1454 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques
for obtaining high-resolution in situ measurements
in near space at relatively low cost. The obvious
limitations are the requirement for a rocket
range where the vehicles can be launched safely and
can impact without danger to either the public or
property, and the relatively short duration of the
measurement.
See also
Electricity, Atmospheric: Ions in the Atmosphere.
Ionosphere. Observations for Chemistry (In Situ):
Chemiluminescent Techniques; Particles. Optics, At-
mospheric: Airglow Instrumentation; Optical Remote
Sensing Instruments. Radar: MST and ST Radars and
Wind Profilers. Satellites: Research (Atmospheric Sci-
ence). Standard Atmosphere. Thermosphere.
OBSERVATIONS FOR CHEMISTRY (IN SITU )
Contents
Chemiluminescent Techniques
Gas Chromatography
Ozone Sondes
Particles
Resonance Fluorescence
Water Vapor Sondes
Chemiluminescent
Techniques
C A Cantrell, National Center for Atmospheric
Research, Boulder, CO, USA
Copyright 2003 Elsevier Science Ltd. All Rights Reserved.
Introduction
There are numerous methods for the detection of gases
in the atmosphere. These include various optical
techniques that are exploited for remote sensing and
in situ observations, as well as application of other
analytical approaches. The techniques discussed here
utilize a property of chemical reactions called chemi-
luminescence. These approaches have been shown to
demonstrate high sensitivity and in some cases high
selectivity. Chemiluminescence-based methods are so
Further Reading
Goldberg RA (1986) Handbook for MAP, vol. 19. Urbana,
IL: SCOSTEP Secretariat, University of Illinois.
Newell HE (1953) High Altitude Rocket Research. New
York: Academic Press.
Pfaff RF, Borovsky JE and Young DT (eds) (1998) Measure-
ment Techniques in Space Plasmas: Fields. Washington,
DC: American Geophysical Union.
Pfaff RF, Borovsky JE and Young DT (eds) (1998) Measure-
ment Techniques in Space Plasmas: Particles. Washing-
ton, DC: American Geophysical Union.
Pfaff RF (1996) In-situ measurement techniques for iono-
spheric research. In: Kohl H, Ruester R and Schlegel K
(eds) Modern Ionospheric Science, pp. 459–551. Katlen-
burg-Lindau: Max-Planck-Institut für Aeronomie.
Wallace HD (1997) Wallops Station and the Creation of an
American Space Program, NASA SP-4311. Washington,
DC: NASA History Office, Office of Policy and Plans.
reliable and sensitive as, in some cases, to be the
standard procedure for quantification of atmospheric
gases. Although some instruments based on chemi-
luminescence have been less successful, they will all be
discussed here. There is also a rich field of investigation
of the phenomenon of chemiluminescence in bio-
logical systems (called bioluminescence) that will not
be addressed in this article. Chemiluminescence has
been applied to a wide array of scientific endeavors. Its
application to the quantification of atmospheric gases
is the present subject.
General Principles of
Chemiluminescence
Chemical reactions that proceed at a significant rate
are exothermic. In other words, energy is released
when the reaction occurs. Often the energy is mani-
fested as translational (movement) or vibrational
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques 1455

(bond stretching or bending) action in the reaction
products, which can be observed as heating. The
opposite of exothermic reactions are endothermic
reactions. These reactions require added energy to
proceed; often this energy comes from the bath gas
(neutral, nonreacting species) or some other source.
The amount of energy released (or absorbed) in a
chemical reaction is readily calculable given the
ground-state energies of the reactants and products
(which are tabulated for many species); the energy
released in a reaction is the difference between the sum
of the energies of the products and the sum of the
energies of the reactants. In extraordinary cases,
enough energy is released in a chemical reaction to
promote products of the reaction into electronically
excited states. Depending on the circumstances, it is
possible for the reaction product then to emit a photon
whose energy corresponds to the difference between
an excited state and the ground state of the molecule.
The wavelengths of these photons correspond to
regions throughout the electronic spectrum, depend-
ing on the exothermicity of the reaction, the nature of
the products, and the location of energy states
of the reaction products; the most useful spectral
regions for trace-gas quantification are the near-
infrared, visible, or near-ultraviolet. Competing with
the emission of radiation by the excited product are
processes of vibrational relaxation, quenching, and
energy transfer. Thus an extremely exothermic reac-
tion does not necessarily have a large chemilumines-
cence yield.
Chemiluminescence is quite analogous to fluores-
cence and phosphorescence, which describe the emis-
sion of photons from species that have been excited by
absorption of photons. The difference in chemilumi-
nescence is that the species are chemically excited:
promoted to excited states through chemical reaction.
Since the only source of photons is chemiluminescence,
the background for chemiluminescent systems is, in
principle, very low. In practice, there are extraneous
sources of light, but appropriate zeroing techniques
can take these into account. The energetics of chemical
reactions that involve chemiluminescence are shown
schematically in Figure 1. The figure portrays progres-
sion of the chemical reaction from reactants to
products with the release of energy ðDEÞ that can be
imparted to the bath gas through collisions, distributed
throughout the molecule through internal processes,
or (more rarely) lead to emission of a photon.
Photons emitted from chemiluminescent reactions
are most often detected by photomultiplier tubes.
These devices convert photons into electric current
with considerable amplification (4106 electrons per
incident photon). Other light-sensitive devices such as
phototubes, photoconductive devices, and photo-
diodes can also be used depending on the application,
but the high sensitivity of photomultiplier tubes favors
their use.

