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Publisher: Taylor & Francis
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Analytical Letters
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http://www.tandfonline.com/loi/lanl20

Gas ChromatographyMass SpectrometryBasic


Principles, Instrumentation and Selected
Applications for Detection of Organic
Compounds
a

J. Sneddon , S. Masuram & J. C. Richert

Department of Chemistry, McNeese State University, Lake Charles,


Louisiana
Version of record first published: 17 May 2007.

To cite this article: J. Sneddon , S. Masuram & J. C. Richert (2007): Gas ChromatographyMass
SpectrometryBasic Principles, Instrumentation and Selected Applications for Detection of Organic
Compounds, Analytical Letters, 40:6, 1003-1012
To link to this article: http://dx.doi.org/10.1080/00032710701300648

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Analytical Letters, 40: 10031012, 2007


Copyright # Taylor & Francis Group, LLC
ISSN 0003-2719 print/1532-236X online
DOI: 10.1080/00032710701300648

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MINI-REVIEW

Gas Chromatography-Mass SpectrometryBasic Principles, Instrumentation and


Selected Applications for Detection of
Organic Compounds
J. Sneddon, S. Masuram, and J. C. Richert
Department of Chemistry, McNeese State University, Lake Charles,
Louisiana

Abstract: This mini-review discusses the analytical technique of gas chromatographymass spectrometry (GC-MS), specifically basic principles and instrumentations. The
applications of GC-MS to a number of studies for determining organic compounds
from around the world are presented and highlight its universal use and acceptance.
Selected applications show that GC-MS is an integral and complimentary part of
many field studies involving organic compound detection and determination.
Keywords: Gas chromatography-mass spectrometry, organic compounds, environmental samples

INTRODUCTION
Since its development in the mid-1950s, gas chromatography-mass spectrometry (GC-MS) has become indispensable in the chemical analysts laboratory. While it can be used to determine drugs and metabolites in the
Received 12 February 2007; accepted 24 February 2007
The authors acknowledge, with thanks, the support of Environmental Protection
Agency, EPA-R-82958401-1. One of us (SM) is a Coastal Restoration and Enhancement through Science and Technology (CREST) Graduate Scholars Fellow. We
thank the Board of Regents (BoR) of Louisiana for a Louisiana Education Quality
Science Fund (LEQSF) Research Teachers Graduate Fellowship for JCR.
Address correspondence to J. Sneddon, Department of Chemistry, McNeese State
University, PO. Box 90455, Lake Charles, Louisiana 70609. E-mail: jsneddon@
mcneese.edu
1003

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pharmaceutical area, and molecular weights and elemental composition in


complex mixtures, its greatest (arguably) use is the determination of
volatile and semi-volatile organic compounds in complex mixtures as well
as waters, soils, and other environmental samples. It is the basis for many
Environmental Protection Agency (EPA) official methods.
This mini-review describes the basic principles and instrumentation used
for GC-MS. It is not intended as a comprehensive review of GC-MS but rather,
provide the reader with knowledge to understand how it works. There are
numerous texts which describe GC-MS in detail and the reader is referred
to several of these (Hites, 1997; McMaster and McMaster, 1998). The
primary object of this review is to present an overview of recent and
selected applications of GC-MS, particularly in the determination of volatile
and semi-volatile organic compounds in soil analysis and closely related
fields of sediments and associated waters. A review on GC-MS with a discussion on quantitation of semi-volatile organic compounds (SVOC) in sediment
sample is available (Kawata et al. 2005). A recent review has more applications to mass spectrometry in general, particularly in chemical processing
(Munoz Llamas et al. 2007). The work to be presented is from around the
world showing the universal, widespread use, and general acceptance of
GC-MS. In many cases the studies involve complementary techniques such
as nuclear magnetic resonance spectroscopy (NMR) and are presented for
completeness. No one analytical technique, including GC-MS, should be
used in a comprehensive and complete field study.

