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    Study: Smoke particles from wildfires can erode the ozone layer

    A wildfire can pump smoke up into the stratosphere, where the particles drift for over a year. A new MIT study has found that while suspended there, these particles can trigger chemical reactions that erode the protective ozone layer shielding the Earth from the sun’s damaging ultraviolet radiation.

    The study, which appears today in Nature, focuses on the smoke from the “Black Summer” megafire in eastern Australia, which burned from December 2019 into January 2020. The fires — the country’s most devastating on record — scorched tens of millions of acres and pumped more than 1 million tons of smoke into the atmosphere.

    The MIT team identified a new chemical reaction by which smoke particles from the Australian wildfires made ozone depletion worse. By triggering this reaction, the fires likely contributed to a 3-5 percent depletion of total ozone at mid-latitudes in the Southern Hemisphere, in regions overlying Australia, New Zealand, and parts of Africa and South America.

    The researchers’ model also indicates the fires had an effect in the polar regions, eating away at the edges of the ozone hole over Antarctica. By late 2020, smoke particles from the Australian wildfires widened the Antarctic ozone hole by 2.5 million square kilometers — 10 percent of its area compared to the previous year.

    It’s unclear what long-term effect wildfires will have on ozone recovery. The United Nations recently reported that the ozone hole, and ozone depletion around the world, is on a recovery track, thanks to a sustained international effort to phase out ozone-depleting chemicals. But the MIT study suggests that as long as these chemicals persist in the atmosphere, large fires could spark a reaction that temporarily depletes ozone.

    “The Australian fires of 2020 were really a wake-up call for the science community,” says Susan Solomon, the Lee and Geraldine Martin Professor of Environmental Studies at MIT and a leading climate scientist who first identified the chemicals responsible for the Antarctic ozone hole. “The effect of wildfires was not previously accounted for in [projections of] ozone recovery. And I think that effect may depend on whether fires become more frequent and intense as the planet warms.”

    The study is led by Solomon and MIT research scientist Kane Stone, along with collaborators from the Institute for Environmental and Climate Research in Guangzhou, China; the U.S. National Oceanic and Atmospheric Administration; the U.S. National Center for Atmospheric Research; and Colorado State University.

    Chlorine cascade

    The new study expands on a 2022 discovery by Solomon and her colleagues, in which they first identified a chemical link between wildfires and ozone depletion. The researchers found that chlorine-containing compounds, originally emitted by factories in the form of chlorofluorocarbons (CFCs), could react with the surface of fire aerosols. This interaction, they found, set off a chemical cascade that produced chlorine monoxide — the ultimate ozone-depleting molecule. Their results showed that the Australian wildfires likely depleted ozone through this newly identified chemical reaction.

    “But that didn’t explain all the changes that were observed in the stratosphere,” Solomon says. “There was a whole bunch of chlorine-related chemistry that was totally out of whack.”

    In the new study, the team took a closer look at the composition of molecules in the stratosphere following the Australian wildfires. They combed through three independent sets of satellite data and observed that in the months following the fires, concentrations of hydrochloric acid dropped significantly at mid-latitudes, while chlorine monoxide spiked.

    Hydrochloric acid (HCl) is present in the stratosphere as CFCs break down naturally over time. As long as chlorine is bound in the form of HCl, it doesn’t have a chance to destroy ozone. But if HCl breaks apart, chlorine can react with oxygen to form ozone-depleting chlorine monoxide.

    In the polar regions, HCl can break apart when it interacts with the surface of cloud particles at frigid temperatures of about 155 kelvins. However, this reaction was not expected to occur at mid-latitudes, where temperatures are much warmer.

    “The fact that HCl at mid-latitudes dropped by this unprecedented amount was to me kind of a danger signal,” Solomon says.

    She wondered: What if HCl could also interact with smoke particles, at warmer temperatures and in a way that released chlorine to destroy ozone? If such a reaction was possible, it would explain the imbalance of molecules and much of the ozone depletion observed following the Australian wildfires.

    Smoky drift

    Solomon and her colleagues dug through the chemical literature to see what sort of organic molecules could react with HCl at warmer temperatures to break it apart.

    “Lo and behold, I learned that HCl is extremely soluble in a whole broad range of organic species,” Solomon says. “It likes to glom on to lots of compounds.”

    The question then, was whether the Australian wildfires released any of those compounds that could have triggered HCl’s breakup and any subsequent depletion of ozone. When the team looked at the composition of smoke particles in the first days after the fires, the picture was anything but clear.

