Gas chromatographymass spectrometry
(Additional Reading)
prof. aza
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Introduction
Gas chromatography-mass spectrometry
(GC-MS) is a method that combines the features
of gas-liquid chromatography and mass
spectrometry to identify different substances
within a test sample. Applications of GC-MS
include drug detection, fire investigation,
environmental analysis, and explosives
investigation. GC-MS can also be used in airport
security to detect substances in luggage or on
human beings. Additionally, it can identify trace
elements in materials that were previously
thought to have disintegrated beyond
identification.
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Introduction, continued
The GC-MS has been widely heralded as a
"gold standard" for forensic substance
identification because it is used to perform a
specific test. A specific test positively identifies
the actual presence of a particular substance in
a given sample. A non-specific test, however,
merely indicates that a substance falls into a
category of substances. Although a non-specific
test could statistically suggest the identity of the
substance, this could lead to false positive
identification.
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Contents
1 History
2 Instrumentation
3 Analysis
4 Applications
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4.1 Environmental Monitoring and Cleanup
4.2 Criminal Forensics
4.3 Law Enforcement
4.4 Security
4.5 Astrochemistry
4.6 Medicine
5 See also
6 External links
7 References
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History
The use of a mass spectrometer as the detector in gas
chromatography was developed during the 1960s. These
sensitive devices were bulky, fragile, and originally
limited to laboratory settings. The development of
affordable and miniaturized computers has helped in the
simplification of the use of this instrument, as well as
allowed great improvements in the amount of time it
takes to analyse a sample. In 1996 the top-of-the-line
high-speed GC-MS units completed analysis of fire
accelerants in less than 90 seconds, whereas firstgeneration GC-MS would have required at least 16
minutes. This has led to their widespread adoption in a
number of fields.
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Instrumentation
The GC-MS is composed of two major building blocks:
the gas chromatograph and the mass spectrometer. The
gas chromatograph uses the difference in the chemical
properties between different molecules in a mixture to
separate the molecules. The molecules take different
amounts of time (called the retention time) to come out
of the gas chromatograph, and this allows the mass
spectrometer downstream to evaluate the molecules
separately in order to identify them. The mass
spectrometer does this by breaking each molecule into
ionized fragments and detecting these fragments using
their mass to charge ratio. Each molecule has a specific
fragment spectrum which allows for its detection.
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Instrumentation
These two components, used together, allow a
much finer degree of substance identification
than either unit used separately. It is possible to
make an accurate identification of a particular
molecule by gas chromatography or mass
spectrometry alone. The mass spectrometry
process normally requires a very pure sample
while gas chromatography can be confused by
different molecular types that both happen to
take about the same amount of time to travel
through the unit (i.e. have the same retention
time).
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Instrumentation, continued
Sometimes two different molecules can also
have a similar pattern of ionized fragments in a
mass spectrometer (mass spectrum). Combining
the two processes makes it extremely unlikely
that two different molecules will behave in the
same way in both a gas chromatograph and a
mass spectrometer. So when an identifying
mass spectrum appears at a characteristic
retention time in a GC-MS analysis, it is usually
taken as proof of the presence of that particular
molecule in the sample.
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Analysis
The primary goal of chemical analysis is to identify a
substance. This is done by comparing the relative
concentrations among the atomic masses in the
generated spectrum. Two kinds of analysis are possible,
comparative and original. Comparative analysis
essentially compares the given spectrum to a spectrum
library to see if its characteristics are present for some
sample in the library. This is best performed by a
computer because there are a myriad of visual
distortions that can take place due to variations in scale.
Computers can also simultaneously correlate more data
(such as the retention times identified by GC), to more
accurately relate certain data.
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Another analysis measures the peaks in relation
to one another, with the tallest peak receiving
100% of the value, and the others receiving
proportionate values, with all values above 3%
being accounted for. The parent peak normally
indicates the total mass of the unknown
compound. This value can then be used to fit to
a chemical formula containing the various
elements assumed to be present in the
compound. The isotope pattern in the spectrum,
which is unique for elements having many
isotopes, can also be used to identify the various
elements present.
