Anal. Chem.

2010, 82, 47754785

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 General Interest and Reviews Texts Review Articles Columns Principles and Technology General Information Stationary Phases Fundamental Characterizations Portable and Microfabricated GC Technology Development Microfabrication Developments Comprehensive Two-Dimensional Gas Chromatography (GC GC) Scope Reviews Instrumentation Data Handling Theory Biological Clinical and Forensics Environmental Flavor and Fragrance Food and Beverage Metabolomics Petrochemical Gas Chromatography Detectors Improvement in GC Detector Techniques GC Detector Improvement through Software Development Development of GC New Detectors Literature Cited 4775 4775 4775 4776 4776 4776 4776 4777 4777 4779 4779 4779 4779 4779 4780 4780 4780 4780 4781 4781 4782 4782 4782 4782 4783 4783 4784

GENERAL INTEREST AND REVIEWS This review of the fundamental developments in gas chromatography (GC) includes articles published following the previous review (1) in 2008 up to March, 2010. Emphasis is given to developments which are considered signicant as far as basic advances. This accounts for a much smaller amount of publications, as the majority of papers deals with applications of the GC technique and, as such, do not necessarily represent advances in
* To whom correspondence should be addressed. 10.1021/ac101156h 2010 American Chemical Society Published on Web 05/26/2010

the fundamentals. A recent search of the literature had slightly more that 800 publications per year that have the broad subject area of gas chromatography. Most of these publications are applied separations which use GC as the separation technique, so this review really focuses on the small subset that are viewed by the authors as improvements in the technique or the understanding of the technique. Despite the large numbers of publications in other separation techniques (HPLC, CE, etc), GC is arguably still the best separation tool that is in common use for the compounds which are amenable to the technique. Possibly, the greatest expansion of this technique that attracts interest from researchers is comprehensive two-dimensional GC (GC GC). Increasing interest from the commercial eld has led to additional instrumentation and improvements in ease of use following the previous review. While this technique is still not common in analytical laboratories, it does account for a signicant amount of the publications and academic research; thus, it occupies a rather extensive portion of this review. Texts. Several texts were published in this period, some of which were revised editions. Of particular note are three rst edition texts: Comprehensive Two Dimensional GC, edited by Ramos (2); Quantication in LC and GC: A Practical Guide to Good Chromatographic Data, edited by Kuss and Kromidas (3); and Ionic Liquids in Chemical Analysis, edited by Koel (4). Also revised during this period was McNairs text on Basic Gas Chromatography (5), which is a text that is often used in the teaching of the GC technique to students. Finally, for the GC/ MS technique, Hubschmann has revised and updated the Handbook of GC/MS text (6). Review Articles. During the time period of this review, approximately 40 review articles were published on various aspects of GC. Many were, again, application driven, or were focused on detection strategies or increasing the instrumental throughput. There were a surprising number of articles, however, that were more focused on the GC separation itself or on expanding the range of compounds which can be analyzed. Often referred to as
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the Achilles heel of GC, the injection technique can be a large source of frustration when analyzing thermally labile compounds. Large volume injection (LVI) methods have been well reviewed (7) including direct sample introduction and through oven transfer adsorption desorption (TOTAD) techniques. Also considered an injection technique, static headspace extraction GC (SHE-GC) was reviewed (8). Methods of extending the working range of volatility for this technique are addressed, and good coverage of the fundamentals is also summarized. Fast GC was also reviewed (9) with particular attention being paid to theory and inuence of various band-broadening mechanisms which can potentially limit this technique. It was demonstrated that peak widths of 1 ms are readily achievable in GC if extra-column band broadening is controlled. A few reviews concerning the role and understanding of the stationary phase in GC separations were published. The rst describes the various retention models used in prediction of retention times based on thermodynamic parameters (10). This also covers the use of thermodynamic modeling to various column arrangements with simultaneous temperature and pressure programming. Also discussed is extension of these techniques to fast GC and GC GC. Most of the stationary phase work published still continues to be nonpolysiloxane materials, and a review of molten salt and ionic liquids as stationary phases for organic compound analysis includes a discussion as to how stationary phases should be selected by potential users (11). A review of the use of metal-containing stationary phases was also published (12). These materials are useful for separation of compounds through a complexation mechanism. Examples of chiral separations were addressed. Finally, several reviews on the GC GC technique were published. The use of this technique for the analysis of complex metabolomic samples was reviewed (13). This is a very challenging analysis in biological uid, and the increase in peak capacity of the GC GC technique may lend considerable benet to these separations. Further, coupling the GC GC to a time-of-ight mass spectrometer (TOFMS) adds another dimension of separation and can be a very powerful analytical technique. Two other general reviews of the GC GC technique also summarize the state of the art of this technique and show numerous relevant applications. The rst includes an industrial perspective as to the benet of GC GC in semiroutine analyses at Dow (14). The second also includes a discussion of the prediction of separation based on thermodynamic properties and attempts to simplify the column selection process (15). COLUMNS PRINCIPLES AND TECHNOLOGY General Information. While the GC column is, of course, the only part of the entire GC system that physically separates compounds from each other, only a small percentage of publications deal with the understanding of this process or the development of new materials. While this may have been a very active area of research years ago, it certainly is viewed as mature in the present day, and as a result, most publications that t into the category of column advancements are very niche in application. Professor Klaus Unger was quoted at the HPLC 2008 meeting as saying that we should put our efforts towards gaining selectivity, not towards the mad rush to increase efciency. He was, of course, discussing the area of small4776 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010

