Laurence Yeung, scientist at Rice University, and colleagues at Rice, Michigan State University, UCLA and the University of New Mexico counted rare molecules in the atmosphere that contain only heavy isotopes of nitrogen and discovered a planetary-scale tug-of-war between life, the deep Earth and the upper atmosphere that is expressed in atmospheric nitrogen.
They were able to do this with the help of a one-of-a-kind instrument that allowed them to hear what the atmosphere is saying with rare nitrogen molecules.
The story revolves around nitrogen, a key element of life that makes up more than three-quarters of Earth's atmosphere. Compared with other key elements of life like oxygen, hydrogen and carbon, nitrogen is very stable. Two atoms of it form N2 molecules that are estimated to hang around in the atmosphere for about 10 million years before being broken apart and reformed.
The vast majority of nitrogen has an atomic mass of 14. Only about 0.4 percent are nitrogen-15, an isotope that contains one extra neutron. Because nitrogen-15 is already rare, N2 molecules that contain two nitrogen-15s, which chemists refer to as 15N15N, are the rarest of all N2 molecules.
“We were delighted to have the opportunity to the measure the abundance of 15N15N for the first time on the Panorama mass spectrometer,” said Nathaniel Ostrom, MSU professor in the Department of Integrative Biology. “The instrument has not only phenomenal mass resolution but also great sensitivity.”
The new study shows that 15N15N is 20 times more enriched in Earth's atmosphere than can be accounted for by processes happening near Earth's surface.
"We think the 15N15N enrichment fundamentally comes from chemistry in the upper atmosphere, at altitudes close to the orbit of the International Space Station," said Yeung, the lead author of the study and an assistant professor of Earth, environmental and planetary sciences at Rice. "The tug-of-war comes from life pulling in the other direction, and we can see chemical evidence of that."
Co-author Edward Young, professor of Earth, planetary and space sciences at UCLA, said, "The enrichment of 15N15N in Earth's atmosphere reflects a balance between the nitrogen chemistry that occurs in the atmosphere, at the surface due to life and within the planet itself. It's a signature unique to Earth, but it also gives us a clue about what signatures of other planets might look like, especially if they are capable of supporting life as we know it."
The chemical processes that produce molecules like N2 can change the odds that isotope clumps like 15N15N will be formed. In previous work, Yeung, Young and colleagues used isotope clumps in oxygen to identify tell-tale signatures of photosynthesis in plants and ozone chemistry in the atmosphere.
The nitrogen study began four years ago when Yeung learned about a first-of-its-kind mass spectrometer that was being installed in Young's lab.
“at that time, no one had a way to reliably quantify 15N15N,” said Yeung. “It has an atomic mass od 30, the same as nitric oxide. The signal from nitric oxide usually overwhelms the signal from 15N15N in mass spectrometers.”
The difference in mass between nitric oxide and 15N15N is about two one-thousandths the mass of a neutron. When Yeung learned that the new machine in Young's lab could discern this slight difference, he applied for grant funding from the National Science Foundation, or NSF, to explore exactly how much 15N15N was in Earth's atmosphere.
"Biological processes are hundreds to a thousand times faster at cycling nitrogen through the atmosphere than are geologic processes," Yeung said. "If it's all business as usual, one would expect that the atmosphere would reflect these biological cycles."
To find out if this was the case, co-authors Ostrom and Joshua Haslun, MSU research associate in the Department of Biochemistry and Molecular Biology, conducted experiments on N2-consuming and N2-producing bacteria to determine their 15N15N signatures.
“Of the three isotopic molecules of nitrogen gas,15N14N, is present at about 0.7 percent where as 15N15N is present at about 13 parts per million.,” Ostrom said. “We generally consider atmospheric nitrogen gas to be inert but our work shows that it is reactive on long time scales and the abundance of 15N15N is a new tracer of biological activity that may provide insight into the presence of life on other planetary bodies.”
These experiments suggested that one should see a bit more 15N15N in air than random pairings of nitrogen-14 and nitrogen-15 would produce, an enrichment of about 1 part per 1,000, Yeung said.
"There was a bit of enrichment in the biological experiments, but not nearly enough to account for what we'd found in the atmosphere," Yeung said. "In fact, it meant that the process causing the atmospheric 15N15N enrichment has to fight against this biological signature. They are locked in a tug-of-war.”
The team eventually found that zapping mixtures of air with electricity, which simulates the chemistry of the upper atmosphere, could produce enriched levels of 15N15N like they measured in air samples. Mixtures of pure nitrogen gas produced very little enrichment, but mixtures approximating the mix of gases in Earth's atmosphere could produce a signal even higher than what was observed in air.
"So far, we've tested natural air samples from ground level and from altitudes of 32 kilometers, as well as dissolved air from shallow ocean water samples," Yeung said. "We've found the same enrichment in all of them. We can see the tug-of-war everywhere."
Co-authors include Huanting Hu, of Rice; Shuning Li, of Peking University; Issaku Kohl and Edwin Schauble, of UCLA; and Tobias Fischer of the University of New Mexico.
The research was supported by the NSF, the Deep Carbon Observatory and the Department of Energy's Great Lakes Bioenergy Research Center.