Vous êtes sur la page 1sur 11

Anal. Chem.

2010, 82, 4775–4785

Gas Chromatography
Frank L. Dorman*

Department of Biochemistry and Molecular Biology, Penn State University, University Park, Pennsylvania 16802

Joshua J. Whiting

LECO-ARD, Saint Joseph, Michigan 49085

Jack W. Cochran

Restek Corporation, Bellefonte, Pennsylvania 16823

Jorge Gardea-Torresdey

Department of Chemistry, University of Texas, El Paso, El Paso, Texas 19968

Review Contents the fundamentals. A recent search of the literature had slightly
General Interest and Reviews 4775 more that 800 publications per year that have the broad subject
Texts 4775 area of “gas chromatography”. Most of these publications are
Review Articles 4775 applied separations which use GC as the separation technique,
Columns Principles and Technology 4776
so this review really focuses on the small subset that are viewed
General Information 4776
Stationary Phases 4776 by the authors as improvements in the technique or the under-
Fundamental Characterizations 4776 standing of the technique. Despite the large numbers of publica-
Portable and Microfabricated GC Technology tions in other separation techniques (HPLC, CE, etc), GC is
Development 4777
Microfabrication Developments 4777 arguably still the best separation tool that is in common use for
Comprehensive Two-Dimensional Gas Chromatography the compounds which are amenable to the technique. Possibly,
(GC × GC) 4779 the greatest expansion of this technique that attracts interest from
Scope 4779
researchers is comprehensive two-dimensional GC (GC × GC).
Reviews 4779
Instrumentation 4779 Increasing interest from the commercial field has led to additional
Data Handling 4779 instrumentation and improvements in ease of use following the
Theory 4780 previous review. While this technique is still not common in
Biological 4780
Clinical and Forensics 4780 analytical laboratories, it does account for a significant amount of
Environmental 4780 the publications and academic research; thus, it occupies a rather
Flavor and Fragrance 4781 extensive portion of this review.
Food and Beverage 4781
Texts. Several texts were published in this period, some of
Metabolomics 4782
Petrochemical 4782 which were revised editions. Of particular note are three first
Gas Chromatography Detectors 4782 edition texts: “Comprehensive Two Dimensional GC”, edited by
Improvement in GC Detector Techniques 4782 Ramos (2); “Quantification in LC and GC: A Practical Guide to
GC Detector Improvement through Software
Development 4783
Good Chromatographic Data”, edited by Kuss and Kromidas (3);
Development of GC New Detectors 4783 and “Ionic Liquids in Chemical Analysis”, edited by Koel (4). Also
Literature Cited 4784 revised during this period was McNair’s text on “Basic Gas
Chromatography” (5), which is a text that is often used in the
GENERAL INTEREST AND REVIEWS teaching of the GC technique to students. Finally, for the GC/
This review of the fundamental developments in gas chroma- MS technique, Hubschmann has revised and updated the Hand-
tography (GC) includes articles published following the previous book of GC/MS text (6).
review (1) in 2008 up to March, 2010. Emphasis is given to Review Articles. During the time period of this review,
developments which are considered significant as far as basic approximately 40 review articles were published on various aspects
advances. This accounts for a much smaller amount of publica- of GC. Many were, again, application driven, or were focused on
tions, as the majority of papers deals with applications of the GC detection strategies or increasing the instrumental throughput.
technique and, as such, do not necessarily represent advances in There were a surprising number of articles, however, that were
more focused on the GC separation itself or on expanding the
* To whom correspondence should be addressed. range of compounds which can be analyzed. Often referred to as
10.1021/ac101156h  2010 American Chemical Society Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4775
Published on Web 05/26/2010
the “Achilles heel” of GC, the injection technique can be a large particle based HPLC separations, but his comments could easily
source of frustration when analyzing thermally labile compounds. apply to GC as well. Most practicing chromatographers have
Large volume injection (LVI) methods have been well reviewed little interest or knowledge in the mechanisms which lead to
(7) including direct sample introduction and through oven transfer separation and often rely on detection techniques to overcome
adsorption desorption (TOTAD) techniques. chromatographic coelutions. While this may give acceptable
Also considered an “injection” technique, static headspace results in some cases, there is still need for development of
extraction GC (SHE-GC) was reviewed (8). Methods of extending new materials which would give additional selectivities and/
the working range of volatility for this technique are addressed, or allow GC to extend further into the analysis of reactive
and good coverage of the fundamentals is also summarized. nonvolatile compounds.
Fast GC was also reviewed (9) with particular attention being Stationary Phases. Clearly, ionic liquids continue to represent
paid to theory and influence of various band-broadening mecha- the highest percentage of papers published using new materials
nisms which can potentially limit this technique. It was demon- as GC stationary phases. To date, these materials have not had
strated that peak widths of 1 ms are readily achievable in GC if the efficiency of the polysiloxanes, but they do offer unique
extra-column band broadening is controlled. selectivities. The use of ionic liquids has been reported in the
A few reviews concerning the role and understanding of the analysis of biodiesel blends (16), another recent topic of interest!
stationary phase in GC separations were published. The first This paper uses one of the commercially available columns which
describes the various retention models used in prediction of is based on the chemistry developed at Dan Armstrong’s group.
retention times based on thermodynamic parameters (10). This The comparison to more standard poly(ethylene glycol) (PEG)
also covers the use of thermodynamic modeling to various column column separations demonstrates the ionic liquid’s benefit of
arrangements with simultaneous temperature and pressure pro- separation of the FAME’s from the less-retained saturates. Other
gramming. Also discussed is extension of these techniques to fast researchers have reported on an ionic liquid bonded polysiloxane
GC and GC × GC. Most of the stationary phase work published stationary phase, which they claim has a “high separation
still continues to be nonpolysiloxane materials, and a review of efficiency” of 3200 plates/m (17). Finally, the development of a
molten salt and ionic liquids as stationary phases for organic new triflate ionic liquid for GC × GC was reported (18). The
compound analysis includes a discussion as to how stationary comparison to more conventional PEG phases as second-dimen-
phases should be selected by potential users (11). A review of sion columns was discussed. The ionic liquid column was stated
the use of metal-containing stationary phases was also published to have significantly larger selectivity for several of the test
(12). These materials are useful for separation of compounds compounds. Second dimension column orthogonality is a very
through a complexation mechanism. Examples of chiral separa- important issue for GC × GC separations, and ionic liquids may
tions were addressed.
have a role here, even if their efficiencies are not as high as more
Finally, several reviews on the GC × GC technique were
routine phases.
published. The use of this technique for the analysis of complex
The separation of polycyclic aromatic hydrocarbons (PAH’s)
metabolomic samples was reviewed (13). This is a very challeng-
has been of increased interest. Several commercial companies
ing analysis in biological fluid, and the increase in peak capacity
have reportedly developed columns specifically for this application.
of the GC × GC technique may lend considerable benefit to these
Most notable, Agilent Technologies (www.agilent.com) and Varian
separations. Further, coupling the GC × GC to a time-of-flight mass
(www.varian.com) have marketed a specific column for this
spectrometer (TOFMS) adds another dimension of separation and
separation. Restek Corporation (www.restek.com) has also re-
can be a very powerful analytical technique. Two other general
ported on the use of molecular modeling techniques to develop a
reviews of the GC × GC technique also summarize the state of
new material that is designed for this separation (19).
the art of this technique and show numerous relevant applications.
Additional work in the area of modified cyclodextrines was
The first includes an industrial perspective as to the benefit of
still an area of research, and one paper (20) discussed the use
GC × GC in semiroutine analyses at Dow (14). The second also
of a maltooctaose derivative as a stationary phase for the
includes a discussion of the prediction of separation based on
separation of enantiomers. Another one (21) used a common
thermodynamic properties and attempts to simplify the column
permethylated β-cyclodextrine diluted in a variety of liquid
selection process (15).
phases in order to determine the role of the polymer type on
COLUMNS PRINCIPLES AND TECHNOLOGY retention. This work used PEG and also SE-30 and SE-54 as
General Information. While the GC column is, of course, liquid phases.
the only part of the entire GC system that physically separates Fundamental Characterizations. During this review period,
compounds from each other, only a small percentage of very little work was published on the modeling or characteriza-
publications deal with the understanding of this process or the tions of stationary phases. Typically, there have been a few papers
