Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

The development of alum rates to enhance the remediation of phosphorus in fluvial systems following manure spills

Following the remediation of animal manure spills that reach surface waters, contaminated streambed sediments are often left in place and become a source for internal phosphorus (P) loading within the stream in subsequent flow. The objective of this study was to develop treatment rates and combinations of alum and CaCO(3) to mitigate P from contaminated sediments of different particle size distributions following a manure spill. Sediment specific alum and CaCO(3) treatment rates were developed based upon the resultant alum treatment ranges established for each sediment type. Clay loam sediments required 54% more alum to mitigate P desorption relative to sediments that contain at least 60% sand. Amending sediments with the highest rates of alum/alum + CaCO(3), resulted in a 98-100% reduction in P desorption and a similar water column pH for all sediments types. Observations from this study demonstrated the effectiveness of alum/alum + CaCO(3) to increase P retention in sediments following a manure spill.     

Reducing health risk assigned to organic emissions from a chemical weapons incinerator

Organic emissions from a chemical weapons incinerator have been characterized with an improved set of analytical methods to reduce the human health risk assigned to operations of the facility. A gas chromatography/mass selective detection method with substantially reduced detection limits has been used in conjunction with scanning electron microscopy/energy dispersive X-ray spectrometry and Fourier transform infrared microscopy to improve the speciation of semi-volatile and non-volatile organics emitted from the incinerator. The reduced detection limits have allowed a significant reduction in the assumed polycyclic aromatic hydrocarbon (PAH) and aminobiphenyl (ABP) emission rates used as inputs to the human health risk assessment for the incinerator. A mean factor of 17 decrease in assigned human health risk is realized for six common local exposure scenarios as a result of the reduced PAH and ABP detection limits.     

Assessing and monitoring semi-arid shrublands using object-based image analysis and multiple endmember spectral mixture analysis

Arid and semi-arid shrublands have significant biological and economical values and have been experiencing dramatic changes due to human activities. In California, California sage scrub (CSS) is one of the most endangered plant communities in the US and requires close monitoring in order to conserve this important biological resource. We investigate the utility of remote-sensing approaches—object-based image analysis applied to pansharpened QuickBird imagery (QBPS/OBIA) and multiple endmember spectral mixture analysis (MESMA) applied to SPOT imagery (SPOT/MESMA)—for estimating fractional cover of true shrub, subshrub, herb, and bare ground within CSS communities of southern California. We also explore the effectiveness of life-form cover maps for assessing CSS conditions. Overall and combined shrub cover (i.e., true shrub and subshrub) were estimated more accurately using QBPS/OBIA (mean absolute error or MAE, 8.9 %) than SPOT/MESMA (MAE, 11.4 %). Life-form cover from QBPS/OBIA at a 25?×?25 m grid cell size seems most desirable for assessing CSS because of its higher accuracy and spatial detail in cover estimates and amenability to extracting other vegetation information (e.g., size, shape, and density of shrub patches). Maps derived from SPOT/MESMA at a 50?×?50 m scale are effective for retrospective analysis of life-form cover change because their comparable accuracies to QBPS/OBIA and availability of SPOT archives data dating back to the mid-1980s. The framework in this study can be applied to other physiognomically comparable shrubland communities.     

Continuous and filter-based measurements of PM2.5 nitrate and sulfate at the Fresno Supersite

PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.     

Comparison of six particle size distribution models on the goodness-of-fit to particulate matter sampled from animal buildings

Lognormal distribution is often used as a default model for regression analysis of particle size distribution (PSD) data; however, its goodness-of-fit to particle matter (PM) sampled from animal buildings and its comparison to other PSD models have not been well examined. This study aimed to evaluate and to compare the goodness-of-fit of six PSD models to total suspended particulate matter (TSP) samples collected from 15 animal buildings. Four particle size analyzers were used for PSD measurement. The models' goodness-of-fit was evaluated based on adjusted R2, Akaike's information criterion (AIC), and mean squared error (MSE) values. Results showed that the models' approximation of measured PSDs differed with particle size analyzer. The lognormal distribution model offered overall good approximations to measured PSD data, but was inferior to the gamma and Weibull distribution models when applied to PSD data derived from the Horiba and Malvern analyzers. Single-variable models including the exponential, Khrgian-Mazin, and Chen's empirical models provided relatively poor approximations and, thus, were not recommended for future investigations. A further examination on model-predicted PSD parameters revealed that even the best-fit model of the six could significantly misestimate mean diameter median diameter; and variance. However, compared with other models, the best-fit model still offered the relatively best estimates of mean and median diameters, whereas the best predicted variances were given by the gamma distribution model.     

Transient and Frequency Response of Air Quality Monitors

Results of dynamic or transient tests and steady state calibration of carbon monoxide and sulfur dioxide continuous air quality monitors are reported. Standard gases and permeation tubes were used to establish low level concentrations bpth for the steady-state calibration and the dynamic testing. The steady-state calibration was in excellent agreement with results obtained from grab samples of the calibration gas stream taken with standard gas bubblers and analyzed by the West and Gaeke procedure. Such tests have been carried out by other investigators with similar results. The important contribution of this paper lies in the application of dynamic testing techniques developed by the senior author and co-workers to determine the transient and frequency response characteristics of these air quality monitors.     

Dry Removal of Gaseous Fluorine Pollutants

The conservation equations governing buoyant plume rise are solved for the case of non-uniform wind conditions. A power law is selected to represent the actual wind profile. Analytical solutions are presented both for uniformly stable and neutral atmospheric conditions. These solutions are shown to be of the same form as those obtained in the simpler uniform case but with the plume rise now depending explicitly on the wind speed shear. A sensitivity analysis of the effects on plume rise of typical variation in wind shear and entrainment reveals that the two quantities have an almost equal effect therefore justifying the use of the present model. To simplify computations a “uniform wind” is introduced such that when used in conjunction with Briggs' equations the results become consistent with those of the present theory.     

An Analysis of Michigan and California CO Remote Sensing Measurements

Abstract

Remote sensing measurements of CO emissions from on-road vehicles were made in California in 1991 and in Michigan in 1992. It was determined that both fleets had a small linear increase in the high emitter frequency (vehicles emitting more than 4% CO) as a function of vehicle age for 1986 and newer model vehicles. Although high emitting vehicles were only a small minority of the fleet, they had a dominant impact on the mean CO and total CO emitted by the fleet. In Michigan, the highest emitting 5% of passenger cars generated 45% of the CO from cars. In California, the highest emitting 5% of passenger cars generated 38% of the CO from cars. There was a high correlation between the mean CO emitted by each model year of vehicle and the frequency of high emitting vehicles within the model year for both the Michigan and California fleets. The frequency of high emitters within any model year had no obvious relation to that model year’s certification standards. The high emitter frequencies for vehicles less than nine years old were very similar for the California and Michigan fleets. An increase in the high emitter frequency in the ten-year-old and older Michigan passenger car fleet (relative to the California passenger car fleet), suggests, but does not conclusively demonstrate, that the rate of high emitters in Michigan and California is reduced by the inspection and maintenance (I/M) programs.     

Air Quality Measurements from the Fresno Supersite

ABSTRACT

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, HNO₃, peroxyacetyl nitrate [PAN], NH₃); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.