Earth’s oxygen levels rose and fell more than once hundreds of millions of years before the planetwide success of the Great Oxidation Event about 2.4 billion years ago, new research from the 91̽�� shows.

The evidence comes from a new study that indicates a second and much earlier “whiff” of oxygen in Earth’s distant past — in the atmosphere and on the surface of a large stretch of ocean — showing that the oxygenation of the Earth was a complex process of repeated trying and failing over a vast stretch of time.

The finding also may have implications in the search for life beyond Earth. Coming years will bring powerful new ground- and space-based telescopes able to analyze the atmospheres of distant planets. This work could help keep astronomers from unduly ruling out “false negatives,” or inhabited planets that may not at first appear to be so due to undetectable oxygen levels.

“The production and destruction of oxygen in the ocean and atmosphere over time was a war with no evidence of a clear winner, until the Great Oxidation Event,” said , a 91̽��doctoral student in Earth and space sciences and lead author of a new published the week of July 9 in the Proceedings of the National Academy of Sciences.

“These transient oxygenation events were battles in the war, when the balance tipped more in favor of oxygenation.”

In 2007, co-author , 91̽��professor of Earth and space sciences, was part of an international team of scientists that found evidence of an episode — a “whiff” — of oxygen some 50 million to 100 million years before the Great Oxidation Event. This they learned by drilling deep into sedimentary rock of the Mount McRae Shale in Western Australia and analyzing the samples for the trace metals molybdenum and rhenium, accumulation of which is dependent on oxygen in the environment.

Now, a team led by Koehler has confirmed a second such appearance of oxygen in Earth’s past, this time roughly 150 million years earlier — or about 2.66 billion years ago — and lasting for less than 50 million years. For this work they used two different proxies for oxygen — nitrogen isotopes and the element selenium — substances that, each in its way, also tell of the presence of oxygen.

“What we have in this paper is another detection, at high resolution, of a transient whiff of oxygen,” said Koehler. “Nitrogen isotopes tell a story about oxygenation of the surface ocean, and this oxygenation spans hundreds of kilometers across a marine basin and lasts for somewhere less than 50 million years.”

The team analyzed drill samples taken by Buick in 2012 at another site in the northwestern part of Western Australia called the Jeerinah Formation.

The researchers drilled two cores about 300 kilometers apart but through the same sedimentary rocks — one core samples sediments deposited in shallower waters, and the other samples sediments from deeper waters. Analyzing successive layers in the rocks years shows, Buick said, a “stepwise” change in nitrogen isotopes “and then back again to zero. This can only be interpreted as meaning that there is oxygen in the environment. It’s really cool — and it’s sudden.”

The nitrogen isotopes reveal the activity of certain marine microorganisms that use oxygen to form nitrate, and other microorganisms that use this nitrate for energy. The data collected from nitrogen isotopes sample the surface of the ocean, while selenium suggests oxygen in the air of ancient Earth. Koehler said the deep ocean was likely anoxic, or without oxygen, at the time.

The team found plentiful selenium in the shallow hole only, meaning that it came from the nearby land, not making it to deeper water. Selenium is held in sulfur minerals on land; higher atmospheric oxygen would cause more selenium to be leached from the land through oxidative weathering — “the rusting of rocks,” Buick said — and transported to sea.

“That selenium then accumulates in ocean sediments,” Koehler said. “So when we measure a spike in selenium abundances in ocean sediments, it could mean there was a temporary increase in atmospheric oxygen.”

The finding, Buick and Koehler said, also has relevance for detecting life on exoplanets, or those beyond the solar system.

“One of the strongest atmospheric biosignatures is thought to be oxygen, but this study confirms that during a planet’s transition to becoming permanently oxygenated, its surface environments may be oxic for intervals of only a few million years and then slip back into anoxia,” Buick said.

“So, if you fail to detect oxygen in a planet’s atmosphere, that doesn’t mean that the planet is uninhabited or even that it lacks photosynthetic life. Merely that it hasn’t built up enough sources of oxygen to overwhelm the ‘sinks’ for any longer than a short interval.

“In other words, lack of oxygen can easily be a ‘false negative’ for life.”

Koehler added: “You could be looking at a planet and not see any oxygen — but it could be teeming with microbial life.”

Koehler’s other co-authors are 91̽��Earth and space sciences doctoral student , former Earth and space sciences postdoctoral researcher — now a faculty member at the University of St. Andrews in Scotland — and Jonathan Zaloumis of Arizona State University.

The research was funded by grants from NASA, the UW-based and the National Science Foundation; drilling was funded by the Agouron Institute.

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For more information, contact Koehler at koehlerm@uw.edu or Buick at 206-543-1913 or buick@ess.washington.edu.

