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Friday, September 21st, 2018

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    9:12a
    Study: Emissions from most diesel cars in Europe greatly exceed laboratory testing levels

    In September 2015, the German automaker Volkswagen was found to have illegally cheated federal emissions tests in the United States, by intentionally programming emissions control devices to turn on only during laboratory testing. The devices enabled more than 11 million passenger vehicles to meet U.S. emissions standards in the laboratory despite producing emissions up to 40 times higher than the legal limit in real-world driving conditions.

    Now a new MIT study reports that Volkswagen is not the only auto manufacturer to make diesel cars that produce vastly more emissions on the road than in laboratory tests. The study, published this month in Atmospheric Environment, finds that in Europe, 10 major auto manufacturers produced diesel cars, sold between 2000 and 2015, that generate up to 16 times more emissions on the road than in regulatory tests — a level that exceeds European limits but does not violate any EU laws.

    What’s more, the researchers predict these excess emissions will have a significant health impact, causing approximately 2,700 premature deaths per year across Europe. These health effects, they found, are “transboundary,” meaning that diesel emissions produced in one country can adversely affect populations in other countries, thousands of kilometers away.

    “You might imagine that where the excess emissions occur is where people might die early,” says study author Steven Barrett, the Raymond L. Bisplinghoff Professor of Aeronautics and Astronautics at MIT. “But instead we find that 70 percent of the total [health] impacts are transboundary. It suggests coordination is needed not at the country, but at the continental scale, to try to solve this problem of excess emissions.”

    The 10 manufacturers’ excess emissions may not be a result of unlawful violations, as was the case with Volkswagen. Instead, the team writes that “permissive testing procedures at the EU level and defective emissions control strategies” may be to blame.

    The researchers report a silver lining: If all 10 auto manufacturers were to improve their emissions control technologies to perform at the same level as the best manufacturer in the group, this would prevent up to 1,900 premature deaths per year.

    “That’s pretty significant in terms of the number of premature mortalities that would be avoided,” Barrett says.

    Barrett’s co-authors at MIT are Guillaume Chossière, Robert Malina (now at Hasselt University), Florian Allroggen, Sebastian Eastham, and Raymond Speth.

    Tuning the knobs

    The study focuses on emissions of nitrogen oxides, or NOx, a type of gas that is produced in diesel exhaust. When the gas gets oxidized and reacts with ammonia in the atmosphere, it forms fine particles and can travel for long distances before settling. When these particles are inhaled, they can lodge deep in the lungs, causing respiratory disease, asthma, and other pulmonary and cardiac conditions. Additionally NOx emissions cause the formation of ozone, a pollutant long associated with adverse health outcomes.

    “There are many times the number of diesel cars in Europe compared to the U.S., partly because the EU started pushing diesel for environmental reasons, as it produces less carbon dioxide emissions compared with [gasoline],” Barrett says. “It’s a case where diesel has probably been beneficial in terms of climate impacts, but it’s come at the cost of human health.”

    Recently, the EU started tightening its standards for diesel exhaust to reduce NOx emissions and their associated health effects. However, independent investigations have found that most diesel cars on the road do not meet the new emissions standards in real driving conditions.  

    “Initially manufacturers were able to genuinely meet regulations, but more recently it seems they’ve almost tweaked knobs to meet the regulations on paper, even if in reality that’s not reproduced on the road,” Barrett says. “And that’s not been illegal in Europe.”

    Life exposure

    In this study, Barrett and his colleagues quantified the health impacts in Europe of excess NOx emissions — emissions that were not accounted for in standard vehicle testing but are produced in actual driving conditions. They also estimated specific manufacturers’ contributions to the total health impacts related to the excess emissions.

    The researchers considered 10 major auto manufacturers of diesel cars sold in Europe, for which lab and on-road emissions data were available: Volkswagen, Renault, Peugeot-Citroën, Fiat, Ford, General Motors, BMW, Daimler, Toyota, and Hyundai. Together, these groups represent more than 90 percent of the total number of diesel cars sold between 2000 and 2015, in 28 member states of the EU, along with Norway and Switzerland.