BASIC PRINCIPLES AND INSTRUMENTATION


When two separate techniques such as gas chromatography (GC) and mass
spectrometry (MS) are successfully combined to form gas chromatographymass spectrometry (GC-MS), the advantages become obvious. GC can
separate many volatile and semi-volatile compounds but not always selectively detect them whereas MS can selectively detect many compounds but
not always separate them. Initial concerns for GC-MS were the significant
differences in pressure-the GC gas exiting the system is around one atmosphere (760 torr) whereas the MS operates at a vacuum of around 1025
1026 torr. Several approaches were proposed including splitting the GC
effluent with about a few percent reaching the MS and the rest being vented
away, and interfaces between the GC and MS to reduce the pressure to that
of the MS. The use of a jet separator was widely adopted for packed
column GC but tends to get easily blocked and requires significant routine
maintenance. If the GC gas flow is low (a few ml/min) and the pumping
speed of the MS vacuum system is high (several hundred liters per second)
then all of the GS effluent can be passed into the MS. This is the most
widely adopted approach for capillary column GC. At present for capillary
GC-MS, the capillary column is inserted directly into the ion source. The

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Gas Chromatography-Mass Spectrometry

1005

effluent leaving the GC is at a temperature of around 3008C (as high as 4008C


possible). As the effluent (individual compounds) elute from the GC, they
enter the MS, typically and most common is the electron ionization
detector. Ion trap or time-of flight can be used to generate ions. At this
time, they are bombarded by a stream of electrons causing them to
fragment. The mass of the fragment divided by the charge is the mass
charge ratio (M/Z ). Almost always the charge is 1, and M/Z ratio represents
the molecular weight of the fragment. A group of four electromagnets, a quadrupole, focus each fragment through a slit into the detector. These quadrupoles
are programmed by a computer to direct only certain fragments. The computer
has the quadrupoles, which cycle these fragments one at a time (scan) until the
range of M/Z is recovered. This produces the mass spectrum which is a graph
of signal intensity (relative abundance) versus M/Z ratios (essentially
molecular weight). Each compound has a unique fingerprint and software is
readily available to provide a library of spectra for unknown compounds.
Recently, three-dimensional GC-MS has become popular.
In summary, GC-MS is an ideal technique for qualitative and quantitative
determination of volatile and semi-volatile organic compounds in a wide
variety of samples. A detection limit as low as sub-ng is possible. The
sample must be in solution for injection into the GC. This can simply be dissolution in a solvent, typically dichloromethane or extraction (with a soxhlet,
which is our most widely used method for extracting hydrocarbons form soil).
Bench type complete instrumentation including computer and software for
library search is available for research and is widely used in teaching from
around $50,000 (mass ranged from around 200 700). More sophisticated
systems used almost exclusively for research cost up to $250,000 but are
capable of mass ranges from around 20 to several thousand.

SELECTED APPLICATIONS FOR DETERMINATION OF


ORGANIC COMPOUNDS
The literature has hundreds of papers on the use of GC-MS. It is beyond the
scope of this review to include all of these papers and results are presented
with a focus. This mini-review has selected a number of works from
various countries around the world to highlight its wide use and general acceptance. Several papers were selected to show the wide range of organic
compounds determined, approaches to sample preparation and the use of
GC-MS as complementary to other analytical techniques such as NMR.
Sixteen Orthic Chernozemic surface soil samples; one half from virgin
prairie and one half from adjacent cultivated prairie (cultivated for 31 94
years), were collected from eight sites throughout Southern Saskatchewan,
Canada. Samples were analyzed for total organic carbon and a number of
other chemical and physical properties (Schnitzer et al. 2006). The virgin
and cultivated soils at site No. 4 were selected for more detailed analysis by