Collisional Light
deactivation emission
h

Excited state

∆E
Energy

Ground state

Reactants Products

Progress of reaction, or reaction coordinate

Figure 1 A schematic diagram of the energetics of a chemical reaction that could result in chemiluminescence. The reactants come
together and react; this might involve proceeding over an energy barrier; progression into an energy well that possesses various energy
states above the well bottom; and finally formation of the reaction products, which are also characterized by excited energy states. The
energy of the reaction ðDE Þ is distributed in one or more of the products, and can then be transferred to the bath gas through collisions
(collisional deactivation), converted into other energy states of the molecule through internal processes, and/or released through emission
of a photon.
1456 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques

The intensity of light detected in a chemilumines-
cent reaction depends on several factors, included in
eqn [1].
d½X

ICL ¼ FCL FE FD
dt
The terms in eqn [1] each control the rate of produc-
tion of photons (ICL ). The first is the rate of reaction of
the species to be measured, X, which is represented as a
derivative, d½X
=dt, describing the number of mole-
cules of X per unit volume reacting per unit time. The
next term is the chemiluminescence yield ðFCL Þ; this is
the fraction of product species that are produced in an
excited state that are capable of emitting photons. FE
is the fraction of excited state product species that emit
photons; the balance ð1  FE Þ is lost through collis-
ional quenching. This may be viewed as a kinetic
competition between the photon emission and these
‘dark’ pathways. An additional factor is the fraction of
photons that are detected ðFD Þ, which depends on the
geometry of the chamber in which the chemistry takes
place, the relative size and location of the detector, and
the efficiency of the detector at the wavelength of the
photons of interest. This factor can be increased (in
principle) through the use of sensors with large active
areas and the coating of reaction chambers with highly
reflective surfaces. The rate of molecules reacting per
unit time within the reaction chamber can be increased
through larger flow rates. Of course, this implies the
use of larger pumps; clearly, a compromise must be
reached given weight and size limitations. A generic
chemiluminescence detector is shown in Figure 2. It
consists of a reaction chamber to which a light detector
is attached. The detector views the chamber through a
window or optical filter; a filter may allow discrimi-
nation between photons originating from the reaction
of X and those from other sources. Ambient air
½1

containing the species to be measured is mixed with
the reagent gas, enters the reaction chamber, and is
pumped away. The reaction chamber can be main-
tained at an optimum pressure (to reduce quenching)
through the use of a limiting orifice at the air sample
inlet, a pressure-controllable valve, and a vacuum
pump. Standard electronics convert the signal from the
detector to a measurable electric current or series of
electrical pulses that can be counted.
Now that the concepts of chemiluminescence have
been described in general terms, specific applications
to the measurement of atmospheric gases will be
addressed. The discussion that follows has been
divided into chemiluminescence involving reactions
between gas-phase species and those involving the
interaction of gas-phase species with a liquid or solid
surface. In each group, several examples are put
forward to demonstrate the range of possibilities for
which chemiluminescence may be applied.
Gas-Phase Chemiluminescence
When the reactants (including the analyte species as
well as added reagents) and products of a chemilumi-
nescent reaction are in the gas phase, the application to
measurement of atmospheric gas-phase species is
obvious and straightforward. An atmospheric sample

