Symposium

From the chemistry of responsibile environmentalism

to environmentally responsible chemistry

The Environmental Chemistry of Trace Atmospheric Gases

William C. Trogler
University of California, San Diego, La Jolla, CA 92093-0358
Concentrations and Lifetimes
of Trace Atmospheric Gases
Excluding water vapor, about 99.93% of the Earth's atmosphere consists of nitrogen, oxygen, and argon. Human activities, called anthropogenic, do not s d l c a n t l y perturb the concentrations of these species. The situation is different for trace
components ofthe atmosphere. Anthropogenic emissions have
noticeably increased theconcentration of several trace gases,
which were set a t a steadv state bv natural formation-dest~ction cycles. Air samples ;an be obtained from bubbles trapped
in glacial ice from the Antarctica or Greenland. Yearly bands
are visible in cores drilled out of the ice, because of the annual
surface thawing and refreezing. This provides an atmospheric
time record that spans over 150,000years. Within the past 100
years, the average concentration of methane in the atmosphere has nearly doubled, and that of carbon dioxide has increased by about 20% (1).New compounds, such as chlorofluorocarbons (CFCs), did not exist 100 years ago but now
make up about 3 ppbv (part per billion by volume) of the atmosphere. For many trace gases, concentrations have increased a t unprecedented rates. The effectof such increases on
the Earth's climate and ecosystem is an area of active scientific
study and political concern.
In studying issues related to the environment, i t is important to separate scientific fact from hypothesis. The
chemical composition and changes in the concentrations of
atmospheric gases can be measured with high precision. I t
is difficult, however, to predict quantitatively how these

changes will alter the climate and ecosystem. In the popnlar press, environmental debates often intermingle scientific facts with hypotheses. This clouds objectivity Facts
can also be presented in different ways. For example, one
person might argue that a species present a t only 1ppbv is
of little significance. On the other hand, another individual
might emphasize that a liter of air you breathe a t sea level
contains 27 trillion molecules of a 1ppbv component. Some
key facts about important trace atmospheric constituents
appear i n Table 1.
Concentrations for atmospheric species are tabulated on
a per volume basis i n a dimensionless unit, which is called
the mixing ratio. For long-lived atmospheric components,
the mixine ratio remains constant. even thoueh the oressure decreases with increasing altitude in the troposphere.
The troposphere is the region 0-15 km above the Earth's
surface; i t contains about 85% of the atmosphere's mass.
Above the troposphere the mixing ratios of gases change,
depending on photo-decomposition eff~ciencies,a s the flux
of high energy ultraviolet radiation increases. The average
atmospheric lifetime (or residence time) given in Table 1
reflects the average time spent in the atmosphere by a n
individual molecule. I t can be calculated from the atmospheric concentration of a compound divided by its estimated rate of supply Atmospheric lifetimes are extremely
important because they represent how long i t takes to restore a perturbed atmospheric concentration.

Volume 72 Number 11 November 1995

973

Table 1. Trace Atmospheric Species of EnvironmentalConcern ( 1 4 , 13.

