Daniel S. Tkacik

Secondary organic aerosol formation from intermediate-volatility organic compounds: cyclic, linear, and branched alkanes.

Intermediate volatility organic compounds (IVOCs) are an important class of secondary organic aerosol (SOA) precursors that have not been traditionally included in chemical transport models. A challenge is that the vast majority of IVOCs cannot be speciated using traditional gas chromatography-based techniques; instead they are classified as an unresolved complex mixture (UCM) that is presumably made up of a complex mixture of branched and cyclic alkanes. To better understand SOA formation from IVOCs, a series of smog chamber experiments was conducted with different alkanes, including cyclic, branched, and linear compounds. The experiments focused on freshly formed SOA from hydroxyl (OH) radical-initiated reactions under high-NO(x) conditions at typical atmospheric organic aerosol concentrations (C(OA)). SOA yields from cyclic alkanes were comparable to yields from linear alkanes three to four carbons larger in size. For alkanes with equivalent carbon numbers, branched alkanes had the lowest SOA mass yields, ranging between 0.05 and 0.08 at a C(OA) of 15 μg m(-3). The SOA yield of branched alkanes also depends on the methyl branch position on the carbon backbone. High-resolution aerosol mass spectrometer data indicate that the SOA oxygen-to-carbon ratios were largely controlled by the carbon number of the precursor compound. Depending on the precursor size, the mass spectrum of SOA produced from IVOCs is similar to the semivolatile-oxygenated and hydrocarbon-like organic aerosol factors derived from ambient data. Using the new yield data, we estimated SOA formation potential from diesel exhaust and predict the contribution from UCM vapors to be nearly four times larger than the contribution from single-ring aromatics and comparable to that of polycyclic aromatic hydrocarbons after several hours of oxidation at typical atmospheric conditions. Therefore, SOA from IVOCs may be an important contributor to urban OA and should be included in SOA models; the yield data presented in this study are suitable for such use.

Measurements of Methane Emissions from Natural Gas Gathering Facilities and Processing Plants: Measurement Results

Facility-level methane emissions were measured at 114 gathering facilities and 16 processing plants in the United States natural gas system. At gathering facilities, the measured methane emission rates ranged from 0.7 to 700 kg per hour (kg/h) (0.6 to 600 standard cubic feet per minute (scfm)). Normalized emissions (as a % of total methane throughput) were less than 1% for 85 gathering facilities and 19 had normalized emissions less than 0.1%. The range of methane emissions rates for processing plants was 3 to 600 kg/h (3 to 524 scfm), corresponding to normalized methane emissions rates <1% in all cases. The distributions of methane emissions, particularly for gathering facilities, are skewed. For example, 30% of gathering facilities contribute 80% of the total emissions. Normalized emissions rates are negatively correlated with facility throughput. The variation in methane emissions also appears driven by differences between inlet and outlet pressure, as well as venting and leaking equipment. Substantial venting from liquids storage tanks was observed at 20% of gathering facilities. Emissions rates at these facilities were, on average, around four times the rates observed at similar facilities without substantial venting.

Methane Emissions from Natural Gas Compressor Stations in the Transmission and Storage Sector: Measurements and Comparisons with the EPA Greenhouse Gas Reporting Program Protocol

