Aerosols from Fossil Fuel Burning
The byproducts of fossil fuel burning are injected into the atmosphere from
both stationary sources, such as factories and powerplants, and mobile sources,
such as motor vehicles. Aerosol particles produced by fossil fuel burning are
concentrated over North America, Europe, China, Japan, India, and other industrialized
regions.
The primary aerosol particles released from fossil fuel burning generally
fall into two categories: (1) soot, and (2) fly ash. Soot is carbonaceous;
it includes both elemental ("black" carbon) and organic compounds.
Soot particles generally belong to the fine particle mode. Fly ash is the non-organic
byproduct of coal burning. Coal contains a lot of residual mineral material,
including clays, shale, sulfides, carbonates, chlorides and various trace metals.
When coal is burned, these parent materials are released unreacted, or thermally
transformed. They take the form of spherical glassy particles in the coarse
particle mode. The combination of soot and fly ash released from coal furnaces
results in a bimodal size distribution of primary aerosol particles. Diesel
engines are the dominant source of soot in some urban environments, but worldwide,
coal burning releases about ten times as much black carbon into the atmosphere
than diesel fuel combustion.
Small spherical soot particles coagulate to form chain-like aggregates. These
irregularly shaped particles have been found to be fractal, and have special
optical properties. The mass median diameter of black carbon in the atmosphere
is very small - between 0.1 and 0.5 µm. In urban air, two size modes can
often be detected, a smaller mode resulting from freshly formed primary aerosol
and a larger mode resulting from coagulation processes. The more remote the
location, the more dominant the larger size mode becomes, reflecting the importance
of coagulation during the aging of carbonaceous aerosol as it is transported
from the site of combustion.
The concentration of organic carbon in aerosol (as opposed to black carbon)
ranges from about 0.6 to 2.6 µg m-3 in rural and remote continental
sites of the United States, with an arithmetic mean of 1.0 µg m-3.
This contrasts with the concentrations found in polluted urban conditions, which
range between about 5 to 35 µg m-3. In the continental United
States, the remote organic carbon aerosol is believed to be about 70% anthropogenic
in origin. In forested tropical regions, similar organic carbon concentrations
(up to 2.6 µg m-3) have been measured in the troposphere, but
these result from the condensation of volatile organic compounds (isoprene,
terpene) released from vegetation.
Particles containing alkanes (saturated hydrocarbons) result both from
fossil fuel combustion and primary biogenic processes (vascular plant waxes,
pollen, etc.). Interestingly, clues about the origin of alkane aerosol are obtained
from the ratio of the concentration of n-alkanes of odd numbers to even
numbers of carbon atoms. Land-based vegetation preferentially releases alkanes
with odd carbon numbers in the C19-C35 range, whereas alkanes of anthropogenic
or marine origin lack such a preference. This parameter is called the Carbon
Preference Index (CPI). Very recently released organic matter can have a
CPI as high as 6-8. The mass mean diameter (MMD) of anthropogenic alkane aerosol
is smaller (0.7-0.9 µm) than the MMD of biogenic alkane aerosol.
The combustion of light organic compounds, such as propane and methane, yields
soot (primary particles), and polycyclic aromatic hydrocarbons (PAH). Benzene
and its homologues are primarily of interest due to their mutagenic and carcinogenic
properties; they are not believed to play an important role in atmospheric processes.
PAHs in aerosol particles are believed to be attached to black carbon, and are
detected in the fine particle mode.