D. R. Gentner

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

Evidence for NOx Control over Nighttime SOA Formation

Nighttime Sources Organic aerosols account for about half of the total mass of small (submicrometer) particles in the troposphere, and most of them are believed to form through the oxidation of volatile molecules, rather than being emitted directly from specific sources. These particles have important roles in many atmospheric processes, and therefore a better understanding of their complex composition and chemistry is desirable. Rollins et al. (p. 1210) report on measurements of particulate organic nitrates, an important class of organic aerosols that form at night. However, they also found that high concentrations of organic molecules can suppress the growth of organic nitrate particles. These observations should help improve efforts to reduce organic aerosol pollution. The growth of particulate organic nitrates can account for much of the nighttime increase in organic aerosol mass. Laboratory studies have established a number of chemical pathways by which nitrogen oxides (NOx) affect atmospheric organic aerosol (OA) production. However, these effects have not been directly observed in ambient OA. We report measurements of particulate organic nitrates in Bakersfield, California, the nighttime formation of which increases with NOx and is suppressed by high concentrations of organic molecules that rapidly react with nitrate radical (NO3)—evidence that multigenerational chemistry is responsible for organic nitrate aerosol production. This class of molecules represents about a third of the nighttime increase in OA, suggesting that most nighttime secondary OA is due to the NO3 product of anthropogenic NOx emissions. Consequently, reductions in NOx emissions should reduce the concentration of organic aerosol in Bakersfield and the surrounding region.

Long-Term Trends in Motor Vehicle Emissions in U.S. Urban Areas

A fuel-based approach is used to estimate long-term trends (1990-2010) in carbon monoxide (CO) emissions from motor vehicles. Non-methane hydrocarbons (NMHC) are estimated using ambient NMHC/CO ratios after controlling for nonvehicular sources. Despite increases in fuel use of ∼10-40%, CO running exhaust emissions from on-road vehicles decreased by ∼80-90% in Los Angeles, Houston, and New York City, between 1990 and 2010. The ratio of NMHC/CO was found to be 0.24 ± 0.04 mol C/mol CO over time in Los Angeles, indicating that both pollutants decreased at a similar rate and were improved by similar emission controls, whereas on-road data from other cities suggest rates of reduction in NMHC versus CO emissions may differ somewhat. Emission ratios of CO/NOx (nitrogen oxides = NO + NO2) and NMHC/NOx decreased by a factor of ∼4 between 1990 and 2007 due to changes in the relative emission rates of passenger cars versus diesel trucks, and slight uptick thereafter, consistent across all urban areas considered here. These pollutant ratios are expected to increase in future years due to (1) slowing rates of decrease in CO and NMHC emissions from gasoline vehicles and (2) significant advances in control of diesel NOx emissions.

Chemical Composition of Gas-Phase Organic Carbon Emissions from Motor Vehicles and Implications for Ozone Production

Motor vehicles are major sources of gas-phase organic carbon, which includes volatile organic compounds (VOCs) and other compounds with lower vapor pressures. These emissions react in the atmosphere, leading to the formation of ozone and secondary organic aerosol (SOA). With more chemical detail than previous studies, we report emission factors for over 230 compounds from gasoline and diesel vehicles via two methods. First we use speciated measurements of exhaust emissions from on-road vehicles in summer 2010. Second, we use a fuel composition-based approach to quantify uncombusted fuel components in exhaust using the emission factor for total uncombusted fuel in exhaust together with detailed chemical characterization of liquid fuel samples. There is good agreement between the two methods except for products of incomplete combustion, which are not present in uncombusted fuels and comprise 32 ± 2% of gasoline exhaust and 26 ± 1% of diesel exhaust by mass. We calculate and compare ozone production potentials of diesel exhaust, gasoline exhaust, and nontailpipe gasoline emissions. Per mass emitted, the gas-phase organic compounds in gasoline exhaust have the largest potential impact on ozone production with over half of the ozone formation due to products of incomplete combustion (e.g., alkenes and oxygenated VOCs). When combined with data on gasoline and diesel fuel sales in the U.S., these results indicate that gasoline sources are responsible for 69-96% of emissions and 79-97% of the ozone formation potential from gas-phase organic carbon emitted by motor vehicles.

