Naomi Zimmerman

Light-absorbing properties of ambient black carbon and brown carbon from fossil fuel and biomass burning sources

The optical properties of ambient black carbon-containing particles and the composition of their associated coatings were investigated at a downtown site in Toronto, Canada, for 2 weeks in June 2013. The objective was to assess the relationship between black carbon (BC) coating composition/thickness and absorption. The site was influenced by emissions from local vehicular traffic, wildfires in Quebec, and transboundary fossil fuel combustion emissions in the United States. Mass concentrations of BC and associated nonrefractory coatings were measured using a soot particle–aerosol mass spectrometer (SP-AMS), while aerosol absorption and scattering were measured using a photoacoustic soot spectrometer (PASS). Absorption enhancement was investigated both by comparing ambient and thermally denuded PASS absorption data and by relating absorption data to BC mass concentrations measured using the SP-AMS. Minimal absorption enhancement attributable to lensing at 781 nm was observed for BC using both approaches. However, brown carbon was detected when the site was influenced by wildfire emissions originating in Quebec. BC coating to core mass ratios were highest during this period (~7), and while direct absorption by brown carbon resulted in an absorption enhancement at 405 nm (>2.0), no enhancement attributable to lensing at 781 nm was observed. The efficiency of BC coating removal in the denuder decreased substantially when wildfire-related organics were present and may represent an obstacle for future similar studies. These findings indicate that BC absorption enhancement due to lensing is minimal for downtown Toronto, and potentially other urban locations, even when impacted by long-range transport events.

Assessing the Climate Trade-Offs of Gasoline Direct Injection Engines.

Compared to port fuel injection (PFI) engine exhaust, gasoline direct injection (GDI) engine exhaust has higher emissions of black carbon (BC), a climate-warming pollutant. However, the relative increase in BC emissions and climate trade-offs of replacing PFI vehicles with more fuel efficient GDI vehicles remain uncertain. In this study, BC emissions from GDI and PFI vehicles were compiled and BC emissions scenarios were developed to evaluate the climate impact of GDI vehicles using global warming potential (GWP) and global temperature potential (GTP) metrics. From a 20 year time horizon GWP analysis, average fuel economy improvements ranging from 0.14 to 14% with GDI vehicles are required to offset BC-induced warming. For all but the lowest BC scenario, installing a gasoline particulate filter with an 80% BC removal efficiency and <1% fuel penalty is climate beneficial. From the GTP-based analysis, it was also determined that GDI vehicles are climate beneficial within <1-20 years; longer time horizons were associated with higher BC scenarios. The GDI BC emissions spanned 2 orders of magnitude and varied by ambient temperature, engine operation, and fuel composition. More work is needed to understand BC formation mechanisms in GDI engines to ensure that the climate impacts of this engine technology are minimal.

Field Measurements of Gasoline Direct Injection Emission Factors: Spatial and Seasonal Variability.

Four field campaigns were conducted between February 2014 and January 2015 to measure emissions from light-duty gasoline direct injection (GDI) vehicles (2013 Ford Focus) in an urban near-road environment in Toronto, Canada. Measurements of CO2, CO, NOx, black carbon (BC), benzene, toluene, ethylbenzene-xylenes (BTEX), and size-resolved particle number (PN) were recorded 15 m from the roadway and converted to fuel-based emission factors (EFs). Other than for NOx and CO, the GDI engine had elevated emissions compared to the Toronto fleet, with BC EFs in the 73rd percentile, BTEX EFs in the 80-90th percentile, and PN EFs in the 75th percentile during wintertime measurements. Additionally, for three campaigns, a second platform for measuring PN and CO2 was placed 1.5-3 m from the roadway to quantify changes in PN with distance from point of emission. GDI vehicle PN EFs were found to increase by up to 240% with increasing distance from the roadway, predominantly due to an increasing fraction of sub-40 nm particles. PN and BC EFs from the same engine technology were also measured in the laboratory. BC EFs agreed within 20% between the laboratory and real-world measurements; however, laboratory PN EFs were an order of magnitude lower due to exhaust conditioning.

Murine precision-cut lung slices exhibit acute responses following exposure to gasoline direct injection engine emissions.

Gasoline direct injection (GDI) engines are increasingly prevalent in the global vehicle fleet. Particulate matter emissions from GDI engines are elevated compared to conventional gasoline engines. The pulmonary effects of these higher particulate emissions are unclear. This study investigated the pulmonary responses induced by GDI engine exhaust using an ex vivo model. The physiochemical properties of GDI engine exhaust were assessed. Precision cut lung slices were prepared using Balb/c mice to evaluate the pulmonary response induced by one-hour exposure to engine-out exhaust from a laboratory GDI engine operated at conditions equivalent to vehicle highway cruise conditions. Lung slices were exposed at an air-liquid interface using an electrostatic aerosol in vitro exposure system. Particulate and gaseous exhaust was fractionated to contrast mRNA production related to polycyclic aromatic hydrocarbon (PAH) metabolism and oxidative stress. Exposure to GDI engine exhaust upregulated genes involved in PAH metabolism, including Cyp1a1 (2.71, SE=0.22), and Cyp1b1 (3.24, SE=0.12) compared to HEPA filtered air (p<0.05). GDI engine exhaust further increased Cyp1b1 expression compared to filtered GDI engine exhaust (i.e., gas fraction only), suggesting this response was associated with the particulate fraction. Exhaust particulate was dominated by high molecular weight PAHs. Hmox1, an oxidative stress marker, exhibited increased expression after exposure to GDI (1.63, SE=0.03) and filtered GDI (1.55, SE=0.04) engine exhaust compared to HEPA filtered air (p<0.05), likely attributable to a combination of the gas and particulate fractions. Exposure to GDI engine exhaust contributes to upregulation of genes related to the metabolism of PAHs and oxidative stress.

