UCSD Chemists Find Extraterrestrial “Anomaly” In Earth’s Rocks

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Kim McDonald, kimmcdonald@ucsd.edu, (858) 534-7572

Chemists at the University of California, San Diego have discovered an
isotope anomaly previously thought unique to meteorites and other
extraterrestrial rocks in sulfate minerals on Earth.

The surprising finding, detailed in the July 13 issue of Nature concludes a
decade-long search in terrestrial rocks and sediments for this “anomalous”
oxygen-isotope signature. Such signatures had been detected before in
gases on Earth. But the inability before now to detect this anomaly in
terrestrial solids had forced scientists to conclude that it was unique to
extraterrestrial sources and an exclusive byproduct of nucleosynthesis
in stars.

Its discovery in terrestrial rocks in a form that showed it could be
produced on Earth not only alters ideas among planetary scientists
about the source of this anomaly. It will now give earth scientists and
atmospheric chemists an important new probe to answer questions about
the composition of Earth’s early atmosphere, the atmospheric processes
of ancient volcanic eruptions, past ocean circulation patterns and early
biological productivity.

“It will enable us to understand more about the history of the Earth and
possibly climate on time scales that were out of reach before,” says
Mark H. Thiemens, a professor of chemistry and dean of UCSD’s Division
of Physical Sciences who headed the research effort.

“It opens up this whole new area for geochemists to look at things like
ancient atmospheric deposits,” says Huiming Bao, a geochemist at UCSD
and the first author of the paper. “Once we figure out the fundamental
sulfur-oxidation processes occurring in the atmosphere, it will provide
a good way to understand ancient atmospheric processes.”

Bao initially discovered the “anomalous” signatures — something odd
about variations of the three stable isotopes of oxygen — in gypsum
deposits from the Namibian desert and in volcanic ash deposits in
Nebraska and South Dakota. Also contributing to the discovery and
analysis were UCSD chemists Thiemens, James Farquhar, Douglas A.
Campbell and Charles Chi-Woo Lee; Klaus Heine of the University of
Regensburg in Germany; and David B. Loope of the University of Nebraska.
The study was financed by the National Aeronautics and Space
Administration and the National Science Foundation.

The scientists knew the anomalous isotope signatures were terrestrial
because they were recorded in sulfate (SO₄^2-) minerals that had been
deposited in volcanic ash beds 20 million years ago or, in the case of
Namibian gypsum deposits, associated with sulfur-producing marine
organisms that emitted dimethyl sulfide into the atmosphere during the
past 10 million years.

“We believe that ultimately these anomalous signatures come from the
Earth’s atmosphere,” says Bao. “And these signatures get transferred
from ozone and other atmospheric oxidants to sulfate during the
oxidation of reduced sulfur gases, such as those emitted by marine
microorganisms or from volcanic eruptions.”

With the exception of the isotopic signatures of gases trapped in ice
cores for the past 200,000 years, scientists have had little knowledge
of how major components in the Earth’s ancient atmosphere — such as
sulfur, carbon, and oxygen — cycled through the oceans and terrestrial
rocks. The UCSD development is important because it now provides a
window into some of these processes extending millions or billions of
years into the Earth’s past.

“To understand how the surface of the planet works, you’d really like to
understand how this cycle couples to the atmosphere,” says Thiemens.
“No one has been able to find a way to do it on Earth except through ice
cores. Now we can go far back in time and that’s never been done before.”

The UCSD researchers believe the signatures in the volcanic ash could
provide geologists with additional information about the chemistry of
volcanic plumes and the nature of the eruptions that produced them.
“Characteristic signatures may also help to temporally correlate
continental deposits among different basins, where such a correlation
has been a challenging task,” says Bao.

Because the coast off central Namibia is a major zone of upwelling
with intense biological activity, the researchers were able to tie the
anomalous sulfate deposits to the activity of nearby sulfur-producing
marine microorganisms and the unique desert environment that is able
to preserve the signature. However, the upwelling current may not have
been constant during the past several millions of years and may be
intimately tied to the change of ancient climatic conditions. “It is too
early to tell,” says Bao, “but if this connection can be made, we may
have a way of gaining insight into past ocean circulation and biological
productivity.”

The UCSD discovery also suggests that planetary geologists need to
be careful in interpreting the origin of oxygen-isotope anomalies on
meteorites, since these signatures can occur in terrestrial as well as
extraterrestrial rocks. “Our observations suggest that caution needs to
be exercised when looking for these anomalies in meteorites, because
some of them may have been imparted during their residence on Earth,”
says Bao. “Some meteorites lay on ice or in the desert for thousands of
years, so the secondary minerals in these meteorites may have originated
on Earth.”

IMAGE CAPTION: [http://ucsdnews.ucsd.edu/graphics/images/namib.jpg]
Fog over the Namibian desert. Credit: NASA