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0422-T0001 Table 1 Some important atmospheric organic species: typical sources, sinks and concentration ranges
Class and Formula Estimated Principal source typesa Principal sinks Typical remote
compound atmospher- mixing ra-
ic tios (ppb)
lifetime
Alkanes
Methane CH4 10 years Microbial natural gas, BB OH, Stratosphere 1.7–1.9
Ethane C2H6 80 days Natural gas, motor vehicles OH 0.2–2
Propane C3H8 17 days LPG, motor vehicles OH 0–1
n-Butane C4H10 6 days Motor vehicles OH 0–0.5
i-Pentane C5H12 4 days Motor vehicles OH 0–0.3
Alkenes
Ethene C2H4 1.7 days Vehicle exhaust, BB, biogenic OH, NO3, O3 0–0.1
Propene C3H6 7 hours Motor vehicles, BB, biogenic OH, NO3, O3 0.01
Isoprene C5H8 1.5 hours Vegetation OH, NO3, O3 0–1
a-Pinene C10H16 3 hours Vegetation OH, NO3, O3 0–1
Alkynes
Ethyne C2H2 24 days Vehicle exhaust, BB OH 0–1
Aromatics
Benzene C6H6 12 days Motor vehicles, solvents OH 0–0.5
Toluene C7H8 2.5 days Motor vehicles, solvents OH 0–0.5
m-Xylene C8H10 0.6 days Motor vehicles, solvents OH 0–0.1
Aldehydes
Formaldehyde HCHO 4 hours HC oxidation, vehicle exhaust, BB OH, NO3, hnn 0.1–0.5
Acetaldehyde CH3CHO 11 hours Vehicle exhaust, HC oxidation, OH, hn 0.1–0.2
biogenic
Ketones
Acetone CH3C(O)CH3 16 days HC oxidation, biogenic OH, hn 0.3–1
Acids
Formic acid HCOOH B1 week HC oxidation, BB, biogenic Scavenging 0–5
Acetic acid CH3COOH B1 week HC oxidation, BB, biogenic Scavenging 0–2
Peroxides
Methyl CH3OOH 2 days HC oxidation Scavenging, OH, hn 0–1
hydroperoxide
Alcohols
Methanol CH3OH 16 days Biogenic, HC oxidation OH 0.4–2.0
Sulfur gas
Dimethyl sulfide CH3SCH3 3 days Oceans OH, NO3 0–200 ppt
a
HC, hydrocarbon; LPG, liquid petroleum gas; BB, biomass burning.
distribution patterns in the atmosphere. Therefore, radicals are formed when ozone (O3) is photolyzed by
direct observations of such patterns play an important sunlight of a particular wavelength range (denoted
role in assessment of emissions and their effect on below as hn) to produce excited ‘‘singlet’’ (O(1D))
atmospheric chemistry. oxygen atoms (eqn [I]).
O3 þ hn ! Oð1 DÞ þ O2 ½I
Hydroxyl Radicals, Atmospheric
Lifetimes, and Ozone Formation These then collide with a water molecule to produce
two hydroxyl free radicals (radical species are here
0422-P0035 Even at relatively low tropospheric mixing ratios indicated by a ‘dot’ ()) (eqn [II]).
(ppbv to pptv levels, Table 1), the high reactivity of
VOCs allows them to play a significant role in Oð1 DÞ þ H2 O ! 2OH ½II
atmospheric chemistry. The main sink of most VOCs
is through photooxidation, initiated typically by The lifetime (t) of a hydrocarbon species RH, as a
reaction with hydroxyl (OH) free radicals. These result of reaction with the hydroxyl radical (eqn [III])
is given by eqn [1], where k is the laboratory highly reactive VOCs and will be photolyzed or
determined reaction rate constant. attacked by OH radicals to produce more peroxy
radicals (Figure 1) and subsequently more ozone.
k
RH þ OH ! products ½III Therefore, under the right conditions, more than one
molecule of ozone is produced for each NMHC
1 oxidized. It is through this cycling of HO2 and NO2
tRHOH ¼ ½1 that VOCs such as NMHCs and other VOCs have an
k½OH
active role in HOx chemistry and in ozone production.
