Application for a newly developed high-capacity NOx denuder: low-NOx diesel transformation experiments.

To conduct low oxides of nitrogen (NOx) chamber experiments with modern diesel emissions (DE), a high-capacity NO, denuder was developed and used at the European Photoreactor (EUPHORE) outdoor simulation chamber. The denuder displayed a sufficient NOx storage capacity for use with DE, and efficient removal of NO, during injections of DE was achieved (>98%). Degradation of the denuder performance after repeated regeneration by heating (400 degrees C) and flushing with an air/oxygen ratio of 2:1 was not observed for a total of nine experiments. Evaluation of dark (with chamber cover closed) experiments (four in total) with and without the denuder in-line revealed some reduction (22%) of diesel particulate matter (DPM) with use of the denuder, most likely a result of impaction or settling of DPM during DE transit. However, DPM reduction may have also been a result of reductions in effective load of the engine-dyno system during the DE injections. Extensive chemical characterization of DPM revealed no significant perturbation of major compound groups associated with denuder use, except for nitrated polyaromatic hydrocarbon (NPAH) concentrations. The implications of high-NOx experiments without the use of a NOx denuder are discussed.

Olfaction-based Detection Distance: A Quantitative Analysis of How Far Away Dogs Recognize Tortoise Odor and Follow It to Source.

The use of detector dogs has been demonstrated to be effective and safe for finding Mojave desert tortoises and provides certain advantages over humans in field surveys. Unlike humans who rely on visual cues for target identification, dogs use primarily olfactory cues and can therefore locate targets that are not visually obvious. One of the key benefits of surveying with dogs is their efficiency at covering ground and their ability to detect targets from long distances. Dogs may investigate potential targets using visual cues but confirm the presence of a target based on scent. Everything that emits odor does so via vapor-phase molecules and the components comprising a particular scent are carried primarily though bulk movement of the atmosphere. It is the ability to search for target odor and then go to its source that makes dogs ideal for rapid target recognition in the field setting. Using tortoises as targets, we quantified distances that dogs detected tortoise scent, followed it to source, and correctly identified tortoises as targets. Detection distance data were collected during experimental trials with advanced global positioning system (GPS) technology and then analyzed using geographic information system (GIS) modeling techniques. Detection distances ranged from 0.5 m to 62.8 m for tortoises on the surface. We did not observe bias with tortoise size, age class, sex or the degree to which tortoises were handled prior to being found by the dogs. The methodology we developed to quantify olfaction-based detection distance using dogs can be applied to other targets that dogs are trained to find.

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.

High-end exposure relationships of volatile air toxics and carbon monoxide to community-scale air monitoring stations in Atlanta, Chicago, and Houston.

Evaporative and exhaust mobile source air toxic (MSAT) emissions of total volatile organic compounds, carbon monoxide, BTEX (benzene, toluene, ethylbenzene, and xylenes), formaldehyde, acetaldehyde, butadiene, methyl tertiary butyl ether, and ethanol were measured in vehicle-related high-end microenvironments (ME) under worst-case conditions plausibly simulating the >99th percentile of inhalation exposure concentrations in Atlanta (baseline gasoline), Chicago (ethanol-oxygenated gasoline), and Houston (methyl tertiary butyl either-oxygenated gasoline) during winter and summer seasons. High-end MSAT values as ratios of the corresponding measurements at nearby air monitoring stations exceeded the microenvironmental proximity factors used in regulatory exposure models, especially for refueling operations and MEs under reduced ventilation. MSAT concentrations were apportioned between exhaust and evaporative vehicle emissions in Houston where methyl tertiary butyl ether could be used as a vehicle emission tracer. With the exception of vehicle refueling operations, the results indicate that evaporative emissions are a minor component of high-end MSAT exposure concentrations.

Real-world particulate matter and gaseous emissions from motor vehicles in a highway tunnel.