development of new materials. While this may have been a very on thermodynamic modeling and also quantitative structure
active area of research years ago, it certainly is viewed as property relationship (QSPR) approaches. There were two papers
“mature” in the present day, and as a result, most publications published, both using QSPR models for retention prediction of
that fit into the category of column advancements are very niche environmentally important compounds. In the first (22), the
in application. Professor Klaus Unger was quoted at the HPLC retention indices of 168 pesticides were used to construct a QSPR
2008 meeting as saying that “we should put our efforts towards model. The second paper (23) used a QSPR approach to
gaining selectivity, not towards the mad rush to increase determine four optimal descriptors which then let the authors
efficiency”. He was, of course, discussing the area of small- predict retention on 18 different GC columns for all 209 PCB
4776 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
performance continues to elude researchers, with the best
performing microfabricated columns performing on par with
comparable commercially coated fused silica columns. These
performance challenges were largely predicted by Golay in 1981
(29) when he described the end effects of high aspect ratio
columns. As novel geometries and fabrication techniques evolve,
the potential exists for greater improvement in these areas. Even
within these current limitations, interest remains high due to the
promise of reduced manufacturing costs by utilizing similar batch
manufacturing techniques now common in the semiconductor
industry for the manufacturing of microprocessors, memory, etc.
However, an important consideration, as the number of research-
ers developing new stationary phase coatings, coating techniques,
column designs, and methods of fabrication increases, is that a
Figure 1. Number of citations by year of Terry, Jerman, and Angel’s
standardized column evaluation method should be developed to
1979 paper describing the first etched silicon GC system.
directly compare their performance and test column reproducibility.
congeners. These approaches should allow for improved column The size and power benefits are both obvious and connected;
selection and also potential identification of congeners that may as one reduces the mass of components, the power required to
not be in a particular user’s calibration standards. heat and cool individual components decreases as well. Several
GC systems have been designed and manufactured using micro-
fabricated components to achieve this end. Examples include the
PORTABLE AND MICROFABRICATED GC Canary line from Defiant Technologies (www.defiant-tech.com)
TECHNOLOGY DEVELOPMENT
which integrates microfabricated GC columns, preconcentrators,
Analytical samples are often at risk for sample contamination,
and detectors for multiple applications; SLS micro’s GCM series
decomposition, degradation, and loss during storage and transport
(www.slsmt.com) which integrates a microfabricated column,
from the collection site to the laboratory for analysis. This has
detector, and sample loop along with the electronics into a PDA
resulted in a growing trend toward efforts to bring the lab to the
sized fluidics package; and Thermo Scientific’s C2 V-200 micro
sample when possible. Significant efforts have been invested to
GC (www.c2v.nl) which integrates a microfabricated inlet and
develop and test portable instrumentation. There have been
detectors with conventional wall coated open tubular fused silica
several recent reports of the development and use of portable GC
systems including work done at the University of Michigan on a columns. Two recent developments include the introduction of
portable GC with a chemiresistor array detector (24). The system an “intelligent” preconcentrator by Defiant Technologies that “on-
was designed for rapid, trace analysis of complex mixtures. It the-fly” determines the appropriate sampling time and the acquisi-
consists of a small, multistage preconcentrator; two series-coupled tion of Concept to Volume (C2 V) by Thermo Scientific. Several
columns with fast, independent temperature programming capa- researchers continue to work on the development of new systems
bilities; pressure control at the junction point between the based on microfabricated components; one recent report describes
columns; and an array of chemiresistors for detection. A new a new portable GC system utilizing a micro electromechanical
commercially available portable GC with detection provided by a system (MEMS) enabled miniaturized GC for the subparts per
toroidal ion trap mass spectrometer has been developed and billion detection and monitoring of aromatic volatiles (30). Zam-
described by researchers at Brigham Young University and Torion polli and others at the CNR-IMM Institute for Microelectronics
Technologies (www.torion.com) (25). The system consists of a and Microsystems in Bologna, Italy, describe a system consisting
SPME injection system, a low-thermal mass GC, and a miniature of a micromachined preconcentrator, a 50 cm × 800 µm × 1 mm
toroidal ion trap mass analyzer housed in a Pelican case. The microfabricated column packed with 80-100 mesh carbograph 2
entire system including pumps and batteries weighs about 13 kg. + 0.2% carbowax particles, and metal oxide (MOX) gas sensors
Two other application studies included the use of portable GC as a detector. The demonstrated system shows separation of BTEX
systems for the analysis of acetaldehyde in tobacco smoke (26) compounds in about 10 min. Another report by Nishino and others
and the clinical measurement of volatile sulfur compounds (VSCs) at Shimadzu describes the development of a prototype instrument
which can be a cause of oral malodor (27). built around a microfabricated column 8.5-17 m in length
Microfabrication Developments. Thirty years after the generating 35 000 theoretical plates with a flame ionization
publication of the seminal paper by Terry, Jerman, and Angell in detector (FID) (31). There remain several research programs
1979 (28), which described the first GC system composed largely focused on the development of new MEMS GC systems including
of microfabricated components, interest in separation systems Sandia National Laboratories and the University of Michigan
facilitated by microfabricated devices continues to grow as WIMS Center.
micromachining capabilities mature. Evidence of this is shown Sandia National Laboratories has had an ongoing development
in Figure 1 which shows the number of citations of the Angell program in the area of microfabricated GC systems since 1996,
paper as a function of publication year. The promise of this primarily geared toward the rapid, portable, low-power detection
research continues to be reduced system size, low-power require- of chemical weapons, explosives, and more recently toxic indus-
ments, enhanced performance, and the promise of batch manu- trial chemicals. Recent advances include the development of mass-
facturing to reduce costs. In practice, significantly enhanced sensitive microfabricated preconcentrators (32), a new selective
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4777
and sensitive chemiresistor GC detector (33), and the demonstra- flow restriction to be very small. The challenges remain in
tion of the first consumable free comprehensive two-dimensional manufacturing uniform channels, both in length and phase volume
GC system (GC × GC) consisting of a pair of microfabricated ratio, distribution of the injection plug equally to all columns, and
columns and a microfabricated detector (34). The mass-sensitive dead volume at the inlet and outlet of the system. Problems in
preconcentrator consists of a thin film resistive heater on the any of these areas will result in band broadening. Agah’s group
surface of a MEMS pivot plate resonator (PPR). The PPR is has demonstrated some success using a MEMS approach to
Lorentz force actuated, and the frequency of the resonator shifts address these problems. Ali and Agah have also demonstrated
with mass loading. When sufficient sample has been collected for MEMS based semipacked columns (48). These columns used
analysis by the downstream microfabricated gas analyzer, the film microfabricated posts in the column channels to decrease diffusion
is heated and the sample is desorbed. Under partial funding from distances and column capacity relative to more traditional WCOT
the Defense Advanced Research Projects Agency Micro Gas columns but still demonstrate significantly reduced pressure drops
Analyzer (DARPA-MGA) program, Sandia developed a sensitive relative to traditional packed columns. Zareian-Jahromi and Agah
chemiresistor utilizing a conjugated molecule linked gold nano- have also reported a novel coating technique using a monolayer
particles in a sol-gel matrix. The chemiresistor demonstrated protected gold stationary phase (49).
significant selectivity for phosphonates (CWA simulants) and There are several other reports of novel column fabrication
sensitivity. The GC × GC utilized a pair of microfabricated GC development. Radadia and Masel at the University of Illinois
columns. The first column was coated with polydimethyl siloxane describe work on an all silicon column using a gold diffusion
and was 90 cm in length; the second column was 30 cm in length eutectic bonding process to bond a silicon lid instead of a Pyrex
and was coated with polyethylene glycol. The modulator was a lid to the silicon channels (50) and a partially buried microcolumn
stop-flow design based on the work of Richard Sacks, and with an interesting cross section (51). Lewis and Milton describe
detection was provided by a nanoelectromechanical systems a microfabricated planar glass column with a circular cross section
(NEMS) cantilever resonator developed by the Roukes group at manufactured in two hemispherical halves and bonded using
Caltech. The system demonstrated a separation of ∼29 compo- epoxy (52). Sun and Chen at the Chinese Academy of Sciences