Hydrocarbons, such as the alikeness, which contain In fact, organic compounds can be classified according
C 5 C double bonds, also undergo addition reactions to their atmospheric reactivity and consequently their
with ozone (Table 1). photochemical ozone creation potential.
0422-P0040 Unlike most hydrocarbons, many nonmethane ox- Other major products are organic nitrates, includ- 0422-P0060
ygenated VOC (OVOC) species such as formaldehyde ing peroxyacyl nitrates such as PAN and organic
(HCHO) can be photolyzed throughout the tropo- nitrates (RONO2) (Figure 1). PAN and O3 are major
sphere (Table 1). Their lifetime as a result of photolysis surface level pollutants, especially in urban areas, and
according to eqn [V] is the inverse of the photolysis are responsible for many of the negative consequences
rate constant (JOVOC ) (eqn [2]). for human health and crop damage associated with
photochemical smog. Organic nitrates have substan-
JOVOC
OVOC þ hn ! products ½IV tially longer photochemical lifetimes than NOx and so
can be effective temporary reservoirs, transporting
reactive nitrogen far from the source and effectively
1
tOVOChn ¼ ½2 expanding the spatial influence of the original emis-
JOVOC sions.
0422-P0045 Ozone can be produced as a result of this oxidation The production of tropospheric ozone is balanced 0422-P0065
of ‘‘atmospheric fuels’’ (CO, methane (CH4) and other by in situ photochemical destruction and by dry
VOCs) in the presence of nitrogen oxides and sunlight. deposition at the Earth’s surface. In the continental
The oxidation of a typical VOC is illustrated in Figure boundary layer, especially above forested regions and
1.
0422-P0050 In parts of the atmosphere remote from sources, the
formation of ozone is dominated by the oxidation of VOC
· ·
CO and CH4. Methane reacts with hydroxyl radicals OH, O3, NO3
species oxidize NO to NO2 to produce O3 and Figure 1 Organic radicals and products in the photooxidation of a 0422-F0001
carbonyl molecules. These carbonyls are themselves typical VOC.
in urbanized and industrialized areas (where the level and ambient temperature at cold start. For example,
of biogenic or anthropogenic hydrocarbons can be two-stroke engines of mopeds tend to have the highest
high), similar cycles involving oxidation of VOCs VOC emissions per unit of fuel used, while gasoline
become dominant mechanisms for the photochemical engines equipped with three-way catalysts have rela-
production of O3. Urban ozone generation is most tively low emissions of noncombusted or partly
efficient when the relative proportions are about 7 to 1 combusted gasoline.
VOC to NOx . Because most areas of the world (even in Another important global source is emissions from 0422-P0085
remote areas) the atmospheric ‘‘fuels’’ are readily the combustion of organic material in oxygen-defi-
available, NOx very often the rate-limiting precursor cient fires, or biomass burning. The combustion of
of ozone formation. Biogenic emissions of VOCs are biomass material is a common practice, principally in
often abundant enough to have a critical influence on the tropics during the dry season. Approximately 90%
this ratio, especially in urban–suburban areas, such as of all biomass burning events are thought to be
Atlanta, Georgia in the United States, and must be initiated by human activities; it is done to clear forest
taken into account when regulating emissions with the land for agriculture and grazing, to burn agricultural
goal of reducing tropospheric ozone pollution. by-products and dry savanna grasses, to maintain soil
fertility, for weed control, to discourage insects and
other pests, and in use as fuel for cooking and heating.
Sources and Sinks This burning leads to the emission of methane,
NMHCs, and a variety of partially oxidized organic
0422-P0070 Fossil fuel production, industries, and automobiles all
compounds (Table 1), often consisting of a high
produce VOCs in varying amounts. Anthropogenic
proportion of medium- and high-molecular weight
sources are a major source of VOCs, especially
gases, in addition to carbon monoxide and particulate
hydrocarbons. A recent estimate of anthropogenic
species. Biomass burning accounts for global NMHC
nonmethane VOC emissions indicates a global source
emissions of about 40 Tg y 1.
of about 140 Tg y 1, or (140
106 t y1 ). However,
About 80% of biomass burning is thought to occur 0422-P0090
natural sources make a significantly larger contribu-
in the tropics, with the majority taking place in Africa,
tion to total emissions, with about 1150 Tg y 1 of
South America, and Asia. These emissions contribute
biogenic origin.
significantly to the local and sometimes regional
0422-P0075 Emissions from different types of sources will result
budgets of organic trace gases and the formation of
in varying atmospheric distributions. Motor vehicles
ozone.
are a large source of VOC emissions in the United
States and most of Europe. They are the result of both
exhaust emissions and evaporation of the unburned
fuel (evaporative emissions). Most VOCs are emitted Methane
over continental regions.