Inlet
Atmospheric Reagent
sample source
Reaction chamber has
reflective coating

Photomultiplier Reaction chamber

at reduced Pressure
tube
Window or pressure control
filter valve

Detector Pump
electronics

Figure 2 A schematic diagram of a generic chemiluminescence instrument. An atmospheric sample containing the species of interest is
sampled either directly from the atmosphere or from the output of a gas chromatograph. The sample is mixed with one or more reagent
gases and then enters a reaction volume. The gas mixture is pumped away. The photons from the chemiluminescent reaction are detected
by some type of light detector (usually a photomultiplier tube) that converts the energy of the photons into an electrical signal. The detector
may observe the reaction chamber through a window or an optical filter to select a specified spectral region. Often the reaction chamber is
equipped with a reflective coating to maximize collection of emitted photons.
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques
is mixed with one or more gas-phase reagent(s) and the
resulting chemiluminescent photons are quantified.
The relationship between the detected signal and the
trace gas concentration, or mixing ratio, is determined
through calibration procedures that involve the addi-
tion of a known quantity of the gas of interest.
NO1O3
An example of a commonly employed gas-phase
chemiluminescent system is the reaction of nitric
oxide (NO) with ozone (O3), through which either
NO or O3 may be quantified. For measurement of NO,
ozone produced by the corona discharge of oxygen is
added as the reagent to an atmospheric sample;
maximum ozone concentrations produced by this
method are typically of order 5%. For measurement of
O3 , pure NO is added as the reagent. Nitrogen dioxide
(NO2) is produced in an excited state that is not fully
characterized because of the complex spectroscopy of
NO2; the state can emit photons at wavelengths
greater than about 590 nm. FCL for this system is only
a few percent; in spite of this, mixing ratios of NO of a
few parts per trillion by volume (pptv) with integration
times of only a few seconds have been determined with
this system. Other nitrogen compounds can also be
determined through the use of photolytic and catalytic
converters that change these species into NO before
entry into the reaction chamber. Photolysis in the
ultraviolet-A spectral region has been used to convert
NO2 into NO for measurement; unfortunately, this
conversion efficiency is less than 100%, so it must be
routinely checked and accounted for. The catalytic
conversion of a wide range of nitrogen compounds on
a heated gold surface in the presence of carbon
monoxide (CO) or hydrogen (H2) has been used to
determine the total reactive nitrogen concentration,
which is often termed NOy . This catalyst effectively
converts NO2 , HNO3 , alkyl nitrates, and peroxy acyl
nitrates to NO; other species containing nitrogen, such
as NH3 , N2O, HCN, and N2 , are not typically
converted with high efficiencies. Other catalysts,
such as FeSO4 , molybdenum, carbon and silver, have
been used with varying degrees of success.
O31Olefins
Another chemiluminescent system commonly used for
atmospheric analysis is the reaction of ozone with
olefins. The attack on double bonds by ozone is
extremely complex and has been the subject of
numerous investigations. The reaction appears to
proceed through the poorly understood Criegee birad-
icals, which are species of the form R1R2COO. A
carbonyl compound is also formed. In the case of
terminal olefins, it appears that excited formaldehyde
1457
(CH2O) may be formed. Emission of photons between
300 and 600 nm has been observed for a number of
short-chain terminal olefins. Emission from vibration-
ally excited hydroxyl radicals (OH) has also been
observed. The ozone–olefin system has been used to
quantify ozone via the reaction with ethene, and
to quantify olefins including isoprene (C5H8). The
chemiluminescent reaction of ozone with other hy-
drocarbons (alkanes and aromatics) has been studied,
and has been shown to possess high sensitivity, but its
use is not widespread.
Metal Carbonyls1O3
Nickel tetracarbonyl (Ni(CO)4) and iron pentacar-
bonyl (Fe(CO)5) yield chemiluminescence in their
reaction with ozone. It is thought that the neutral
metal atom, formed from unknown processes, reacts
to yield the metal oxide in an excited state. For
example, the reaction of nickel is as shown in eqn [I].
Ni þ O3 ! NiOn þ O2 ½I

It appears that nickel atoms can also be regenerated by
the reaction of NiO with ozone. NiO and FeO emit in
different spectral regions, so analytical techniques can
be developed that are specific to each. The chemilu-
minescence of nickel carbonyl with ozone has been
used to monitor the workspace of nickel-refining
plants.
Hydrides1O3
Hydrides of phosphorus (PH3), arsenic (AsH3), sele-
nium (SeH3), antimony (SbH3), silica (SiH4), tin
(SnH4), and boron (BH3) have been detected through
their chemiluminescence with ozone. It appears that
the key step in each case involves the neutral atom,
formed from unknown processes, reacting with ozone
to yield the oxide in an excited state. The reaction for
arsenic is shown in eqn [II].
As þ O3 ! AsOn þ O2 ½II