nents in less than 8 s. report the development of a silicon/Pyrex microfabricated 100
The NSF funded Wireless Integrated MicroSystems (WIMS) µm × 100 µm × 6 m column generating 4850 theoretical plates
Engineering Research Center (ERC) (www.wimserc.org) is in the (53). There are also reports of new column coatings which have
final year of NSF funding for the center and is transitioning from also been developed.
an ERC to the WIMS institute. The center has been developing Researchers from both the University of Washington/Lawrence
several parallel MEMS GC based systems for multiple applications, Livermore National Laboratories (54) and University of Tokyo
such as breath analysis (35), explosives detection (36), extrater- (55) describe the use of CNTs as stationary phases. Nakai et al.
restrial exploration (37), and indoor air quality monitoring (38). from the University of Tokyo also reports on the use of a
They have developed new gas phase detectors such as nanoscale functionalized parylene (56) as a stationary phase. A report by
chemiresistor arrays (39) and microdischarge detectors (40). The researchers at the WIMS center at the University of Michigan
WIMS center has also demonstrated the first thermally modulated highlighted an often overlooked aspect of microfabricated col-
GC × GC system utilizing microfabricated columns (41). umns: column reproducibility. The study compared the perfor-
While these efforts continue, much of the research being mance of several (2-8) columns with different preparations to
reported has focused on the development of microfabricated develop a column coating strategy (57).
components such as preconcentrators, columns, and detectors. There have been several advances in the area of microfabri-
In the area of preconcentrators, several groups are exploring the cated and miniaturized GC detectors including mass analyzers,
use of carbon nanotubes (CNTs) as a sorbent material. CNTs ion mobility spectrometers (IMS), optical sensors, and microcan-
demonstrate excellent adsorption and desorption characteristics tilever (MC) arrays. Malcom and Finlay at Micorsaic Systems,
due to low mass transfer resistance because of the nonporous Ltd. and the Imperial College describe a microengineered quad-
nature of the material (42, 43). Other materials investigated for rupole mass filter consisting of microfabricated components to
use as sorbents in microfabricated preconcentrators include the fabricate a quadrupole mass filter with dimensions of 35 mm × 6
use of microporous activated carbon (44), chemically polymerized mm × 1.5 mm (58). Researchers at the University of Cordoba
polypyrrole (45), as sorbent materials, and inkjet printing of describe a system that couples a multicapillary column with a
polymer sorbents prior to anodic bonding (46). miniaturized IMS for rapid GC × IMS separations (59). Research-
In the area of column development, there have been several ers from the University of Missouri and ICx Nomadics have
reported advances. Zareian-Jahromi and Agah at Virginia Tech reported on the use of a optofluidic ring resonator (OFRR) sensor
have recently reported revisiting the concept of multicapillary for on-column detection (60-62). The OFRR is a thin walled fused
columns (MCCs) (47). MCCs are a concept first operatively silica capillary. The inner wall of the capillary is coated with a
demonstrated by researchers in Novosibirsk, Russia, in the 1980′s thin polymer film. The circular cross-section of the capillary forms
and exist now as a commercial product sold by Multichrom, Ltd. an optical ring resonator where circulating waveguide modes are
(www.mcc-chrom.com). The principal concept is to get around supported by total internal reflection of light along the curved
the column capacity limitations and pressure restrictions of inner and outer boundary. The evanescent field extends into the
microbore columns using a bundle of identical microbore columns core and is sensitive to the refractive index change induced by
in parallel. This allows a fraction of each injection to be separated the interaction between the analyte and the stationary phase. Long
on each column preventing overloading and enables the overall and Sepaniak at the University of Tennessee report on the use of
4778 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
MC arrays for gas phase sensing (63). MC arrays have similar can now be added to those already realized in flow modulation:
response mechanisms to quartz crystal microbalances and surface less expensive hardware and no cryogenic fluid use. Pizzutti et
acoustic wave sensors; however, they demonstrate better mass al. derived a better compressed air modulator (69) from an earlier
sensitivity, smaller dimensions, and decreased fabrication costs. model (70) to address developing countries’ needs for low-cost
systems. While the volatility range is limited for this air modulator,
COMPREHENSIVE TWO-DIMENSIONAL GAS with breakthrough shown for tetradecane, lower volatility pesti-
CHROMATOGRAPHY (GC × GC) cides ranging from Trifluralin to Deltamethrin were successfully
Scope. This GC × GC review covers literature published analyzed in grapes with GC × GC-ECD.
mostly from 2009 until the end of April 2010, when it was compiled, Begnaud et al. modified the Marriott longitudinally modulated
but unlike GC × GC, it is not comprehensive because of the large cryogenic system (LMCS) to temperature program the cooling
number of papers found during the search. The number of papers
chamber in conjunction with the GC oven, which reportedly
published in the review period was around 100, about a 10%
increases the modulation efficiency across a wide range of
increase over the last review done for Analytical Chemistry across
compound volatilities while simultaneously reducing cryogenic
a similar time period (64). Only select articles of the 100 or so
fluid use (71). The use of the LMCS as the heart of a switchable
are covered, broken down into distinct topic lines as seen below.
multidimensional/GC × GC system was described and then tested
Reviews. Cortes et al. reviewed the achievements in GC ×
with compounds important to essential oil analysis and lavender
GC across 2007 until October 2008 citing 121 contributions from
oil (72). A microfluidic Deans switch placed after a primary GC
that period (65). They noted how GC × GC work has shifted from
column, upstream of the LMCS, allowed selection of either a
instrumentation development to practical applications and listed
longer second column for heart-cutting work or a shorter column
those for petroleum, polymer, pharmaceutical, flavor and fra-
for GC × GC. The system was flexible enough to allow switching
grance, metabolomics, and environmental. Interestingly, they
from heart-cut to GC × GC multiple times in one analytical run.
commented that mass spectrometry (MS) is the detector of choice,
Although not demonstrated, the system is proposed to be
now and in the future, for GC × GC, with time-of-flight (TOF) MS
especially effective for heart-cut olfactory work, where broader
outpacing the quadrupole due to having the faster acquisition rates
peaks are necessary for sensory perception.
to define ultra narrow peaks from GC × GC but predicted that
Klee and Blumberg performed flow modulation of methane-
the use of differential flow modulation (DFM) will increase (as
doped carrier gas, which allowed direct observation/calculation
an alternative to cryogenically modulated systems); DFM is not
of second dimension hold-up times in GC × GC (73). Subse-
inherently compatible with the pumping capacity of most MS
quently, they calculated/visualized retention factors for alkanes
systems, with the supersonic molecular beam approach of Amirav
and diesel components in both columns for GC × GC. Unfortu-
being an exception (66). DFM should be more appropriate for
field and process instruments that employ alternate detectors such nately, for cryofocusing modulator users, this approach will not
as flame ionization detection (FID). Although we may disagree work since methane cannot be trapped with current systems. The
on predictions for DFM, we concur on one statement in their tendency for those users to employ stationary phase bleed from
review; “beer is a highly popular alcoholic beverage around the the first column as a way to calculate hold-up time was discour-
world.” In conclusion, Cortes puts emphasis on the need for aged upon proving that stationary phase bleed was retained
improved quantification and qualitative data analysis software and (versus methane) by the second dimension column. However, the
suggests that computational chemistry methods combined with authors’ setup did not consider an independently temperature-
GC × GC chromatogram structure and retention data for known programmed secondary oven that could be positively offset versus
compounds can yield identifications for unknown components. a primary column oven. Primary and secondary column temper-
Hamilton specifically reviewed the use of GC × GC to study atures were the same in their experiments.
the atmosphere (67). GC × GC, especially with MS, is ideally Tobias et al. gave the first report on the coupling of GC × GC
suited for this research given the complex array of natural and to combustion isotope ratio MS and used their system to
manmade emissions and oxidation products present in the demonstrate the analysis of steroids relevant to sports perfor-
atmosphere. An important observation by the author was the need mance enhancement (74). They also suggested applications for
for sophisticated data handling approaches, including image food authentication and environmental pollutant tracing, where
processing, to deal with the wealth of information generated using sample complexity may make one-dimensional GC insufficient.
GC × GC/MS. Data Handling. Given the high data density of GC × GC,
Instrumentation. Research devoted specifically to modulation especially when TOFMS is used, the sample complexity that
