PubMed Health⌕ Search

Biomedical subjects

Robert A Harley

Publications and source records attributed to Robert A Harley.

8 recordsLinked to original sources
PubMed2006

Effects of reformulated gasoline and motor vehicle fleet turnover on emissions and ambient concentrations of benzene.

Gasoline-powered motor vehicles are a major source of toxic air contaminants such as benzene. Emissions from light-duty vehicles were measured in a San Francisco area highway tunnel during summers 1991, 1994-1997, 1999, 2001, and 2004. Benzene emission rates decreased over this time period, with a large (54 +/- 5%) decrease observed between 1995 and 1996 when California phase 2 reformulated gasoline (RFG) was introduced. We attribute this one-year change in benzene mainly to RFG effects: 36% from lower aromatics in gasoline that led to a lower benzene mass fraction in vehicle emissions, 14% due to RFG effects on total nonmethane organic compound mass emissions, and the remaining 4% due to fleet turnover. Fleet turnover effects accumulate over longer time periods: between 1995 and 2004, fleet turnover led to a 32% reduction in the benzene emission rate. A approximately 4 microg m(-3) decrease in benzene concentrations was observed at a network of ambient air sampling sites in the San Francisco Bay area between the late 1980s and 2004. The largest decrease in annual average ambient benzene concentrations (1.5 +/- 0.7 microg m(-3) or 42 +/- 19%) was observed between 1995 and 1996. The reduction in ambient benzene between spring/summer months of 1995 and 1996 due to phase 2 RFG was larger (60 +/- 20%). Effects of fuel changes on benzene during fall/winter months are difficult to quantify because some wintertime fuel changes had already occurred prior to 1995.

Air Pollutants↗
PubMed2006

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.

Air Pollutants↗
PubMed2006

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.

Air Pollutants↗
PubMed2005

Changes in motor vehicle emissions on diurnal to decadal time scales and effects on atmospheric composition.

Emissions from gasoline and diesel engines vary on time scales including diurnal, weekly, and decadal. Temporal patterns differ for these two engine types that are used predominantly for passenger travel and goods movement, respectively. Rapid growth in diesel fuel use and decreasing NOx emission rates from gasoline engines have led to altered emission profiles. During the 1990s, on-road use of diesel fuel grew 3 times faster than gasoline. Over the same time period, the NOx emission rate from gasoline engines in California was reduced by a factor of approximately 2, while the NOx emission rate from diesel engines decreased only slightly. Diesel engines therefore grew in both relative and absolute terms as a source of NOx, accounting for about half of all on-road NO, emissions as of 2000. Diesel truck emissions decrease by 60-80% on weekends. Counterintuitive responses to these emission changes are seen in measured concentrations of ozone. In contrast, elemental carbon (EC) concentrations decrease on weekends as expected. Weekly and diurnal patterns in diesel truck activity contribute to variability in the ratio of organic carbon (OC) to EC in primary source emissions, and this could be a source of bias in assessments of the importance of secondary organic aerosol.

Air Pollutants↗
PubMed2005

Temporal changes in U.S. benzene emissions inferred from atmospheric measurements.

The 1990 Clean Air Act Amendments required the United States Environmental Protection Agency (U.S. EPA) to enact stricter regulations aimed at reducing benzene emissions. In an effort to determine whether these new regulations have been successful in reducing atmospheric benzene concentrations, we have evaluated benzene-to-acetylene ratios from data sets spanning nearlythree decades, collected during several field studies and from the U.S. EPA's Photochemical Assessment Monitoring Station (PAMS) network. The field-study data indicate a decrease in benzene relative to acetylene of approximately 40% from 1994 to 2002. This corresponds to a decrease in benzene alone of approximately 56% over the same period. In contrast, the PAMS data exhibit high interannual variability with no discernible trend. This discrepancy is attributed to measurement problems in the PAMS data sets.

Air Pollutants↗
PubMed2003

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.

Air Pollutants↗
PubMed2002

Modeling the effect of weekday-weekend differences in motor vehicle emissions on photochemical air pollution in central California.

Ambient ozone concentrations vary by day of week in some locations, often with higher concentrations observed on weekends in urban and downwind areas. Emissions of ozone precursors appear to be lower on weekends, so the behavior of ozone concentrations on weekends may indicate the outcome of particular ozone control strategies. To examine the influence of day-of-week differences in motor vehicle emissions on ambient ozone concentrations, we combine a fuel-based motor vehicle emission inventory containing weekend-specific activity with an Eulerian photochemical airshed model applied to central California. Emissions of NOx on weekends are approximately 30% lower than on weekdays due to a large drop in heavy-duty diesel truck activity, and emissions of VOC are only slightly lower on weekends. In rural areas, passenger car traffic and the associated emissions are highest on Fridays and Sundays. The combination of VOC sensitivity and reduced emissions of NOx on weekends results in higher ozone concentrations on weekends. Changes in the timing of emissions also contribute to the weekend ozone effect, but sensitivity tests show that changes in emissions timing have a minor effect compared to changes in total mass of emissions on weekends. Even in situations where reductions in NOx emissions lead to higher ozone concentrations, NOx reductions may still be necessary for control of other air pollutants such as nitrogen dioxide, nitric acid, and aerosol nitrate.

Aerosols↗