particle based HPLC separations, but his comments could easily apply to GC as well. Most practicing chromatographers have little interest or knowledge in the mechanisms which lead to separation and often rely on detection techniques to overcome chromatographic coelutions. While this may give acceptable results in some cases, there is still need for development of new materials which would give additional selectivities and/ or allow GC to extend further into the analysis of reactive nonvolatile compounds. Stationary Phases. Clearly, ionic liquids continue to represent the highest percentage of papers published using new materials as GC stationary phases. To date, these materials have not had the efciency of the polysiloxanes, but they do offer unique selectivities. The use of ionic liquids has been reported in the analysis of biodiesel blends (16), another recent topic of interest! This paper uses one of the commercially available columns which is based on the chemistry developed at Dan Armstrongs group. The comparison to more standard poly(ethylene glycol) (PEG) column separations demonstrates the ionic liquids benet of separation of the FAMEs from the less-retained saturates. Other researchers have reported on an ionic liquid bonded polysiloxane stationary phase, which they claim has a high separation efciency of 3200 plates/m (17). Finally, the development of a new triate ionic liquid for GC GC was reported (18). The comparison to more conventional PEG phases as second-dimension columns was discussed. The ionic liquid column was stated to have signicantly larger selectivity for several of the test compounds. Second dimension column orthogonality is a very important issue for GC GC separations, and ionic liquids may have a role here, even if their efciencies are not as high as more routine phases. The separation of polycyclic aromatic hydrocarbons (PAHs) has been of increased interest. Several commercial companies have reportedly developed columns specically for this application. Most notable, Agilent Technologies (www.agilent.com) and Varian (www.varian.com) have marketed a specic column for this separation. Restek Corporation (www.restek.com) has also reported on the use of molecular modeling techniques to develop a new material that is designed for this separation (19). Additional work in the area of modied cyclodextrines was still an area of research, and one paper (20) discussed the use of a maltooctaose derivative as a stationary phase for the separation of enantiomers. Another one (21) used a common permethylated -cyclodextrine diluted in a variety of liquid phases in order to determine the role of the polymer type on retention. This work used PEG and also SE-30 and SE-54 as liquid phases. Fundamental Characterizations. During this review period, very little work was published on the modeling or characterizations of stationary phases. Typically, there have been a few papers on thermodynamic modeling and also quantitative structure property relationship (QSPR) approaches. There were two papers published, both using QSPR models for retention prediction of environmentally important compounds. In the rst (22), the retention indices of 168 pesticides were used to construct a QSPR model. The second paper (23) used a QSPR approach to determine four optimal descriptors which then let the authors predict retention on 18 different GC columns for all 209 PCB

Figure 1. Number of citations by year of Terry, Jerman, and Angels 1979 paper describing the rst etched silicon GC system.

congeners. These approaches should allow for improved column selection and also potential identication of congeners that may not be in a particular users calibration standards. PORTABLE AND MICROFABRICATED GC TECHNOLOGY DEVELOPMENT Analytical samples are often at risk for sample contamination, decomposition, degradation, and loss during storage and transport from the collection site to the laboratory for analysis. This has resulted in a growing trend toward efforts to bring the lab to the sample when possible. Signicant efforts have been invested to develop and test portable instrumentation. There have been several recent reports of the development and use of portable GC systems including work done at the University of Michigan on a portable GC with a chemiresistor array detector (24). The system was designed for rapid, trace analysis of complex mixtures. It consists of a small, multistage preconcentrator; two series-coupled columns with fast, independent temperature programming capabilities; pressure control at the junction point between the columns; and an array of chemiresistors for detection. A new commercially available portable GC with detection provided by a toroidal ion trap mass spectrometer has been developed and described by researchers at Brigham Young University and Torion Technologies (www.torion.com) (25). The system consists of a SPME injection system, a low-thermal mass GC, and a miniature toroidal ion trap mass analyzer housed in a Pelican case. The entire system including pumps and batteries weighs about 13 kg. Two other application studies included the use of portable GC systems for the analysis of acetaldehyde in tobacco smoke (26) and the clinical measurement of volatile sulfur compounds (VSCs) which can be a cause of oral malodor (27). Microfabrication Developments. Thirty years after the publication of the seminal paper by Terry, Jerman, and Angell in 1979 (28), which described the rst GC system composed largely of microfabricated components, interest in separation systems facilitated by microfabricated devices continues to grow as micromachining capabilities mature. Evidence of this is shown in Figure 1 which shows the number of citations of the Angell paper as a function of publication year. The promise of this research continues to be reduced system size, low-power requirements, enhanced performance, and the promise of batch manufacturing to reduce costs. In practice, signicantly enhanced