Methane is the most abundant hydrocarbon in the 0422-P0095
atmosphere. Its global sources total about 540 Tg y 1,
with about 160 Tg y 1 from natural sources (mostly
Combustion Processes wetlands), and about 380 Tg y 1 from anthropogenic
0422-P0080 The major products of complete combustion of fossil sources (principally fossil fuels, livestock, and rice
fuels are carbon dioxide and water. However, in paddies). Of this, emissions from landfills, tropical
practice, actual combustion processes are less com- swamps, rice fields, biomass burning, and termites
plete. One common reason is lack of oxygen; or the total about 300 Tg y 1. Annual methane destruction
combustion temperature might be low; alternatively rates total about 515 Tg y 1 with approximately
the residence time of the fuel in the burner zone may be 445 Tg by OH oxidation, 40 Tg by loss to the
too short. This incomplete combustion of fossil fuels stratosphere, and 30 Tg by soil absorption. This
leads to emissions of CO and VOCs. Hydrocarbons implies that identified total sources exceed sinks by
can be emitted in a partly oxidized form (e.g., about 20 Tg y 1. However, recent temporal increases
aldehydes) or even in an unoxidized form (e.g., alkanes illustrated in Figure 2, are more consistent with
and aromatics). In addition, new hydrocarbons (e.g., sources exceeding sinks by about 35–40 Tg y 1.
alkenes, alkynes, and aromatics) may be formed by Methane levels began to increase rapidly about 0422-P0100
radical reactions. The more incomplete the reaction is, 1800 and have more than doubled over the past 200
the greater the resultant VOC emissions. Exhaust years (Figure 2) as a consequence of modern industrial,
emissions of VOCs from motor vehicles are strongly agricultural, and residential activities. For example,
dependent on engine type, emission control technol- since about 1800, the number of domestic ruminants
ogy, driving modes (open highway or heavy traffic), (which produce methane by enteric fermentation of
1650
} Antarctica
1450
} Greenland
1050
850
650
1000 1200 1400 1600 1800 2000
Year
0422-F0002 Figure 2 Methane mixing ratios over the last 1000 years as determined from ice cores from Antarctica and Greenland. (Reproduced
from Intergovernmental Panel on Climate Change (IPCC) (1955) Climate Change 1994: Radioactive Forcing of Climate Change and an
Evaluation of the IPCC IS92 Emission Scenarios. Cambridge: Cambridge University Press. 1995.)
biomass burning. They are also formed as secondary Nevertheless, the organic chemical composition of the
products of photochemical gas phase reactions of troposphere is far from adequately characterized and
ozone with alkenes and liquid phase cloud-water the comprehensive determination of tropospheric
reactions. Neither photolysis nor reaction with OH VOC concentrations is still a challenging and evolving
represent a significant sink, but organic acids are field.
quickly removed from the atmosphere by scavenging
out of the gas phase by coming into contact with Sampling Methods
atmospheric water and aerosol particles (Table 1).
In situ instrumentation is often unavailable or 0422-P0150
However, their chemistry is at best highly uncertain.
impractical for use in the field to measure the range
0422-P0130 In general, measurements of organic oxygenated
of VOCs of interest. There are numerous sampling
species in the remote troposphere are extremely sparse techniques, the most popular of which are whole air
and often limited to a few species. However, a large
sampling into a container, and sampling on solid
number of oxygenated organic chemicals, including
adsorbents. The combination of sampling on solid
PAN, alkyl nitrates, acetone, formaldehyde, metha-
adsorbents, followed by solvent extraction and sub-
nol, methylhydroperoxide, acetic acid, and formic
sequent analysis, F for example, by high-pressure
acid, were measured during the October/November
liquid chromatography (HPLC) or gas chromatogra-
1997 NASA SONEX (SASS Ozone and Nitrogen
phy – mass spectrometry (GC–MS) F is the most
Oxide Experiment) mission over the North Atlantic
widely used, but a high incidence of sampling artifacts
region. SONEX revealed that the total atmospheric have hitherto confined them principally to studies in
abundance or these oxygenated species nearly equals
urban areas or studies of indoor pollution, rather than
that of total NMHCs.