hardware was relatively light during the review period, although predetermines GC × GC use for an application, and the special
the group of Shellie contributed a substantial piece on designing needs of the metabolomics community in particular, it is not
flexible, pulsed flow modulation systems (68). Drawbacks of flow surprising to discover reports on data handling outside of what is
modulation setups, versus the cryogenic approach, include pneu- already provided by an instrument vendor. Vial et al. used dynamic
matic complexity, multiple connecting pieces, baseline instabilities, time warping to align second dimension peaks in GC × GC
and lack of flexibility for changing modulation times. In particular, chromatograms, followed by multivariate analysis to distinguish
inability to vary the modulation time is problematic for flow three types of tobacco (75). Through additional interpretation,
modulated systems due to the potential for wrap-around. Shellie marker compounds for a tobacco could be identified via the
developed a dynamic flow model and employed a postfirst- collected mass spectrometry data. An imaging process technique
dimension-column restrictor that offsets some of these disadvan- borrowed from the proteomics field was used to compare fruit
tages, including allowing different modulation times. That benefit aromas represented by contour plots after analysis by headspace
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4779
solid phase microextraction (SPME) GC × GC/MS (76). Image World Anti-Doping Agency. Quantification with TOFMS can even
profiles created by the process can be used for statistical analysis proceed on ions chosen after analysis since a full mass spectrum
and suggesting sample origin. While seemingly very powerful, is collected. One of the downsides of TOFMS for this application,
the authors noted that any mass spectrometry data collected though, was its apparent lower sensitivity for higher m/z ions in
during GC × GC is “off-line” to the imaging software, a distinct the anabolic agent trimethylsilyl derivatives versus other mass
disadvantage compared to other GC × GC data processing analyzers, such as quadrupoles. This issue can compromise not
software. Almstetter et al. used GC × GC-TOFMS vendor software only sensitivity if those ions are chosen as quantification masses
that included automated baseline correction, peak finding, spectral but also qualitative searches via standard mass spectral libraries.
deconvolution, and library searching prior to applying retention In the latter case, the authors recommend creating TOFMS
time normalization and data alignment to compare two strains of spectral libraries specific for the antidoping compounds of interest
Escherichia coli (77). They exported peak lists from the vendor from authentic reference materials.
software and aligned peaks with a model fitted to known deriva- In breath analysis research for clinical purposes, novel multi-
tized fatty acids in the samples, followed by principal component sorbent needle traps were used for sampling prior to desorption
analysis to achieve metabolic fingerprinting. to GC × GC-TOFMS (84). The needle traps performed relatively
Theory. Blumberg and Klee took a critical look at definitions well and could even be autosampled, although they were subject
for multidimensional separations, including GC × GC, discussing to rapid contamination in some hospital environments. GC × GC-
Giddings concepts and proposing a new definition that includes TOFMS showed the capability to detect low levels of breath
only “analytical separations” (78). Seeley et al. developed a components and the potential for identifying previously unknown
simplified solvation parameter model to predict GC × GC com- compounds. The authors correctly suggested that thicker film
pound retention behavior on a variety of stationary phase columns are necessary for volatiles work (versus the 0.25 mm
combinations using literature values for solute and stationary ×0.25 µm used in their first dimension), both to provide better
phase descriptors (79). They saw excellent agreement of the analyte focusing during needle trap desorption and to avoid
model and experimental GC × GC data and suggested the model overload of higher concentration components.
could be used to design optimal column setups. Hoggard et al. exploited the separation ability of GC × GC-
Biological. Kalinová et al. investigated the male wing gland TOFMS with sophisticated chemometrics to detect and identify
secretions of a bumblebee parasite, the wax moth Aphomia 29 impurities in six samples of commercially obtained dimethyl-
sociella, with SPME GC × GC-TOFMS (80). Bumblebees are methylphosphonate (DMMP), a chemical weapon simulant (85).
important pollinators in greenhouses and are being considered They then used statistical analysis to classify the DMMPs, finding
for open agricultural field pollination given the recent decline of that two had identical impurity profiles; the chemical supplier later
the domesticated honeybee. Chemically understanding gland confirmed them to be from the same source. On the basis of their
secretions may allow the creation of effective lures for bumblebee success, the authors will continue to develop these methods for
parasite control. GC × GC-TOFMS, in conjunction with GC- impurity profiling that support forensic investigations of chemical-
electroantennographic detection (EAD) and GC-FT-IR, identified attack crime scenes.
several compounds as potential sex pheromones for the wax moth. Environmental. The electron capture detector (ECD) is
With perhaps the most provocative title in this review, Irresistible widely used in the analysis of environmental samples for poly-
Bouquet of Death, only topped by the keywords, Carcass Attractive- chlorinated biphenyls (PCBs), toxaphene, organochlorine pesti-
ness, Kalinová et al. again used SPME with GC × GC-TOFMS and cides (OCPs), chlorinated benzenes (CBs), and other halogenated
GC-EAD, this time to study how burying beetles are attracted to pollutants, even today, often operated with a parallel dual-GC
dead mice (81). GC × GC-TOFMS allowed the identification of column configuration. In the parallel dual-column GC-ECD ap-
sulfur-containing volatile organic chemicals evolved after death proach, two different stationary phases are employed to enhance
that are likely stimulants for carrion location by the beetles. selectivity and elucidate possible quantification bias. However, for
Although a very interesting read, this is one paper not to be unknown reasons to this reviewer, GC × GC-ECD, which is similar
studied over lunch. in a “two independent separations” regard, is still a relatively little-
Clinical and Forensics. GC × GC-TOFMS was used to used technique for environmental analysis. Muscalu and others
analyze opiates and benzodiazepines in human serum after solid recently demonstrated the power of GC × GC-ECD when they
phase extraction and derivatization (82). Excellent second dimen- analyzed PCBs, OCPs, and CBs in sludge and sediment samples
sion separations from the higher-concentration matrix interfer- (86). A 100% dimethyl polysiloxane column was used in the
ences were achieved for the subject compounds on the 50% phenyl- first dimension coupled to a secondary column that has
type column. A limit of quantification of approximately 5 ng/mL selectivity toward mono-ortho and coplanar PCBs. Only 2 of
was noted for Flunitrazepam in serum, significant since it is the 64 PCBs investigated coeluted, congeners 4 and 10 (BZ#s).
necessary to detect therapeutic levels at <10 ng/mL. The authors Given that environmental samples are often extremely complex,
suggested that the full mass-range approach of TOFMS could the authors investigated the potential for chlorinated dioxins
allow nontarget compound analysis. This same benefit is desirable and furans, toxaphene, chlorinated diphenyl ethers, and chlo-
in sports antidoping applications for retroactive searches of data rinated naphthalenes to coelute with the PCBs, OCPs, and CBs
for nontarget compounds and “designer steroids”, as voiced by of interest. There were no interferences. Standard reference
the group of Marriott (83). They thoroughly tested GC × GC- materials of sludge and sediment analyzed with GC × GC-ECD
TOFMS for anabolic agents in urine and reported limits of after pressurized fluid extraction and silica and copper treat-
detection below or at the required performance levels set by the ments, showed acceptable accuracy and precision. In addition,
4780 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
other compounds, such as polychlorinated alkanes, were seen and quadrupole MS, against one-dimensional GC/MS, to evaluate
in the extracts. simultaneous steam-distillation, supercritical fluid, microwave-
A hot topic in environmental analysis is pharmaceuticals and assisted, and Soxhlet extraction methods for Thai vetiver root (96).
personal care products in waters. GC × GC-TOFMS with SPE was Vetiver root oil is apparently an excellent fixative for perfumes.
recently used to effect parts per trillion level determinations for Sixty-four compounds were identified using GC/MS with an
13 pharmaceuticals, 18 plasticizers, 8 personal care products, 9 additional 43 identified (out of the many more separated) with
acid herbicides, 8 triazines, 10 organophosphorous compounds, GC × GC/MS. Relative quantification for those compounds for
5 phenylureas, 12 organochlorine biocides, 9 polycyclic aromatic the different extraction methods was done via GC × GC-FID.
hydrocarbons (PAHs), and 5 benzothiazoles and benzotriazoles Tranchida et al. used GC × GC with a fast scanning quadrupole
in river water (87). Although a 5% phenyl × 50% phenyl column MS to characterize fresh and aged tea tree essential oils, including
combination gave the best separation for the compounds of for potential allergenic components, some of which were found
concern, the reverse setup gave a good correlation between in both fresh and aged oils (97). Although substantial differences