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 researchers developing new stationary phase coatings, coating techniques, column designs, and methods of fabrication increases, is that a standardized column evaluation method should be developed to directly compare their performance and test column reproducibility. The size and power benets are both obvious and connected; as one reduces the mass of components, the power required to heat and cool individual components decreases as well. Several GC systems have been designed and manufactured using microfabricated components to achieve this end. Examples include the Canary line from Deant Technologies (www.deant-tech.com) which integrates microfabricated GC columns, preconcentrators, and detectors for multiple applications; SLS micros GCM series (www.slsmt.com) which integrates a microfabricated column, detector, and sample loop along with the electronics into a PDA sized uidics package; and Thermo Scientics C2 V-200 micro GC (www.c2v.nl) which integrates a microfabricated inlet and detectors with conventional wall coated open tubular fused silica columns. Two recent developments include the introduction of an intelligent preconcentrator by Deant Technologies that onthe-y determines the appropriate sampling time and the acquisition of Concept to Volume (C2 V) by Thermo Scientic. Several researchers continue to work on the development of new systems based on microfabricated components; one recent report describes a new portable GC system utilizing a micro electromechanical system (MEMS) enabled miniaturized GC for the subparts per billion detection and monitoring of aromatic volatiles (30). Zampolli and others at the CNR-IMM Institute for Microelectronics and Microsystems in Bologna, Italy, describe a system consisting of a micromachined preconcentrator, a 50 cm 800 m 1 mm microfabricated column packed with 80-100 mesh carbograph 2 + 0.2% carbowax particles, and metal oxide (MOX) gas sensors as a detector. The demonstrated system shows separation of BTEX compounds in about 10 min. Another report by Nishino and others at Shimadzu describes the development of a prototype instrument built around a microfabricated column 8.5-17 m in length generating 35 000 theoretical plates with a ame ionization detector (FID) (31). There remain several research programs focused on the development of new MEMS GC systems including Sandia National Laboratories and the University of Michigan WIMS Center. Sandia National Laboratories has had an ongoing development program in the area of microfabricated GC systems since 1996, primarily geared toward the rapid, portable, low-power detection of chemical weapons, explosives, and more recently toxic industrial chemicals. Recent advances include the development of masssensitive microfabricated preconcentrators (32), a new selective
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and sensitive chemiresistor GC detector (33), and the demonstration of the rst consumable free comprehensive two-dimensional GC system (GC GC) consisting of a pair of microfabricated columns and a microfabricated detector (34). The mass-sensitive preconcentrator consists of a thin lm resistive heater on the surface of a MEMS pivot plate resonator (PPR). The PPR is Lorentz force actuated, and the frequency of the resonator shifts with mass loading. When sufcient sample has been collected for analysis by the downstream microfabricated gas analyzer, the lm is heated and the sample is desorbed. Under partial funding from the Defense Advanced Research Projects Agency Micro Gas Analyzer (DARPA-MGA) program, Sandia developed a sensitive chemiresistor utilizing a conjugated molecule linked gold nanoparticles in a sol-gel matrix. The chemiresistor demonstrated signicant selectivity for phosphonates (CWA simulants) and sensitivity. The GC GC utilized a pair of microfabricated GC columns. The rst column was coated with polydimethyl siloxane and was 90 cm in length; the second column was 30 cm in length and was coated with polyethylene glycol. The modulator was a stop-ow design based on the work of Richard Sacks, and detection was provided by a nanoelectromechanical systems (NEMS) cantilever resonator developed by the Roukes group at Caltech. The system demonstrated a separation of 29 components in less than 8 s. The NSF funded Wireless Integrated MicroSystems (WIMS) Engineering Research Center (ERC) (www.wimserc.org) is in the nal year of NSF funding for the center and is transitioning from an ERC to the WIMS institute. The center has been developing several parallel MEMS GC based systems for multiple applications, such as breath analysis (35), explosives detection (36), extraterrestrial exploration (37), and indoor air quality monitoring (38). They have developed new gas phase detectors such as nanoscale chemiresistor arrays (39) and microdischarge detectors (40). The WIMS center has also demonstrated the rst thermally modulated GC GC system utilizing microfabricated columns (41). While these efforts continue, much of the research being reported has focused on the development of microfabricated components such as preconcentrators, columns, and detectors. In the area of preconcentrators, several groups are exploring the use of carbon nanotubes (CNTs) as a sorbent material. CNTs demonstrate excellent adsorption and desorption characteristics due to low mass transfer resistance because of the nonporous nature of the material (42, 43). Other materials investigated for use as sorbents in microfabricated preconcentrators include the use of microporous activated carbon (44), chemically polymerized polypyrrole (45), as sorbent materials, and inkjet printing of polymer sorbents prior to anodic bonding (46). In the area of column development, there have been several reported advances. Zareian-Jahromi and Agah at Virginia Tech have recently reported revisiting the concept of multicapillary columns (MCCs) (47). MCCs are a concept rst operatively demonstrated by researchers in Novosibirsk, Russia, in the 1980s and exist now as a commercial product sold by Multichrom, Ltd. (www.mcc-chrom.com). The principal concept is to get around the column capacity limitations and pressure restrictions of microbore columns using a bundle of identical microbore columns in parallel. This allows a fraction of each injection to be separated on each column preventing overloading and enables the overall
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ow restriction to be very small. The challenges remain in manufacturing uniform channels, both in length and phase volume ratio, distribution of the injection plug equally to all columns, and dead volume at the inlet and outlet of the system. Problems in any of these areas will result in band broadening. Agahs group has demonstrated some success using a MEMS approach to address these problems. Ali and Agah have also demonstrated MEMS based semipacked columns (48). These columns used microfabricated posts in the column channels to decrease diffusion distances and column capacity relative to more traditional WCOT columns but still demonstrate signicantly reduced pressure drops relative to traditional packed columns. Zareian-Jahromi and Agah have also reported a novel coating technique using a monolayer protected gold stationary phase (49). There are several other reports of novel column fabrication development. Radadia and Masel at the University of Illinois describe work on an all silicon column using a gold diffusion eutectic bonding process to bond a silicon lid instead of a Pyrex lid to the silicon channels (50) and a partially buried microcolumn with an interesting cross section (51). Lewis and Milton describe a microfabricated planar glass column with a circular cross section manufactured in two hemispherical halves and bonded using epoxy (52). Sun and Chen at the Chinese Academy of Sciences report the development of a silicon/Pyrex microfabricated 100 m 100 m 6 m column generating 4850 theoretical plates (53). There are also reports of new column coatings which have also been developed. Researchers from both the University of Washington/Lawrence Livermore National Laboratories (54) and University of Tokyo (55) describe the use of CNTs as stationary phases. Nakai et al. from the University of Tokyo also reports on the use of a functionalized parylene (56) as a stationary phase. A report by researchers at the WIMS center at the University of Michigan highlighted an often overlooked aspect of microfabricated columns: column reproducibility. The study compared the performance of several (2-8) columns with different preparations to develop a column coating strategy (57). There have been several advances in the area of microfabricated and miniaturized GC detectors including mass analyzers, ion mobility spectrometers (IMS), optical sensors, and microcantilever (MC) arrays. Malcom and Finlay at Micorsaic Systems, Ltd. and the Imperial College describe a microengineered quadrupole mass lter consisting of microfabricated components to fabricate a quadrupole mass lter with dimensions of 35 mm 6 mm 1.5 mm (58). Researchers at the University of Cordoba describe a system that couples a multicapillary column with a miniaturized IMS for rapid GC IMS separations (59). Researchers from the University of Missouri and ICx Nomadics have reported on the use of a optouidic ring resonator (OFRR) sensor for on-column detection (60-62). The OFRR is a thin walled fused silica capillary. The inner wall of the capillary is coated with a thin polymer lm. The circular cross-section of the capillary forms an optical ring resonator where circulating waveguide modes are supported by total internal reection of light along the curved inner and outer boundary. The evanescent eld extends into the core and is sensitive to the refractive index change induced by the interaction between the analyte and the stationary phase. Long and Sepaniak at the University of Tennessee report on the use of