clean background conditions. The costly practice of
collecting whole air into evacuated stainless steel
canisters (either at ambient pressure or above, em-
Sampling and Analysis ploying a sampling pump) has proved successful for
the sampling of low- to medium-weight VOCs, par-
0422-P0135 Accurate measurements of the spatial distributions of
ticularly NMHCs and halocarbons, down to very low
VOCs on both a local and global scale can reveal a mixing ratios in air. However, compounds greater than
great deal about the magnitude and distribution of
about C10 are likely to adsorb onto the walls of the
their sources and sinks, and provide essential insights
canister during storage, leading to an underestimation
into the origin of tropospheric ozone. Halocarbon and
of their ambient concentrations.
NMHC gases are useful tracers of anthropogenic and
A substantial number of atmospheric VOCs are 0422-P0155
biogenic emissions, and for characterizing marine
either highly polar (such as aldehydes and ketones) or
boundary layer (MBL) air.
thermally unstable (e.g., PAN). This limits the use of
0422-P0140 With their relatively short atmospheric lifetimes
the conventional sampling techniques described
(Table 1), the number of VOCs that can be found in the above.
atmosphere, often at low but relevant levels (Table 1),
is very substantial. Depending on the measurement Analytical Methods
site, thousands of individual VOCs can be detected in
ambient air. The analysis of such a wide range of Because of the typically low ambient VOC mixing 0422-P0160
compounds requires a variety of different approaches ratios, some kind of preconcentration or sample
and techniques with high separation power or highly enrichment step is needed prior to sample analysis.
specific detection methods. Measurement of any single Most commonly, whole air samples are passed
class of organic compound often presents unique through a cold trap where the VOCs are condensed
problems associated with sampling, standardization, cryogenically, then warmed and flushed from the trap
analysis, and detection. These problems are multiplied to a gas chromatographic (GC) column for separation
when the simultaneous measurement of different of the complex mixture of components. Flame ioniza-
compound classes is desired. tion detection (FID), electron capture detection (ECD)
0422-P0145 There has been tremendous progress in measure- and mass spectrometry (MS) are the most widely used
ment techniques for atmospheric VOCs over the past detection methods whole air samples.
10–15 years, and existing techniques allow measure-
ment of a broad range of VOCs in concentrations
ranging down to a few pptv and even below. VOCs
Distributions
have been measured in a wide variety of atmospheric Trace gas distributions provide information crucial to 0422-P0165
environments, from urban to the most remote loca- establishing the extent of continental influence on the
tions over the tropical oceans and polar regions. chemical environment of the remote troposphere. The
average atmospheric lifetimes of ethane, ethyne, and inputs into computer models of atmospheric chemis-
C2Cl4 are much less than the 1-year average inter- try. Such calculations test our understanding of the fate
hemispheric exchange time. However, they are com- and impact of VOCs on the photochemistry in the
parable to mixing times within a hemisphere (about 2– troposphere.
6 weeks depending on latitude and season). Therefore, Tropospheric O3 has two predominant sources, in 0422-P0180
the NMHCs and C2Cl4 show significant latitudinal, situ photochemical production from its precursors
seasonal, and vertical gradients in the atmosphere. (CO, NMHCs, and NOx ) as outlined above, and
0422-P0170 Because OH, the main sink of VOCs is generated downward mixing from the stratosphere. When com-
photochemically during daylight (see above), the bined with meteorological trajectory analysis, the
strength of this sink varies diurnally and seasonally. contributions of different combinations of VOCs
Minimum OH levels at high latitudes are found in associated with the different source types discussed
winter, resulting in significantly reduced removal rates above enables the use of VOCs as chemical tracers
for many trace gases. In the remote atmosphere, the playing a crucial role in establishing the most likely
most abundant NMHC compounds are the longest- origin of O3-enriched layers. For example, incomplete
lived group of light hydrocarbons (i.e., ethane, ethyne, combustion, including urban fossil fuel use and
and propane). Figure 3 shows sharp latitude gradients biomass burning, is the principal global source of
in ethane and propane, with higher mixing ratios in the ethane (C2H6), and ethyne (C2H2); however, some
Northern Hemisphere during the winter months of gases such as C2Cl4 are specific to industrial/urban
March and December Figure 4 illustrates how these activities, and serve as markers for such urban
same samples fit to a seasonal cycle, with much higher effluents. Biomass burning is an important global
mixing ratios of ethane in the Northern Hemisphere, source of CH3Cl (approximately 25–50%) and mix-
close to the major anthropogenic source regions ing ratios of CH3Cl typically are not elevated in
compared to the maximum ethane levels reached in northern cities (i.e., those that do not rely heavily on
the Southern Hemisphere winter. biomass fuels), consistent with CH3Cl having no
0422-P0175 VOCs have been used in the study of the dynamical significant urban/industrial origins. This makes
structure of such regions as the intertropical conver- CH3Cl a particularly useful diagnostic for biomass
gence zone (ITCZ). The ITCZ is a zone of convective burning emissions.