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Once a chemical formula has been matched to the
spectrum, the molecular structure and bonding can be
identified, and needs to be consistent with a substance
with the characteristics recorded by GC/MS. The fitting is
normally done automatically by programmes which come
with the machine, given a list of the elements which
could be present in the sample.
A “full spectrum” analysis considers all the “peaks” within
a spectrum. However, selective ion monitoring (SIM)
which looks only at a few characteristic peaks associated
with a candidate substance, can also be done.
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This is done on the assumption that at a given
retention time, a set of ions is characteristic of a
certain compound. This is a fast and efficient
analysis, especially if you have some prior
information about a sample or are looking for a
specific compound. When the amount of
information collected about the ions in a given
gas chromatographic peak is reduced, the
sensitivity of the analysis goes up. So, SIM
analysis allows a smaller quantity of a
compound to be detected and measured, but the
degree of certainty about the identity of that
compound is reduced
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Applications
Environmental Monitoring and Cleanup
Criminal Forensics
Law Enforcement
Security
Astrochemistry
Medicine
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Environmental Monitoring and Cleanup
GC-MS is becoming the tool of choice for
tracking organic pollutants in the environment.
The cost of GC-MS equipment has fallen
significantly, and the reliability has increased at
the same time, which has contributed to its
increased adoption in environmental studies as
cost is always a major consideration in this kind
of work. There are some compounds for which
GC-MS is not sufficiently sensitive, including
certain pesticides and herbicides, but for most
organic analysis of environmental samples,
including many major classes of pesticides, it is
very sensitive and effective
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Criminal Forensics
GC-MS can analyze the particles from a
human body in order to help link a criminal
to a crime. The analysis of fire debris
using GC-MS is well established, and
there is even an established American
Society for Testing Materials (ASTM)
standard for fire debris analysis.
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Law Enforcement
GC-MS is increasingly used for
detection of illegal narcotic, and may
eventually supplant drug-sniffing dogs
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Security
A post-September 11 development, explosives-detection
systems have become a part of all US airports. These
systems run on a host of technologies, many of them
based on GC-MS. There are only three manufacturers
certified by the FAA to provide these systems (citation
needed), one of which is Thermo Detection (formerly
Thermedics), which produces the EGIS, a GC-MS-based
line of explosives detectors. The other two
manufacturers are Barringer Technologies, now owned
by Smith's Detection Systems and Ion Track
Instruments, part of General Electric Infrastructure
Security Systems.
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Astrochemistry
Several GC-MS have left earth. Two were
brought to mars by the Viking program.[1]
Venera 11 and 12 and Pioneer Venus analysed
the atmosphere of venus with GC-MS.[2] The
Huygens probe of the Cassini-Huygens mission
landed one GC-MS on Saturn's largest moon,
Titan.[3] The material in the comet
67P/Churyumov-Gerasimenko will be analysed
by the Rosetta mission with a chiral GC-MS in
2014. [4]
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Medicine
In combination with isotopic labelling of
metabolic compounds, the GC-MS is used
for determining metabolic activity. Most
applications are based on the use of C13
as the labelling and the measurement of
C13/C12 ratios with an isotope ratio mass
spectrometer (IRMS); an MS with a
detector designed to measure a few select
ions and return values as ratios.
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Medicine
In combination with isotopic labelling of
metabolic compounds, the GC-MS is used
for determining metabolic activity. Most
applications are based on the use of C13
as the labelling and the measurement of
C13/C12 ratios with an isotope ratio mass
spectrometer (IRMS); an MS with a
detector designed to measure a few select
ions and return values as ratios.
