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"Chemistry in the Clouds" by: Dana E. Bauer (Research/Penn State,
Vol. 18, no. 1 (January, 1997))
Instead of traveling to Antarctica to study the ozone hole,
why not bring Antarctica to Central Pennsylvania?
Penn State graduate students Ed Mereand, Ron MacTaylor, and
John Gilligan do something like that every day, recreating the
Antarctic atmosphere in the comfort of A. Welford
Castleman's chemistry lab.
"We make clouds and we make them cold," Mereand
explains. As cold as -225 degrees Fahrenheit, matching the frigid
winter conditions in the stratosphere a half a dozen miles above
the south pole. To do so, they use a cloud-making machine called
VERA, for Variable Energy Reaction Apparatus.
The machine, spread out over a lab table, is a mass of tanks
and tubes, some wrapped in electrical tape and aluminum foil.
"I know it looks like spaghetti," says Mereand,
"but this is the bare bones." Since it was first
conceived by atmospheric scientists at NOAA, the National Oceanic
and Atmospheric Administration, variations on this type of
machine have been used to make different kinds of ions for more
than 30 years. Where Castleman's is unique, however, is that
it makes water cluster ions: charged ice particles that mimic, on
a minute scale, the shape and composition of polar stratospheric
clouds. Actual cloud particles contain on the order of millions
of molecules. VERA's clusters consist of three to 30
molecules.
The presence of polar stratospheric clouds is key to the
ozone-depleting chemical reactions that take place above the
pole.Each spring, the ozone concentration above Antarctica drops
by about half. But the destruction actually begins in the dark
winter months when polar winds circle Antarctica, forming what
Mereand calls "a leaky beaker in the sky." Air trapped
in the beaker becomes extremely cold during the night.
Temperatures drop low enough to form clouds even in the very dry
stratosphere. These clouds provide the necessary surface for a
series of ion-molecule reactions.
First, inert chlorine compounds, mostly from
chlorofluorocarbons (CFCs) released at ground level,
photochemically react, releasing their chlorine. This, in the
formof chlorine nitrate and hydrochloric acid, dissolves on the
cloud surfaces to form chlorine ions. There, the ions react to
form more active chlorine species. These active molecules
don't destroy ozone immediately, but lie dormant until the
polar night lifts and spring sunshine breaks them down into
aggressive chlorine atoms.
Ordinarily, as Mereand explains, these atoms would be bound up
by nitrogen compounds present in the atmosphere, as part of a
natural atmospheric equilibrium, and returned to an inert state.
Unfortunately, however, the nitrogen compounds are themselves
trapped in an inactive form by the presence of the polar
stratospheric clouds. The combined effect -- immobilization of
the nitrogen compounds and the overabundance of chlorine --
disrupts the critical balance between ozone destruction and
formation.
In the lab, miniature polar stratospheric clouds are created
in a plexiglas tube called a "poor man's ion
source." An electrical discharge zaps water molecules to
form the charged clusters. Helium gas cools them down. Once
cooled, the clusters flow into what looks like a thermos bottle.
Gaseous chlorine and nitrogen compounds, pumped into the
container through teflon tubes, collide with the water clusters
and react, simulating the beaker in the Antarctic sky.
"We're interested in the reaction rates,"
explains MacTaylor -- in how fast the reactions are taking place.
Adds Castleman, "When cloud particles are present, these
reaction rates change dramatically." Pinning down these
reaction rates and showing how they change will help computer
modellers make larger and more realistic representations of the
upper atmosphere -- and perhaps see how to fix the ozone hole.
Ron MacTaylor and John Gilligan are doctoral students in
chemistry in the Eberly College of Science; Ed Mereand received
his Ph.D. in chemistry in August 1996. Their advisor is A.
Welford Castleman Jr., Ph.D., professor of chemistry, 128 Davey
Lab, University Park, PA 16802; 814-865-7242. This project is
funded by the Atmospheric Sciences Section of the National
Science Foundation.
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