second dimension retention times for compounds and their log were noted between fresh and aged (or oxidized) oils, many of
Kow values. This relationship was proposed as an identification the compounds in the oxidized oil went unidentified due to lack
confirmation tool. of library mass spectral data.
Mao et al. better estimated ecotoxicity of petroleum hydro- In a study on Indian cress (also known as nasturtium) essential
carbon mixtures in soil using HPLC-GC × GC-FID, versus poorly oil, GC × GC-TOFMS was used in conjunction with GC-O, mainly
performing, simple one-dimensional total petroleum hydrocarbon to identify low-level odorants that would otherwise need tedious
tests (88). sample enrichment (98).
The remaining environmental GC × GC papers cited here are Food and Beverage. Food origin and authentication studies
applications accomplished by taking advantage of the three most are made easier by comprehensive GC approaches, since food
important features of GC × GC-TOFMS: chromatographic sup-
samples are typically very complex. Stanimirova et al. geographi-
pression/elimination of matrix interferences that thwart target or
cally defined Corsican honeys via their volatile organic chemicals
nontarget compound identification, enhanced sensitivity for trace
profile with headspace SPME GC × GC-TOFMS and statistical
residue levels through modulation focusing, and having a full mass
pattern recognition techniques as an alternate to traditional pollen
spectrum for compound identification through interpretation or
examination (99). Theoretically, their approach could be used to
library searching. In environmental analysis concerning petroleum
identify cases of intentional honey product mislabeling. Cajka et
samples, structure-of-chromatogram can be added as a benefit. The
al. used essentially the same techniques, analytical and statistical,
list includes analysis of: biodegraded crude oil (89); nonylphenols
to divide Ligurian and other non-Ligurian Mediterranean olive oils
in groundwater and wastewater (90); heavy oil from natural seeps
(100). The Ligurian oil is a premium product that is relatively
into the ocean (91); benzothiazoles, benzotriazoles, and benzosul-
scarce. The authors remarked that while SPME GC/MS produced
fonamides in wastewater, raw sewage, and river water (92); organic
sufficient marker compounds for chemometric profiling of the oils,
nitrogen compounds in urban aerosols (93); and organic compounds
GC × GC-TOFMS offered a more comprehensive fingerprint and
from wood combustion aerosol nanoparticles (94).
better mass spectral qualities.
Flavor and Fragrance. Rochat, Egger, and Chaintreau inves-
Janssen, Steenbergen, and de Koning reviewed the use of
tigated shrimp aroma not only with GC × GC-TOFMS but also
comprehensive chromatography techniques, including GC × GC,
with GC-olfactometry (GC-O) and multidimensional (heart-cut)
GC/MS with olfactometry (MDGC/MS/O) (95). Each system had for the analysis of edible oils and fats, indicating that GC × GC
its strong and weak points, and ultimately the techniques were was well-suited for target compound analysis, group-type separa-
complementary. GC × GC had superior sensitivity, which endorsed tion, and chromatographic fingerprinting (101). An example of
its use for identification of trace-level odorants noted during GC-O target-compound analysis was provided by Biedermann and Grob
or MDGC/MS/O. Difficulties in retrieving matching odorant who used GC × GC with FID and MS after HPLC separation to
peaks for mass spectral identification from the complex GC × GC determine mineral oil adulteration in sunflower soil (102).
chromatogram were overcome to some extent by correlating the Lojzova et al. used headspace SPME and compared GC-ion
linear retention indices from an Adams’ database to retention on trap MS, GC-TOFMS, and GC × GC-TOFMS for the analysis of
the first dimension column of the GC × GC setup. Of course, both 13 alkylpyrazines and other volatile compounds in potato chips
stationary phases must be the same for this approach to work, arising from the Maillard reaction during their production (103).
and in one important case, that of attempted confirmation of the While none of the instrumental techniques allowed unequivocal
intense odorant 2-ethyl-3,5-dimethylpyrazine, even the separating determination of all targeted alkylpyrazines, GC × GC-TOFMS was
power of GC × GC and spectral deconvolution did not resolve declared superior to the other two because of lower limits of
interferences that corrupted its mass spectrum. Extracted ion plots quantification and enhanced nontarget compound screening
and “reverse search” of the coeluted mass spectrum provided capability.
tentative identification of the pyrazine. In all, over 40 odorants Beverage-related studies conducted with GC × GC included
were listed for shrimp odor, although with descriptors like the trace-level analysis of the potent odorants, 3-alkyl-2-methoxy-
“garbage, foot, rancid, dirty socks, awful, not well, etc” for some pyrazines, in wine grapes (104) and the characterization of
compounds, one has to wonder if further work will be attempted! Brazilian cachaca (105), a sugar cane derived liquor that surpris-
From shrimp odor to perfumery, Pripdeevech, Wongpornchaia, ingly is the third most consumed distilled alcoholic beverage in
and Marriott turned in a report on the use of GC × GC with FID the world (after vodka and soju).
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4781
Because of the increase in sensitivity due to the modulation ature and flow limitations, GC column stationary phase tem-
process, GC × GC is appropriate for trace residue analysis in a perature limits (more polar phases), and even the press-fit
variety of food sample types. Hoh et al. demonstrated this with connectors sometimes used to seal GC × GC columns together.
quantification for a variety of halogenated compounds, including However, Dutriez et al. overcame these hindrances to offer a
PCBs, OCPs, and polybrominated diphenyl ethers (PBDEs), in high-temperature GC × GC analysis of vacuum gas oils up to
fish oils, using gel permeation chromatography and a large- nC60 (118). They used a short, wide bore, thin-film (10 m ×
volume, direct sample-introduction technique with GC × GC- 0.32 mm ×0.10 µm), high-temperature dimethyl polysiloxane
TOFMS (106). They also identified nontarget halogenated natural column in the first dimension and a high-temperature stable
products, including halogenated 1′-methyl-1,2′-bipyrroles (MBPs), 50% silphenylene polysilphenylene-siloxane column (0.5 m ×
DMBPs, methoxylated PBDEs, polybrominated hexahydroxan- 0.10 mm ×0.10 µm) in the second dimension. Unfortunately,
thene derivatives, and polybromoindoles in the oils. Even “PCB- there is no mention of the type of connector they used to join
free” cod liver oils had PCBs. Ratel and Engel reported a 7-fold these columns, an important consideration given that their GC
increase in benzenenic and halogenated volatiles detected in lamb, oven temperature program goes to 370 °C, a temperature where
milk, and oyster samples analyzed with GC × GC-TOFMS versus a press-fit connection rarely survives for any length of time.
GC-quadrupole MS (107). Interestingly, their modulation period was 20 s, perhaps a
Humston et al. contributed a piece on cacao bean quality, record for the longest second dimension separation in GC ×
proposing to identify moisture damage before visible signs of mold GC, but they determined it was necessary for elution of tetra-
on beans, using headspace SPME GC × GC-TOFMS and chemo- aromatics within the modulation cycle (penta- and hepta-
metric software (108). aromatics wrapped around). Benefits of the approach were
Metabolomics. Metabolomics samples are usually extremely obtaining boiling point distribution (HT-SimDist) and aromatic
complex and will show many overlapping peaks, even when family quantification for petroleum fractions.
analyzed by efficient, high resolution GC, so it is not surprising Kohl et al. characterized military fog oil, an exceedingly
to see GC × GC studies in the literature. In addition to full complex middle distillate petroleum product used as an ob-
characterization of samples and possible diagnostic value, biom- scurant in soldier field training, with several GC × GC column
arker discoveries for diabetes (109) and organic acidurias in setups on FID and TOFMS (119). Mass spectra and the
infants (110) have been facilitated by GC × GC-TOFMS. GC × structure of the GC × GC chromatogram, combined with data
GC-TOFMS was used as a complementary technique to liquid mining at the edges of the unresolved complex mixture, allowed
chromatography-tandem quadrupole MS to examine targeted the authors to propose a composition for the fog oil. It contains
metabolites of a bacterium Methylobacterium extorquens AM1 mainly aliphatic compounds ranging from C10 to C30, where
naphthenes are the major fraction. Aromatics are high in
grown on two different carbon sources (111). Mateus et al. used
diversity but low in overall concentration, being purposely
GC × GC with TOFMS to characterize volatile chemicals from 11
removed in the “newer” oils to reduce toxicity. More specifi-
species of pine trees (112). In addition to more traditional GC ×
cally, alkanes, cyclohexanes, hexahydroindanes, decalins, ada-
GC separations, they showed elegant enantioselective GC × GC
mantanes, bicyclohexanes, alkylbenzenes, indanes, tetrahy-
chromatograms for chiral terpenes that may have importance in
dronaphthalenes, partially hydrogenated polycyclic aromatic
insect-host pine relationships. Finally, GC × GC-TOFMS allowed
hydrocarbons, biphenyls, dibenzofurans, and dibenzothiophenes
terpenoid profiling of two lines of transgenic Artemisia annua L.,
were identified using GC × GC-TOFMS.
an important plant in traditional Chinese medicine that contains
Artemisinin, which is used in combination therapies to treat GAS CHROMATOGRAPHY DETECTORS
malaria (113). In the biennium 2008 to 2009, many research articles and a