NASA grant NNX16A137G
NSF FESD grant 338810

The amount of biomass – life – in Earth’s ancient oceans may have been limited due to low recycling of the key nutrient , according to new research by the 91̽�� and the University of St. Andrews in Scotland.

The research, published Nov. 22 in the journal Science Advances, also comments on the role of volcanism in supporting Earth’s early biosphere — and may even apply to the search for life on other worlds.

The paper’s lead author is , a 91̽��doctoral student in Earth and space sciences; coauthor is , a research fellow at the University of St. Andrews and former 91̽��postdoctoral researcher. , 91̽��professor of Earth and space sciences, advised the researchers.

Their aim, Kipp said, was to use theoretical modeling to study how ocean phosphorus levels have changed throughout Earth’s history.

“We were interested in phosphorus because it is thought to be the nutrient that limits the amount of life there is in the ocean, along with carbon and nitrogen,” said Kipp. “You change the relative amount of those and you change, basically, the amount of biological productivity.”

Kipp said their model shows the ability of phosphorus to be recycled in the ancient ocean “was much lower than today, maybe on the order of 10 times less.”

All life needs abundant food to thrive, and the chemical element phosphorus – which washes into the ocean from rivers as phosphate — is a key nutrient. Once in the ocean, phosphorus gets recycled several times as organisms such as plankton or eukaryotic algae that “eat” it are in turn consumed by other organisms.

“As these organisms use the phosphorus, they in turn get grazed upon, or they die and other bacteria decompose their organic matter,” said Kipp, “and they release some of that phosphorus back into the ocean. It actually cycles through several times,” allowing the liberated phosphorus to build up in the ocean. The amount of recycling is a key control on the amount of total phosphorus in the ocean, which in turn supports life.

Buick explained: “Every gardener knows that their plants grow only small and scraggly without phosphate fertilizer. The same applies for photosynthetic life in the oceans, where the phosphate ‘fertilizer’ comes largely from phosphorus liberated by the degradation of dead plankton.”

But all of this requires oxygen. In today’s oxygen-rich oceans, nearly all phosphorus gets recycled in this way and little falls to the ocean floor.

Several billion years ago, in the Precambrian era, however, there was little or no oxygen in the environment.

“There are some alternatives to oxygen that certain bacteria could use, said co-author Stüeken. “Some bacteria can digest food using sulfate. Others use iron oxides.” Sulfate, she said, was the most important control on phosphorus recycling in the Precambrian era.

“Our analysis shows that these alternative pathways were the dominant route of phosphorus recycling in the Precambrian, when oxygen was very low,” Stüeken said. “However, they are much less effective than digestion with oxygen, meaning that only a smaller amount of biomass could be digested. As a consequence, much less phosphorus would have been recycled, and therefore total biological productivity would have been suppressed relative to today.”

Kipp likened early Earth’s low-oxygen ocean to a kind of “canned” environment, with oxygen sealed out: “It’s a closed system. If you go back to the early Precambrian oceans, there’s not very much going on in terms of biological activity.”

Stüeken noted that volcanoes were the biggest source of sulfate in the Precambrian, unlike now, and so they were necessary for sustaining a significant biosphere by enabling phosphorus recycling.

In fact, minus such volcanic sulfate, Stüeken said, Earth’s biosphere would have been very small, and may not have survived over billions of years. The findings, then, illustrate “how strongly life is tied to fundamental geological processes such as volcanism on the early Earth,” she said.

Kipp and Stüeken’s modeling may have implications as well for the search for life beyond Earth.

Astronomers will use upcoming ground- and space-based telescopes such as the James Webb Space Telescope, set for launch in 2019, to look for the impact of a marine biosphere, as Earth has, on a planet’s atmosphere. But low phosphorus, the researchers say, could cause an inhabited world to appear uninhabited — making a sort of “false negative.”

Kipp said, “If there is less life — basically, less photosynthetic output — it’s harder to accumulate atmospheric oxygen than if you had modern phosphorus levels and production rates. This could mean that some planets might appear to be uninhabited due to their lack of oxygen, but in reality they have biospheres that are limited in extent due to low phosphorus availability.

”These ‘false negatives’ are one of the biggest challenges facing us in the search for life elsewhere,” said , 91̽��astronomy professor and principal investigator for the NASA Astrobiology Institute’s , based at the UW.

“But research on early Earth’s environments increases our chance of success by revealing processes and planetary properties that guide our search for life on nearby exoplanets.”

The work was funded by grants from NASA and the National Science Foundation.

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For more information, contact Kipp at kipp@uw.edu, Buick at 206-543-1913 or buick@ess.washington.edu or Stüeken at
ees4@st-andrews.ac.uk.

NASA Exobiology grant NNX16AI37G to Prof. Buick.