MC arrays for gas phase sensing (63). MC arrays have similar response mechanisms to quartz crystal microbalances and surface acoustic wave sensors; however, they demonstrate better mass sensitivity, smaller dimensions, and decreased fabrication costs. COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY (GC GC) Scope. This GC GC review covers literature published mostly from 2009 until the end of April 2010, when it was compiled, but unlike GC GC, it is not comprehensive because of the large number of papers found during the search. The number of papers published in the review period was around 100, about a 10% increase over the last review done for Analytical Chemistry across a similar time period (64). Only select articles of the 100 or so are covered, broken down into distinct topic lines as seen below. Reviews. Cortes et al. reviewed the achievements in GC GC across 2007 until October 2008 citing 121 contributions from that period (65). They noted how GC GC work has shifted from instrumentation development to practical applications and listed those for petroleum, polymer, pharmaceutical, avor and fragrance, metabolomics, and environmental. Interestingly, they commented that mass spectrometry (MS) is the detector of choice, now and in the future, for GC GC, with time-of-ight (TOF) MS outpacing the quadrupole due to having the faster acquisition rates to dene ultra narrow peaks from GC GC but predicted that the use of differential ow modulation (DFM) will increase (as an alternative to cryogenically modulated systems); DFM is not inherently compatible with the pumping capacity of most MS systems, with the supersonic molecular beam approach of Amirav being an exception (66). DFM should be more appropriate for eld and process instruments that employ alternate detectors such as ame ionization detection (FID). Although we may disagree on predictions for DFM, we concur on one statement in their review; beer is a highly popular alcoholic beverage around the world. In conclusion, Cortes puts emphasis on the need for improved quantication and qualitative data analysis software and suggests that computational chemistry methods combined with GC GC chromatogram structure and retention data for known compounds can yield identications for unknown components. Hamilton specically reviewed the use of GC GC to study the atmosphere (67). GC GC, especially with MS, is ideally suited for this research given the complex array of natural and manmade emissions and oxidation products present in the atmosphere. An important observation by the author was the need for sophisticated data handling approaches, including image processing, to deal with the wealth of information generated using GC GC/MS. Instrumentation. Research devoted specically to modulation hardware was relatively light during the review period, although the group of Shellie contributed a substantial piece on designing exible, pulsed ow modulation systems (68). Drawbacks of ow modulation setups, versus the cryogenic approach, include pneumatic complexity, multiple connecting pieces, baseline instabilities, and lack of exibility for changing modulation times. In particular, inability to vary the modulation time is problematic for ow modulated systems due to the potential for wrap-around. Shellie developed a dynamic ow model and employed a postrstdimension-column restrictor that offsets some of these disadvantages, including allowing different modulation times. That benet