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References
Eiceman, G.A. (2000). Gas Chromatography. In R.A. Meyers (Ed.),
Encyclopedia of Analytical Chemistry: Applications, Theory, and
Instrumentation, pp. 10627. Chichester: Wiley. ISBN 0-471-97670-9
Giannelli, Paul C. and Imwinkelried, Edward J. (1999). Drug Identification:
Gas Chromatography. In Scientific Evidence 2, pp. 362. Charlottesville:
Lexis Law Publishing. ISBN 0-327-04985-5.
^ The Development of the Viking GCMS
^ V. A. Krasnopolsky, V. A. Parshev (1981). "Chemical composition of the
atmosphere of Venus". Nature 292: 610 - 613. DOI:10.1038/292610a0.
^ H. B. Niemann, S. K. Atreya, S. J. Bauer, G. R. Carignan, J. E. Demick, R.
L. Frost, D. Gautier, J. A. Haberman, D. N. Harpold, D. M. Hunten, G. Israel,
J. I. Lunine, W. T. Kasprzak, T. C. Owen, M. Paulkovich, F. Raulin, E.
Raaen, S. H. Way (2005). "The abundances of constituents of Titan’s
atmosphere from the GCMS instrument on the Huygens probe". Nature 438:
77-9-784. DOI:10.1038/nature04122.
^ Goesmann F, Rosenbauer H, Roll R, Bohnhardt H (2005). "COSAC
onboard Rosetta: A bioastronomy experiment for the short-period comet
67P/Churyumov-Gerasimenko". Astrobiology 5 (5): 622-631.
DOI:10.1089/ast.2005.5.622.
Retrieved from "http://en.wikipedia.org/wiki/Gas_chromatographymass_spectrometry"
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Gas Chromatography-Mass
Spectroscopy
background
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Introduction
Gas chromatography-mass spectroscopy (GC-MS) is
one of the so-called hyphenated analytical techniques.
As the name implies, it is actually two techniques that
are combined to form a single method of analyzing
mixtures of chemicals. Gas chromatography separates
the components of a mixture and mass spectroscopy
characterizes each of the components individually. By
combining the two techniques, an analytical chemist can
both qualitatively and quantitatively evaluate a solution
containing a number of chemicals.
The uses for GC-MS are numerous. They are used
extensively in the medical, pharmacological,
environmental, and law enforcement fields. This
laboratory exercise will look at how environmental
chemists evaluate samples containing the pollutants
called PAHs.
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SRIF's GC-MS System
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Gas Chromatography
In general, chromatography is used to separate
mixtures of chemicals into individual
components. Once isolated, the components
can be evaluated individually.
In all chromatography, separation occurs when
the sample mixture is introduced (injected) into a
mobile phase. In liquid chromatography (LC),
the mobile phase is a solvent. In gas
chromatography (GC), the mobile phase is an
inert gas such as helium.
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The mobile phase carries the sample
mixture through what is referred to as a
stationary phase. The stationary phase is
a usually chemical that can selectively
attract components in a sample mixture.
The stationary phase is usually contained
in a tube of some sort. This tube is
referred to as a column. Columns can be
glass or stainless steel of various
dimensions.
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The mixture of compounds in the mobile phase
interacts with the stationary phase. Each
compound in the mixture interacts at a different
rate. Those that interact the fastest will exit
(elute from) the column first. Those that interact
slowest will exit the column last. By changing
characteristics of the mobile phase and the
stationary phase, different mixtures of chemicals
can be separated. Further refinements to this
separation process can be made by changing
the temperature of the stationary phase or the
pressure of the mobile phase.
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Our GC has a long, thin column containing
a thin interior coating of a solid stationary
phase (5% phenyl-, 95% dimethylsiloxane
polymer). This 0.25 mm diameter column
is referred to as a capillary column. This
particular column is used for semivolatile,
non-polar organic compounds such as the
PAHs we will look at. The compounds
must me in an organic solvent.
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The capillary column is held in an oven that can
be programmed to increase the temperature
gradually (or in GC terms, ramped). this helps
our separation. As the temperature increases,
those compounds that have low boiling points
elute from the column sooner than those that
have higher boiling points. Therefore, there are
actually two distinct separating forces,
temperature and stationary phase interactions
mentioned previously.