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cross-polarization magic angle spinning (CP-MAS) 13C NMR, Curie-pointpyrolysis-gas chromatograph-mass spectrometry (Cp-Py-GC-MS), and by
pyrolysis-field ionization mass spectrometry (Py-FIMS). Long-term cultivation resulted in a large significant decrease in total soil organic matter
(SOM), as represented by total soil organic carbon. There were significant
increases in aromaticity of the SOM as a result of long-term cultivation as
indicated by CP-MAS 13C NMR spectroscopy. This was mainly attributable
to the result of cultivation-enhanced degradation of aliphatic carbon relative
to aromatic carbon. Organic compounds identified in the Cp-Py-GC-MS
spectra of the virgin and cultivated soils at site No. 4 consisted of n-alkanes
(ranging from C11 to C22) and alkenes (ranging from C7:1 to C21:1), with
the virgin soil being richer in alkenes than the cultivated soil. Other components identified were cyclic aromatics, carbo-cyclics, N-containing
aromatics, N-heterocyclics, benzene and substituted benzenes, phenols and
substituted phenols, and substituted furans. The compounds identified
appeared to originate from long-chain aliphatics, lignins, polyphenols,
aromatics, polysaccharides, and N-containing compounds in the two soils.
While similar compounds were identified by Py-FIMS in the two soils, the
total ion intensity (TII) of the virgin soil was almost 2.5 times as high as
that of the cultivated soil. This suggests that cultivation made the organic
matter less volatile, either by favoring the formation of higher molecular
weight organic matter or by promoting the formation of non-volatile metalorganic matter complexes. The Py-FIMS spectra showed that the virgin soil
contained relatively more lignin dimers, lipids, sterols, and n-C16 to n-C34
fatty acids than the cultivated soil. Thus, conversely, the cultivated soil was
richer in carbohydrates, phenols and lignin monomers, alkyl aromatics and
N-containing compounds, including peptides, than the virgin soil.
Soil organic matter (SOM) in five soil horizons from Arctic tundra and one
soil horizon from a temperate region was collected and separated into an extractable fraction (EF) and a non-extractable fraction (NEF) by dilute alkali (Dai
et al. 2002). The modified classical fractionation method was applied to characterize SOM in the EF; and the wet chemistry fractionation scheme, cross-polarization magic angle spinning (CP-MAS) 13C NMR, and pyrolysis-gas
chromatography-mass spectrometry (Py-GC-MS) techniques were used to
characterize SOM in the NEF. Each of these methods provided information
on the chemical compounds of SOM at varying angles. The NEF comprises a
large amount of SOM in these Arctic tundra soils and has great potential to
influence carbon cycling in these ecosystems with climate warming.
The relationship between the chemistry, biochemistry, and spectroscopic
characteristics of humic substances and clay mineralogy was studied (Laird
et al. 2001). Clay-humic complexes were separated from a Webster soil
(fine-loamy, mixed, superactive Typic Endoaquoll) by an invasive sonication-centrifugation technique. The samples were analyzed for mineralogy
by XRD (X-ray diffraction), chemical composition by inductively coupled
plasma-optical emission spectroscopy (ICP-OES), C and N by thermal

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combustion, C chemistry by solid state 13C magic angle spinning-NMR


spectroscopy (MAS-NMR), and both GC and GC-MS.
The feasibility of different clean-up procedures was studied for the determination of polycyclic aromatic hydrocarbons (PAHs) in biota samples such
as oysters, mussels, and fish liver (Navarro et al. 2006). Once the samples were
extractedessentially with acetone and in a microwave systemand before
they could be analyzed by gas chromatography-mass spectrometry (GCMS), three different approaches were studied for the clean-up step: solid
phase extraction (SPE), microwave-assisted saponification (MAS), and gel
permeation chromatography (GPC). The main aim of this work was to
maximize the recoveries of PAHs and to minimize the presence of interfering
compounds in the last extraction. In the case of SPE, Florisil cartridges of 1, 2,
and 5 g, and silica cartridges of 5 g were studied. In that case, and with oysters
and mussels, microwave-assisted extraction, and 5 g Florisil cartridges
provided good results. In addition, the concentrations obtained for Standard
Reference Material (SRM) NIST 2977 (mussel tissue) were in good
agreement with the certified values. In the case of microwave-assisted saponification, the extracts were not as clean as those obtained with 5 g Florisil and
this fact lead to overestimate the concentration of the heaviest PAHs. Finally,
the cleanest extracts were obtained by GPC. The method was successfully
applied to mussels, oysters, and hake liver, and the results obtained for
NIST 2977 (mussel tissue) were within the confidence interval of the
certified reference material for most of the certified analytes.
The effects of thermal evolution on the composition and structure of
aquatic humic substances (AHS) heated at temperatures from 100 to 5008C
in presence of helium were investigated (Lu et al. 2001) using elemental
analysis, FTIR, solid state 13C CP-MAS NMR spectroscopy, and Py-GCMS spectrometry. Elemental composition results showed that with increase
in heating temperatures, there was an increase in the atomic H/C ratio and
a decrease in the atomic O/C ratio in the AHS. FTIR, solid state 13C CP/
MAS NMR, and Py-GC-MS results showed decreasing amounts of oxygencontaining groups, followed by their subsequent disappearance at higher
temperatures. Formation of aromatics was observed at the expense of aliphatics at higher temperatures. This study has given a substantial amount of
information on mass loss, structural evolution, and the degree of maturity as
the humic substances are heated with increasing temperatures, suggesting
that thermal evolution may play an important role in the contribution of the
AHS as a precursor of coal like organic materials.
In the last 10 years, PETROBRAS has experienced significant oil spills
and the PETROBRAS Research Center (Brazil) plays an important role in
a company emergency response program by characterizing the spilled oil,
monitoring affected ecosystems, determining the fate of oil in the environment, and subsequently, helping the company assess the environmental
damage (Meniconi et al. 2002). The use of advanced chemical analytical
methods (gas chromatography-flame ionization detection, purge-and-trap