can now be added to those already realized in ow modulation: less expensive hardware and no cryogenic uid use. Pizzutti et al. derived a better compressed air modulator (69) from an earlier model (70) to address developing countries needs for low-cost systems. While the volatility range is limited for this air modulator, with breakthrough shown for tetradecane, lower volatility pesticides ranging from Triuralin to Deltamethrin were successfully analyzed in grapes with GC GC-ECD. Begnaud et al. modied the Marriott longitudinally modulated cryogenic system (LMCS) to temperature program the cooling chamber in conjunction with the GC oven, which reportedly increases the modulation efciency across a wide range of compound volatilities while simultaneously reducing cryogenic uid use (71). The use of the LMCS as the heart of a switchable multidimensional/GC GC system was described and then tested with compounds important to essential oil analysis and lavender oil (72). A microuidic Deans switch placed after a primary GC column, upstream of the LMCS, allowed selection of either a longer second column for heart-cutting work or a shorter column for GC GC. The system was exible enough to allow switching from heart-cut to GC GC multiple times in one analytical run. Although not demonstrated, the system is proposed to be especially effective for heart-cut olfactory work, where broader peaks are necessary for sensory perception. Klee and Blumberg performed ow modulation of methanedoped carrier gas, which allowed direct observation/calculation of second dimension hold-up times in GC GC (73). Subsequently, they calculated/visualized retention factors for alkanes and diesel components in both columns for GC GC. Unfortunately, for cryofocusing modulator users, this approach will not work since methane cannot be trapped with current systems. The tendency for those users to employ stationary phase bleed from the rst column as a way to calculate hold-up time was discouraged upon proving that stationary phase bleed was retained (versus methane) by the second dimension column. However, the authors setup did not consider an independently temperatureprogrammed secondary oven that could be positively offset versus a primary column oven. Primary and secondary column temperatures were the same in their experiments. Tobias et al. gave the rst report on the coupling of GC GC to combustion isotope ratio MS and used their system to demonstrate the analysis of steroids relevant to sports performance enhancement (74). They also suggested applications for food authentication and environmental pollutant tracing, where sample complexity may make one-dimensional GC insufcient. Data Handling. Given the high data density of GC GC, especially when TOFMS is used, the sample complexity that predetermines GC GC use for an application, and the special needs of the metabolomics community in particular, it is not surprising to discover reports on data handling outside of what is already provided by an instrument vendor. Vial et al. used dynamic time warping to align second dimension peaks in GC GC chromatograms, followed by multivariate analysis to distinguish three types of tobacco (75). Through additional interpretation, marker compounds for a tobacco could be identied via the collected mass spectrometry data. An imaging process technique borrowed from the proteomics eld was used to compare fruit aromas represented by contour plots after analysis by headspace
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solid phase microextraction (SPME) GC GC/MS (76). Image proles created by the process can be used for statistical analysis and suggesting sample origin. While seemingly very powerful, the authors noted that any mass spectrometry data collected during GC GC is off-line to the imaging software, a distinct disadvantage compared to other GC GC data processing software. Almstetter et al. used GC GC-TOFMS vendor software that included automated baseline correction, peak nding, spectral deconvolution, and library searching prior to applying retention time normalization and data alignment to compare two strains of Escherichia coli (77). They exported peak lists from the vendor software and aligned peaks with a model tted to known derivatized fatty acids in the samples, followed by principal component analysis to achieve metabolic ngerprinting. Theory. Blumberg and Klee took a critical look at denitions for multidimensional separations, including GC GC, discussing Giddings concepts and proposing a new denition that includes only analytical separations (78). Seeley et al. developed a simplied solvation parameter model to predict GC GC compound retention behavior on a variety of stationary phase combinations using literature values for solute and stationary phase descriptors (79). They saw excellent agreement of the model and experimental GC GC data and suggested the model could be used to design optimal column setups. Biological. Kalinova et al. investigated the male wing gland secretions of a bumblebee parasite, the wax moth Aphomia sociella, with SPME GC GC-TOFMS (80). Bumblebees are important pollinators in greenhouses and are being considered for open agricultural eld pollination given the recent decline of the domesticated honeybee. Chemically understanding gland secretions may allow the creation of effective lures for bumblebee parasite control. GC GC-TOFMS, in conjunction with GCelectroantennographic detection (EAD) and GC-FT-IR, identied several compounds as potential sex pheromones for the wax moth. With perhaps the most provocative title in this review, Irresistible Bouquet of Death, only topped by the keywords, Carcass Attractiveness, Kalinova et al. again used SPME with GC GC-TOFMS and GC-EAD, this time to study how burying beetles are attracted to dead mice (81). GC GC-TOFMS allowed the identication of sulfur-containing volatile organic chemicals evolved after death that are likely stimulants for carrion location by the beetles. Although a very interesting read, this is one paper not to be studied over lunch. Clinical and Forensics. GC GC-TOFMS was used to analyze opiates and benzodiazepines in human serum after solid phase extraction and derivatization (82). Excellent second dimension separations from the higher-concentration matrix interferences were achieved for the subject compounds on the 50% phenyltype column. A limit of quantication of approximately 5 ng/mL was noted for Flunitrazepam in serum, signicant since it is necessary to detect therapeutic levels at <10 ng/mL. The authors suggested that the full mass-range approach of TOFMS could allow nontarget compound analysis. This same benet is desirable in sports antidoping applications for retroactive searches of data for nontarget compounds and designer steroids, as voiced by the group of Marriott (83). They thoroughly tested GC GCTOFMS for anabolic agents in urine and reported limits of detection below or at the required performance levels set by the
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World Anti-Doping Agency. Quantication with TOFMS can even proceed on ions chosen after analysis since a full mass spectrum is collected. One of the downsides of TOFMS for this application, though, was its apparent lower sensitivity for higher m/z ions in the anabolic agent trimethylsilyl derivatives versus other mass analyzers, such as quadrupoles. This issue can compromise not only sensitivity if those ions are chosen as quantication masses but also qualitative searches via standard mass spectral libraries. In the latter case, the authors recommend creating TOFMS spectral libraries specic for the antidoping compounds of interest from authentic reference materials. In breath analysis research for clinical purposes, novel multisorbent needle traps were used for sampling prior to desorption to GC GC-TOFMS (84). The needle traps performed relatively well and could even be autosampled, although they were subject to rapid contamination in some hospital environments. GC GCTOFMS showed the capability to detect low levels of breath components and the potential for identifying previously unknown compounds. The authors correctly suggested that thicker lm columns are necessary for volatiles work (versus the 0.25 mm 0.25 m used in their rst dimension), both to provide better analyte focusing during needle trap desorption and to avoid overload of higher concentration components. Hoggard et al. exploited the separation ability of GC GCTOFMS with sophisticated chemometrics to detect and identify 29 impurities in six samples of commercially obtained dimethylmethylphosphonate (DMMP), a chemical weapon simulant (85). They then used statistical analysis to classify the DMMPs, nding that two had identical impurity proles; the chemical supplier later conrmed them to be from the same source. On the basis of their success, the authors will continue to develop these methods for impurity proling that support forensic investigations of chemicalattack crime scenes. Environmental. The electron capture detector (ECD) is widely used in the analysis of environmental samples for polychlorinated biphenyls (PCBs), toxaphene, organochlorine pesticides (OCPs), chlorinated benzenes (CBs), and other halogenated pollutants, even today, often operated with a parallel dual-GC column conguration. In the parallel dual-column GC-ECD approach, two different stationary phases are employed to enhance selectivity and elucidate possible quantication bias. However, for unknown reasons to this reviewer, GC GC-ECD, which is similar in a two independent separations regard, is still a relatively littleused technique for environmental analysis. Muscalu and others recently demonstrated the power of GC GC-ECD when they analyzed PCBs, OCPs, and CBs in sludge and sediment samples (86). A 100% dimethyl polysiloxane column was used in the rst dimension coupled to a secondary column that has selectivity toward mono-ortho and coplanar PCBs. Only 2 of the 64 PCBs investigated coeluted, congeners 4 and 10 (BZ#s). Given that environmental samples are often extremely complex, the authors investigated the potential for chlorinated dioxins and furans, toxaphene, chlorinated diphenyl ethers, and chlorinated naphthalenes to coelute with the PCBs, OCPs, and CBs of interest. There were no interferences. Standard reference materials of sludge and sediment analyzed with GC GC-ECD after pressurized uid extraction and silica and copper treatments, showed acceptable accuracy and precision. In addition,