Real-World Emission of Particles from Vehicles: Volatility and the Effects of Ambient Temperature

A majority of the ultrafine particles observed in real-world conditions are systematically excluded from many measurements that help to guide regulation of vehicle emissions. To investigate the impact of this exclusion, coincident near-road particle number (PN) emission factors were quantified up- and downstream of a thermodenuder during two seasonal month-long campaigns with wide-ranging ambient temperatures (-19 to +30 °C) to determine the volatile fraction of particles. During colder temperatures (<0 °C), the volatile fraction of particles was 94%, but decreased to 85% during warmer periods (>20 °C). Additionally, mean PN emission factors were a factor of 3.8 higher during cold compared to warm periods. On the basis of 130 000 vehicle plumes including three additional campaigns, fleet mean emission factors were calculated for PN (8.5 × 1014 kg-fuel-1), black carbon (37 mg kg-fuel-1), organic aerosol (51 mg kg-fuel-1), and particle-bound polycyclic aromatic hydrocarbons (0.7 mg kg-fuel-1). These findings demonstrate that significant differences exist between particles in thermally treated vehicle exhaust as compared to in real-world vehicle plumes to which populations in near-road environments are actually exposed. Furthermore, the magnitude of these differences are dependent upon season and may be more extreme in colder climates.

Carbonaceous aerosol sampling of gasoline direct injection engine exhaust with an integrated organic gas and particle sampler

Positive and negative artifacts of particle-phase organic carbon (p-OC) and the polycyclic aromatic hydrocarbons (PAHs) in gasoline direct injection (GDI) engine exhaust particulate matter (PM) were assessed using an integrated organic gas and particle sampler (IOGAPS). Three configurations (denuder + sorbent impregnated filters (SIFs), upstream Zefluor filter + denuder + SIFs, and standard filter pack + SIFs) were used to collect GDI exhaust samples at cold start and highway cruise operating conditions with no aftertreatment. Approximately 35% of the measured GDI p-OC was attributed to positive artifacts; negative artifacts were not detectable due to low overall SVOC concentrations. GDI engine exhaust PAH concentrations were approximately 10 times higher during cold start than highway cruise. At highway cruise, pyrene and fluoranthene were the dominant PAHs in the undenuded filter pack; downstream of the denuder benzo(a)anthracene was the dominant PAH. From a comparison of our findings to published PAH emission factors we estimate that three-way catalyst conversion efficiencies of PAHs were approximately 80% for 3 of the 15 PAHs measured during highway cruise operation. These conversion efficiencies may be considerably lower during cold start operation when the three-way catalyst has not reached its operating temperature. Our previous work showed that adverse biological responses to GDI engine exhaust exposure may be dominated by the particle phase when measured downstream of a Teflon filter. Understanding the partitioning characteristics of PAHs may help elucidate specific PAHs contributing to this effect.

Comparison of Airway Responses Induced in a Mouse Model by the Gas and Particulate Fractions of Gasoline Direct Injection Engine Exhaust

Diesel exhaust has been associated with asthma, but its response to other engine emissions is not clear. The increasing prevalence of vehicles with gasoline direct injection (GDI) engines motivated this study, and the objective was to evaluate pulmonary responses induced by acute exposure to GDI engine exhaust in an allergic asthma murine model. Mice were sensitized with an allergen to induce airway hyperresponsiveness or treated with saline (non-allergic group). Animals were challenged for 2-h to exhaust from a laboratory GDI engine operated at conditions equivalent to a highway cruise. Exhaust was filtered to assess responses induced by the particulate and gas fractions. Short-term exposure to particulate matter from GDI engine exhaust induced upregulation of genes related to polycyclic aromatic hydrocarbon (PAH) metabolism (Cyp1b1) and inflammation (TNFα) in the lungs of non-allergic mice. High molecular weight PAHs dominated the particulate fraction of the exhaust, and this response was therefore likely attributable to the presence of these PAHs. The particle fraction of GDI engine exhaust further contributed to enhanced methacholine responsiveness in the central and peripheral tissues in animals with airway hyperresponsiveness. As GDI engines gain prevalence in the vehicle fleet, understanding the health impacts of their emissions becomes increasingly important.

Reduced Ultrafine Particle Concentration in Urban Air: Changes in Nucleation and Anthropogenic Emissions

Nucleation is an important source of ambient ultrafine particles (UFP). We present observational evidence of the changes in the frequency and intensity of nucleation events in urban air by analyzing long-term particle size distribution measurements at an urban background site in Pittsburgh, Pennsylvania during 2001-2002 and 2016-2017. We find that both frequency and intensity of nucleation events have been reduced by 40-50% over the past 15 years, resulting in a 70% reduction in UFP concentrations from nucleation. On average, the particle growth rates are 30% slower than 15 years ago. We attribute these changes to dramatic reductions in SO2 (more than 90%) and other pollutant concentrations. Overall, UFP concentrations in Pittsburgh have been reduced by ∼48% in the past 15 years, with a ∼70% reduction in nucleation, ∼27% in weekday local sources (e.g., weekday traffic), and 49% in the regional background. Our results highlight that a reduction in anthropogenic emissions can considerably reduce nucleation events and UFP concentrations in a polluted urban environment.