Petrochemical. Adam et al. delivered the first report for online worth reading review describing the advances in gas chromatog-
supercriticial fluid chromatography (SFC) connected to twin-GC raphy were available to the scientific community. The review,
× GC-FID and used this sophisticated system for thorough updated to 2009 (120), describes multiple applications of GC and
characterization of middle distillates, including the complete the properties of detectors. This review states that, during this
separation of saturated and unsaturated compounds (114). period, the most common GC detector for environmental applica-
Fischer-Tropsch reaction products, including paraffins, olefins, tion was the ion trap-mass spectrometric (ITMS) detector (GC-
and oxygenates, were probed using GC × GC-TOFMS by Bert- ITMS). This GC system demonstrated its capabilities for trace
oncini et al. (115). level determination of contaminants in diverse environmental
Some of the GC × GC petrochemical contributions are notable samples. Nanogram per liter concentrations of polybromine
for their use of detection systems in addition to, or other than, compounds in earthworms and triclosan in rivers and coastal water
TOFMS. Basic and neutral nitrogen speciation and quantification samples were detected using GC-ITMS.
in middle distillates with GC × GC and a nitrogen-chemilumines- Improvement in GC Detector Techniques. During this
cence detector was accomplished by Adam et al. (116). A rare period, different GC available techniques were modified to fit
use of GC × GC with positive chemical ionization and quadrupole specific requirements. For instance, two-dimensional gas chro-
MS, for lower molecular weight fatty alcohol alkoxylate analysis, matography (GC × GC) was coupled to online combustion isotope
yielded much more information than could be obtained by electron ratio mass spectrometry (C-IRMS) to enhance peak capacity and
ionization MS alone (117). signal in the GC × GC system without interference with high-
Historically, the volatility range of GC × GC for petroleum precision carbon isotope analysis in urinary steroid samples (121).
applications has been rather limited due to modulator temper- Siegler et al. (122) increased the selectivity in a comprehensive
4782 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
three-dimensional gas chromatography-flame ionization detector GC Detector Improvement through Software Develop-
(GC-FID) by utilizing an ionic liquid stationary phase column in ment. Another approach consisted in the development of a radial
one dimension. With this modification, the authors reported the basis functional neural network (RBFNN) to model the nonlinear
resolution of 180 peaks per minute in a 3D diesel sample calibration curves of four hexachlorocyclohexane (HCH) isomers
separation. obtained with gas chromatography-electron capture detector (GC-
The presence of arsine and phosphine in light hydrocarbons at ECD) (129). The RBFNN method with logarithm-transform and
the part-per-billion level was determined by capillary flow technique normalization on the calibration data modeled the nonlinear
and gas chromatography with a dielectric barrier discharge detector calibration curves for the four HCH isomers.
(GC-DBDD) (123). The method includes a large volume injection, A new algorithm was developed for detecting fragmentation
capillary flow technology, and the DBDD operating in argon mode. patterns in complex samples such as plant tissues and a new
The researchers reported that the system needed 4 min for complete scheme to examine GC/MS spectra (130). The technique uses a
analysis and remained reliable for 6 months in continuous operation. metabolite database called KNApSAcK and currently includes
In addition, the development of microscale-preparative multidimen- 49 165 species-metabolite relations from 24 847 metabolites.
sional gas chromatography coupled to 2-dimensional nuclear mag- Development of GC New Detectors. In addition to modifica-
netic resonance (MDGC-2D NMR) was proposed to isolate and tion of current methodologies/equipment, new detectors were
identify pure volatile compounds from a complex sample (124). The developed during this period. Li and co-workers (131) developed
system was used to isolate geraniol from an essential oil matrix and a miniaturized atmospheric pressure dielectric barrier discharge
quantitatively resolved from 15 partially coeluting compounds from (DBD) to be used as GC detector for the analysis of volatile
the first column. chlorinated hydrocarbons (VCHCs). The methodology uses
A new generation of electron capture detection (nonradioac- chemiluminescence emission from the reaction of DBD-split
tive) with a short, nonpolar and wide-bore column was developed VCHCs with luminal solution. This detector is of simple construc-
for the analysis of isosorbide dinitrate in human serum (125). The tion and an energy saver, with sensitivity at subnanomole
method was linear between 5 and 50 ng/mL with accuracy of 90% concentrations. Another novelty during this biennium was the use
and recovery of 99-108%. Another innovation was the combination of carbon nanotubes as GC detectors (132). The methodology is
of electron ionization mass spectrometry and inductively coupled based on the gas sensing capability of carbon nanotubes, particu-
plasma mass spectrometry (GC-EI-MS/ICPMS) for determining larly in field-effect transistors. A carbon nanotube field-effect
volatile arsenic compounds formed by fecal microorganisms (126). transistor was coupled to a gas chromatographer (GC-NTFET)
The element sensitivity of the ICPMS and molecular identification for the separation of BTEX compounds. The system showed good
by EI-MS allowed for the first time the identification of three response for 4 weeks with a detection limit lower than 4 µg/L.
Results from the GC- NTFET were comparable to results obtained
arsenic species (methyl-methylthio-ethylthio-arsine (MeAs(S-
with a GC-FID system.
Me)(SEt)), dimethyl-methylseleno-arsine (Me2AsSeMe), and thio-
bis(dimethylarsine) (Me2As)2S) in environmental samples or Frank L. Dorman is an Associate Professor of Biochemistry and
Molecular Biology in the Forensics Science Program at Penn State
human matrixes. University. Frank’s research has been in the area of the development of
To overcome some of the disadvantages of current flame new capillary column stationary phases through the use of computer
photometric detectors for the determination of sulfur and phos- modeling and development of applications for the analysis of environ-
mental and forensic compounds of interest using various GC × GC, GC,
phorus in hydrocarbons, a multiple flame photometric detector and HPLC techniques. Previously, he was the Director of Technical
(mFPD) was developed (GC-mFPD) (127). The researchers tested Development at Restek Corporation in Bellefonte, PA. He received his
five flames on quenching resistance hydrocarbons and found an Ph.D. in Analytical Chemistry from the University of Vermont in
Burlington, VT. Prior to joining Restek, Frank was employed by Inchcape
improvement of nearly 20-fold relative to a single flame mode and Testing Services-Environmental Laboratories in several roles, eventually
almost 10-fold relative to a dual flame mode. The minimum becoming Senior Chemist for methods development. Frank also holds the
detectable limits for the mFPD were 4 × 10-11 g S/s and 3 × 10-12 position of Research Professor at Juniata College in Huntingdon, PA.
g P/s, for sulfur and phosphorus, respectively. In addition, the Joshua J. Whiting is a Research Analytical Chemist and head of the
ARD at LECO, Corp. in St. Joseph, MI. Prior to that, he was a Senior
system maintained about 60% of its original analyte chemilumi- Member of the Technical Staff at Sandia National Laboratories in the
nescence even under the presence of 100 mL/min of methane Micro Total Analytical Systems Department. He received his M.S. in
flow into the detector, which demonstrate the robustness of the chemistry from Wright State University in 2000, and his Ph.D. in
analytical chemistry from the University of Michigan in 2004 working
system for quenching resistant hydrocarbons. for Professor Richard Sacks. His research interests include development
Silva and co-workers (128) developed a methodology for the of portable, low-power, GC systems for rapid detection and identification
analysis of some alcohols as an alternative to the NIOSH of analytes of interest utilizing MEMS components.
recommended method (Method 1405) for organic vapors detec- Jack W. Cochran is the Director of New Business and Technology for
Restek Corporation after working for LECO Corporation as their Director
tion. The methodology combines gas chromatography separation for Separation Science for 7 years with their GC- and GC × GC-time-
with a detector made of an optical fiber sensitized with a thin of-flight mass spectrometers. Formerly, he worked at the Illinois Hazardous
polymeric film of poly[methyl(3,3,3-trifluoropropyl)siloxane] (PMT- Waste Research and Information Center and the U.S. Environmental
Protection Agency in Oklahoma doing analytical method development for
FPS). With the GC-OF operating in the visible region (650 nm), environmentally significant compounds in air, water, sediment, tissue,
nine different alcohols (allyl alcohol, n-propyl alcohol, secbutyl soil, and other types of samples. His analytical interests include novel
alcohol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, methyl sample preparation and cleanup methods such as QuEChERS and
dispersive solid phase extraction, GC × GC with new capillary column
isobutyl carbinol, cyclohexanol, and diacetone alcohol) were stationary phases, time-of-flight mass spectrometry, and vacuum-outlet GC.
separated. Results were satisfactory compared to the results Jorge Gardea-Torresdey is the Richard M. and Frances M. Dudley
obtained using a GC-FID system. Professor of Chemistry in the Department of Chemistry at The University

Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4783
of Texas at El Paso in El Paso, TX. He received his Ph.D. in 1988 at (33) Dirk, S. M.; Howell, S. W.; Price, B. K.; Fan, H.; Washburn, C.; Wheeler,
New Mexico State University in Las Cruces, NM. His research interests D. R.; Tour, J. M.; Whiting, J.; Simonson, R. J. J. Nanomater. 2009, 481270
include environmental chemistry of hazardous heavy metals and organic (Article ID).
compounds, gas chromatography, gas chromatography/mass spectroscopy, (34) Whiting, J. J.; Fix, C. S.; Anderson, J. M.; Staton, A. W.; Manginell, R. P.;
atomic absorption and emission spectroscopy, inductively coupled plasma/ Wheeler, R. D.; Myers, E. B.; Roukes, M. L.; Simonson, R. J. High-Speed
mass spectroscopy, X-ray absorption spectroscopy, and investigation of Two-Dimensional Gas Chromatography Using Microfabricated Gc Col-
metal binding to biological systems for remediation of contaminated waters umns Combined With Nanoelectromechanical Mass Sensors. Proceedings
and soils (e.g., phytoremediation) and the study of the fate of nanoparticles of IEEE Transducers, Denver, CO, June 2009, p. 1666.
in the environment. The scientific contributions of Dr. Gardea have (35) Kim, S. K.; Chang, H.; Zellers, E. T. Prototype Micro Gas Chromatograph
allowed him to receive many honors throughout his professional life. He for Breath Biomarkers of Respiratory Disease. IEEE International Confer-
just received the 2009 SACNAS Distinguished Scientist of the Year Award. ence on Solid-State Sensors and Actuators (Transducers), Denver, CO, June
In 2009, Dr. Gardea was highlighted by prestigious journals including 2009, pp 128-131.
the December 3, 2009 Issue of Nature. He has authored or coauthored (36) Serrano, G.; Chang, H.; Zellers, E. T. A Micro Gas Chromatograph for
over 300 research articles and book chapters. He has taught analytical High-Speed Determinations of Explosive Vapors. IEEE International
chemistry and instrumental analysis at the undergraduate level and Conference on Solid-State Sensors and Actuators (Transducers), Denver,
advanced analytical chemistry and environmental chemistry at the CO, June2009, pp 1654-1657.
graduate level. He is also currently Editor of the Journal of Hazardous (37) WIMS ERC Annual Report, 43, 2009.
Materials. (38) Zhong, Q.; Steinecker, W. H.; Zellers, E. T. Analyst 2009, 134, 283.
(39) Bohrer, F. I.; Covington, E.; Kurdak, C.; Zellers, E. T. Nanoscale
Chemiresistor Arrays with Patterned Nanoparticle Interface Layers for
LITERATURE CITED Micro Gas Chromatography. Transducers 2009, Denver, CO, June 2009,
(1) Dorman, F.; Overton, E.; Whiting, J.; Cochran, J. W.; Gardea-Torresdey, pp 148-151.
J. Anal. Chem. 2008, 80, 4487–4497. (40) Mitra, B.; Gianchandani, Y. B. IEEE Sens. J. 2008, 8, 1445.
(2) Ramos, L., Ed. Comprehensive Two Dimensional Gas Chromatography; (41) Serrano, G.; Reidy, S. M.; Wise, K. D.; Zellers, E. T. DRIE-SI Gas
Elsevier: New York, 2009. Chromatography Columns: Efficiency and Thermal Stability of Stationary
(3) Kuss, H. J., Kromidas, S., Eds. Quantification in LC and GC: A Practical Phases for Comprehensive Two-Dimensional (GC × GC) Separations, Solid
Guide to Good Chromatographic Data; Wiley-VCH: New York, 2009. State Sensor, Actuator and Microsystems Workshop (Hilton Head), Hilton
(4) Koel, M., Ed. Ionic Liquids in Chemical Analysis; CRC Press: Boca Raton, Head Island, SC, June 2008, pp 260-263.
FL, 2009. (42) Hussain, C. M.; Saridara, C.; Mitra, S. J. Chromatogr., A 2009, 1185, 161.
(5) McNair, H.; Miller, J. M. Basic Gas Chromatography; John Wiley & Sons: (43) Hussain, C. M.; Saridara, C.; Mitra, S. Analyst 2008, 133, 1076.
Hoboken, NJ, 2009. (44) Blanco, F.; Vilanova, X.; Fierro, V.; Celzard, A.; Ivanov, P.; Llobet, E.;
(6) Hubschmann, H. J. Ed. Handbook of GC/MS: Frndamentals and Applica- Canellas, N.; Ramirez, J. L.; Correig, X. Sens. Actuators, B 2008, 132, 90.
tions, Wiley-VCH: New York, 2009. (45) Strand, N.; Bhushan, A.; Schivo, M.; Kenyon, N. J.; Davis, C. E. Sens.
(7) Hoh, E.; Mastovska, K. J. Chromatogr., A 2008, 1186, 2–15. Actuators, B 2010, 143, 516.
(8) Snow, N. H.; Bullock, G. P. J. Chromatogr., A 2010, 1217, 2726–2735. (46) Alfeeli, B.; Cho, D.; Khorassani, M. A.; Taylor, L. T.; Agah, M. Sens.
(9) Reid, V. R.; Synovec, R. E. Talanta 2008, 76, 703–717. Actuators, B 2008, 133, 24.
(10) Castello, G.; Moretti, P.; Vezzani, S. J. Chromatogr., A 2009, 1216, 1607– (47) Zareian-Jahromi, M. A.; Ashraf-Khorassani, M.; Taylor, L. T.; Agah, M. J.
1623. MEMS 2009, 18, 28.
(11) Yao, C.; Anderson, J. L. J. Chromatogr., A 2009, 1216, 1658–1712. (48) Ali, S.; Ashraf-Khrassani, M.; Taylor, L.; Agah, M. Sens. Actuators, B 2009,
(12) Rykowska, I.; Wasiak, W. J. Chromatogr., A 2009, 1216, 1713–1722. 141, 309.
(13) Pasikanti, K. K.; Ho, P. C.; Chan, E. C. Y. J. Chromatogr., B 2008, 871, (49) Zareian-Jahromi, M.; Agah, M. J. MEMS 2009, 19, 294.
202–211. (50) Radadia, A. D.; Salchi-Khojin, A.; Masel, R. I.; Shannon, M. A. J. Micromech.
(14) Cortes, H. J.; Winniford, B.; Luong, J.; Pursch, M. J. Sep. Sci. 2009, 32, Microeng. 2010, 20, 015002(article).
883–904. (51) Radadia, A. D.; Morgan, R. D.; Masel, R. I.; Shannon, M. A. Anal. Chem.
(15) Ryan, D.; Marriott, P. Adv. Chromatogr. 2008, 46, 451–467. 2009, 81, 3471.
(16) Ragonese, C.; Tranchida, P. Q.; Sciarrone, D.; Mondello, L. J. Chromatogr., (52) Lewis, A. C.; Hamilton, J. F.; Rhodes, C. N.; Halliday, J.; Bartle, K. D.;
A 2009, 1216, 8992–8997. Homewood, P.; Grenfell, R. J. P.; Goody, B.; Harling, A. M.; Brewer, P.;
(17) Sun, X. J.; Zhang, S. W.; Wang, F.; Zheng, J. J.; Wu, C. Y.; Xing, J. Chem. Vargha, G.; Milton, M. J. T. J. Chromatogr., A 2010, 1217, 768.
J. Chin. Univ. 2009, 30, 1326–1328. (53) Sun, J.; Cui, D.; Li, Y.; Zhang, L.; Chen, J.; Li, H.; Chen, X. Sens. Actuators,
(18) Reid, V. R.; Crank, J. A.; Armstrong, D. W.; Synovec, R. E. J. Sep. Sci. B 2009, 141, 431.
2008, 31, 3429–3436. (54) Reid, V. R.; Stadermann, M.; Bakajin, O.; Synovec, R. E. Talanta 2009,
(19) Dorman, F. L.; Schettler, P. D.; Wittrig, M.; Lautamo, R.; Cochran, J. W.; 77, 1420.
Thomas, J.; Smith, A.; Gardner, S.; Bloom, A.; Federle, S. ISCC&E (55) Nakai, T.; Okawa, J.; Takada, S.; Shuzo, M.; Shiomi, J.; Delaunay, J. J.;
Symposium, May 2009, Portland, OR. Maruyama, S.; Yamada, I. Olfaction and Electronic Nose: Proceedings of
(20) Sicoli, G.; Tomoyuki, I.; Jicsinszky, L.; Schurig, V. Eur. J. Org. Chem. 2008, the 13th International Symposium, Brescia, Italy, 2009, pp 15-17.
25, 4241–4244. (56) Nakai, T.; Nishiyama, S.; Shuzo, M.; Shiomi, J.; Delaunay, J. J.; Yamada,
(21) Grisales, J. O.; Lebed, P. J.; Keunchkarian, S.; Gonzalez, F. R.; Castells, I. J. Micromech. Microeng. 2009, 19, 065032(article).
C. B. J. Chromatogr., A 2009, 1216, 6844–6851. (57) Serrano, G.; Reidy, S. M.; Zellers, E. T. Sens. Actuators, B 2009, 141,
(22) Jalali-Heravi, M.; Ebrahimi-Najafabadi, H.; Khodabandehloo, A. QSAR 217.
Comb. Sci. 2009, 28, 1432–1441. (58) Malcom, A.; Wright, S.; Syms, R. R. A.; Dash, N.; Schwab, M. A.; Finlay,
(23) Ghavami, R.; Sadeghi, F. Chromatographia 2009, 70, 851–868. A. Anal. Chem. 2010, 82, 1751.
(24) Zhong, Q.; Steinecker, W. H.; Zellers, E. T. Analyst 2009, 134, 283. (59) Aguilera-Herrador, E.; Cardenas, S.; Ruzsanyi, V.; Sielemann, S.; Valcarcel,
(25) Contreras, J. A.; Murray, J. A.; Tolley, S. E.; Oliphant, J. L.; Tolley, H. D.; M. J. Chromatogr., A 2008, 1214, 143.
Lammert, S. A.; Lee, E. D.; Later, D. W.; Lee, M. L. J. Am. Soc. Mass (60) Shopova, S. I.; White, I. M.; Sun, Y.; Zhu, H.; Fan, X.; Frye-Mason, G.;
Spectrom. 2008, 19, 1425. Thompson, A.; Ja, S. Anal. Chem. 2008, 80, 2232.
(26) Lin, H.; Ye, Q.; Deng, C.; Zhang, X. J. Chromatogr., A 2008, 1198, 34. (61) Sun, Y.; Liu, J.; Frye-Mason, G.; Ja, S.; Thompson, A.; Fan, X. Analyst 2009,
(27) Vandekerckhove, B.; Vanden Velde, S.; De Smit, M.; Dadamio, J.; 134, 1386.
Teughels, W.; Van Tornout, M.; Quiryen, M. J. Clin. Periodontol. 2009, (62) Sun, Y.; Liu, J.; Howard, D. J.; Frye-Mason, G.; Thompson, A.; Ja, S.; Fan,
36, 964. X. Analyst 2010, 135, 165.
(28) Terry, S. C.; Jerman, J. H.; Angell, J. B. IEEE Trans. Electron Devices 1979, (63) Long, Z.; Storey, J.; Lewis, S.; Sepaniak, M. J. Anal. Chem. 2009, 81,
26, 1880. 2575.
(29) Golay, M. J. E. J. Chromatogr., A , 216, 1. (64) Dorman, F. L.; Overton, E. B.; Whiting, J. J.; Cochran, J. W.; Gardea-
(30) Zampolli, S.; Elmi, I.; Mancarella, F.; Betti, P.; Dalcanale, E.; Cardinali, Torresdey, J. Anal. Chem. 2008, 80, 4487–4497.
G. C.; Severi, M. Sens. Actuators, B 2009, 141, 322. (65) Cortes, H. J.; Winniford, B.; Luong, J.; Pursch, M. J. Sep. Sci. 2009, 32,
(31) Nishino, M.; Takemori, Y.; Matsuoka, S.; Kanai, M.; Nishimoto, T.; Ueda, 883–904.
M.; Komori, K. IEEE Trans. 2009, 4, 358. (66) Amirav, A.; Gordin, A.; Poliak, M.; Fialkov, A. B. J. Mass Spectrom. 2008,
(32) Manginell, R. P.; Hadizadeh, R.; Porter, D. A.; Hietala, V. M.; Bryan, J. R.; 43, 141–163.
Wheeler, D. R.; Pfeifer, K. B.; Rumpf, A. J. MEMS 2008, 17, 1396. (67) Hamilton, J. F. J. Chromatogr. Sci. 2010, 48, 274–282.