    “I looked at that stuff and threw up my hands and thought, there’s so much stuff in there, how am I ever going to figure this out?” Solomon recalls. “But then I realized it had actually taken some weeks before you saw the HCl drop, so you really need to look at the data on aged wildfire particles.”

    When the team expanded their search, they found that smoke particles persisted over months, circulating in the stratosphere at mid-latitudes, in the same regions and times when concentrations of HCl dropped.

    “It’s the aged smoke particles that really take up a lot of the HCl,” Solomon says. “And then you get, amazingly, the same reactions that you get in the ozone hole, but over mid-latitudes, at much warmer temperatures.”

    When the team incorporated this new chemical reaction into a model of atmospheric chemistry, and simulated the conditions of the Australian wildfires, they observed a 5 percent depletion of ozone throughout the stratosphere at mid-latitudes, and a 10 percent widening of the ozone hole over Antarctica.

    The reaction with HCl is likely the main pathway by which wildfires can deplete ozone. But Solomon guesses there may be other chlorine-containing compounds drifting in the stratosphere, that wildfires could unlock.

    “There’s now sort of a race against time,” Solomon says. “Hopefully, chlorine-containing compounds will have been destroyed, before the frequency of fires increases with climate change. This is all the more reason to be vigilant about global warming and these chlorine-containing compounds.”

    This research was supported, in part, by NASA and the U.S. National Science Foundation. More

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    Methane research takes on new urgency at MIT

    One of the most notable climate change provisions in the 2022 Inflation Reduction Act is the first U.S. federal tax on a greenhouse gas (GHG). That the fee targets methane (CH4), rather than carbon dioxide (CO2), emissions is indicative of the urgency the scientific community has placed on reducing this short-lived but powerful gas. Methane persists in the air about 12 years — compared to more than 1,000 years for CO2 — yet it immediately causes about 120 times more warming upon release. The gas is responsible for at least a quarter of today’s gross warming. 

    “Methane has a disproportionate effect on near-term warming,” says Desiree Plata, the director of MIT Methane Network. “CH4 does more damage than CO2 no matter how long you run the clock. By removing methane, we could potentially avoid critical climate tipping points.” 

    Because GHGs have a runaway effect on climate, reductions made now will have a far greater impact than the same reductions made in the future. Cutting methane emissions will slow the thawing of permafrost, which could otherwise lead to massive methane releases, as well as reduce increasing emissions from wetlands.  

    “The goal of MIT Methane Network is to reduce methane emissions by 45 percent by 2030, which would save up to 0.5 degree C of warming by 2100,” says Plata, an associate professor of civil and environmental engineering at MIT and director of the Plata Lab. “When you consider that governments are trying for a 1.5-degree reduction of all GHGs by 2100, this is a big deal.” 

    Under normal concentrations, methane, like CO2, poses no health risks. Yet methane assists in the creation of high levels of ozone. In the lower atmosphere, ozone is a key component of air pollution, which leads to “higher rates of asthma and increased emergency room visits,” says Plata. 

    Methane-related projects at the Plata Lab include a filter made of zeolite — the same clay-like material used in cat litter — designed to convert methane into CO2 at dairy farms and coal mines. At first glance, the technology would appear to be a bit of a hard sell, since it converts one GHG into another. Yet the zeolite filter’s low carbon and dollar costs, combined with the disproportionate warming impact of methane, make it a potential game-changer.

    The sense of urgency about methane has been amplified by recent studies that show humans are generating far more methane emissions than previously estimated, and that the rates are rising rapidly. Exactly how much methane is in the air is uncertain. Current methods for measuring atmospheric methane, such as ground, drone, and satellite sensors, “are not readily abundant and do not always agree with each other,” says Plata.  

    The Plata Lab is collaborating with Tim Swager in the MIT Department of Chemistry to develop low-cost methane sensors. “We are developing chemiresisitive sensors that cost about a dollar that you could place near energy infrastructure to back-calculate where leaks are coming from,” says Plata.  

    The researchers are working on improving the accuracy of the sensors using machine learning techniques and are planning to integrate internet-of-things technology to transmit alerts. Plata and Swager are not alone in focusing on data collection: the Inflation Reduction Act adds significant funding for methane sensor research. 

    Other research at the Plata Lab includes the development of nanomaterials and heterogeneous catalysis techniques for environmental applications. The lab also explores mitigation solutions for industrial waste, particularly those related to the energy transition. Plata is the co-founder of an lithium-ion battery recycling startup called Nth Cycle. 

