Nitrogen fingerprint in biomolecules could be from early sun

Ultraviolet light splits more readily splits molecules of nitrogen gas if one or both are the heavier isotope, nitrogen-15. Free nitrogen atoms combine with hydrogen to form ammonia molecules enriched in nitrogen-15. Credit: Image courtesy of University of California - San Diego

Chemical fingerprints of the element nitrogen vary by extremes in materials from the molecules of life to the solar wind to interstellar dust. Ideas for how this great variety came about have included alien molecules shuttled in by icy comets from beyond our solar system and complex chemical scenarios.

New experiments using a powerful source of ultraviolet light have shown that no extra-solar explanation is needed and the chemistry is straight forward, scientists from the University of California, San Diego, Hebrew University and UCLA report in the early online edition of the Proceedings of the National Academy of Sciences the week of September 29.

Nitrogen occurs in two stable forms. Nitrogen-14, with an equal number of protons and neutrons in its nucleus, is most abundant. Nitrogen-15, with an extra neutron, is far more rare, but biological molecules like proteins have larger proportions; they're enriched in nitrogen-15 relative to the nitrogen gas in Earth's atmosphere. And Earth's atmosphere itself has relatively more nitrogen-15 than other sources, such as the solar wind and Jupiter's atmosphere.

Samples from the icy comet Wild 2, retrieved by NASA's Stardust mission, and several kinds of meteorites also have relatively more nitrogen-15, and within the inhomogenous mix that makes up stony meteorites are inclusions, individual crystals that can have extremely high proportions of nitrogen-15. These observations led to the idea that the building blocks of life could have been 'seeded' on Earth, delivered perhaps by comet.

The new experiments render that hypothesis unnecessary. "We can generate this nitrogen enrichment inside the solar system. You can form all these building blocks of life inside our solar system. You don't have to bring the pieces in from outside," said Subrata Chakraborty, a project scientist in chemistry at UC San Diego and lead author of the report.

By shining a bright beam of very short wave ultraviolet light through nitrogen and hydrogen gas, Chakraborty and colleagues generated ammonia with drastically skewed ratios of nitrogen-15 relative to that found in the initial gas, which matched that of Earth's atmosphere. Pairs of nitrogen atoms -- the molecules of the gas -- were more likely to be split by UV photons if one or both atoms are the heavier version. Those freed nitrogen atoms recombined with hydrogen to form ammonia.

Ammonia molecules, a nitrogen atom bound to three hydrogen atoms, makes up a fundamental chemical group, the 'amines' the characterize amino acids, which link up in long chains to form proteins. They also join aromatic rings of carbon to form nitrogenous bases, the information carrying components of DNA and RNA. And RNA is how many think life got its start.

Light like this, with wavelengths this short, doesn't make it to Earth anymore. It's deflected by Earth's atmosphere. In fact, the experiments took place in a custom-engineered vacuum chamber aligned with the Lawrence Berkeley National Laboratory's Advanced Light Source synchrotron and were a challenge to pull off.

The chemical events that produced amines with extra nitrogen-15 would have happened long ago, probably in the icy outer reaches of the early solar nebula said Mark Thiemens, professor of chemistry at UC San Diego who directed the work. "It's the right time for this to have happened: before planets, before life."

Additional authors include Harel Muskatel of Hebrew University in Jerusalem, Teresa Jackson of UC San Diego, Musahid Ahmed of Lawrence Berkeley National Laboratory and R.D. Levine of Hebrew University and UCLA. NASA's Cosmochemistry and Origins of Solar System programs funded this work. The U.S. Department of Energy supports the operation of the Advanced Light Source.

Source:  University of California - San Diego

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Groundwater patches play important role in forest health, water quality

This is Kevin McGuire, associate director of the Virginia Water Resources Research Center. Credit: Virginia Tech

Even during summer dry spells, some isolated patches of soil in forested watersheds remain waterlogged.

These patches act as hot spots of microbial activity that remove nitrogen from groundwater and return it to the atmosphere, researchers from several institutions, including Virginia Tech, report in a leading scientific journal.

The discovery provides insight into the health of a forest. Nitrogen is an important nutrient for plant growth and productivity, but in streams, it can be a pollutant.

"The importance of these fragmented patches of saturated soil and their role in the fate of nitrogen in forested watersheds has been underappreciated until recently," said Kevin McGuire, an associate director of the Virginia Water Resources Research Center based in Virginia Tech's College of Natural Resources and Environment, co-author of the article to be published in the Proceedings of the National Academy of Sciences.

"We were able to determine the importance of denitrification in patches of shallow groundwater, which have largely been overlooked control points for nitrogen loss from temperate forested watersheds," McGuire said.

Most nitrogen is deposited by rain. Temperate forests receive much larger inputs of nitrogen from the atmosphere than they export to streams. Once nitrogen leaves the forest in streams, it can become a water pollutant.

"In some ecosystems, there have been long-term declines in stream water export of nitrogen when inputs have remained elevated," said co-author Christine Goodale, an associate professor of ecology and evolutionary biology at Cornell University.

"Understanding the fate of this nitrogen has been a challenge because denitrification -- a gaseous loss of nitrogen to the atmosphere -- is notoriously difficult to measure," said co-author Peter Groffman, an expert on denitrification at the Cary Institute of Ecosystem Studies.

Denitrification removes nitrogen from water and can therefore improve water quality in downstream lakes and estuaries.

However, nitrogen is also an important nutrient for plant growth in the forest so removals of nitrogen by natural processes can reduce the productivity of the forest.
The research, led by Sarah Wexler while she was a postdoctoral associate in hydrology and stable isotope geochemistry at Cornell University, took place in the Hubbard Brook Experimental Forest in the White Mountains of New Hampshire, where the atmosphere annually deposits five to seven pounds of nitrogen per acre.

The Hubbard Brook Experimental Forest is part of the National Science Foundation's Long Term Ecological Research Network.

McGuire, also an associate professor of hydrology in the Department of Forest Resources and Environmental Conservation, led another National Science Foundation-funded project at the site, which developed an organizing framework to describe and map variations of soil in the watershed that explain shallow groundwater occurrence and frequency.
Groundwater wells from this earlier study were used in the new research to monitor soils that may have had the right conditions to function as hot spots for denitrification.

At sites throughout the forest, the research team measured the presence of nitrate, a form of nitrogen that is highly mobile and reactive in the environment, determined whether the nitrate is a result of atmospheric deposition or microbial conversion, and discovered the nitrogen loss to the atmosphere.

"We were able to differentiate sources of nitrate and show that some of the nitrate was lost to the atmosphere by looking at nitrate at the atomic level, that is, at the isotopic composition of the nitrogen and oxygen in nitrate," said Wexler, who is now at the School of Environmental Sciences at the University of East Anglia in the United Kingdom. "The isotopic composition of nitrate provides a natural way to directly track the details of nitrogen cycling."

McGurie said, "Some work remains to be done, but the aim is to be able to develop a better sense of where and how nitrogen is processed in the environment and be in a position to predict how changes in climate, for example warmer and wetter conditions, affect nitrogen cycling and water quality in forested ecosystems."

Source: Virginia Tech

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