Recent studies have linked atmospheric particulate matter with human health problems. In many urban areas, mobile sources are a major source of particulate matter (PM) and the dominant source of fine particles or PM2.5 (PM smaller than 2.5 pm in aerodynamic diameter). Dynamometer studies have implicated diesel engines as being a significant source of ultrafine particles (< 0.1 microm), which may also exhibit deleterious health impacts. In addition to direct tailpipe emissions, mobile sources contribute to ambient particulate levels by brake and tire wear and by resuspension of particles from pavement. Information about particle emission rates, size distributions, and chemical composition from in-use light-duty (LD) and heavy-duty (HD) vehicles is scarce, especially under real-world operating conditions. To characterize particulate emissions from a limited set of in-use vehicles, we studied on-road emissions from vehicles operating under hot-stabilized conditions, at relatively constant speed, in the Tuscarora Mountain Tunnel along the Pennsylvania Turnpike from May 18 through 23, 1999. There were five specific aims of the study. (1) obtain chemically speciated diesel profiles for the source apportionment of diesel versus other ambient constituents in the air and to determine the chemical species present in real-world diesel emissions; (2) measure particle number and size distribution of chemically speciated particles in the atmosphere; (3) identify, by reference to data in years past, how much change has occurred in diesel exhaust particulate mass; (4) measure particulate emissions from LD gasoline vehicles to determine their contribution to the observed particle levels compared to diesels; and (5) determine changes over time in gas phase emissions by comparing our results with those of previous studies. Comparing the results of this study with our 1992 results, we found that emissions of C8 to C20 hydrocarbons, carbon monoxide (CO), and carbon dioxide (CO2) from HD diesel emissions substantially decreased over the seven-year period. Particulate mass emissions showed a similar trend. Considering a 25-year period, we observed a continued downward trend in HD particulate emissions from approximately 1,100 mg/km in 1974 to 132 mg/km (reported as PM2.5) in this study. The LD particle emission factor was considerably less than the HD value, but given the large fraction of LD vehicles, emissions from this source cannot be ignored. Results of the current study also indicate that both HD and LD vehicles emit ultrafine particles and that these particles are preserved under real-world dilution conditions. Particle number distributions were dominated by ultrafine particles with count mean diameters of 17 to 13 nm depending on fleet composition. These particles appear to be primarily composed of sulfur, indicative of sulfuric acid emission and nucleation. Comparing the 1992 and 1999 HD emission rates, we observed a 48% increase in the NOx/CO2 emissions ratio. This finding supports the assumption that many new-technology diesel engines conserve fuel but increase NOx emissions.

Source apportionment of airborne fine particulate matter in an underground mine.

The chemical mass balance source apportionment technique was applied to an underground gold mine to assess the contribution of diesel exhaust, rock dust, oil mists, and cigarette smoke to airborne fine (<2.5 microm) particulate matter (PM). Apportionments were conducted in two locations in the mine, one near the mining operations and one near the exit of the mine where the ventilated mine air was exhausted. Results showed that diesel exhaust contributed 78-98% of the fine particulate mass and greater than 90% of the fine particle carbon, with rock dust making up the remainder. Oil mists and cigarette smoke contributions were below detection limits for this study. The diesel exhaust fraction of the total fine PM was higher than the recently implemented mine air quality standards based on total carbon at both sample locations in the mine.

Emissions from charbroiling and grilling of chicken and beef.

Emission rates for fine particle (<2.5 microm) mass (PM2.5), carbon (organic/elemental), inorganic ions (SO4(2-), NO3-, NH4+), elements (primarily metals), and speciated organic compounds are reported for charbroiling hamburger, steak, and chicken. The PM2.5 rates for charbroiling meats ranged from 4.4 to 11.6 g/kg of uncooked meat in this study. No mass-emission rates are available from grilling, but the speciated organic data are available for these samples. Emission rates varied by type of appliance, meat, meat-fat content, and cooking conditions. High-fat hamburger cooked on an underfired charbroiler emitted the highest amount of PM2.5. The emissions were almost exclusively composed of organic carbon, with small amounts of elements and inorganic ions. Water-soluble K+ and Cl-, which are used as indicators of wood smoke in source apportionment studies, were also present in meat-cooking emissions. The speciated organic compounds that were measured include polycyclic aromatic hydrocarbons (PAHs), cholesterol, and the long-chain gamma-lactones. Charbroiling emissions yielded an average of approximately 3-5 times more PAHs, approximately 20 times more cholesterol, and approximately 10 times more lactones than grilling. These data were utilized in the ambient source apportionment analysis for the 1997 Northern Front Range Air Quality Study source apportionment.

Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin.

For at least 30 years, ozone (O3) levels on weekends in parts of California's South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O3 precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NOx) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O3 formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NOx associated with black carbon (BC) to NOx associated with carbon monoxide (CO) were approximately 1.25 +/- 0.22 during weekdays and 0.76 +/- 0.07 and 0.52 +/- 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NOx emissions from diesel exhaust can be a major factor causing lower NOx mixing ratios and higher NMHC/NOx ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NOx ratios on weekend mornings.

Characterization of the volatile organic compounds present in the headspace of decomposing animal remains, and compared with human remains.

Human Remains Detection (HRD) dogs can be a useful tool to locate buried human remains because they rely on olfactory rather than visual cues. Trained specifically to locate deceased humans, it is widely believed that HRD dogs can differentiate animal remains from human remains. This study analyzed the volatile organic compounds (VOCs) present in the headspace above partially decomposed animal tissue samples and directly compared them with results published from human tissues using established solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) methods. Volatile organic compounds present in the headspace of four different animal tissue samples (bone, muscle, fat and skin) from each of cow, pig and chicken were identified and compared to published results from human samples. Although there were compounds common to both animal and human remains, the VOC signatures of each of the animal remains differed from those of humans. Of particular interest was the difference between pigs and humans, because in some countries HRD dogs are trained on pig remains rather than human remains. Pig VOC signatures were not found to be a subset of human; in addition to sharing only seven of thirty human-specific compounds, an additional nine unique VOCs were recorded from pig samples which were not present in human samples. The VOC signatures from chicken and human samples were most similar sharing the most compounds of the animals studied. Identifying VOCs that are unique to humans may be useful to develop human-specific training aids for HRD canines, and may eventually lead to an instrument that can detect clandestine human burial sites.