The emitting species in each case is not known
with certainty and may actually involve multiple
species. The total chemiluminescence intensity in
each case shows good linearity with the gas-phase
concentration, which makes these phenomena
useful for monitoring of these species in the workplace
and elsewhere. The fact that all of these hydrides
yield chemiluminescence signals makes their quanti-
fication in complex mixtures of several hydrides
difficult.
Fluorine1Reduced Sulfur Compounds
Molecular fluorine reacts with organic sulfur com-
pounds such as methyl mercaptan (CH3S), dimethyl
1458 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques
sulfide ((CH3)2S), carbon disulfide (CS2), and their
longer-chained homologs to yield chemiluminescence.
The emitting species include HF, CH2S, HCF, and FCS.
The mechanism is complex and poorly understood,
but appears to involve attack of F2 on the sulfur
compound as a fundamental step. Fluorine atoms may
subsequently be formed, but are not critical in the
initiation of the chemistry. This system has achieved
particular use as a gas chromatographic detector, but
recently has been superseded by ozone-induced chemi-
luminescence in a flame. Chemiluminescence also
occurs in the reaction of F2 with organic selenium and
tellurium compounds, but these are not expected to be
very abundant in the atmosphere.
Reactions of Atoms
Oxygen, nitrogen, hydrogen, and halogen atoms are
very effective as reactants in chemiluminescent reac-
tions. These have mostly been used for detection of
species in laboratory studies of gas-phase reactions,
but they could be applied, in principle, to quantifica-
tion of atmospheric trace gases. Many of these
reactions also occur in the atmosphere and lead to
observations of atmospheric ‘airglow’.
Finally in this section we describe chemical reac-
tions in flames that are chemiluminescent and that
have been exploited for the analysis of atmospheric
species. The principles are the same as for room-
temperature chemiluminescence, except that meta-
stable reactants and atoms are more readily exploited.
Often the flame-based detector is used as part of
a gas chromatographic system.
Sulfur
Sulfur compounds that are introduced into a reducing
flame lead to blue emission attributed to the combi-
nation of sulfur atoms leading to excited S2. Spectral
analysis reveals a series of emission bands from 250 to
600 nm. This system has good sensitivity and has
found widespread use, but suffers from the disadvan-
tage that the signal is proportional to the square of the
sulfur concentration ([S]2). The addition of ozone to
the flame results in intense chemiluminescence that has
been attributed to reactions [III] and [IV]; the chemi-
luminescence in this case is proportional to the sulfur
concentration.
SO þ O3 ! SOn2 þ O2 ½III

SOn2 ! SO2 þ hn ½IV

By adjusting the flame conditions, conversion of a
wide variety of sulfur compounds to SO with reason-
able efficiency is possible. It has been used for total
sulfur measurement and also as a detector in gas
chromatographic systems.
A wide variety of trace gas species from a number of
chemical families have been successfully measured
using the technique of gas-phase chemiluminescence.
The next section describes the use of multiphase
systems to measure gas-phase species.
Liquid-Phase and Solid-Phase
Chemiluminescence
Quantification of atmospheric trace gases has been
made through the gas–surface reaction of a species of
interest with a liquid or solid of the appropriate
composition. The chemiluminescent photons are then
emitted from the interface of the gas and the con-
densed phase. Alternatively, the gas-phase species can
be adsorbed into a solution (with or without chemical
reaction), which can then be mixed with the appro-
priate reagents to lead to chemiluminescence entirely
within the condensed phase. The mixing can be
accomplished in a batch or flow mode, with the latter
approach more common and generally more useful.
The description of the instrumentation for these
systems is as described earlier, with perhaps more
complexity in the sampling system. Several examples
of the application of liquid-phase chemiluminescence
are given next, followed by demonstrations of the use
of solid-phase chemiluminescence.
Luminol
Luminol (5-amino-2,3-dihydrophthalazine-1,4-dione)
has been studied for decades and has proved to be
quite versatile for quantitative analysis of several
atmospheric species. It is exploited by exposing
luminol to various oxidizing systems that lead to
conversion of luminol to an aminodiphthalate ion
with concomitant production of molecular nitrogen
and photons in the blue region.
O
CO2−
NH
+ Oxidant +N2 + h