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As the compounds are separated, they elute
from the column and enter a detector. The
detector is capable of creating an electronic
signal whenever the presence of a compound is
detected. The greater the concentration in the
sample, the bigger the signal. The signal is then
processed by a computer. The time from when
the injection is made (time zero) to when elution
occurs is referred to as the retention time (RT).
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While the instrument runs, the computer generates a
graph from the signal. (See figure 1). This graph is called
a chromatogram. Each of the peaks in the
chromatogram represents the signal created when a
compound elutes from the GC column into the detector.
The x-axis shows the RT, and the y-axis shows the
intensity (abundence) of the signal. In Figure 1, there are
several peaks labeled with their RTs. Each peak
represents an individual compound that was separated
from a sample mixture. The peak at 4.97 minutes is from
dodecane, the peak at 6.36 minutes is from biphenyl, the
peak at 7.64 minutes is from chlorobiphenyl, and the
peak at 9.41 minutes is from hexadecanoic acid methyl
ester.
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Figure 1: Chromatogram generated by a GC.
If the GC conditions (oven temperature ramp,
column type, etc.) are the same, a given
compound will always exit (elute) from the
column at nearly the same RT. By knowing the
RT for a given compound, we can make some
assumptions about the identity of the compound.
However, compounds that have similar
properties often have the same retention times.
Therefore, more information is usually required
before an analytic al chemist can make an
identification of a compound in a sample
containing unknown components.
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Mass Spectroscopy
As the individual compounds elute from the GC
column, they enter the electron ionization (mass
spec) detector. There, they are bombarded with
a stream of electrons causing them to break
apart into fragments. These fragments can be
large or small pieces of the original molecules.
The fragments are actually charged ions with a
certain mass. The mass of the fragment divided
by the charge is called the mass to charge ratio
(M/Z). Since most fragments have a charge of
+1, the M/Z usually represents the molecular
weight of the fragment.
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A group of 4 electromagnets (called a quadrapole,
focuses each of the fragments through a slit and into the
detector. The quadropoles are programmed by the
computer to direct only certain M/Z fragments through
the slit. The rest bounce away. The computer has the
quadrapoles cycle through different M/Z's one at a time
until a range of M/Z's are covered. This occurs many
times per second. Each cycle of ranges is referred to as
a scan.
The computer records a graph for each scan. The x-axis
represents the M/Z ratios. The y-axis represents the
signal intensity (abundance) for each of the fragments
detected during the scan. This graph is referred to as a
mass spectrum (see Figure 2).
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Figure 2: Mass-spectrum generated by an MS.
The mass spectrum produced by a given chemical
compound is essentially the same every time. Therefore,
the mass spectrum is essentially a fingerprint for the
molecule. This fingerprint can be used to identify the
compound. The mass spectrum in Figure 2 was
produced by dodecane. The computer on our GC-MS
has a library of spectra that can be used to identify an
unknown chemical in the sample mixture. The library
compares the mass spectrum from a sample component
and compares it to mass spectra in the library. It reports
a list of likely identifications along with the statistical
probability of the match
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GC-MS
When GC is combined with MS, a
powerful analytical tool is created. A
researcher can take an organic solution,
inject it into the instrument, separate the
individual components, and identify each
of them. Furthermore, the researcher can
determine the quantities (concentrations)
of each of the components.
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Figure 3 represents a three-dimensional graph
generated when the GC is combined with the
MS. Try to visualize how the chromatogram
combines with the mass spectrum to produce
this image. It is important for you to be able to
picture this 3D image and translate it into the
previous 2D graphs. (This image is not made
from the same compounds in the previous
figures.) Note that you can create either a mass
spectrum or a chromatogram by making the
appropriate cross section of this 3D image. Try
to visualize which cross section would produce a
spectrum and which would produce a
chromatogram.
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Figure 3: 3D Depiction of GC-MS output
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