wavelength (or 625 em-'), which lies i n the

infrared spectral region. Greenhouse warmConstituent
Avg. Concentration Avg. Atmospheric Rate of increase
ing occurs because the atmosphere transmits
(PP~V)
Residence Time
per Year
visible and ultraviolet light that the surface
absorbs,
but the greenhouse gases trap much
2600
ppbv/yr
COz (carbon dioxide) 355.000
5&2W yr
of the infrared radiation emanated from the
CH4 (methane)
1.700
10 yr
1&13 ppbvlyr
surface. Without the greenhouse effect, the
0.6-0.9 ppbvlyr Earth would likely be below 0 OC, and most
N 2 0 (nitrous oxide)
310
150 yr
-0.05
3 (per Ci atom)
6C-150 yr
water would exist as ice.
CFCs (avg.)
The main constituents of the dry atmos-0.017
0.484
130 yr
CCi2Fz (CFC-12)
phere (Nz, Oz, and Ar) are either infrared
-0.01
0.28
65 yr
CC13F (CFC-11)
inactive (the N-N a n d 0-0 stretching vi0.001-50
1-3 days
NO,(nitrogen oxides)
brations cannot absorb infrared radiation
0.01-50
14 days
by a n electric dipole allowed process) or do
SO2 (sulfur dioxide)
not Dossess a vibration (Ar). Water vapor i s
the hominant species t h a t absorbs (-8b% of
Developed countries have agreed to phase out CFCs by
thegreenhouseeffect)infraredradiation from the Earth's
1996, because CFCs deplete stratospheric ozone. However,
surface. That i s why night-time cooling occurs rapidly i n
i t will be decades before CFC concentrations i n the stratodry climates (deserts and Antarctica). Besides water, the
sphere will decrease significantly, The reductions in emisinfrared absorbing trace gases (COz, CH4, CFCs, a n d
sions necessary to stabilize atmospheric concentrations a t
NzO) contribute significantly to radiative forcing.
their present values are >60% for COz, 15-20% for methCarbon dioxide is the sewnd most important greenhouse
ane, 1 5 8 5 % for CFC-12, and 70-80% for NzO (2, 3). In
contrast, short-lived species, such a s NO, (refers to reacgas. Numerical studies suggest that it accounts for about 55%
tive oxides of nitrogen, such a s NO, NOz, NOa, and NzOd
of the increased radiative forcing by anthropogenic emissions
and SOz, are unlikely to become unbalanced on a global
to the atmosphere (2,3). It has two vibrations nu(OCO bendscale because they are removed rapidly from the atmosing) and &+(OCO asymmetric stretch) capable of directly
phere by oxidation and rain out. I n this case the deposited
absorbing infrared radiatiou, whereas Zg+ (OCO symmetric
secondary products, nitric acid and sulfuric acid, may
stretch) is inactive. Molecules of higher complexity and lower
cause regional imbalances in sensitive ecosystems. So, alsymmetry possess more vibrations that are capable of abthough anthropogenic emissions of NO, and SOz are large,
sorbing infrared radiation. The relative absorbing strength
elevated atmospheric concentrations only occur locally
averaged over a given atmospheric lifetime is given by the
near their sources (e.g., cities).
global warming parameter (GWP). These parameters are
normalized to COz with a GWP of 1.Values for selected trace
The Greenhouse Effect
gases are given in Table 2. The net wntribution to global
A p1ant.t'~atmosphere plays an important role in deterwarming depends on the product of the GWP and the amount
minine its sutiare temperature. Scattermg of solar mdiaof anthropogenic emissions for a specific gas. These values
tiou by atmospheric gaHes and clouds decreases the energy
appear in the last column of Table 2.
flux to a planet's surface. The fraction of solar radiation
The high global warming potential of the CFCs reflects
scattered, called the albedo, is 0.29 for Earth. Mars, whose
surface atmospheric pressure i s only 5 torr, has a n albedo
their complex molecular structure. They contain low freof 0.15 and Venus (surface pressure of 92 atm) has an alquency vibrational modes that absorb infrared radiation i n
bedo of 0.77 (4). If a planet behaves a s blackbody, this rea region where water and COz do not absorb. Nitrous oxide
quires thar the emitted ritdiatlon equals the absorbed solar
lacks a center of symmetry. Unlike COz, all three of its funr:tdia~ionat its equilihr~umsurface temperatun, rT,]. Thls
damental vibrations (n,&+,and Xgt) are infrared absorbobeys the simple relation:
ing. This and the greater intrinsic dipole moment change
for N20 vibrations result in a.GWP 270 times that of COz.
fraction of radiation not
black-body radiative
T h e GWP values have important implications for proscattered by the atmosphere
energy emitted per
grams directed toward the reduction of greenhouse gas
times the solar radiation flux
area
emissions. For example, the removal of one mole of CFC-11
emissions is as effective a s the removal of 3400 moles of
carbon dioxide.
4rr Rp2 s Te4 = aRP2 (1 -Ap)Fs
Table 2. Global Warming Potentials (GWP) Integrated
u
Over a 100-year Period for Key Trace Gases and the
f
Relative Anthropogenic Contributions to the Increased
\disk
area of Earth
surface area
Greenhouse Warming (1-3).
exposed to the Sun
of Earth