Field capability of dogs to locate individual human teeth.

Avulsed teeth can be difficult if not impossible to recover in the outdoor environment, yet are important for victim identification. This study assessed dog teams as a resource to locate human teeth in a field setting and related performance in training with field capability. Standardized, objective training data were recorded and analyzed followed by double-blind capability trials. In the double-blind trials, 10 teeth were placed in each of six (10 m(2)) plots. Search time per plot ranged from 27 to 50 min, and the proportion of teeth found by the teams varied between 0.20 and 0.79. Using 0.45 m as a distance criterion for a "find," the proportion of false positives ranged between 0.07 and 0.75. Results show that dog teams are capable of recovering individual human teeth in the field setting with high precision although capability varies. Training records support a team's expected field performance. Additional studies are needed.

Measurements of Dioxin and Furan Emission Factors from Heavy-Duty Diesel Vehicles.

This note describes the results of a study of the on-road emissions of dioxins and furans from mobile sources. This work was performed in response to the U.S. Environmental Protection Agency's (EPA) draft document on dioxin reassessment, which used data from sources outside the United States to estimate an emission factor of 0.8 ng-TEQ/veh-mi for the U.S. fleet. The primary objective of this work was to measure on-road chlorinated dioxin and furan emission factors from in-use vehicles operating in the United States, with emphasis on heavy-duty vehicles. The experimental approach was to measure emissions in the Fort McHenry Tunnel in Baltimore, MD. All air entering and leaving the tunnel was sampled for concentrations of dioxins and furans (during 10 24-h sampling periods). The difference between the mass of material entering and the mass of material leaving the tunnel was taken to be the amount produced by the vehicles in transit. These measurements were combined with information on vehicle counts (obtained through videotapes) and tunnel length to determine average emission factors. For the limited range of vehicle operating conditions present in the tunnel experiment, the average heavy-duty diesel emission factor determined in this study was 0.28 ± 0.13 ng-TEQ/veh-mi, a factor of 3 lower than the EPA estimate.

The Impact of California Phase 2 Reformulated Gasoline on Real-World Vehicle Emissions.

In mid-1996, California implemented Phase 2 Reformulated Gasoline (RFG). The new fuel was designed to further decrease emissions of hydrocarbons (HCs), oxides of nitrogen (NOx), carbon monoxide (CO), sulfur dioxide (SO2), and other toxic species. In addition, it was formulated to reduce the ozone-forming potential of the HCs emitted by vehicles. Previous studies have observed that emissions from on-road vehicles can differ significantly from those predicted by mobile source emissions models, and so it is important to quantify the change in emissions in a real-world setting. In October 1995, prior to the introduction of California Phase 2 RFG, the Desert Research Institute (DRI) performed a study of vehicle emissions in Los Angeles' Sepulveda Tunnel. This study provided a baseline against which the results of a second experiment, conducted in July 1996, could be compared to evaluate the impact of California Phase 2 RFG on emissions from real-world vehicles. Compared with the 1995 experiment, CO and NOx emissions exhibited statistically significant decreases, while the decrease in non-methane hydrocarbon emissions was not statistically significant. Changes in the speciated HC emissions were evaluated. The benzene emission rate decreased by 27% and the overall emission rate of aromatic compounds decreased by 22% comparing the runs with similar speeds. Emissions of alkenes were virtually unchanged; however, emissions of combustion related unsaturates (e.g., acetylene, ethene) increased, while heavier alkenes decreased. The emission rate of methyl tertiary butyl ether (MTBE) exhibited a larger increase. Overall changes in the ozone-forming potential of the emissions were not significantly different, with the increased contributions to reactivity from paraffins, ole-fins, and MTBE being offset by a large decrease in reactivity due to aromatics.

Assessment of Nontailpipe Hydrocarbon Emissions from Motor Vehicles.

This report evaluates tailpipe and nontailpipe hydrocarbon (HC) emissions from light-duty spark-ignition (SI) vehicles. The sources of information were unpublished data sets, generated mainly from 1990 through 1994, on emissions from volunteer fleets of in-use vehicles in chassis dynamometer and sealed housing for evaporative determination tests, and published chemical mass balance (CMB) source apportionments of HC in roadway tunnels and in urban air. The nontailpipe emissions evaluated comprise running-loss, hot soak, diurnal emissions, and resting-loss emissions. Relations between pressure and purge test failures and actual nontailpipe emissions were also examined.