NH
CO2−
NH2 O NH2
½V

Gas-phase hydrogen peroxide (H2O2) and hydrogen
peroxide in fog and rainwater have been quantified
using luminol chemiluminescence. The reaction re-
quires a basic solution and a transition metal (usually
copper) catalyst, but it suffers from reduced sensitivity
if manganese or iron is present. Nitrogen dioxide
(NO2) in air samples has also been measured using
luminol. Here the solution is also basic but must be
free of metal ions. Interference from ozone can be
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Chemiluminescent Techniques
reduced (although not eliminated) by addition of
sulfite salts to the solution. Peroxyacetyl nitrate (PAN)
also produces chemiluminescence. This is been ex-
ploited to measure NO2 and PAN-like compounds as a
detector in a capillary gas chromatographic system. A
disadvantage of luminol detection of NO2 is that the
light emission depends on the square of the NO2
concentration, at least up to the point at which the
solution is saturated with NO2 (aqueous). This can be
overcome in part by the addition of a known, stable
amount of NO2 to the ambient air flow. Other organic
reactants leading to chemiluminescence similar to that
of luminol have found some success, including
lucigenin and lophine.
Oxylates
H2O2 oxidizes peroxylate and bis(2,4,5-trichloro-6-
phenyl)oxylate (TCPO) to form an excited di-
oxetanedione. The chemiluminescence is transmitted
to perylene, which then fluoresces. This is referred to
as indirect chemiluminescence. This system is very
efficient and shows no interference from metal ions
or ozone. Nitrite, sulfite and formaldehyde show
slight negative interference. The combinations of
peroxyoxylate and Rhodamine B, of bis[4-nitro-2-
3,6,9-trioxadecyloxycarbanyl)phenyl]oxylate and sulfo-
rhodamine 101, and of 1,1 0 -oxalyldiimidazole (ODI)
and 3-aminofluoranthene have also been used for the
sensitive quantification of hydrogen peroxide. Indeed,
a wide range of substituted oxylates have been studied,
which possess varying chemiluminescence efficiencies.
One of the most challenging aspects of atmospheric
H2O2 measurement is the potential problem of arti-
facts produced in the interaction of ozone with water.
The use of wetted glass coils appears to be the best
solution.
Permanganate
Sulfur dioxide can be quantified by the chemilumines-
cence produced in the aqueous phase oxidation by
potassium permanganate (KMnO4). It appears to be
straightforward, but comparisons with other tech-
niques have revealed significant differences. Gas-
phase SO2 can be collected into aqueous solution or
onto tetrachloromercurate-impregnated filters before
exposure to the permanganate.
Chlorine and Ammonia
Molecular chlorine (Cl2) and ammonia react in a basic
medium to produce chemiluminescence from 500 to
800 nm, peaking at 690 nm. The method is not
particularly sensitive (detection limit of 7 ppb NH3),
but can be applied to the detection of ammonia or
1459
chlorine. H2O2 interferes somewhat in the measure-
ment of ammonia, but this depends on the solution pH
and thus the interference can be minimized. Fluores-
cence experiments indicate that the emitting species
may be NH2Cl, but this is not certain. Similar
chemiluminescence that is centered at 850 nm is seen
in the reaction between molecular bromine (Br2) and
ammonia.
Other Liquid-Phase Chemiluminescence Systems
Ozone reacts in a number of systems to produce
chemiluminescence, including aldehydes, particularly
aromatic ones, polyphenols, fluorescein, umbellifer-
one, luminol, acridine, and acridone, although there
has been little if any work to use these for the
quantification of atmospheric ozone. Singlet molecu-
lar oxygen has also been shown to yield chemilumi-
nescence in a number of reacting systems, but the
exploitation of these systems in the application of
quantification of atmospheric species has not yet been
reported.
Solid-Phase Chemiluminescence
A number of systems have been reported that produce
chemiluminescence in which one of the reactants is in
the solid phase. These include the oxidation of
siloxene and white phosphorus. However, the appli-
cation to measurement of atmospheric species is
limited to the reaction of ozone with Rhodamine-B
dye supported on silica gel. This method is sensitive
but suffers from problems of calibration instability,
and perhaps unacceptable interference from other
atmospheric species.
Conclusions
Chemiluminescence-based detection of atmospheric
trace gases has been critical in improving our under-
standing of their distribution and fluxes. Gas-phase
chemiluminescence has been shown to be the most
useful and reliable, but liquid and solid phase systems
have been used with some success. Chemilumines-
cence has proved to be so useful because it is sensitive
