Source Apportionment of Ambient Methane Enhancements in Los Angeles, California, To Evaluate Emission Inventory Estimates.

Rapid increase in atmospheric methane (CH4) mixing ratios over the past century is attributable to the intensification of human activities. Information on spatially explicit source contributions is needed to develop efficient and cost-effective CH4 emission reduction and mitigation strategies to addresses near-term climate change. This study collected long-term ambient CH4 measurements at Mount Wilson Observatory (MWO) in Los Angeles, California, to estimate the annual CH4 emissions from the portion of Los Angeles County that is within the South Coast Air Basin (SCLA). The measurement-based CH4 emission estimates for SCLA ranged from 3.95 to 4.89 million metric tons (MMT) carbon dioxide equivalent (CO2e) per year between 2012 and 2016. Source apportionment of CH4, CO, CO2, and volatile organic compounds (VOCs) measurements were used to evaluate source categories that contributed to ambient CH4 mixing ratio enhancements (ΔCH4) at SCLA between 2014 and 2016. Results suggested ΔCH4 contributions of 56-79% from natural gas sources, 7-31% from landfills, and 4-15% from transportation sources. The SCLA-specific CH4 emission estimate made using a research grade gridded CH4 emission inventory suggested contributions of 47% from natural gas sources and 50% from landfills. Subsequent airborne measurements determined that CH4 emissions from two major CH4 sources in SCLA were significantly smaller in magnitude than previously thought. This study highlights the importance of studying the variabilities of CH4 emissions across California for policy makers and stakeholders alike.

Volatility of primary organic aerosol emitted from light duty gasoline vehicles.

Primary organic aerosol (POA) emitted from light duty gasoline vehicles (LDGVs) exhibits a semivolatile behavior in which heating the aerosol and/or diluting the aerosol leads to partial evaporation of the POA. A single volatility distribution can explain the median evaporation behavior of POA emitted from LDGVs but this approach is unable to capture the full range of measured POA volatility during thermodenuder (TD) experiments conducted at atmospherically relevant concentrations (2-5 µg m(-3)). Reanalysis of published TD data combined with analysis of new measurements suggest that POA emitted from gasoline vehicles is composed of two types of POA that have distinctly different volatility distributions: one low-volatility distribution and one medium-volatility distribution. These correspond to fuel combustion-derived POA and motor oil POA, respectively. Models that simultaneously incorporate both of these distributions are able to reproduce experimental results much better (R(2) = 0.94) than models that use a single average or median distribution (R(2) = 0.52). These results indicate that some fraction of POA emitted from LDGVs is essentially nonvolatile under typical atmospheric dilution levels. Roughly 50% of the vehicles tested in the current study had POA emissions dominated by fuel combustion products (essentially nonvolatile). Further testing is required to determine appropriate fleet-average emissions rates of the two POA types from LDGVs.

Real-time emission factor measurements of isocyanic acid from light duty gasoline vehicles.

Exposure to gas-phase isocyanic acid (HNCO) has been previously shown to be associated with the development of atherosclerosis, cataracts and rheumatoid arthritis. As such, accurate emission inventories for HNCO are critical for modeling the spatial and temporal distribution of HNCO on a regional and global scale. To date, HNCO emission rates from light duty gasoline vehicles, operated under driving conditions, have not been determined. Here, we present the first measurements of real-time emission factors of isocyanic acid from a fleet of eight light duty gasoline-powered vehicles (LDGVs) tested on a chassis dynamometer using the Unified Driving Cycle (UC) at the California Air Resources Board (CARB) Haagen-Smit test facility, all of which were equipped with three-way catalytic converters. HNCO emissions were observed from all vehicles, in contrast to the idealized laboratory measurements. We report the tested fleet averaged HNCO emission factors, which depend strongly on the phase of the drive cycle; ranging from 0.46 ± 0.13 mg kg fuel(-1) during engine start to 1.70 ± 1.77 mg kg fuel(-1) during hard acceleration after the engine and catalytic converter were warm. The tested eight-car fleet average fuel based HNCO emission factor was 0.91 ± 0.58 mg kg fuel(-1), within the range previously estimated for light duty diesel-powered vehicles (0.21-3.96 mg kg fuel(-1)). Our results suggest that HNCO emissions from LDGVs represent a significant emission source in urban areas that should be accounted for in global and regional models.

Daily trends and source apportionment of ultrafine particulate mass (PM0.1) over an annual cycle in a typical California city.

Toxicology studies indicate that inhalation of ultrafine particles (Dp < 0.1 µm) causes adverse health effects, presumably due to their large surface area-to-volume ratio that can drive heterogeneous reactions. Epidemiological associations between ultrafine particles and health effects, however, have been difficult to identify due to the lack of appropriate long-term monitoring and exposure data. The majority of the existing ultrafine particle epidemiology studies are based on exposure to particle number, although an independent analysis suggests that ultrafine particle mass (PM0.1) correlates better with particle surface area. More information is needed to characterize PM0.1 exposure to fully evaluate the health effects of ultrafine particles using epidemiology. The present study summarizes 1 year of daily PM0.1 chemistry and source apportionment at Sacramento, CA, USA. Positive matrix factorization (PMF) was used to resolve PM0.1 source contributions from old-technology diesel engines, residential wood burning, rail, regional traffic, and brake wear/road dust. Diesel PM0.1 and total PM0.1 concentrations were reduced by 97 and 26%, respectively, as a result of the adoption of cleaner diesel technology. The strong linear correlation between PM0.1 and particle surface area in central California suggests that the adoption of clean diesel engines reduced particle surface area by similar amounts. PM0.1 sulfate reduction occurred as a result of reduced primary particle surface area available for sulfate condensation. The current study demonstrates the capability of measuring PM0.1 source contributions over a 12 month period and identifies the extended benefits of emissions reduction efforts for diesel engines on ambient concentrations of primary and secondary PM0.1.

Real-time black carbon emission factor measurements from light duty vehicles.

Eight light-duty gasoline low emission vehicles (LEV I) were tested on a Chassis dynamometer using the California Unified Cycle (UC) at the Haagen-Smit vehicle test facility at the California Air Resources Board in El Monte, CA during September 2011. The UC includes a cold start phase followed by a hot stabilized running phase. In addition, a light-duty gasoline LEV vehicle and ultralow emission vehicle (ULEV), and a light-duty diesel passenger vehicle and gasoline direct injection (GDI) vehicle were tested on a constant velocity driving cycle. A variety of instruments with response times ≥0.1 Hz were used to characterize how the emissions of the major particulate matter components varied for the LEVs during a typical driving cycle. This study focuses primarily on emissions of black carbon (BC). These measurements allowed for the determination of BC emission factors throughout the driving cycle, providing insights into the temporal variability of BC emission factors during different phases of a typical driving cycle.