    For each manufacturer, the team calculated the total amount of excess emissions produced by that manufacturer’s diesel car models, based on available emissions data from laboratory testing and independent on-road tests. They found that overall, diesel cars produce up to 16 times more NOx emissions on the road than in lab tests.

    They then calculated the excess emissions associated with each manufacturer’s diesel car, by accounting for the number of those cars that were sold between 2000 and 2015, for each country in which those cars were sold.

    The team used GEOS-Chem, a chemistry transport model that simulates the circulation of chemicals and particles through the atmosphere, to track where each manufacturer’s excess NOx emissions traveled over time. They then overlaid a population map of the EU onto the atmospheric model to identify specific populations that were most at risk of exposure to the excess NOx emissions.  

    Finally, the team consulted epidemiological work to relate various populations’ NOx exposure to their estimated health risk. The researchers considered four main populations in these calculations: adults with ischemic heart disease, stroke, chronic obstructive pulmonary disease, and lung cancer.

    Overall, they estimated that, each year, 2,700 people within these populations will lose at least a decade of their life due to exposure to excess NOx emissions from passenger cars. They broke this number down by manufacturer and found a wide spread of health impact contributions: Volkswagen, Renault, and General Motors produced diesel cars associated with the most yearly premature deaths, each numbering in the hundreds, while Toyota, Hyundai, and BMW were associated with fewer early deaths.

    “The variation across manufacturers was more than a factor of five, which was much bigger than we expected,” Barrett says.

    “There’s no safe level”

    For each country, the team also compared the excess emissions that it produced itself, versus the number of premature deaths that its population incurred, and found virtually no relationship. That is, some countries, such as Poland and Switzerland, produced very little NOx emissions and yet experienced a disproportionate number of premature deaths from excess emissions originating in other countries.

    Barrett says this transboundary effect may be due to the nature of NOx emissions. Unlike particulate matter spewed from smokestacks, such as soot, which mostly settles out in the local area, NOx is first emitted as a gas, which can be carried easily by the wind across thousands of kilometers, before reacting with ammonia to form particulates, a form of the chemical that can ultimately cause respiratory and cardiac problems.

    “There’s almost no correlation between who drives [diesel cars] and who incurs the health disbenefits, because the impacts are so diffuse through all of Europe,” Barrett says.

    The study ends with a final result: If all 10 manufacturers were to meet the on-road emissions performance of the best manufacturer in the group, this would avoid 1,900 premature deaths due to NOx exposure. But Barrett says ultimately, regulators and manufacturers will have to go even further to prevent emissions-associated mortalities.

    “The solution is to eliminate NOx altogether,” Barrett says. “We know there are human health impacts right down to pre-industrial levels, so there’s no safe level. At this point in time, it’s not that we have to go back to [gasoline]. It’s more that electricification is the answer, and ultimately we do have to have zero emissions in cities.”

    12:06p
    New battery gobbles up carbon dioxide

    A new type of battery developed by researchers at MIT could be made partly from carbon dioxide captured from power plants. Rather than attempting to convert carbon dioxide to specialized chemicals using metal catalysts, which is currently highly challenging, this battery could continuously convert carbon dioxide into a solid mineral carbonate as it discharges.

    While still based on early-stage research and far from commercial deployment, the new battery formulation could open up new avenues for tailoring electrochemical carbon dioxide conversion reactions, which may ultimately help reduce the emission of the greenhouse gas to the atmosphere.

    The battery is made from lithium metal, carbon, and an electrolyte that the researchers designed. The findings are described today in the journal Joule, in a paper by assistant professor of mechanical engineering Betar Gallant, doctoral student Aliza Khurram, and postdoc Mingfu He.

    Currently, power plants equipped with carbon capture systems generally use up to 30 percent of the electricity they generate just to power the capture, release, and storage of carbon dioxide. Anything that can reduce the cost of that capture process, or that can result in an end product that has value, could significantly change the economics of such systems, the researchers say.

    However, “carbon dioxide is not very reactive,” Gallant explains, so “trying to find new reaction pathways is important.” Generally, the only way to get carbon dioxide to exhibit significant activity under electrochemical conditions is with large energy inputs in the form of high voltages, which can be an expensive and inefficient process. Ideally, the gas would undergo reactions that produce something worthwhile, such as a useful chemical or a fuel. However, efforts at electrochemical conversion, usually conducted in water, remain hindered by high energy inputs and poor selectivity of the chemicals produced.