4784 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
(68) Harvey, P. McA.; Robert, A.; Shellie, R. A.; Haddad, P. R. J. Chromatogr. (100) Cajka, T.; Riddellova, K.; Klimankova, E.; Cerna, M.; Pudil, F.; Hajslova,
Sci. 2010, 48, 245–250. J. Food Chem. 2010, 121, 282–289.
(69) Pizzutti, I. R.; Vreuls, R. J. J.; de Kok, A.; Roehrsd, R.; Martel, S.; Friggi, (101) Janssen, H.-G.; Steenbergen, H.; de Koning, S. Eur. J. Lipid Sci. Technol.
C. A.; Zanella, R. J. Chromatogr., A 2009, 1216, 3305–3311. 2009, 111, 1171–1184.
(70) Eric Jover, E.; Adahchour, M.; Bayona, J. M.; Vreuls, R. J. J.; Brinkman, (102) Biedermann, M.; Grob, K. J. Sep. Sci. 2009, 32, 3726–3737.
U. A. Th. J. Chromatogr., A 2005, 1086, 2–11. (103) Lojzova, L.; Riddellova, K.; Hajslova, J.; Zrostlikova, Z.; Schurek, J.; Cajka,
(71) Begnaud, F.; Debonneville, C.; Probst, J.-P.; Chaintreau, A.; Morrison, P. D.; T. Anal. Chim. Acta 2009, 641, 101–109.
Adcock, J. L.; Marriott, P. J. J. Sep. Sci. 2009, 32, 3144–3151. (104) Ryona, I.; Pan, B. S.; Sacks, G. L. J. Agric. Food Chem. 2009, 57, 8250–
(72) Maikhunthod, B.; Morrison, P. D.; Small, D. M.; Marriott, P. J. J. Chro- 8257.
matogr., A 2010, 1217, 1522–1529. (105) de Souza, P. P.; de L. Cardeal, Z.; Augusti, R.; Morrison, P.; Marriott, P. J.
(73) Klee, M. S.; Blumberg, L. M. J. Chromatogr., A 2010, 1217, 1830–1837. J. Chromatogr., A 2009, 1216, 2881–2890.
(74) Tobias, H. J.; Sacks, G. L.; Zhang, Y.; Brenna, J. T. Anal. Chem. 2008, (106) Hoh, E.; Lehotay, S. J.; Pangallo, K. C.; Mastovska, K.; Ngo, H. L.; Reddy,
80, 8613–8621. C. M.; Vetter, W. J. Agric. Food Chem. 2009, 57, 2653–2660.
(75) Vial, J.; Nocairi, H.; Sassiat, P.; Mallipatu, S.; Cognon, G.; Thiébaut, D.; (107) Ratel, J.; Engel, E. J. Chromatogr., A 2009, 1216, 7889–7898.
Teillet, B.; Rutledge, D. N. J. Chromatogr., A 2009, 1216, 2866–2872. (108) Humston, E. M.; Knowles, J. D.; McShea, A.; Synovec, R. E. J. Chromatogr.,
(76) Schmarr, H.-G.; Bernhardt, J. J. Chromatogr., A 2010, 1217, 565–574. A 2010, 1217, 1963–1970.
(77) Almstetter, M. F.; Appel, I. J.; Gruber, M. A.; Lottaz, C.; Timischl, B.; Spang, (109) Li, X.; Xub, Z.; Lu, X.; Yang, X.; Yin, P.; Kong, H.; Yu, Y.; Xu, G. Anal.
R.; Dettmer, K.; Oefner, P. J. Anal. Chem. 2009, 81, 5731–5739. Chim. Acta 2009, 633, 257–262.
(78) Blumberg, L.; Klee, M. S. J. Chromatogr., A 2010, 1217, 99–103. (110) Kouremenosa, K. A.; Pitt, J.; Marriott, P. J. J. Chromatogr., A 2010, 1217,
(79) Seeley, J. V.; Elise, M.; Libby, E. M.; Hill Edwards, K. A.; Seeley, S. K.
104–111.
J. Chromatogr., A 2009, 1216, 1650–1657.
(111) Yang, S.; Sadilek, M.; Synovec, R. E.; Lidstrom, M. E. J. Chromatogr., A
(80) Kalinová, B.; Kindl, J.; Jiroš, P.; Žáček, P.; Vašı́čková, S.; Buděšı́nský, M.;
2009, 1216, 3280–3289.
Valterová, I. J. Nat. Prod. 2009, 72, 8–13.
(112) Mateusa, E.; Baratab, R. C.; Zrostlı́ková, J.; Gomes da Silva, M. D. R.; Paiva,
(81) Kalinová, B.; Podskalská, H.; Růžička, J.; Hoskovec, M. Naturwissenschaften
M. R. J. Chromatogr., A 2010, 1217, 1845–1855.
2009, 96, 889–899.
(113) Chenfei Ma, C.; Wang, H.; Lu, X.; Wang, H.; Xu, G.; Liu, B. Metabolomics
(82) Guthery, B.; Bassindale, A.; Pillinger, C. T.; Morgan, G. H. Rapid Commun.
2009, 5, 497–506.
Mass Spectrom. 2009, 23, 340–348.
(114) Adam, F.; Thiébaut, D.; Bertoncini, F.; Courtiade, M.; Hennion, M.-C.
(83) Mitrevski, B. S.; Wilairat, P.; Marriott, P. J. J.Chromatogr., A 2010, 1217,
J. Chromatogr., A 2010, 1217, 1386–1394.
127–135.
(115) Bertoncini, F.; Marion, M. C.; Brodusch, N.; Esnault, S. Oil Gas Sci.Technol.
(84) Mieth, M.; Schubert, J. K.; Gröger, T.; Sabel, B.; Kischkel, S.; Fuchs, P.;
2009, 64, 79–90.
Hein, D.; Zimmermann, R.; Miekisch, W. Anal. Chem. 2010, 82, 2541–
2551. (116) Adam, F.; Bertoncini, F.; Dartiguelongue, C.; Marchand, K.; Thiébaut, D.;
(85) Hoggard, J. C.; Wahl, J. H.; Synovec, R. E.; Mong, G. M.; Fraga, C. G. Hennion, M.-C. Fuel 2009, 88, 938–946.
Anal. Chem. 2010, 82, 689–698. (117) Dück, R.; Wulf, V.; Geiβler, M.; Baier, H.-U.; Wirtz, M.; Kling, H.-W.; Gäb,
(86) Muscalua, A. M.; Reiner, E. J.; Liss, S. N.; Chen, T. Int. J. Environ. Anal. S.; Schmitz, O. J. Anal. Bioanal. Chem. 2010, 396, 2273–2283.
Chem. 2010, 90, 1–13. (118) Dutriez, T.; Courtiade, M.; Thiébautb, D.; Dulot, H.; Bertoncinia, F.; Vial,
(87) Matamoros, V.; Eric Jover, E.; Bayona, J. M. Anal. Chem. 2010, 82, 699– J.; Hennion, M.-C. J. Chromatogr., A 2009, 1216, 2905–2912.
706. (119) Kohl, A.; Cochran, J.; Cropek, D. M. J. Chromatogr., A 2010, 1217, 550–
(88) Mao, D.; Lookman, R.; Van De Weghe, H.; Weltens, R.; Vanermen, G.; 557.
De Brucker, N.; Diels, L. Chemosphere 2009, 77, 1508–1513. (120) Rubio, S.; Perez-Bendito, D. Anal. Chem. 2009, 81, 4601–4622.
(89) Melbye, A. G.; Brakstad, O. G.; Hostad, J. N.; Gregersen, I. K.; Hansen, (121) Tobias, H. J.; Sacks, G. L.; Zhang, Y.; Brenna, J. T. Anal. Chem. 2008,
B. H.; Booth, A. M.; Rowland, S. J.; Tollefsen, K. E. Environ. Toxicol. Chem. 80, 8613–8621.
2009, 28, 1815–1824. (122) Siegler, W. C.; Crank, J. A.; Armstrong, D. W.; Synovec, R. E. J. Chro-
(90) Eganhouse, R. P.; Pontillo, J.; Gaines, R. B.; Frysinger, G. S.; Gabriel, matogr., A 2010, 1279, 3144–3149.
F. L. P.; Kohler, H.-P. E.; Giger, W.; Barber, L. B. Environ. Sci. Technol. (123) Gras, R.; Luong, J.; Hawryluk, M.; Monagle, M. J. Chromatogr., A 2010,
2009, 43, 9306–9313. 1217, 348–352.
(91) Farwell, C.; Reddy, C. M.; Peacock, E.; Nelson, R. K.; Washburn, L.; (124) Eyres, G. T.; Urban, S.; Morrison, P. D.; Dufor, J. P.; Marriot, P. J. Anal.
Valentine, D. L. Environ. Sci. Technol. 2009, 43, 3542–3548. Chem. 2008, 80, 62-93–6299.
(92) Jover, E.; Matamoros, V.; Bayona, J. M. J. Chromatogr., A 2009, 1216, (125) Mahmoudian, M.; Falahatpishe, H.; Gholamine, B.; Tayebi, L. Iran.
4013–4019. J. Pharm. Res. 2009, 8, 251–255.
(93) Özel, M. Z.; Ward, M. W.; Hamilton, J. F.; Alastair Lewis, A. C.; Raventós- (126) Diaz-Bone, R. A.; Hollmann, M.; Wuerfel, O.; Pieper, D. J. Anal. At.
Duran, T.; Harrison, R. M. Aerosol Sci. Technol. 2009, 44, 109–116. Spectrom. 2009, 24, 808–814.
(94) Laitinena, T.; Martı́n, S. H.; Parshintseva, J.; Hyötyläinena, T.; Hartonena, (127) Hayward, T. C.; Thurbide, K. B. Anal. Chem. 2009, 81, 8858–8867.
K.; Riekkolaa, M.-L.; Kulmalac, M.; Pavón, J. L. P. J. Chromatogr., A 2010, (128) Silva, L. I. B.; Rocha-Santos, T. A. P.; Duarte, A. C. Talanta 2008, 76,
1217, 151–159. 395–399.
(95) Rochat, S.; Egger, J.; Chaintreau, A. J. Chromatogr., A 2009, 1216, 6424– (129) Chen, Y.; He, J.; Zhang, J.; Yu, Z. Talanta 2009, 79, 916–925.
6432. (130) Oishi, T.; Tanaka, K.-I.; Hashimoto, T.; Shinbo, Y.; Jumtee, K.; Bamba, T.;
(96) Pripdeevech, P.; Wongpornchai, S.; Marriott, P. J. Phytochem. Anal. 2010, Fukusaki, E.; Suzuki, H.; Shibata, D.; Takahashi, H.; et al. Plant Biotechnol.
21, 163–173. (Japan) 2009, 26, 167–174.
(97) Tranchida, P. Q.; Shellie, R. A.; Purcaro, G.; Conte, L. S.; Dugo, P.; Dugo, (131) Li, Y.; Hu, J.; Tang, L.; He, Y.; Wu, X.; Hou, X.; Lv, Y. J. Chromatogr., A
G.; Mondello, L. J. Chromatogr. Sci. 2010, 48, 262–266. 2008, 1192, 194–197.
(98) Breme, K.; Tournayre, P.; Fernandez, X.; Meierhenrich, U. J.; Brevard, (132) Silva, L. I. B.; Ferreira, F. D. P.; Rocha-Santos, T. A. P.; Duarte, A. C.
H.; Joulain, D.; Berdague, J. L. J. Agric. Food Chem. 2010, 58, 473–480. J. Chromatogr., A 2009, 1216, 6517–6521.
(99) Stanimirova, I.; Üstün, B.; Cajka, T.; Riddelova, K.; Hajslova, J.; Buydens,
L. M. C.; Walczak, B. Food Chem. 2010, 118, 171–176. AC101156H

Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4785

Vous aimerez peut-être aussi