Equipment- and site-level methane emissions from 45 compressor stations in the transmission and storage (T&S) sector of the US natural gas system were measured, including 25 sites required to report under the EPA greenhouse gas reporting program (GHGRP). Direct measurements of fugitive and vented sources were combined with AP-42-based exhaust emission factors (for operating reciprocating engines and turbines) to produce a study onsite estimate. Site-level methane emissions were also concurrently measured with downwind-tracer-flux techniques. At most sites, these two independent estimates agreed within experimental uncertainty. Site-level methane emissions varied from 2-880 SCFM. Compressor vents, leaky isolation valves, reciprocating engine exhaust, and equipment leaks were major sources, and substantial emissions were observed at both operating and standby compressor stations. The site-level methane emission rates were highly skewed; the highest emitting 10% of sites (including two superemitters) contributed 50% of the aggregate methane emissions, while the lowest emitting 50% of sites contributed less than 10% of the aggregate emissions. Excluding the two superemitters, study-average methane emissions from compressor housings and noncompressor sources are comparable to or lower than the corresponding effective emission factors used in the EPA greenhouse gas inventory. If the two superemitters are included in the analysis, then the average emission factors based on this study could exceed the EPA greenhouse gas inventory emission factors, which highlights the potentially important contribution of superemitters to national emissions. However, quantification of their influence requires knowledge of the magnitude and frequency of superemitters across the entire T&S sector. Only 38% of the methane emissions measured by the comprehensive onsite measurements were reportable under the new EPA GHGRP because of a combination of inaccurate emission factors for leakers and exhaust methane, and various exclusions. The bias is even larger if one accounts for the superemitters, which were not captured by the onsite measurements. The magnitude of the bias varied from site to site by site type and operating state. Therefore, while the GHGRP is a valuable new source of emissions information, care must be taken when incorporating these data into emission inventories. The value of the GHGRP can be increased by requiring more direct measurements of emissions (as opposed to using counts and emission factors), eliminating exclusions such as rod-packing vents on pressurized reciprocating compressors in standby mode under Subpart-W, and using more appropriate emission factors for exhaust methane from reciprocating engines under Subpart-C.

Secondary Organic Aerosol Formation from in-Use Motor Vehicle Emissions Using a Potential Aerosol Mass Reactor

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.

Intermediate-Volatility Organic Compounds: A Large Source of Secondary Organic Aerosol

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 μg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

Primary gas- and particle-phase emissions and secondary organic aerosol production from gasoline and diesel off-road engines.

Dilution and smog chamber experiments were performed to characterize the primary emissions and secondary organic aerosol (SOA) formation from gasoline and diesel small off-road engines (SOREs). These engines are high emitters of primary gas- and particle-phase pollutants relative to their fuel consumption. Two- and 4-stroke gasoline SOREs emit much more (up to 3 orders of magnitude more) nonmethane organic gases (NMOGs), primary PM and organic carbon than newer on-road gasoline vehicles (per kg of fuel burned). The primary emissions from a diesel transportation refrigeration unit were similar to those of older, uncontrolled diesel engines used in on-road vehicles (e.g., premodel year 2007 heavy-duty diesel trucks). Two-strokes emitted the largest fractional (and absolute) amount of SOA precursors compared to diesel and 4-stroke gasoline SOREs; however, 35-80% of the NMOG emissions from the engines could not be speciated using traditional gas chromatography or high-performance liquid chromatography. After 3 h of photo-oxidation in a smog chamber, dilute emissions from both 2- and 4-stroke gasoline SOREs produced large amounts of semivolatile SOA. The effective SOA yield (defined as the ratio of SOA mass to estimated mass of reacted precursors) was 2-4% for 2- and 4-stroke SOREs, which is comparable to yields from dilute exhaust from older passenger cars and unburned gasoline. This suggests that much of the SOA production was due to unburned fuel and/or lubrication oil. The total PM contribution of different mobile source categories to the ambient PM burden was calculated by combining primary emission, SOA production and fuel consumption data. Relative to their fuel consumption, SOREs are disproportionately high total PM sources; however, the vastly greater fuel consumption of on-road vehicles renders them (on-road vehicles) the dominant mobile source of ambient PM in the Los Angeles area.

Secondary Organic Aerosol Formation from Photo-Oxidation of Unburned Fuel: Experimental Results and Implications for Aerosol Formation from Combustion Emissions

We conducted photo-oxidation experiments in a smog chamber to investigate secondary organic aerosol (SOA) formation from eleven different unburned fuels: commercial gasoline, three types of jet fuel, and seven different diesel fuels. The goals were to investigate the influence of fuel composition on SOA formation and to compare SOA production from unburned fuel to that from diluted exhaust. The trends in SOA production were largely consistent with differences in carbon number and molecular structure of the fuel, i.e., fuels with higher carbon numbers and/or more aromatics formed more SOA than fuels with lower carbon numbers and/or substituted alkanes. However, SOA production from different diesel fuels did not depend strongly on aromatic content, highlighting the important contribution of large alkanes to SOA formation from mixtures of high carbon number (lower volatility) precursors. In comparison to diesels, SOA production from higher volatility fuels such as gasoline appeared to be more sensitive to aromatic content. On the basis of a comparison of SOA mass yields (SOA mass formed per mass of fuel reacted) and SOA composition (as measured by an aerosol mass spectrometer) from unburned fuels and diluted exhaust, unburned fuels may be reasonable surrogates for emissions from uncontrolled engines but not for emissions from engines with after treatment devices such as catalytic converters.