    Gallant and her co-workers, whose expertise has to do with nonaqueous (not water-based) electrochemical reactions such as those that underlie lithium-based batteries, looked into whether carbon-dioxide-capture chemistry could be put to use to make carbon-dioxide-loaded electrolytes — one of the three essential parts of a battery — where the captured gas could then be used during the discharge of the battery to provide a power output.

    This approach is different from releasing the carbon dioxide back to the gas phase for long-term storage, as is now used in carbon capture and sequestration, or CCS. That field generally looks at ways of capturing carbon dioxide from a power plant through a chemical absorption process and then either storing it in underground formations or chemically altering it into a fuel or a chemical feedstock.

    Instead, this team developed a new approach that could potentially be used right in the power plant waste stream to make material for one of the main components of a battery.

    While interest has grown recently in the development of lithium-carbon-dioxide batteries, which use the gas as a reactant during discharge, the low reactivity of carbon dioxide has typically required the use of metal catalysts. Not only are these expensive, but their function remains poorly understood, and reactions are difficult to control.

    By incorporating the gas in a liquid state, however, Gallant and her co-workers found a way to achieve electrochemical carbon dioxide conversion using only a carbon electrode. The key is to preactivate the carbon dioxide by incorporating it into an amine solution.

    “What we’ve shown for the first time is that this technique activates the carbon dioxide for more facile electrochemistry,” Gallant says. “These two chemistries — aqueous amines and nonaqueous battery electrolytes — are not normally used together, but we found that their combination imparts new and interesting behaviors that can increase the discharge voltage and allow for sustained conversion of carbon dioxide.”

    They showed through a series of experiments that this approach does work, and can produce a lithium-carbon dioxide battery with voltage and capacity that are competitive with that of state-of-the-art lithium-gas batteries. Moreover, the amine acts as a molecular promoter that is not consumed in the reaction.

    The key was developing the right electrolyte system, Khurram explains. In this initial proof-of-concept study, they decided to use a nonaqueous electrolyte because it would limit the available reaction pathways and therefore make it easier to characterize the reaction and determine its viability. The amine material they chose is currently used for CCS applications, but had not previously been applied to batteries.

    This early system has not yet been optimized and will require further development, the researchers say. For one thing, the cycle life of the battery is limited to 10 charge-discharge cycles, so more research is needed to improve rechargeability and prevent degradation of the cell components. “Lithium-carbon dioxide batteries are years away” as a viable product, Gallant says, as this research covers just one of several needed advances to make them practical.

    But the concept offers great potential, according to Gallant. Carbon capture is widely considered essential to meeting worldwide goals for reducing greenhouse gas emissions, but there are not yet proven, long-term ways of disposing of or using all the resulting carbon dioxide. Underground geological disposal is still the leading contender, but this approach remains somewhat unproven and may be limited in how much it can accommodate. It also requires extra energy for drilling and pumping.

    The researchers are also investigating the possibility of developing a continuous-operation version of the process, which would use a steady stream of carbon dioxide under pressure with the amine material, rather than a preloaded supply the material, thus allowing it to deliver a steady power output as long as the battery is supplied with carbon dioxide. Ultimately, they hope to make this into an integrated system that will carry out both the capture of carbon dioxide from a power plant’s emissions stream, and its conversion into an electrochemical material that could then be used in batteries. “It’s one way to sequester it as a useful product,” Gallant says.

    “It was interesting that Gallant and co-workers cleverly combined the prior knowledge from two different areas, metal-gas battery electrochemistry and carbon-dioxide capture chemistry, and succeeded in increasing both the energy density of the battery and the efficiency of the carbon-dioxide capture,” says Kisuk Kang, a professor at Seoul National University in South Korea, who was not associated with this research.

    “Even though more precise understanding of the product formation from carbon dioxide may be needed in the future, this kind of interdisciplinary approach is very exciting and often offers unexpected results, as the authors elegantly demonstrated here,” Kang adds.

    MIT’s Department of Mechanical Engineering provided support for the project.

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