other compounds, such as polychlorinated alkanes, were seen in the extracts. A hot topic in environmental analysis is pharmaceuticals and personal care products in waters. GC GC-TOFMS with SPE was recently used to effect parts per trillion level determinations for 13 pharmaceuticals, 18 plasticizers, 8 personal care products, 9 acid herbicides, 8 triazines, 10 organophosphorous compounds, 5 phenylureas, 12 organochlorine biocides, 9 polycyclic aromatic hydrocarbons (PAHs), and 5 benzothiazoles and benzotriazoles in river water (87). Although a 5% phenyl 50% phenyl column combination gave the best separation for the compounds of concern, the reverse setup gave a good correlation between second dimension retention times for compounds and their log Kow values. This relationship was proposed as an identication conrmation tool. Mao et al. better estimated ecotoxicity of petroleum hydrocarbon mixtures in soil using HPLC-GC GC-FID, versus poorly performing, simple one-dimensional total petroleum hydrocarbon tests (88). The remaining environmental GC GC papers cited here are applications accomplished by taking advantage of the three most important features of GC GC-TOFMS: chromatographic suppression/elimination of matrix interferences that thwart target or nontarget compound identication, enhanced sensitivity for trace residue levels through modulation focusing, and having a full mass spectrum for compound identication through interpretation or library searching. In environmental analysis concerning petroleum samples, structure-of-chromatogram can be added as a benet. The list includes analysis of: biodegraded crude oil (89); nonylphenols in groundwater and wastewater (90); heavy oil from natural seeps into the ocean (91); benzothiazoles, benzotriazoles, and benzosulfonamides in wastewater, raw sewage, and river water (92); organic nitrogen compounds in urban aerosols (93); and organic compounds from wood combustion aerosol nanoparticles (94). Flavor and Fragrance. Rochat, Egger, and Chaintreau investigated shrimp aroma not only with GC GC-TOFMS but also with GC-olfactometry (GC-O) and multidimensional (heart-cut) GC/MS with olfactometry (MDGC/MS/O) (95). Each system had its strong and weak points, and ultimately the techniques were complementary. GC GC had superior sensitivity, which endorsed its use for identication of trace-level odorants noted during GC-O or MDGC/MS/O. Difculties in retrieving matching odorant peaks for mass spectral identication from the complex GC GC chromatogram were overcome to some extent by correlating the linear retention indices from an Adams database to retention on the rst dimension column of the GC GC setup. Of course, both stationary phases must be the same for this approach to work, and in one important case, that of attempted conrmation of the intense odorant 2-ethyl-3,5-dimethylpyrazine, even the separating power of GC GC and spectral deconvolution did not resolve interferences that corrupted its mass spectrum. Extracted ion plots and reverse search of the coeluted mass spectrum provided tentative identication of the pyrazine. In all, over 40 odorants were listed for shrimp odor, although with descriptors like garbage, foot, rancid, dirty socks, awful, not well, etc for some compounds, one has to wonder if further work will be attempted! From shrimp odor to perfumery, Pripdeevech, Wongpornchaia, and Marriott turned in a report on the use of GC GC with FID

and quadrupole MS, against one-dimensional GC/MS, to evaluate simultaneous steam-distillation, supercritical uid, microwaveassisted, and Soxhlet extraction methods for Thai vetiver root (96). Vetiver root oil is apparently an excellent xative for perfumes. Sixty-four compounds were identied using GC/MS with an additional 43 identied (out of the many more separated) with GC GC/MS. Relative quantication for those compounds for the different extraction methods was done via GC GC-FID. Tranchida et al. used GC GC with a fast scanning quadrupole MS to characterize fresh and aged tea tree essential oils, including for potential allergenic components, some of which were found in both fresh and aged oils (97). Although substantial differences were noted between fresh and aged (or oxidized) oils, many of the compounds in the oxidized oil went unidentied due to lack of library mass spectral data. In a study on Indian cress (also known as nasturtium) essential oil, GC GC-TOFMS was used in conjunction with GC-O, mainly to identify low-level odorants that would otherwise need tedious sample enrichment (98). Food and Beverage. Food origin and authentication studies are made easier by comprehensive GC approaches, since food samples are typically very complex. Stanimirova et al. geographically dened Corsican honeys via their volatile organic chemicals prole with headspace SPME GC GC-TOFMS and statistical pattern recognition techniques as an alternate to traditional pollen examination (99). Theoretically, their approach could be used to identify cases of intentional honey product mislabeling. Cajka et al. used essentially the same techniques, analytical and statistical, to divide Ligurian and other non-Ligurian Mediterranean olive oils (100). The Ligurian oil is a premium product that is relatively scarce. The authors remarked that while SPME GC/MS produced sufcient marker compounds for chemometric proling of the oils, GC GC-TOFMS offered a more comprehensive ngerprint and better mass spectral qualities. Janssen, Steenbergen, and de Koning reviewed the use of comprehensive chromatography techniques, including GC GC, for the analysis of edible oils and fats, indicating that GC GC was well-suited for target compound analysis, group-type separation, and chromatographic ngerprinting (101). An example of target-compound analysis was provided by Biedermann and Grob who used GC GC with FID and MS after HPLC separation to determine mineral oil adulteration in sunower soil (102). Lojzova et al. used headspace SPME and compared GC-ion trap MS, GC-TOFMS, and GC GC-TOFMS for the analysis of 13 alkylpyrazines and other volatile compounds in potato chips arising from the Maillard reaction during their production (103). While none of the instrumental techniques allowed unequivocal determination of all targeted alkylpyrazines, GC GC-TOFMS was declared superior to the other two because of lower limits of quantication and enhanced nontarget compound screening capability. Beverage-related studies conducted with GC GC included the trace-level analysis of the potent odorants, 3-alkyl-2-methoxypyrazines, in wine grapes (104) and the characterization of Brazilian cachaca (105), a sugar cane derived liquor that surprisingly is the third most consumed distilled alcoholic beverage in the world (after vodka and soju).
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Because of the increase in sensitivity due to the modulation process, GC GC is appropriate for trace residue analysis in a variety of food sample types. Hoh et al. demonstrated this with quantication for a variety of halogenated compounds, including PCBs, OCPs, and polybrominated diphenyl ethers (PBDEs), in sh oils, using gel permeation chromatography and a largevolume, direct sample-introduction technique with GC GCTOFMS (106). They also identied nontarget halogenated natural products, including halogenated 1-methyl-1,2-bipyrroles (MBPs), DMBPs, methoxylated PBDEs, polybrominated hexahydroxanthene derivatives, and polybromoindoles in the oils. Even PCBfree cod liver oils had PCBs. Ratel and Engel reported a 7-fold increase in benzenenic and halogenated volatiles detected in lamb, milk, and oyster samples analyzed with GC GC-TOFMS versus GC-quadrupole MS (107). Humston et al. contributed a piece on cacao bean quality, proposing to identify moisture damage before visible signs of mold on beans, using headspace SPME GC GC-TOFMS and chemometric software (108). Metabolomics. Metabolomics samples are usually extremely complex and will show many overlapping peaks, even when analyzed by efcient, high resolution GC, so it is not surprising to see GC GC studies in the literature. In addition to full characterization of samples and possible diagnostic value, biomarker discoveries for diabetes (109) and organic acidurias in infants (110) have been facilitated by GC GC-TOFMS. GC GC-TOFMS was used as a complementary technique to liquid chromatography-tandem quadrupole MS to examine targeted metabolites of a bacterium Methylobacterium extorquens AM1 grown on two different carbon sources (111). Mateus et al. used GC GC with TOFMS to characterize volatile chemicals from 11 species of pine trees (112). In addition to more traditional GC GC separations, they showed elegant enantioselective GC GC chromatograms for chiral terpenes that may have importance in insect-host pine relationships. Finally, GC GC-TOFMS allowed terpenoid proling of two lines of transgenic Artemisia annua L., an important plant in traditional Chinese medicine that contains Artemisinin, which is used in combination therapies to treat malaria (113). Petrochemical. Adam et al. delivered the rst report for online supercriticial uid chromatography (SFC) connected to twin-GC GC-FID and used this sophisticated system for thorough characterization of middle distillates, including the complete separation of saturated and unsaturated compounds (114). Fischer-Tropsch reaction products, including parafns, olens, and oxygenates, were probed using GC GC-TOFMS by Bertoncini et al. (115). Some of the GC GC petrochemical contributions are notable for their use of detection systems in addition to, or other than, TOFMS. Basic and neutral nitrogen speciation and quantication in middle distillates with GC GC and a nitrogen-chemiluminescence detector was accomplished by Adam et al. (116). A rare use of GC GC with positive chemical ionization and quadrupole MS, for lower molecular weight fatty alcohol alkoxylate analysis, yielded much more information than could be obtained by electron ionization MS alone (117). Historically, the volatility range of GC GC for petroleum applications has been rather limited due to modulator temper4782 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010