The albedo (Ap),Stephen-Boltzmann constant (s), solar

flux(Fa)a t the edge of the la net's atmosphere, and the
planet's radius ( R ~can
) be used to solve for T,,This equation underestimates the surface t e m ~ e r a t u r eof Mars by
onlv 6 K, the Earth's temperature by 32 K, and that of vLnus by 5'00 K.
The enhanced surface warmina- that correlates with the
pressure of a planet's atmosphere is called radiative forcing. I t is also referred to a s thegreenhouse effect. (4).The
effect results from the atmosphere's ability to absorb the
blackbody radiation emitted from a planet's surface. The
peak in the Earth's blackbody emission occurs a t 16 Fm
974

Journal of Chemical Education

Gas
Con
CH,

Major Human Sources

combustion, deforestation
rice fields, cattle, landfills,oil
production
N20
fertilizers, deforestation,nitric
acid and adipic acid synthesis
CFC-11 plastic foam blowing solvent,
electronic circuit board
cleaning solvent
CFC-12 refrigeration compressor fluid

GWP

1
11

Est.
Contribution to
Increase
55%
15%

270

6%

3400

7%

7100

10%

Table 3. Estimated Sources and Sinks of Methane and Nitrous Oxide (3).
Prospects for the Future
-~
- -There is little douht that the concentraMethane
T4 CH4 per y e T ~ i t r & Oxide
s
Tq N per yea?
tions of trace atmospheric gases a r e in- -.
I
- --I Natural Sources
creasing. There i s little douht t h a t these Natural Sources
gases trap infrared radiation and will enhance the greenhouse effect of the Earth's
oceans
atmosphere. Quantitative estimates of the
freshwater
a m o u n t of future greenhouse warming
CHn hvdrate
-. - --have sparked vigorous debate. Tempera- Anthrooooen~c
Sources
/ Anthrooosen~c
Sources
. .
t u r e measurements during this century
agriculture
0.03-3.0
petroleum/gas
70-120
suggest that a warming of about 0.5 OC has
blomass burning
0.2-1 O
.
rlce paddies
20-150
power
plants
0.1-0.3
cattle
flatulence
65-100
occurred, but the scatter i n t h e d a t a i s
combustion engines
0.2-0.6
animal waste
20-30
nearly as large as the estimated increase
sewa e treatment
-25
(2, 3). There is also debate about how one
adipic acid prod.
0.4-0.6
landfifs
20-70
nitrlc acid prod.
0.1-0.3
biomass burning
20-80
measures a n accurate "average" temperature given the Earth's different climates.
Experiments have been proposed to obtain
atmospheric oxdn
450-520
stratospheric removal
7-13
average global oceanic temperatures by
so11removal
545
-- - 1measuring the way sound waves propagate
across the oceans (5-8).
28-37
Net Atmospheric Increase
3-4.5
Net Atmospheric Increase
.Without conclusive temperature records,
"1 Tg (termgram) = 10'' g
computer simulations have been used extensively to estimate future global warmdata shwmng a large decrease in methane's atmosphsric
iug. coupled atmosphere-ocean general circulation modgrowth rate in 1992 t 12 I. 'l'hv reason for thts obser\mion is
els (GCM) predict a 1.5-4.5 OC warming if the present at&der debate (13, 14). Much remains to be done i n obtainmospheric COz level doubles during the next 100 years (2,
ing reliable values for global sources and sinks.
3). The are many uncertainties in the parameterized GCM
models, such a s the diff~cultyof modeling cloud processes,
Nitrous Oxide
ocean currents, polar ice sheet melting, coupling to plant
Our specific research interest in nitrous oxide stemmed
growth, and other factors. These models assume a n equifrom using i t to illustrate reaction mechanisms i n a n introlibrium state and the time to reach equilibrium (someductory chemistry course a t UCSD. Measurements of the
times thousands of years in the simulations) remains unamount of NzO entrapped in polar ice show that the global
certain. There are also fundamental uncertainties in COz
concentration of nitrous oxide remained constant a t about
sources and sinks, and new factors continue to he discov285 ppbv until the mid 1700s. Then its concentration inered. Recent estimates of the effect of sulfate aerosol parcreased to 310 pphv a t present (2, 3). The increasing conticles (acid rain particles from SOz pollution) suggest that
centration of atmospheric nitrous oxide (0.2-0.3 %/yr), its
they may increase the local albedo over heavily populated