air near the Equator, which forms a barrier to mixing The most comprehensive speciation, combined with 0422-P0185
between the air of the Northern and Southern Hem- spatial coverage to date has been achieved by sampling
ispheres. In addition, VOCs are useful probes with aboard specially modified aircraft. In particular, the
which to constrain atmospheric concentrations of NASA Global Tropospheric Experiment (GTE) field
OH and atomic chlorine (Cl) radicals. Speciated campaigns have examined specific aspects of the
sources, sinks, and distributions of VOCs are crucial tropospheric ozone budget and have amassed a
ETHANE
2000
1500
1000
500
0
60° 30° 0° −30°−60° 60° 30° 0° −30° −60° 60° 30° 0° −30° −60° 60° 30° 0° −30° −60°
N Latitude S N Latitude S N Latitude S N Latitude S
March June September December
1400
Mixing ratio (pptv)
1200 PROPANE
1000
800
600
400
200
0
60° 30° 0° −30° −60° 60° 30° 0° −30°−60° 60° 30° 0° −30° −60° 60° 30° 0° −30°−60°
N Latitude S N Latitude S N Latitude S N Latitude S
0422-F0003 Figure 3 Latitude distribution of ethene and propane mixing ratios near the surface of the Pacific during March, June, September, and
December for samples collected and analyzed quarterly by the University of California, Irvine between March 1994 and March 1999.
300
because this is the predominant region from which
the surviving gases and aerosols are transported
200
upward into the lower stratosphere. Therefore, un-
derstanding the influence of tropical sources, such as
biomass burning, on the production of O3 is necessary
100
for assessing the impact of tropical fires both on the
global oxidizing capacity of the atmosphere and on the
0
Mar Jun Sep Dec radiative forcing of O3 in the upper troposphere.
It was reported above that burning of the world’s 0422-P0195
0422-F0004 Figure 4 Composite seasonal cycle of average (71SD) ethane forests, grasslands, and agricultural lands has a strong
mixing ratios for high northern (301–711 N) and southern (141– influence on VOC emissions. It therefore affects global
481 S) latitudes for samples collected quarterly by the University of
California, Irvine between March 1994 and March 1999.
atmospheric chemistry and is associated with climate
change. Regional pollution episodes are known to
have a significant impact on South East Asian air
significant database of tropospheric VOC measure- quality. Aircraft investigations such as the NASA GTE
ments, including, NMHCs, dimethyl sulfide, halocar- experiments TRACE-A (Transport and Atmospheric
bons, formaldehyde, methyl peroxide, and acetone Chemistry near the Equator – Atlantic) and PEM-
distributions (see http://www-gte.larc.nasa.gov). Be- Tropics A (Pacific Exploratory Mission – Pacific)
10 CH3Cl
C2Cl4 O3 CO C2H2
8
Altitude (km)
0
0 20 40 60 80 100 0 20 40 60 80 100 120 140
Mixing ratio O3 and CO (ppbv) Mixing ratio C2H2 (pptv)
0422-F0005 Figure 5 Vertical profile through a layer of biomass burning pollution sampled by the NASA DC-8 aircraft near Tahiti on September 5,
1996. Mixing ratios of selected VOCs, CO, and ozone are shown.