ature and ow limitations, GC column stationary phase temperature limits (more polar phases), and even the press-t connectors sometimes used to seal GC GC columns together. However, Dutriez et al. overcame these hindrances to offer a high-temperature GC GC analysis of vacuum gas oils up to nC60 (118). They used a short, wide bore, thin-lm (10 m 0.32 mm 0.10 m), high-temperature dimethyl polysiloxane column in the rst dimension and a high-temperature stable 50% silphenylene polysilphenylene-siloxane column (0.5 m 0.10 mm 0.10 m) in the second dimension. Unfortunately, there is no mention of the type of connector they used to join these columns, an important consideration given that their GC oven temperature program goes to 370 C, a temperature where a press-t connection rarely survives for any length of time. Interestingly, their modulation period was 20 s, perhaps a record for the longest second dimension separation in GC GC, but they determined it was necessary for elution of tetraaromatics within the modulation cycle (penta- and heptaaromatics wrapped around). Benets of the approach were obtaining boiling point distribution (HT-SimDist) and aromatic family quantication for petroleum fractions. Kohl et al. characterized military fog oil, an exceedingly complex middle distillate petroleum product used as an obscurant in soldier eld training, with several GC GC column setups on FID and TOFMS (119). Mass spectra and the structure of the GC GC chromatogram, combined with data mining at the edges of the unresolved complex mixture, allowed the authors to propose a composition for the fog oil. It contains mainly aliphatic compounds ranging from C10 to C30, where naphthenes are the major fraction. Aromatics are high in diversity but low in overall concentration, being purposely removed in the newer oils to reduce toxicity. More specically, alkanes, cyclohexanes, hexahydroindanes, decalins, adamantanes, bicyclohexanes, alkylbenzenes, indanes, tetrahydronaphthalenes, partially hydrogenated polycyclic aromatic hydrocarbons, biphenyls, dibenzofurans, and dibenzothiophenes were identied using GC GC-TOFMS. GAS CHROMATOGRAPHY DETECTORS In the biennium 2008 to 2009, many research articles and a worth reading review describing the advances in gas chromatography were available to the scientic community. The review, updated to 2009 (120), describes multiple applications of GC and the properties of detectors. This review states that, during this period, the most common GC detector for environmental application was the ion trap-mass spectrometric (ITMS) detector (GCITMS). This GC system demonstrated its capabilities for trace level determination of contaminants in diverse environmental samples. Nanogram per liter concentrations of polybromine compounds in earthworms and triclosan in rivers and coastal water samples were detected using GC-ITMS. Improvement in GC Detector Techniques. During this period, different GC available techniques were modied to t specic requirements. For instance, two-dimensional gas chromatography (GC GC) was coupled to online combustion isotope ratio mass spectrometry (C-IRMS) to enhance peak capacity and signal in the GC GC system without interference with highprecision carbon isotope analysis in urinary steroid samples (121). Siegler et al. (122) increased the selectivity in a comprehensive