long atmo;iphcrtc lifetime 1- 150 yr,, its conrrihution ds :I
areas and lead to cooling that will partially counteract the
~ ~ t v m h ~ ,gas
u i etG117'270 , a n d its r d a as a it~;itosphcric
increased greenhouse effect (9, 10). In discussing future
ozone sink make i t a n important trace atmospheric composcenarios with students, i t is important to distinguish facts
nent. The ozone-depleting role of NzO arises from its refrom estimates and hypotheses.
markable atmosnheric stahilitv.
After 3-5 yea& a long-liveri gas emitted a t the Earth's
Global Scale Budgets
surface is t r a n s ~ o r t e dto the s t r a t o s ~ h e r ebv diffusion and
The prediction of future atmospheric concentrations reatmospheric circulation. I t i s important to recognize that
quires a knowledge of all sources and sinks of a given spethe predominance of turbulent mixing prevents appreciacies. When the sources exceed the sinks, then the concenble mass separation of the atmosphere with altitude. Extration should increase. The global budget for CFCs is
perimental proof for this has been obtained by the measdefined accurately because their sources derive only from
u r e m e n t of t i m e s elapsed between t h e emission of
industrial production, which is known well. Atmospheric
radioactive aerosols and gases a t ground level and their
concentrations of CFCs and their trends have also been
detection later in the stratosphere (15). This debunks a
measured accurately. This information has facilitated the
"fact" often cited by talk show hosts and the popular press,
development of treaties limiting CFC emissions, where the
that heavy molecules (like CFCs) can't rise to the stratofuture outcome can be predicted with confidence.
sphere. The only known sinks for NzO are stratospheric
Other trace eases have manv natural and anthropogenic
photolysis (eq 1) and reaction with oxygen atoms (eq 2)
sources and sinks. Predicting [he net concrntrdtior;rl;Age
that are produced in the stratosphere by 0 3 and Oz phofrom the hudmt d e ~ e n d son calculating m a l l dtfltrencrs
tolysis. About 80% of the stratospheric sink of NzO occurs
between largenumbers, which may notbe well defined. At
by eq 1and the remaining 20% by eq 2 (16, 17). The most
present the carbon dioxide budget is lacking enough sinks,
significant reaction path i s that of eq 2, which produces NO
because its experimentally observed atmospheric concenin the stratosphere. Astratospheric source of NO is importration is increasing slower than expected based on the
tant. Most of the NO, produced in the troposphere cannot
known sources and sinks. I n fact, the growth rate'of COz
reach the stratosphere directly, because of its short lifehas unexpectedly slowed from 2.5 ppmvlyr in 1988 to 0.6
time (Tahle 1).
ppmv a s of 1992 (11).A decrease i n fossil fuel emissions
cannot explain this large change. The nitrous oxide budget
i s uncertain i n both sources and sinks. The methane
budget is only approximately balanced. A summary of the
budgets for NzO and CH4 appears i n Tahle 3. Notice that
the net atmospheric increase of these gases is less than the
estimated ranges for several of the component sources and
sinks. An illustration of the problem is provided by recent
~~~~

11

Volume 72 Number 11 November 1995

975

Nitric oxide is a free radical that catalyzes stratospheric

ozone destruction bv a radical chain mechanism (eqs 3-51
analogous to one of the cycles by which chlorine radicals
(produced by photolysis of CFCs in the stratosphere) deplete ozone (1,2, 4, 15, 18-20),

net

03+NO+02+N02

03+C1+

NO,+O+ N 0 + 0 2

C10+0+ C1+02

03+0 + 202

02+C10

O3+O-t2O2

( 3)

(4)
(5)

Natural sources of NzO primarily arise a s byproducts of

biological nitrification (oxidation of NH4') and denitrification (reduction of N03-) (19, 21-23). Since about 1982, the
sequence of eqs 3-5 was thought to be the main sink
(-60%) for removal of 0 8 in the lower stratosphere (4).
Recent in situ spectroscopic measurements suggest a
lesser role for NO in the lower stratosphere (-20% of the
ozone sink), and a more important role for the peroxy radical HOO (24). The reduced role of NO is due in part to the
mitigating effect that NO and NOz have on the ozone depleting potential of HOO and C10. Nitric oxide intercepts