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gas chromatography-photo-ionization detection, and GC-MS) in some


Brazilian oil spill studies to determine fractions and individual petroleum
hydrocarbons in different matrixes, e.g., water, groundwater, sediment,
sand, fish, and spilled oil, are discussed. Spill studies encompassed crude
and fuel oil releases on land and coastal ecosystems related to the incidents
in Guanabara Bay (Rio de Janeiro), the Barigui and Iguassu rivers (Parana),
and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons, nalkanes, isoprenoids, unresolved complex mixtures, volatile monoaromatic
compounds (benzene, toluene, ethylbenzene, and xylenes), parent and
alkylated homolog polycyclic aromatic hydrocarbons (PAH), and terpanes
and steranes were characterized to determine correlation to the spilled oil
and other known oil sources and environmental assessment.
GC-MS was used for the study of pollution in the Slovenia area (Dereani
et al. 2002). Extraction with methanol in HCl and ethylation with Na-tetraethyl borate was used. Accuracy was assessed using standard mussel tissue.
The analysis of sediments in non-exposed areas indicated a low extent of
pollution with OTCs while in marina and in dockyard, a moderate extent
of pollution was found. The analyses of mussels exhibited a higher extent
of pollution by tributlytin (TBT) and its degradation products in summer
than in winter. It was observed that phenytin was not detected.
A method for detecting benzophenone-based compounds present
in samples of water, soil, blood, etc. by simultaneously reacting it with trifluoroacetamide and obtaining benzophenone derivatives, is described (Ryu
and Jean, 2005). The method comprises the steps of extraction of benzophenone-based compounds present in a sample with an organic solvent, and
reacting this extract with trifluoroacetamide, to prepare a benzophenone
derivative for subsequent quantitation and/or qualitative the benzophenone
derivative directly by GC-MS. Preferably the sample was selected from the
group consisting of water, soil, and blood; the organic solvent was selected
from the group consisting of di-ethyl ether, hexane, chloroform, ethyl
acetate, dichloromethane, and a low molecular weight alcohol of C1 C4;
and the first step was carried out at a temperature of 80 1008C for 30 min
or more.
The CH2Cl2 extracted samples of industrial wastes collected from GIDC
Vapi and GIDC Ankaleshwar (Gujarat) were recorded for Infra-Red (IR) and
GC-MS (Mahajan and Shrivastava, 2005). Several organic compounds were
found including organophosphorus pesticide. These compounds ultimately
affect the soil and groundwater quality of the area.
The direct coupling of a headspace sampler with a mass spectrometer was
proposed as a screening tool for the rapid detection of soil pollution by hydrocarbons from petroleum and derivatives (Perez et al. 2004). The samples are
subjected to the headspace generation process, with no prior treatment, and the
volatiles generated are introduced directly into the mass spectrometer, thereby
obtaining a fingerprint of the sample analyzed. Suitable treatment of the signal
by chemometric techniques allowed unequivocal characterization of the

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different types of sample. The use of fast gas chromatography with a mass
spectrometer detector coupled to the headspace sampler allows identification
of the major hydrocarbons present in the mineral and organic polluted
samples; interpretation of the results obtained, and demonstrates the analytical
potential of headspace-mass spectrometry coupling.
Four recent applications of analytical pyrolysis in environmental science
and engineering are discussed (White et al. 2004). In all applications, samples
were analyzed to provide information about the origin of organic matter or
changes to an organic matrix. In the first application, GC/MS and
pyrolysis-GC/flame ionization detection (FID) were used to classify the
origin of natural organic matter (NOM) buried in the Antarctic. In the
second application, pyrolysis-GC-MS was used to compare the recalcitrance
of NOM to biodegradation. In the third application, pyrolysis-GC-FID was
used to quantatively differentiate between lipogenic NOM and petroleum
pollution in highly organic soil. In the fourth application, pyrolysis-GC-MS
was used to fingerprint organic matter in water samples to describe the
relationship between surface water, groundwater, and springs in a complex
watershed. In all applications, the benefits of pyrolysis analysis are still
being discovered.
A method for determining of all phenols, alkylphenols, and chlorophenols
in organic matter extracted from bottom sediments is presented (Czaplicka
2001). The analytical procedure comprises extraction with dichloromethane
in an ultrasonic field, separation of acidic compounds using acid-basic extraction, and determination of the phenols and chlorophenols using GC-MS. The
method has demonstrated the presence of phenol, its alkyl derivatives, and
chlorophenols, the last in insignificant amounts.
Collection and analysis of organic pollutants at depth without bringing
soil to the surface is described (Robbat 2001). A thermal extraction cone
penetrometer (TECP) probe was used to extract soil-bound semi-volatile
organics, transferring them to the surface for ultra-fast GC-MS analysis.
Findings showed that polychlorinated biphenyls, polycyclic aromatic hydrocarbons, chlorinated pesticides, and explosives could be collected and
analyzed in 5 min when soil water content was , 20% and in 15 min when
soil water content was 20 35%. When the TECP was directly connected to
the GC-MS, TNT and four of its synthetic precursors were speciated in 20
s. Moreover, 51 volatile organic compounds were detected by membraneinlet mass spectrometry in approximately 10 s. Organics were sniffed from
a vial and were identified using ion fingerprint detection software. The algorithms provide the means to untangle complex mass spectra making real-time,
electronic nose detection, and identification by MS possible.
A method of using headspace-GC-MS system to detect volatile organic
compounds in water is described (Cantu et al. 2004). This method corresponds
to the performance requirements for the analysis of drinking water. The
equipment setup and parameters are given along with a list of successfully
detected compounds.