three-dimensional gas chromatography-ame ionization detector (GC-FID) by utilizing an ionic liquid stationary phase column in one dimension. With this modication, the authors reported the resolution of 180 peaks per minute in a 3D diesel sample separation. The presence of arsine and phosphine in light hydrocarbons at the part-per-billion level was determined by capillary ow technique and gas chromatography with a dielectric barrier discharge detector (GC-DBDD) (123). The method includes a large volume injection, capillary ow technology, and the DBDD operating in argon mode. The researchers reported that the system needed 4 min for complete analysis and remained reliable for 6 months in continuous operation. In addition, the development of microscale-preparative multidimensional gas chromatography coupled to 2-dimensional nuclear magnetic resonance (MDGC-2D NMR) was proposed to isolate and identify pure volatile compounds from a complex sample (124). The system was used to isolate geraniol from an essential oil matrix and quantitatively resolved from 15 partially coeluting compounds from the rst column. A new generation of electron capture detection (nonradioactive) with a short, nonpolar and wide-bore column was developed for the analysis of isosorbide dinitrate in human serum (125). The method was linear between 5 and 50 ng/mL with accuracy of 90% and recovery of 99-108%. Another innovation was the combination of electron ionization mass spectrometry and inductively coupled plasma mass spectrometry (GC-EI-MS/ICPMS) for determining volatile arsenic compounds formed by fecal microorganisms (126). The element sensitivity of the ICPMS and molecular identication by EI-MS allowed for the rst time the identication of three arsenic species (methyl-methylthio-ethylthio-arsine (MeAs(SMe)(SEt)), dimethyl-methylseleno-arsine (Me2AsSeMe), and thiobis(dimethylarsine) (Me2As)2S) in environmental samples or human matrixes. To overcome some of the disadvantages of current ame photometric detectors for the determination of sulfur and phosphorus in hydrocarbons, a multiple ame photometric detector (mFPD) was developed (GC-mFPD) (127). The researchers tested ve ames on quenching resistance hydrocarbons and found an improvement of nearly 20-fold relative to a single ame mode and almost 10-fold relative to a dual ame mode. The minimum detectable limits for the mFPD were 4 10-11 g S/s and 3 10-12 g P/s, for sulfur and phosphorus, respectively. In addition, the system maintained about 60% of its original analyte chemiluminescence even under the presence of 100 mL/min of methane ow into the detector, which demonstrate the robustness of the system for quenching resistant hydrocarbons. Silva and co-workers (128) developed a methodology for the analysis of some alcohols as an alternative to the NIOSH recommended method (Method 1405) for organic vapors detection. The methodology combines gas chromatography separation with a detector made of an optical ber sensitized with a thin polymeric lm of poly[methyl(3,3,3-triuoropropyl)siloxane] (PMTFPS). With the GC-OF operating in the visible region (650 nm), nine different alcohols (allyl alcohol, n-propyl alcohol, secbutyl alcohol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, methyl isobutyl carbinol, cyclohexanol, and diacetone alcohol) were separated. Results were satisfactory compared to the results obtained using a GC-FID system.

GC Detector Improvement through Software Development. Another approach consisted in the development of a radial basis functional neural network (RBFNN) to model the nonlinear calibration curves of four hexachlorocyclohexane (HCH) isomers obtained with gas chromatography-electron capture detector (GCECD) (129). The RBFNN method with logarithm-transform and normalization on the calibration data modeled the nonlinear calibration curves for the four HCH isomers. A new algorithm was developed for detecting fragmentation patterns in complex samples such as plant tissues and a new scheme to examine GC/MS spectra (130). The technique uses a metabolite database called KNApSAcK and currently includes 49 165 species-metabolite relations from 24 847 metabolites. Development of GC New Detectors. In addition to modication of current methodologies/equipment, new detectors were developed during this period. Li and co-workers (131) developed a miniaturized atmospheric pressure dielectric barrier discharge (DBD) to be used as GC detector for the analysis of volatile chlorinated hydrocarbons (VCHCs). The methodology uses chemiluminescence emission from the reaction of DBD-split VCHCs with luminal solution. This detector is of simple construction and an energy saver, with sensitivity at subnanomole concentrations. Another novelty during this biennium was the use of carbon nanotubes as GC detectors (132). The methodology is based on the gas sensing capability of carbon nanotubes, particularly in eld-effect transistors. A carbon nanotube eld-effect transistor was coupled to a gas chromatographer (GC-NTFET) for the separation of BTEX compounds. The system showed good response for 4 weeks with a detection limit lower than 4 g/L. Results from the GC- NTFET were comparable to results obtained with a GC-FID system.
Frank L. Dorman is an Associate Professor of Biochemistry and Molecular Biology in the Forensics Science Program at Penn State University. Franks research has been in the area of the development of new capillary column stationary phases through the use of computer modeling and development of applications for the analysis of environmental and forensic compounds of interest using various GC GC, GC, and HPLC techniques. Previously, he was the Director of Technical Development at Restek Corporation in Bellefonte, PA. He received his Ph.D. in Analytical Chemistry from the University of Vermont in Burlington, VT. Prior to joining Restek, Frank was employed by Inchcape Testing Services-Environmental Laboratories in several roles, eventually becoming Senior Chemist for methods development. Frank also holds the position of Research Professor at Juniata College in Huntingdon, PA. 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 Member of the Technical Staff at Sandia National Laboratories in the Micro Total Analytical Systems Department. He received his M.S. in chemistry from Wright State University in 2000, and his Ph.D. in analytical chemistry from the University of Michigan in 2004 working for Professor Richard Sacks. His research interests include development of portable, low-power, GC systems for rapid detection and identication of analytes of interest utilizing MEMS components. Jack W. Cochran is the Director of New Business and Technology for Restek Corporation after working for LECO Corporation as their Director for Separation Science for 7 years with their GC- and GC GC-timeof-ight mass spectrometers. Formerly, he worked at the Illinois Hazardous Waste Research and Information Center and the U.S. Environmental Protection Agency in Oklahoma doing analytical method development for environmentally signicant compounds in air, water, sediment, tissue, soil, and other types of samples. His analytical interests include novel sample preparation and cleanup methods such as QuEChERS and dispersive solid phase extraction, GC GC with new capillary column stationary phases, time-of-ight mass spectrometry, and vacuum-outlet GC. Jorge Gardea-Torresdey is the Richard M. and Frances M. Dudley Professor of Chemistry in the Department of Chemistry at The University
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of Texas at El Paso in El Paso, TX. He received his Ph.D. in 1988 at New Mexico State University in Las Cruces, NM. His research interests include environmental chemistry of hazardous heavy metals and organic compounds, gas chromatography, gas chromatography/mass spectroscopy, atomic absorption and emission spectroscopy, inductively coupled plasma/ mass spectroscopy, X-ray absorption spectroscopy, and investigation of metal binding to biological systems for remediation of contaminated waters and soils (e.g., phytoremediation) and the study of the fate of nanoparticles in the environment. The scientic contributions of Dr. Gardea have allowed him to receive many honors throughout his professional life. He just received the 2009 SACNAS Distinguished Scientist of the Year Award. In 2009, Dr. Gardea was highlighted by prestigious journals including the December 3, 2009 Issue of Nature. He has authored or coauthored over 300 research articles and book chapters. He has taught analytical chemistry and instrumental analysis at the undergraduate level and advanced analytical chemistry and environmental chemistry at the graduate level. He is also currently Editor of the Journal of Hazardous Materials.

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