the peroxy radical by eq 6.
H 0 2 + NO -t OH + NO,
(6)
This short circuits its ozone depleting mechanism (eqs
7-91,
O,+OH+

net

H02+02

(7)

H 0 2 + 0 3 + OH+202

(8)

20, + 30,

(9)

I n the halogen loss cycles for ozone (e.g., eqs 3-51, NOz
can intercept the key intermediate C10 to form stable
ClONOz (chlorine nitrate). This removes chlorine from the
radical forms necessary to cause ozone loss. The coupling
of NO and NOz to the ozone loss mechanisms for oxygen
and chlorine radicals can even lead to a n inverse dependence of ozone loss on the NOx concentration a t low concentrations. Such behavior contributes to formation of the
Antarctic ozone hole. Here the conversion of ClONOz and
NO2 to HN03 is catalyzed by the surfaces of polar stratospheric cloud aerosol particles. This enhances the contribution of stratos~hericchlorine to ozone depletion, a s it
htwmes conven&l into reactive forms, whilethe nitrogen
oxides are conver~edinto Icis reactive HNO3.
Identification of an Industrial Source of Nitrous Oxide
The estimated excess NzO emissions of -1 Tg Nlyr in the
Northern Hemisphere suggested possible industrial
sources, since more industrialized cities lie in the Northern Hemisphere (23). This was puzzling because nitrous
oxide's uses a s a dental anesthetic (laughing gas) and as a
propellant in canned whipping cream were too small to be
significant. I n 1990, we became aware that NzO is produced a s a byproduct from the manufacture of adipic acid.
Large amounts of adipic acid are synthesized yearly, primarily a s a component of 6,6-nylon. The imbalance between the estimated atmospheric emissions of NzO in the
two hemispheres, and its role as a greenhouse gas and
ozone depletion agent, led us to study the stoichiometry of
the overall reaction (25). The oxidation of cyclohexanoWcyclohexanone mixtures with 50% nitric acid charged with
VOs-, Cu2+catalysts evolved about 1mole of NzO gas for
each mole of adipic acid isolated. The gas was collected
quantitatively by Toepler pumping, analyzed by infrared
spectroscopy and mass spectrometry, and separated from
NO and COz byproducts. The yearly production of adipic
acid requires that 0.4-0.6 Tg Nlyr are produced by this
process. Since nitrous oxide is a relatively nontoxic natural
atmospheric component, there were no restrictions on its

976

Journal of Chemical Education

emissions. We estimated t h a t most NzO produced by

manufacturing adipic acid escaped to the atmosphere.
These emissions can account for about half the difference
seen in NzO emission rates from the Northern and Southern Hemispheres. Publication of the first large industrial
source of NzO received media coverage. Within two months
worldwide nylon producers voluntarily committed to a
five-year phase out of NzO emissions. The EPAC'GreenNylon" program will meet 10% of the target U S . greenhouse
gas emission reduction goals by placing controls on adipic
acid manufacturing facilities. I t is much more effective to
control NzO emissions (GWP = 270) than COz (GWP = 1).
Summary
The atmospheric chemistry of trace gases illustrates fundamental principles in kinetics, bonding, reaction mechanisms, photochemistry, spectroscopy, and geochemical cycling. Selected topics are useful in introductory chemistry,
analytical chemistry, physical chemistry, and spectroscopy
courses. The rapidly developing aspect of the science can
be used to show how new experiments may contradict earlier ones. The corresponding evolution of hypotheses provides insight into how the scientific process works. Perhaps most important, this approach relates fundamental
chemical facts and concepts to environmental issues of
widespread interest. Students readily participate in class
debates about what should be done (if anything) about the
increasing atmospheric concentrations of trace gases.
Acknowledgment
I thank the undergraduate students in introductory
chemistry a t UCSD, whose lack pf enthusiasm for kinetics
motivated me to make the topic more appealing with a n
atmospheric approach. The National Science Foundation
is acknowledged for supporting research in my group related to inorganic atmospheric problems.
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