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A method was proposed for determination of trace organic compounds


such as PCB, dioxin, hormone, waste plastic, explosive, agrochemicals, and
medicine (Tsukahara et al. 2003). The device comprises an UV-Vis spectrophotometer, a solid phase absorbent, and a detector. Silica gel or alumina
was used as adsorbent for gathering the target organic compounds. GC-MS,
GC-electron capture detector, or GC-MS-electron capture detector was used
for detection. The method could be used for monitoring the harmful
compounds in natural water and waste water.
A method for the collection of river sediments and subsequent extraction
of micro-organism pollutants is presented (Long et al. 2000). Continuous flow
configuration was an efficient method to collect suspended and bed sediments.
The authors stated that it was particularly applicable to environmental
sampling of organic pollutants due to the immediate separation of the solid
and fluid stages. An analytical method is described for the supercritical fluid
extraction (SCP) of a wide range of common organic pollutants from such
sediments, including pesticides (ranging in chemical characteristics fromr
hydrophilic triazine herbicides to the hydrophobic pyrethroid insecticides)
and polyaromatic hydrocarbsons.
Persistent pollutants (dioxins) were collected with solvents (acetonitrile
and acetone), their concentration determined by absorption photometry
(240 320 nm), adsorbed (with silica gel) and leached with non-polar
solvents, and determined by GC-MS (Sawatsubashi et al. 2003).
A method for the determination of PCB and dioxins in waste and processing water was proposed (Tsukahara et al. 2002). The compounds were
adsorbed on silica gel or alumina solid phase followed by elution and quantitative and qualitative measurement. Non-polar solvent such as n-hexane,
methanol, ethanol, toluene, dichloromethane, or acetonitrile were used for
elution. The analysis was performed using GC-MS or GC coupled with an
electron capture detector.
The detection of polyaromatic hydrocarbons (PAHs) in soil samples by
GC-MS originating from restored marshes at Sabine National Wildlife
Refuge in Southwestern Louisiana was studied (Noble et al. 1998). The hydrocarbons were extracted from the soil using a variation of EPA Method 3540
and determined by GC-MS. Five sites were chosen including some
developed almost 20 years ago. No PAHs were found but trace quantites of
hexachlorobenzene and hexachlorobutadiene were found.
The photolytic degradation of frequently applied s-triazine type pesticides
was investigated (Kiss et al. 2007). A special, immersible UV-light source was
applied in order to carry out photodegradation. The degradation processes
were followed by thin layer chromatography (TLC), GC, and GC-MS techniques. Following the irradiation of the sample, the degradation products
were isolated by SPE column chromatography. EI mass spectrometry was
used to identify the degradation species. All four of the different s-triazine
type pesticides studied underwent photolytic decomposition. The kinetic
aspect of photodegradation of prometryn, terbutryn, simazine, and atrazine

Gas Chromatography-Mass Spectrometry

1011

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was revealed completely, while in case of prometryn and terbutryn a detailed


mechanism of photolytic transformation was established. Four degradation
species were detected, as a consequence of two parallel ways of degradation.
Both pesticides suffered the loss of thio-methyl groups prior to cleavage of the
alkyl groups. Deamination did not occur under the conditions applied. The
kinetic behavior with respect to photodegradation displayed significant differences when comparing the decomposition of s-triazine type pesticides:
prometryn decomposed 10 times faster than terbutryn.

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