Methane Emissions from United States Natural Gas Gathering and Processing

New facility-level methane (CH4) emissions measurements obtained from 114 natural gas gathering facilities and 16 processing plants in 13 U.S. states were combined with facility counts obtained from state and national databases in a Monte Carlo simulation to estimate CH4 emissions from U.S. natural gas gathering and processing operations. Total annual CH4 emissions of 2421 (+245/-237) Gg were estimated for all U.S. gathering and processing operations, which represents a CH4 loss rate of 0.47% (±0.05%) when normalized by 2012 CH4 production. Over 90% of those emissions were attributed to normal operation of gathering facilities (1697 +189/-185 Gg) and processing plants (506 +55/-52 Gg), with the balance attributed to gathering pipelines and processing plant routine maintenance and upsets. The median CH4 emissions estimate for processing plants is a factor of 1.7 lower than the 2012 EPA Greenhouse Gas Inventory (GHGI) estimate, with the difference due largely to fewer reciprocating compressors, and a factor of 3.0 higher than that reported under the EPA Greenhouse Gas Reporting Program. Since gathering operations are currently embedded within the production segment of the EPA GHGI, direct comparison to our results is complicated. However, the study results suggest that CH4 emissions from gathering are substantially higher than the current EPA GHGI estimate and are equivalent to 30% of the total net CH4 emissions in the natural gas systems GHGI. Because CH4 emissions from most gathering facilities are not reported under the current rule and not all source categories are reported for processing plants, the total CH4 emissions from gathering and processing reported under the EPA GHGRP (180 Gg) represents only 14% of that tabulated in the EPA GHGI and 7% of that predicted from this study.

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

Biomass burning (BB) is a major source of atmospheric pollutants. Field and laboratory studies indicate that secondary organic aerosol (SOA) formation from BB emissions is highly variable. We investigated sources of this variability using a novel dual-smog-chamber method that directly compares the SOA formation from the same BB emissions under two different atmospheric conditions. During each experiment, we filled two identical Teflon smog chambers simultaneously with BB emissions from the same fire. We then perturbed the smoke with UV-lights, UV-lights plus HONO, or dark ozone in one or both chambers. These perturbations caused SOA formation in nearly every experiment with an average organic aerosol (OA) mass enhancement ratio of 1.78 ± 0.91 (mean ± 1σ). However, the effects of the perturbations were highly variable ranging with OA mass enhancement ratios ranging from 0.7 (30% loss of OA mass) to 4.4 across the set of perturbation experiments. There was no apparent relationship between OA enhancement and perturbation type, fuel type, and modified combustion efficiency. To better isolate the effects of different perturbations, we report dual-chamber enhancements (DUCE), which quantity the effects of a perturbation relative to a reference condition. DUCE values were also highly variable, even for the same perturbation and fuel type. Gas measurements indicate substantial burn-to-burn variability in the magnitude and composition of SOA precursor emissions, even in repeated burns of the same fuel under nominally identical conditions. Therefore, the effects of different atmospheric perturbations on SOA formation from BB emissions appear to be less important than burn-to-burn variability.

Mass accommodation coefficients of fresh and aged biomass-burning emissions

ABSTRACT Most chemical transport models treat the partitioning of semi-volatile organic compounds (SVOCs) with the assumption of instantaneous thermodynamic equilibrium. However, the mass accommodation coefficients, α, of biomass-burning organic aerosol (BBOA) are largely unconstrained. During the FLAME-IV campaign, we thermally perturbed aged and fresh BBOA with a variable residence time thermodenuder and measured the resulting change in particle mass concentration to restore equilibrium. We used this equilibration profile to retrieve an effective α for components of BBOA that dictated this profile and found that the mass accommodation coefficients lie within the range 0.1 ≪ α ⩽ 1. A simple plume dilution model shows a maximum of only a 7% difference between a dynamical and an instantaneous equilibrium partitioning model using our best-estimate value for α. This supports continued use of the equilibrium assumption to treat partitioning of biomass-burning emissions in chemical-transport models. Copyright