Soil mineral surfaces linked to key atmospheric processes

Pictured are, from left, are David Bish, Melissa Donaldson and Jonathan Raff. Credit: Indiana University

Research by Indiana University scientists finds that soil may be a significant and underappreciated source of nitrous acid, a chemical that plays a pivotal role in atmospheric processes such as the formation of smog and determining the lifetime of greenhouse gases.

The study shows for the first time that the surface acidity of common minerals found in soil determines whether the gas nitrous acid will be released into the atmosphere. The finding could contribute to improved models for understanding and controlling air pollution, a significant public health concern.

"We find that the surfaces of minerals in the soil can be much more acidic than the overall pH of the soil would suggest," said Jonathan Raff, assistant professor in the School of Public and Environmental Affairs and Department of Chemistry. "It's the acidity of the soil minerals that acts as a knob or a control lever, and that determines whether nitrous acid outgasses from soil or remains as nitrite."

The article, "Soil surface acidity plays a determining role in the atmospheric-terrestrial exchange of nitrous acid," will be published this week in the journal Proceedings of the National Academy of Sciences. Melissa A. Donaldson, a Ph.D. student in the School of Public and Environmental Affairs, is the lead author. Co-authors are Raff and David L. Bish, the Haydn Murray Chair of Applied Clay Mineralogy in the Department of Geological Sciences.

Nitrous acid, or HONO, plays a key role in regulating atmospheric processes. Sunlight causes it to break down into nitric oxide and the hydroxyl radical, OH. The latter controls the atmospheric lifetime of gases important to air quality and climate change and initiates the chemistry leading to the formation of ground-level ozone, a primary component of smog.
Scientists have known about the nitrous acid's role in air pollution for 40 years, but they haven't fully understood how it is produced and destroyed or how it interacts with other substances, because HONO is unstable and difficult to measure.

"Only in the last 10 years have we had the technology to study nitrous acid under environmentally relevant conditions," Raff said.

Recent studies have shown nitrous acid to be emitted from soil in many locations. But this was unexpected because, according to basic chemistry, the reactions that release nitrous acid should take place only in extremely acidic soils, typically found in rain forests or the taiga of North America and Eurasia.

The standard method to determine the acidity of soil is to mix bulk soil with water and measure the overall pH. But the IU researchers show that the crucial factor is not overall pH but the acidity at the surface of soil minerals, especially iron oxides and aluminum oxides. At the molecular level, the water adsorbed directly to these minerals is unusually acidic and facilitates the conversion of nitrite in the soil to nitrous acid, which then volatilizes.

"With the traditional approach of calculating soil pH, we were severely underestimating nitrous acid emissions from soil," Raff said. "I think the source is going to turn out to be more important than was previously imagined."

The research was carried out using soil from a farm field near Columbus, Ind. But aluminum and iron oxides are ubiquitous in soil, and the researchers say the results suggest that about 70 percent of Earth's soils could be sources of nitrous acid.

Ultimately, the research will contribute to a better understanding of how nitrous acid is produced and how it affects atmospheric processes. That in turn will improve the computer models used by the U.S. Environmental Protection Agency and other regulatory agencies to control air pollution, which the World Health Organization estimates contributes to 7 million premature deaths annually.

"With improved models, policymakers can make better judgments about the costs and benefits of regulations," Raff said. "If we don't get the chemistry right, we're not going to get the right answers to our policy questions regarding air pollution."

Source: Indiana University

No laughing matter: Nitrous oxide rose at end of last ice age

Researchers measured increases in atmospheric nitrous oxide concentrations about 16,000 to 10,000 years ago using ice from Taylor Glacier in Antarctica. Credit: Adrian Schilt

Nitrous oxide (N₂O) is an important greenhouse gas that doesn't receive as much notoriety as carbon dioxide or methane, but a new study confirms that atmospheric levels of (N₂O) rose significantly as the Earth came out of the last ice age and addresses the cause.