    On a more fundamental level, the Plata Lab is exploring how to develop products with environmental and social sustainability in mind. “Our overarching mission is to change the way that we invent materials and processes so that environmental objectives are incorporated along with traditional performance and cost metrics,” says Plata. “It is important to do that rigorous assessment early in the design process.”

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    MIT amps up methane research 

    The MIT Methane Network brings together 26 researchers from MIT along with representatives of other institutions “that are dedicated to the idea that we can reduce methane levels in our lifetime,” says Plata. The organization supports research such as Plata’s zeolite and sensor projects, as well as designing pipeline-fixing robots, developing methane-based fuels for clean hydrogen, and researching the capture and conversion of methane into liquid chemical precursors for pharmaceuticals and plastics. Other members are researching policies to encourage more sustainable agriculture and land use, as well as methane-related social justice initiatives. 

    “Methane is an especially difficult problem because it comes from all over the place,” says Plata. A recent Global Carbon Project study estimated that half of methane emissions are caused by humans. This is led by waste and agriculture (28 percent), including cow and sheep belching, rice paddies, and landfills.  

    Fossil fuels represent 18 percent of the total budget. Of this, about 63 percent is derived from oil and gas production and pipelines, 33 percent from coal mining activities, and 5 percent from industry and transportation. Human-caused biomass burning, primarily from slash-and-burn agriculture, emits about 4 percent of the global total.  

    The other half of the methane budget includes natural methane emissions from wetlands (20 percent) and other natural sources (30 percent). The latter includes permafrost melting and natural biomass burning, such as forest fires started by lightning.  

    With increases in global warming and population, the line between anthropogenic and natural causes is getting fuzzier. “Human activities are accelerating natural emissions,” says Plata. “Climate change increases the release of methane from wetlands and permafrost and leads to larger forest and peat fires.”  

    The calculations can get complicated. For example, wetlands provide benefits from CO2 capture, biological diversity, and sea level rise resiliency that more than compensate for methane releases. Meanwhile, draining swamps for development increases emissions. 

    Over 100 nations have signed onto the U.N.’s Global Methane Pledge to reduce at least 30 percent of anthropogenic emissions within the next 10 years. The U.N. report estimates that this goal can be achieved using proven technologies and that about 60 percent of these reductions can be accomplished at low cost. 

    Much of the savings would come from greater efficiencies in fossil fuel extraction, processing, and delivery. The methane fees in the Inflation Reduction Act are primarily focused on encouraging fossil fuel companies to accelerate ongoing efforts to cap old wells, flare off excess emissions, and tighten pipeline connections.  

    Fossil fuel companies have already made far greater pledges to reduce methane than they have with CO2, which is central to their business. This is due, in part, to the potential savings, as well as in preparation for methane regulations expected from the Environmental Protection Agency in late 2022. The regulations build upon existing EPA oversight of drilling operations, and will likely be exempt from the U.S. Supreme Court’s ruling that limits the federal government’s ability to regulate GHGs. 

    Zeolite filter targets methane in dairy and coal 

    The “low-hanging fruit” of gas stream mitigation addresses most of the 20 percent of total methane emissions in which the gas is released in sufficiently high concentrations for flaring. Plata’s zeolite filter aims to address the thornier challenge of reducing the 80 percent of non-flammable dilute emissions. 

    Plata found inspiration in decades-old catalysis research for turning methane into methanol. One strategy has been to use an abundant, low-cost aluminosilicate clay called zeolite.  

    “The methanol creation process is challenging because you need to separate a liquid, and it has very low efficiency,” says Plata. “Yet zeolite can be very efficient at converting methane into CO2, and it is much easier because it does not require liquid separation. Converting methane to CO2 sounds like a bad thing, but there is a major anti-warming benefit. And because methane is much more dilute than CO2, the relative CO2 contribution is minuscule.”  

    Using zeolite to create methanol requires highly concentrated methane, high temperatures and pressures, and industrial processing conditions. Yet Plata’s process, which dopes the zeolite with copper, operates in the presence of oxygen at much lower temperatures under typical pressures. “We let the methane proceed the way it wants from a thermodynamic perspective from methane to methanol down to CO2,” says Plata. 

    Researchers around the world are working on other dilute methane removal technologies. Projects include spraying iron salt aerosols into sea air where they react with natural chlorine or bromine radicals, thereby capturing methane. Most of these geoengineering solutions, however, are difficult to measure and would require massive scale to make a difference.  

