
tion.

0165-9936/$ - see front matter 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2012.02.006 67
Trends
Analytical process step
Sample collection
Location of
line, at line
Transport and storage
Sample preparation
Chromatographic separation
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 collec-
tion, 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 ana-
lytical chemists 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 direct-injection 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 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 35, 2012
Avoiding the step
Passive dosimetry
enables analyte
device in- preconcentration
during sample
or on-line collection
Introduction of direct techniques
Direct injection mass spectrometry for
volatile compounds in gas samples
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, non-polar column stationary phase and dense,
polar, cross-linked phases are used. Recent developments
in the quality of column stationary phases and novel
methods of cross-linking 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
Analytical methodologies for the determin
ation of analytes in a complex matrix
sample
Mode of measurement
Direct techniques
No sample preparation is required
Potentiometry
Graphite furnace atomic
absorption spectrometry
Inductively coupled plasma
techniques
Neutron activation analysis
X-ray fluorescence
Immunoanalysis
Direct sample injection into
chromatographic column
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 non-polar analytes, while venting polar solvent.
Trends
Indirect techniques
The sample is analyzed following
its pretreatment
Extraction
(nowadays often solventless)
Mineralization
Derivatization
Homogenization
Clean-up
Drying
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
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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 Analytes Injection mode Sample LOD [lg/L] RSD [%] Ref.
volume [lL]
GC-ECD
Water 11 VOX On-column 60C 1 110 2.15.7 [18]
Water 6 VOX On-column 4 0.30.8 2.13 [19]
Water 12 VOX including Cold on-column 2 0.021.6 1.222 [20]
chlorobenzenes
Rainwater and snow (after melting) 7 VOX Cold on-column 2 0.010.2 Not specified [41]
Water and wastewater 26 VOX Cold on-column 2 0.0153.9 1.712 [22]

GC-FID
Water BTEX Injector liner filled 250 0.61.1 Not specified [24]
with sorbent
Wine, whisky, other beverages Methanol Splitless 0.1 1000 1.31.7 for wine [27]
2.83.7 for whisky

GC-MS
Surface and groundwater 24 VOCs Cold on-column 110 0.16 1.843 [30]
Surface and groundwater 13 VOCs Cold on-column 110 0.0531 223 [29]
Wastewater 170 VOCs and semi- PTV-PTV 12 1000 Not specified [33]
VOCs
Gasoline MTBE Splitless 1 Not specified 0.73.3 [34]
Wine 13 Carboxylic acids PTV 50 Not specified 4.525 [36]
and alcohols
Whisky 21 Compounds Sorbent-packed liner 5 not specified 1.926 [38]

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 by-
products in drinking water [17]. Compared to the purge-
and-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%, 85124% 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,
100 lg/L and 100 lg/L for chloroform, bromodichlo-
romethane, 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 halome-
thanes, 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

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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
non-polar 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 com-
pounds 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
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 moni-
toring 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 in-line 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 pre-
cision 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
direct-injection chromatography. 21 trace components
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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 Analytes Analytical technique Sample LOD [lg/L] RSD [%] Ref.
volume [lL]
Water 12 Herbicides LC-ESI-MS2 50 0.05 4.515 [41]
Water 4-Chloro-2-methylphenoxyacetic LC-ESI-MS2 100 0.2 211 [42]
acid and metabolite
Wastewater 4 Fatty acids and 10 resin acids LC-APCI-MS 100 0.53 27 [44]
Wine trans-Resveratrol LC-DAD 100 25 1.45 [46]
Wine trans-Resveratrol LC-chemiluminescence detection 50 0.17 1.16 [46]
Olive oil 5 Phenols and phospholipids LC-UV/Vis 50 0.020.15 122 [47]
Serum Barbiturates LC-UV/Vis 20 3070 0.31.8 [48]

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].
4. Liquid-chromatography techniques
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 (ESI-
MS2) has been developed for the determination of her-
bicides in water samples [41]. The recoveries for treated
water, surface water and groundwater were in the 82
109% range [42]. Herbicide 4-chloro-2-methylphe-
noxyacetic 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
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 en-
abled the direct injection of oil and simultaneous deter-
mination of phenols and phospholipids.
Analytical methods based on micellar LC were devel-
oped 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

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Trends in Analytical Chemistry, Vol. 35, 2012
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 pro-
duction 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 gen-
erated during time-consuming sample treatment can be
avoided without detriment to analytical parameters (e.g.,
precision, accuracy or LOD). However, better under-
standing 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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