An international team of scientists analyzed air extracted from bubbles enclosed in ancient polar ice from Taylor Glacier in Antarctica, allowing for the reconstruction of the past atmospheric composition. The analysis documented a 30 percent increase in atmospheric nitrous oxide concentrations from 16,000 years ago to 10,000 years ago. This rise in N2O was caused by changes in environmental conditions in the ocean and on land, scientists say, and contributed to the warming at the end of the ice age and the melting of large ice sheets that then existed.

The findings add an important new element to studies of how Earth may respond to a warming climate in the future. Results of the study, which was funded by the U.S. National Science Foundation and the Swiss National Science Foundation, are being published this week in the journal Nature.

"We found that marine and terrestrial sources contributed about equally to the overall increase of nitrous oxide concentrations and generally evolved in parallel at the end of the last ice age," said lead author Adrian Schilt, who did much of the work as a post-doctoral researcher at Oregon State University. Schilt then continued to work on the study at the Oeschger Centre for Climate Change Research at the University of Bern in Switzerland.

"The end of the last ice age represents a partial analog to modern warming and allows us to study the response of natural nitrous oxide emissions to changing environmental conditions," Schilt added. "This will allow us to better understand what might happen in the future."

Nitrous oxide is perhaps best known as laughing gas, but it is also produced by microbes on land and in the ocean in processes that occur naturally, but can be enhanced by human activity. Marine nitrous oxide production is linked closely to low oxygen conditions in the upper ocean and global warming is predicted to intensify the low-oxygen zones in many of the world's ocean basins. N2O also destroys ozone in the stratosphere.

"Warming makes terrestrial microbes produce more nitrous oxide," noted co-author Edward Brook, an Oregon State paleoclimatologist whose research team included Schilt. "Greenhouse gases go up and down over time, and we'd like to know more about why that happens and how it affects climate."

Nitrous oxide is among the most difficult greenhouse gases to study in attempting to reconstruct Earth's climate history through ice core analysis. The specific technique that the Oregon State research team used requires large samples of pristine ice that date back to the desired time of study -- in this case, between about 16,000 and 10,000 years ago.

The unusual way in which Taylor Glacier is configured allowed the scientists to extract ice samples from the surface of the glacier instead of drilling deep in the polar ice cap because older ice is transported upward near the glacier margins, said Brook, a professor in Oregon State's College of Earth, Ocean, and Atmospheric Sciences.

The scientists were able to discern the contributions of marine and terrestrial nitrous oxide through analysis of isotopic ratios, which fingerprint the different sources of N2O in the atmosphere.

"The scientific community knew roughly what the N2O concentration trends were prior to this study," Brook said, "but these findings confirm that and provide more exact details about changes in sources. As nitrous oxide in the atmosphere continues to increase -- along with carbon dioxide and methane -- we now will be able to more accurately assess where those contributions are coming from and the rate of the increase."

Atmospheric N2O was roughly 200 parts per billion at the peak of the ice age about 20,000 years ago then rose to 260 ppb by 10,000 years ago. As of 2014, atmospheric N2Owas measured at about 327 ppb, an increase attributed primarily to agricultural influences.
Although the N2O increase at the end of the last ice age was almost equally attributable to marine and terrestrial sources, the scientists say, there were some differences.

"Our data showed that terrestrial emissions changed faster than marine emissions, which was highlighted by a fast increase of emissions on land that preceded the increase in marine emissions," Schilt pointed out. "It appears to be a direct response to a rapid temperature change between 15,000 and 14,000 years ago."

That finding underscores the complexity of analyzing how Earth responds to changing conditions that have to account for marine and terrestrial influences; natural variability; the influence of different greenhouse gases; and a host of other factors, Brook said.

"Natural sources of N2O are predicted to increase in the future and this study will help up test predictions on how the Earth will respond," Brook said.

Source: Oregon State University