Formation and growth of ultrafine particles from secondary sources in Bakersfield, California

carbon (EC) and the AMS tracer C4H9 for hydrocarbon-like organic aerosol (HOA) peaked in the early morning during rush hour, indicative of primary emissions. The fact that the particle number concentration peaked in the afternoon, when EC was at minimum, indicates that the midday increase in number concentration was likely due to new particle formation. The potential importance of solar radiation, the condensation sink of vapor on existing particles, concentrations of OH, O3 ,S O2 ,N H3, and VOCs for both condensational growth and new particle formation is evaluated based on the covariation of these parameters with ultrafine mass. The results suggest that the ultrafine particles are from secondary sources that are co-emitted or co-produced with glyoxal and formaldehyde.

Ozone deposition to an orange orchard: Partitioning between stomatal and non-stomatal sinks

Orange trees are widely cultivated in regions with high concentrations of tropospheric ozone. Citrus absorb ozone through their stomata and emit volatile organic compounds (VOC), which, together with soil emissions of NO, contribute to non-stomatal ozone removal. In a Valencia orange orchard in Exeter, California, we used fast sensors and eddy covariance to characterize water and ozone fluxes. We also measured meteorological parameters necessary to model other important sinks of ozone deposition. We present changes in magnitude of these ozone deposition sinks over the year in response to environmental parameters. Within the plant canopy, the orchard constitutes a sink for ozone, with non-stomatal ozone deposition larger than stomatal uptake. In particular, soil deposition and reactions between ozone, VOC and NO represented the major sinks of ozone. This research aims to help the development of metrics for ozone-risk assessment and advance our understanding of citrus in biosphere-atmosphere exchange.

Oil sands operations as a large source of secondary organic aerosols

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

Atmospheric benzenoid emissions from plants rival those from fossil fuels

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y−1), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

Sesquiterpenoid emissions from agricultural crops: correlations to monoterpenoid emissions and leaf terpene content.

Emissions of biogenic volatile organic compounds (BVOCs) are important precursors to both ozone and secondary organic aerosol formation. In this study, we identify and quantify volatile (C(10)) and intermediate-volatility (C(15)) BVOCs stored in and emitted from 22 prominent woody and herbaceous crops with a particular focus on sesquiterpenoids (SQTs), which have presented measurement challenges in previous studies. Monoterpenoids (MNTs) and SQTs were simultaneously emitted from all the crops studied; there were significant correlations between emission rates and leaf content for both MNTs and SQTs and additional correlations between MNTs and SQTs in both emissions and leaf content. Our results suggest that species with high concentrations of stored terpenoids in their leaves, such as those grown commercially for their essential oil content, are likely high BVOC emitters. Emissions from agricultural species were dominated by SQTs at low MNT emission rates (on the order of several tens of ng/(g(DM)*h)), while at higher MNT levels (on the order of several hundreds of ng/(g(DM)*h)), SQT emissions were approximately equivalent. Based on our empirical correlations, we estimate that global SQT emissions are similar to MNT emissions and on the order of 100 Tg yr(-1), which justifies the need for better representation of SQTs in both BVOC emission and atmospheric models.

Volatile chemical products emerging as largest petrochemical source of urban organic emissions

Air pollution evolution Transport-derived emissions of volatile organic compounds (VOCs) have decreased owing to stricter controls on air pollution. This means that the relative importance of chemicals in pesticides, coatings, printing inks, adhesives, cleaning agents, and personal care products has increased. McDonald et al. show that these volatile chemical products now contribute fully one-half of emitted VOCs in 33 industrialized cities (see the Perspective by Lewis). Thus, the focus of efforts to mitigate ozone formation and toxic chemical burdens need to be adjusted. Science, this issue p. 760; see also p. 744 Chemical products contribute as much organic air pollution as transportation emissions in many cities. A gap in emission inventories of urban volatile organic compound (VOC) sources, which contribute to regional ozone and aerosol burdens, has increased as transportation emissions in the United States and Europe have declined rapidly. A detailed mass balance demonstrates that the use of volatile chemical products (VCPs)—including pesticides, coatings, printing inks, adhesives, cleaning agents, and personal care products—now constitutes half of fossil fuel VOC emissions in industrialized cities. The high fraction of VCP emissions is consistent with observed urban outdoor and indoor air measurements. We show that human exposure to carbonaceous aerosols of fossil origin is transitioning away from transportation-related sources and toward VCPs. Existing U.S. regulations on VCPs emphasize mitigating ozone and air toxics, but they currently exempt many chemicals that lead to secondary organic aerosols.