Assessment of Regional Methane Emission Inventories through Airborne Quantification in the San Francisco Bay Area.

This study derives methane emission rates from 92 airborne observations collected over 23 facilities including 5 refineries, 10 landfills, 4 wastewater treatment plants (POTWs), 2 composting operations, and 2 dairies in the San Francisco Bay Area. Emission rates are measured using an airborne mass-balance technique from a low-flying aircraft. Annual measurement-based sectorwide methane emissions are 19,000 ± 2300 Mg for refineries, 136,700 ± 25,900 Mg for landfills, 11,900 ± 1,500 Mg for POTWs, and 11,100 ± 3,400 Mg for composting. The average of measured emissions for each refinery ranges from 4 to 23 times larger than the corresponding emissions reported to regulatory agencies, while measurement-derived landfill and POTW estimates are approximately twice the current inventory estimates. Significant methane emissions at composting facilities indicate that a California mandate to divert organics from landfills to composting may not be an effective measure for mitigating methane emissions unless best management practices are instituted at composting facilities. Complementary evidence from airborne remote sensing imagery indicates atmospheric venting from refinery hydrogen plants, landfill working surfaces, composting stockpiles, etc., to be among the specific source types responsible for the observed discrepancies. This work highlights the value of multiple measurement approaches to accurately estimate facility-scale methane emissions and perform source attribution at subfacility scales to guide and verify effective mitigation policy and action.

Spatial variations of particulate matter and air toxics in communities adjacent to the Port of Oakland.

The Bay Area Air Quality Management District (BAAQMD) sponsored the West Oakland Monitoring Study (WOMS) to provide supplemental air quality monitoring that will be used by the BAAQMD to evaluate local-scale dispersion modeling of diesel emissions and other toxic air contaminants for the area within and around the Port of Oakland. The WOMS was conducted during two seasonal periods of 4 weeks in summer 2009 and winter 2009/2010. Monitoring data showed spatial patterns of pollutant concentrations that were generally consistent with proximity to vehicle traffic. Concentrations of directly emitted pollutants were highest on heavily traveled roads with consistently lower concentrations away from the roadways. Pollutants that have higher emission rates from diesel trucks (nitric oxide, black carbon) tended to exhibit sharper gradients than pollutants that are largely associated with gasoline vehicles, such as carbon monoxide and volatile organic compounds, including benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX concentrations in West Oakland were similar to those measured at the three air toxics monitoring network sites in the Bay Area (San Francisco, Fremont, and San Jose). Aldehyde levels were higher in Fremont and San Jose than in West Oakland, reflecting greater contributions from photo-oxidation of hydrocarbons downwind of the Bay Area. A 2005 modeling-based health risk assessment of diesel particulate matter concentrations is consistent with aerosol carbon concentrations measured during the WOMS after adjusting for recent mitigation measures and improved estimates of heavy-duty truck traffic volumes.

Rate of gas phase association of hydroxyl radical and nitrogen dioxide.

The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) is among the most influential in atmospheric chemistry. Despite its importance, the rate coefficient remains poorly determined under tropospheric conditions because of difficulties in making laboratory rate measurements in air at 760 torr and uncertainties about a secondary channel producing peroxynitrous acid (HOONO). We combined two sensitive laser spectroscopy techniques to measure the overall rate of both channels and the partitioning between them at 25°C and 760 torr. The result is a significantly more precise value of the rate constant for the HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) molecule(-1) s(-1) (1 SD) at 760 torr of air, which lies toward the lower end of the previously established range. We demonstrate the impact of the revised value on photochemical model predictions of ozone concentrations in the Los Angeles airshed.

Adjoint sensitivity analysis for a three-dimensional photochemical model: application to Southern California.

An adjoint method was used to investigate the sensitivity of peak ozone at selected sites in Southern California to nearly 900 model inputs including surface emissions, reaction rate coefficients, dry deposition velocities, boundary conditions, and initial conditions. Simulations showed large changes in ozone and ozone sensitivities at three sites investigated between summers 1987 and 1997 due to emission reductions. However, only small changes in ozone and ozone sensitivities were predicted between 1997 and 2010. Sensitivities of the differences in ozone between simulations with different emission scenarios were calculated and compared to sensitivities of ozone in each simulation. In some cases, the sensitivities of ozone differences were smaller than those of ozone itself, but in other cases, such as when the sensitivityto NOx emissions changed sign, sensitivities of differences were larger. The adjoint method was most useful for determining when and where model inputs affect, or have the potential to affect, an ozone response. For example, the method was used to plot the spatial distribution of important emission source regions to 1-hour versus 8-hour peak ozone. Changes in the distribution and sign of the adjoint function for emitted species revealed changes in the area of influence of pollutant emissions on peak ozone due to emission controls. The adjoint method provides useful information complementary to that obtained from forward sensitivity analysis methods.

Adjoint sensitivity analysis for a three-dimensional photochemical model: implementation and method comparison.

Photochemical air pollution forms when emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOC) react in the atmosphere in the presence of sunlight. The goal of applying three-dimensional photochemical air quality models is usually to conduct sensitivity analysis: for example, to predict changes in an ozone response due to changes in NO(x) and VOC emissions or other model data. Forward sensitivity analysis methods are best suited to investigating sensitivities of many model responses to changes in a few inputs or parameters. Here we develop a continuous adjoint model and demonstrate an adjoint sensitivity analysis procedure that is well-suited to the complementary case of determining sensitivity of a small number of model responses to many parameters. Sensitivities generated using the adjoint method agree with those generated using other methods. Compared to the forward method, the adjoint method had large disk storage requirements but was more efficient in terms of computer processor time for receptor-based investigations focused on a single response at a specified site and time. The adjoint method also generates sensitivity apportionment fields, which reveal when and where model data are important to the target response.

Evaluation of incremental reactivity and its uncertainty in Southern California.

The incremental reactivity (IR) and relative incremental reactivity (RIR) of carbon monoxide and 30 individual volatile organic compounds (VOC) were estimated for the South Coast Air Basin using two photochemical air quality models: a 3-D, grid-based model and a vertically resolved trajectory model. Both models include an extended version of the SAPRC99 chemical mechanism. For the 3-D modeling, the decoupled direct method (DDM-3D) was used to assess reactivities. The trajectory model was applied to estimate uncertainties in reactivities due to uncertainties in chemical rate parameters, deposition parameters, and emission rates using Monte Carlo analysis with Latin hypercube sampling. For most VOC, RIRs were found to be consistent in rankings with those produced by Carter using a box model. However, 3-D simulations show that coastal regions, upwind of most of the emissions, have comparatively low IR but higher RIR than predicted by box models for C4-C5 alkenes and carbonyls that initiate the production of HOx radicals. Biogenic VOC emissions were found to have a lower RIR than predicted by box model estimates, because emissions of these VOC were mostly downwind of the areas of primary ozone production. Uncertainties in RIR of individual VOC were found to be dominated by uncertainties in the rate parameters of their primary oxidation reactions. The coefficient of variation (COV) of most RIR values ranged from 20% to 30%, whereas the COV of absolute incremental reactivity ranged from about 30% to 40%. In general, uncertainty and variability both decreased when relative rather than absolute reactivity metrics were used.