Study improves accuracy of models for predicting ozone levels in urban areas

November 01, 2010

A team of scientists has, for the first time, completely characterized an important chemical reaction that is critical to the formation of ground-level ozone in urban areas. The team's results indicate that computer models may be underestimating ozone levels in urban areas during episodes of poor air quality (smoggy days) by as much as five to 10 percent.

Ground level ozone poses significant health hazards to people, animals and plants; is the primary ingredient of smog; and gives polluted air its characteristic odor. It is known that even small increases in ozone concentrations can lead to increases in death from respiratory problems. Because of the health hazards caused by ozone exposure, the research team's results may have regulatory implications.

The team's research, which was funded by the National Science Foundation (NSF), NASA and the California Air Resources Board CARB), appears in the October 29 issue of Science.

Big role of one reaction in predicting ozone in smoggy air

The reaction studied by the researchers plays an important role in controlling the efficiency of a sunlight-driven cycle of reactions that continuously generates ozone. In this reaction, a hydroxyl radical (OH) combines with nitrogen dioxide (NO2), which is produced from emissions generated by vehicles, various industrial processes and some biological processes.

When a hydroxyl radical and nitrogen dioxide collide, these molecules may stick together to form a stable byproduct known as nitric acid (HONO2). Because of the stability of nitric acid, its formation locks up hydroxyl radicals and nitrogen dioxide, and thereby prevents these molecules from contributing to ozone formation; this reaction thereby slows the formation of ozone.

Although scientists have long recognized the importance of the formation of nitric acid, they have, until now, been unable to agree on the speed, or "rate," at which hydrogen radicals and nitrogen dioxide combine to form this end product. "This reaction, which slows down ozone production, has been among the greatest sources of uncertainty in predicting ozone levels," said Mitchio Okumura of the California Institute of Technology--a member of the research team. This uncertainty has affected computer models that simulate air pollution chemistry.

An experimental challenge

Why is there so much uncertainty about the speed or rate of formation of nitric acid? In large part, because instead of combining to form a stable form of nitric acid, a hydroxyl radical may combine with nitrogen dioxide to form a less stable form of nitric acid (HOONO)--a snake-like molecule that quickly breaks apart in the atmosphere. This breakdown of the unstable form of nitric acid releases its hydroxyl radical back into the atmosphere where it may once again become available to form ozone; this breakdown therefore speeds the formation of ozone. Nevertheless questions about the existence, amount, speed and formation of the unstable form of nitric acid have, until now, complicated measurements of the speed or rate of the formation of the more stable form of nitric acid.

But through experiments conducted at the Jet Propulsion Laboratory (JPL) and at the California Institute of Technology using state-of-the-art techniques, Okumura and his colleague, Stanley P. Sander at JPL, led a team of researchers that accurately measured: 1) the overall speed at which hydroxyl radicals and nitrogen dioxide combine, or react, in given atmospheric conditions; 2) the ratio of stable nitric acid to unstable nitric acid that is formed under given atmospheric conditions.

In addition, new laser methods enabled researchers to directly detect the presence of the unstable form of nitric acid in microseconds. And with the help of companion calculations performed at Ohio State by Anne McCoy, they could quantify its yield as soon as it was formed.

The research team's experiments show that the stable form of nitric acid forms slower than previously believed. These results indicate that there is more OH available in polluted, ground-level air for the formation of ozone than previously believed, and thus probably more ozone in the atmosphere than previously predicted.

More ozone than previously believed

To demonstrate the significance of the new results, modelers on the research team led by Robert Harley and William Carter fed their newly quantified reaction rates and ratios into computer models to predict levels of ground-level ozone during the summer of 2010 in the Los Angeles Basin. Their results indicate that many current models have been underestimating ground-level ozone levels in the most polluted areas (where nitrogen dioxide is highest) by about 5 to 10 percent. The research team concluded that relatively small changes in the rates and proportions of reactions forming unstable and stable nitric acid could lead to small but significant changes in ground-level ozone levels.

The importance of the study

"The study illustrates the importance of developing new and improved experimental approaches that interrogate atmospheric systems at the molecular level with high accuracy," said Zeev Rosenweig, an NSF program officer. "This is imperative to reducing uncertainties in atmospheric model predictions."

"The determination of a more accurate value of the rate of nitric acid formation from a hydroxyl radical and nitrogen dioxide will be important in future air-quality modeling," said Anne B. McCoy, a member of the research team. "The research was made possible by bringing together several laboratories with different capabilities and expertise, including my lab at Ohio State, and labs at CalTech, JPL and Berkeley."

Regulatory implications

The ozone prediction models incorporated into the research team's study are similar to those used by regulatory agencies, such as the Environmental Protection Agency and the California Air Resources Board. Therefore, the team's results may have implications for future predictions of ground-level ozone used by regulatory agencies in developing air quality management plans.
-end-


National Science Foundation

Related Ozone Articles from Brightsurf:

Investigating the causes of the ozone levels in the Valderejo Nature Reserve
The UPV/EHU's Atmospheric Research Group (GIA) has presented a database comprising over 60 volatile organic compounds (VOC) measured continuously over the last ten years in the Valderejo Nature Reserve (Álava, Basque Country).

FSU Research: Despite less ozone pollution, not all plants benefit
Policies and new technologies have reduced emissions of precursor gases that lead to ozone air pollution, but despite those improvements, the amount of ozone that plants are taking in has not followed the same trend, according to Florida State University researchers.

Iodine may slow ozone layer recovery
Air pollution and iodine from the ocean contribute to damage of Earth's ozone layer.

Ozone threat from climate change
We know the recent extreme heat is something that we can expect more of as a result of increasing temperatures due to climate change.

Super volcanic eruptions interrupt ozone recovery
Strong volcanic eruptions, especially when a super volcano erupts, will have a strong impact on ozone, and might interrupt the ozone recovery processes.

How severe drought influences ozone pollution
From 2011 to 2015, California experienced its worst drought on record, with a parching combination of high temperatures and low precipitation.

New threat to ozone recovery
A new MIT study, published in Nature Geoscience, identifies another threat to the ozone layer's recovery: chloroform -- a colorless, sweet-smelling compound that is primarily used in the manufacturing of products such as Teflon and various refrigerants.

Ozone hole modest despite optimum conditions for ozone depletion
The ozone hole that forms in the upper atmosphere over Antarctica each September was slightly above average size in 2018, NOAA and NASA scientists reported today.

Increased UV from ozone depletion sterilizes trees
UC Berkeley paleobotanists put dwarf, bonsai pine trees in growth chambers and subjected them to up to 13 times the UV-B radiation Earth experiences today, simulating conditions that likely existed 252 million years ago during the planet's worst mass extinction.

Ozone at lower latitudes is not recovering, despite Antarctic ozone hole healing
The ozone layer -- which protects us from harmful ultraviolet radiation -- is recovering at the poles, but unexpected decreases in part of the atmosphere may be preventing recovery at lower latitudes.

Read More: Ozone News and Ozone Current Events
Brightsurf.com is a participant in the Amazon Services LLC Associates Program, an affiliate advertising program designed to provide a means for sites to earn advertising fees by advertising and linking to Amazon.com.