    Plata is focusing her zeolite filters on environments where concentrations are high, but not so high as to be flammable. “We are trying to scale zeolite into filters that you could snap onto the side of a cross-ventilation fan in a dairy barn or in a ventilation air shaft in a coal mine,” says Plata. “For every packet of air we bring in, we take a lot of methane out, so we get more bang for our buck.”  

    The major challenge is creating a filter that can handle high flow rates without getting clogged or falling apart. Dairy barn air handlers can push air at up to 5,000 cubic feet per minute and coal mine handlers can approach 500,000 CFM. 

    Plata is exploring engineering options including fluidized bed reactors with floating catalyst particles. Another filter solution, based in part on catalytic converters, features “higher-order geometric structures where you have a porous material with a long path length where the gas can interact with the catalyst,” says Plata. “This avoids the challenge with fluidized beds of containing catalyst particles in the reactor. Instead, they are fixed within a structured material.”  

    Competing technologies for removing methane from mine shafts “operate at temperatures of 1,000 to 1,200 degrees C, requiring a lot of energy and risking explosion,” says Plata. “Our technology avoids safety concerns by operating at 300 to 400 degrees C. It reduces energy use and provides more tractable deployment costs.” 

    Potentially, energy and dollar costs could be further reduced in coal mines by capturing the heat generated by the conversion process. “In coal mines, you have enrichments above a half-percent methane, but below the 4 percent flammability threshold,” says Plata. “The excess heat from the process could be used to generate electricity using off-the-shelf converters.” 

    Plata’s dairy barn research is funded by the Gerstner Family Foundation and the coal mining project by the U.S. Department of Energy. “The DOE would like us to spin out the technology for scale-up within three years,” says Plata. “We cannot guarantee we will hit that goal, but we are trying to develop this as quickly as possible. Our society needs to start reducing methane emissions now.”  More

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    Understanding air pollution from space

    Climate change and air pollution are interlocking crises that threaten human health. Reducing emissions of some air pollutants can help achieve climate goals, and some climate mitigation efforts can in turn improve air quality.

    One part of MIT Professor Arlene Fiore’s research program is to investigate the fundamental science in understanding air pollutants — how long they persist and move through our environment to affect air quality.

    “We need to understand the conditions under which pollutants, such as ozone, form. How much ozone is formed locally and how much is transported long distances?” says Fiore, who notes that Asian air pollution can be transported across the Pacific Ocean to North America. “We need to think about processes spanning local to global dimensions.”

    Fiore, the Peter H. Stone and Paola Malanotte Stone Professor in Earth, Atmospheric and Planetary Sciences, analyzes data from on-the-ground readings and from satellites, along with models, to better understand the chemistry and behavior of air pollutants — which ultimately can inform mitigation strategies and policy setting.

    A global concern

    At the United Nations’ most recent climate change conference, COP26, air quality management was a topic discussed over two days of presentations.

    “Breathing is vital. It’s life. But for the vast majority of people on this planet right now, the air that they breathe is not giving life, but cutting it short,” said Sarah Vogel, senior vice president for health at the Environmental Defense Fund, at the COP26 session.

    “We need to confront this twin challenge now through both a climate and clean air lens, of targeting those pollutants that warm both the air and harm our health.”

    Earlier this year, the World Health Organization (WHO) updated its global air quality guidelines it had issued 15 years earlier for six key pollutants including ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), and carbon monoxide (CO). The new guidelines are more stringent based on what the WHO stated is the “quality and quantity of evidence” of how these pollutants affect human health. WHO estimates that roughly 7 million premature deaths are attributable to the joint effects of air pollution.

    “We’ve had all these health-motivated reductions of aerosol and ozone precursor emissions. What are the implications for the climate system, both locally but also around the globe? How does air quality respond to climate change? We study these two-way interactions between air pollution and the climate system,” says Fiore.

    But fundamental science is still required to understand how gases, such as ozone and nitrogen dioxide, linger and move throughout the troposphere — the lowermost layer of our atmosphere, containing the air we breathe.

    “We care about ozone in the air we’re breathing where we live at the Earth’s surface,” says Fiore. “Ozone reacts with biological tissue, and can be damaging to plants and human lungs. Even if you’re a healthy adult, if you’re out running hard during an ozone smog event, you might feel an extra weight on your lungs.”

    Telltale signs from space

    Ozone is not emitted directly, but instead forms through chemical reactions catalyzed by radiation from the sun interacting with nitrogen oxides — pollutants released in large part from burning fossil fuels—and volatile organic compounds. However, current satellite instruments cannot sense ground-level ozone.