and in many cases highly selective, but it is not
universally applicable because of the requirement that
the energy released in a chemical reaction must be
manifest as emission of photons. Interferences and
nonlinear behavior can complicate some chemilumi-
nescence systems. The possibility certainly exists for
development of new detection schemes based on
chemiluminescence to be applied to the detection of
atmospheric gases.
1460 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Gas Chromatography
See also
Chemistry of the Atmosphere: Gas Phase Reactions.
Observations for Chemistry (In Situ): Gas Chromatog-
raphy. Optics, Atmospheric: Airglow Instrumentation.
Ozone: Photochemistry of Ozone. Stratospheric Chem-
istry and Composition: Overview.
Further Reading
Birks JW (ed.) (1988) Chemiluminescence and Photochemical
Reaction Detection in Chromatography. New York: VCH.
Burr JG (ed.) (1985) Chemi- and Bioluminescence. New
York: Marcel Dekker.
Cornier MJ, Hercules DM and Lee J (eds) (1973) Chemilu-
minescence and Bioluminescence. New York: Plenum
Press.
DeLuca MA and McElroy WD (1981) Bioluminescence and
Chemiluminscence: Basic Chemistry and Analytical Ap-
plications. New York: Academic Press.
Fontijn A (ed.) (1985) Gas Phase Chemiluminescence and
Chemiionization. New York: North Holland Physics
Publishing.
Gas Chromatography
A C Lewis, University of Leeds, Leeds, UK
Copyright 2003 Elsevier Science Ltd. All Rights Reserved.
Introduction
The measurement of biogenic and anthropogenic
organic species in the atmosphere is a key area in air
chemistry research. Nearest to the Earth’s surface,
within the boundary layer of the troposphere, the
determination of reactive hydrocarbon species is
important because of their ability to interact rapidly
with NOx in the presence of sunlight to form
photochemical smog. At the other extreme, in the
stratosphere, remote measurements of very long-lived
halogenated species are required because of their
critical impact on ozone destruction. In addition,
other stable molecules such as methane, present
throughout the atmosphere, have importance as
greenhouse gases and influence global climate and
temperature change.
The wide range of both short-lived and long-lived
species that are of interest in atmospheric science,
coupled to extremely low concentrations and a
requirement often for in situ automated analysis, has
lead to the development of many novel chromato-
graphic techniques and methodologies. While some
atmospheric species, such as organic acids, peroxides,
Garcı́a-Campaña AM and Baeyans WRG (eds) (2001)
Chemiluminescence in Analytical Chemistry. New York:
Marcel Dekker.
Kricka LJ (1984) Analytical Applications of Biolumines-
cence and Chemiluminescence. London: Academic
Press.
Navas MJ, Jiménez AM and Galán G (1997) Air
analysis: determination of nitrogen compounds by
chemiluminescence. Atmospheric Environment 31:
3603–3608.
Ridley BA (1978) Measurements of minor constituents in the
stratosphere by chemiluminescence. Atmospheric Tech-
nology 9: 27–34.
Sievers RE (1995) Selective Detectors: Environmental,
Industrial, and Biomedical Applications. New York:
Wiley.
Stanley PE and Kricka LJ (1991) Bioluminescence and
Chemiluminescence: Current Status. New York: Wiley.
Van Dyke K (1985) Bioluminescence and Chemilumines-
cence: Instruments and Applications. Boca Raton, FL:
CRC Press.
Web page: http://www.shsu.edu/~chm_tgc/chemilumdir/
chemiluminescence2.html
and aldehydes, are measured using high-performance
liquid chromatography (HPLC), the majority of
organic species are analyzed using capillary gas
chromatography (GC). The diversity of compounds
that are of interest has resulted in almost every kind of
analytical detector finding a role within atmospheric
analysis by gas chromatography.
This article deals only with the analysis of species
found in the gas phase; many organic compounds
present in the atmosphere are bound to particles or are
in aerosol form (polycyclic aromatics compounds,
polychlorinated biphenyls, dioxins, etc). A vast
number of methodologies exist for the analysis of
these species, although, in common with many gas-
phase species, gas chromatography with mass spectro-
metry (GC-MS) is the core methodology used in their
analysis.
The range of techniques that are in use is so broad
that a complete review of analytical methods is
impractical. Many individual methods, however,
have common components or key procedural steps
and these will be discussed. A general outline of a
typical atmospheric determination can be broken
down into sample acquisition, preparation, separa-
tion, and detection, with the first two stages of
acquisition and preparation often proving the most
challenging. A number of chromatograms obtained
from atmospheric analysis are also presented.