    “We can’t retrieve surface- or even near-surface ozone from space,” says Fiore of the satellite data, “although the anticipated launch of a new instrument looks promising for new advances in retrieving lower-tropospheric ozone”. Instead, scientists can look at signatures from other gas emissions to get a sense of ozone formation. “Nitrogen dioxide and formaldehyde are a heavy focus of our research because they serve as proxies for two of the key ingredients that go on to form ozone in the atmosphere.”

    To understand ozone formation via these precursor pollutants, scientists have gathered data for more than two decades using spectrometer instruments aboard satellites that measure sunlight in ultraviolet and visible wavelengths that interact with these pollutants in the Earth’s atmosphere — known as solar backscatter radiation.

    Satellites, such as NASA’s Aura, carry instruments like the Ozone Monitoring Instrument (OMI). OMI, along with European-launched satellites such as the Global Ozone Monitoring Experiment (GOME) and the Scanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY), and the newest generation TROPOspheric Monitoring instrument (TROPOMI), all orbit the Earth, collecting data during daylight hours when sunlight is interacting with the atmosphere over a particular location.

    In a recent paper from Fiore’s group, former graduate student Xiaomeng Jin (now a postdoc at the University of California at Berkeley), demonstrated that she could bring together and “beat down the noise in the data,” as Fiore says, to identify trends in ozone formation chemistry over several U.S. metropolitan areas that “are consistent with our on-the-ground understanding from in situ ozone measurements.”

    “This finding implies that we can use these records to learn about changes in surface ozone chemistry in places where we lack on-the-ground monitoring,” says Fiore. Extracting these signals by stringing together satellite data — OMI, GOME, and SCIAMACHY — to produce a two-decade record required reconciling the instruments’ differing orbit days, times, and fields of view on the ground, or spatial resolutions. 

    Currently, spectrometer instruments aboard satellites are retrieving data once per day. However, newer instruments, such as the Geostationary Environment Monitoring Spectrometer launched in February 2020 by the National Institute of Environmental Research in the Ministry of Environment of South Korea, will monitor a particular region continuously, providing much more data in real time.

    Over North America, the Tropospheric Emissions: Monitoring of Pollution Search (TEMPO) collaboration between NASA and the Smithsonian Astrophysical Observatory, led by Kelly Chance of Harvard University, will provide not only a stationary view of the atmospheric chemistry over the continent, but also a finer-resolution view — with the instrument recording pollution data from only a few square miles per pixel (with an anticipated launch in 2022).

    “What we’re very excited about is the opportunity to have continuous coverage where we get hourly measurements that allow us to follow pollution from morning rush hour through the course of the day and see how plumes of pollution are evolving in real time,” says Fiore.

    Data for the people

    Providing Earth-observing data to people in addition to scientists — namely environmental managers, city planners, and other government officials — is the goal for the NASA Health and Air Quality Applied Sciences Team (HAQAST).

    Since 2016, Fiore has been part of HAQAST, including collaborative “tiger teams” — projects that bring together scientists, nongovernment entities, and government officials — to bring data to bear on real issues.

    For example, in 2017, Fiore led a tiger team that provided guidance to state air management agencies on how satellite data can be incorporated into state implementation plans (SIPs). “Submission of a SIP is required for any state with a region in non-attainment of U.S. National Ambient Air Quality Standards to demonstrate their approach to achieving compliance with the standard,” says Fiore. “What we found is that small tweaks in, for example, the metrics we use to convey the science findings, can go a long way to making the science more usable, especially when there are detailed policy frameworks in place that must be followed.”

    Now, in 2021, Fiore is part of two tiger teams announced by HAQAST in late September. One team is looking at data to address environmental justice issues, by providing data to assess communities disproportionately affected by environmental health risks. Such information can be used to estimate the benefits of governmental investments in environmental improvements for disproportionately burdened communities. The other team is looking at urban emissions of nitrogen oxides to try to better quantify and communicate uncertainties in the estimates of anthropogenic sources of pollution.

    “For our HAQAST work, we’re looking at not just the estimate of the exposure to air pollutants, or in other words their concentrations,” says Fiore, “but how confident are we in our exposure estimates, which in turn affect our understanding of the public health burden due to exposure. We have stakeholder partners at the New York Department of Health who will pair exposure datasets with health data to help prioritize decisions around public health.

    “I enjoy working with stakeholders who have questions that require science to answer and can make a difference in their decisions.” Fiore says. More