Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Fate of Manganese Exhaust Products

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been marketed as a combustion improver for fuel oil and turbine fuel. Use concentrations for this purpose are about 0.025 g manganese/gal in fuel oil and 0.08 to 0.5 g/gal in turbine fuels. In addition, it has been used to a small extent in gasoline.     

Sulfate Emissions from Vehicles on the Road

Experiments have been conducted to measure vehicle sulfate emissions, by vehicle type, at two tunnels on the Pennsylvania Turnpike. A satisfactory balance between estimated fuel sulfur consumption and observed emissions of sulfur compounds corrected for ambient-air contributions was obtained. This work started in 1974 before the introduction of catalyst-equipped automobiles and continued into 1976. The sulfate contributed by vehicles even in the tunnels was found to be generally modest relative to rural ambient sulfate levels. Average sulfate emission rates were found to be ~30 mg/km (50 mg/mi) from heavy-duty Diesel trucks, <15 mg/km from catalyst-equipped cars (probably in the range 4 to 7 mg/km), and probably <1 mg/km from non-catalyst cars. The overall SO₂ —* SO₄ ^-2 conversion of the vehicle emissions was 2 %.     

Estimations of Real-World N2O Emissions from Road Vehicles by Means of Measurements in a Traffic Tunnel

Abstract

Ambient air measurements of N₂O, NO_x, CO, and HC based on grab sampling were conducted in a major traffic tunnel in Sweden, that carries up to 4,000 vehicles per hour, in order to estimate real-world emissions of N₂O for road traffic. Two different methods—relative and mass balance—were used to calculate a N₂O emission factor for the mixed vehicle fleet, which gave an average emission factor, at average speeds of 30-70 km/h, of approximately 25 mg N₂O/ km, with a range of 7-56 mg/km.     

Influence of Oxygenated Fuels on the Emissions from Three Pre-1985 Light-Duty Passenger Vehicles

Tailpipe and evaporative emissions from three pre-1985 passenger motor vehicles operating on an oxygenated blend fuel and on a nonoxygenated base fuel were characterized. Emission data were collected for vehicles operating over the Federal Test Procedure at 40,75, and 90°F to simulate ambient driving conditions. The two fuels tested were a commercial summer grade regular gasoline (the nonoxygenated base fuel) and an oxygenated fuel containing 9.5 percent methyl tert-butyl ether (MTBE), more olefins, and fewer aromatics than the base fuel. The emissions measured were total hydrocarbons (THCs), speciated hydrocarbons, speciated aldehydes, carbon monoxide (CO), oxides of nitrogen (NO_x), benzene, and 1,3-butadiene.

This study showed no pattern of tailpipe regulated emission reduction when oxygenated fuel was used. Tailpipe emissions from the 1984 Buick Century without a catalyst and the 1977 Mustang with catalyst decreased with the MTBE fuel. However, emissions from the 1984 Buick Century and the 1980 Chevrolet Citation, both fitted with catalysts increased. The vehicles emitted more 1,3- butadiene and, in general, more NO_x when operated with the base fuel.

THC, CO, benzene, and 1,3-butadiene emissions from both fuels and all vehicles, in general, decreased with increasing test temperature, whereas NO_x emissions, in general, increased with increasing test temperature. Formaldehyde, acetaldehyde, and total aldehydes also showed a decrease in emissions as test temperature increased. More formaldehyde was emitted when the MTBE fuel was used.

Evaporative, diurnal, and hot soak emissions from the base fuel were greater than those from the MTBE fuel. The evaporated emissions from both fuels increased with increasing test temperatures. Diurnal data indicate that canister conditioning (bringing the evaporative charcoal canister to equilibrium) is required before testing.     

Characterization of Emissions from Vehicles Using Methanol and Methanol-Gasoline Blended Fuels

Exhaust and evaporative emissions were examined from vehicles fueled with methanol or a gasoline-methanol blend. Regulated automobile pollutants, as well as detailed hydrocarbons, methanol, and aldehydes were measured, and exhaust emission trends were obtained for vehicle operation over five different driving cycles. Results indicated that use of the blended fuel does not generally have any significant effect on base-line exhaust emission rates of regulated pollutants; however, emission rates of aldehydes increased during the Federal Test Procedure. Aldehyde emissions from the methanol-fueled car were roughly an order of magnitude higher than those resulting from blended fuel usage. The hydrocarbon composition of evaporative emissions with the blended fuel was similar to that with the base-line fuel except when canister breakthrough occurred. Evaporative emissions during breakthrough were comprised chiefly of N-butane.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Emissions from lit-use Motor Vehicles in Los Angeles: A Pilot Study of Remote Sensing and the Inspection and Maintenance Program

As part of a major field study to understand the causes of persistent, elevated carbon monoxide pollution episodes in Los Angeles, we performed a project to understand the emissions of vehicles in use. In this experiment, we assessed the accuracy of a remote sensing instrument designed to measure CO concentrations from vehicles as they were driven on the road. The remote sensor was shown to be accurate within ten percent of the directly measured tailpipe value. We performed a roadside inspection on 60 vehicles and demonstrated that the remote sensor could be used as an effective surveillance tool to identify high CO-emitting vehicles. We also compared the roadside data set to the biennial Smog Check (I/M) tests for the same vehicles, and observed that carbon monoxide and exhaust hydrocarbons from high emitters were much higher than when the vehicles received their routine inspection. Furthermore, for the high-emitting vehicles in this data set, the length of time since the biennial Smog Check had little influence on the cars’ emissions in the roadside inspection.     

Field Measurements of Particulate Matter Emissions,Carbon Monoxide,and Exhaust Opacity from Heavy-Duty Diesel Vehicles

ABSTRACT

Diesel particulate matter (PM) is a significant contributor to ambient air PM₁₀ and PM_2.5 particulate levels. In addition, recent literature argues that submicron diesel PM is a pulmonary health hazard. There is difficulty in attributing PM emissions to specific operating modes of a diesel engine, although it is acknowledged that PM production rises dramatically with load and that high PM emissions occur during rapid load increases on turbocharged engines. Snap-acceleration tests generally identify PM associated with rapid transient operating conditions, but not with high load. To quantify the origin of PM during transient engine operation, continuous opacity measurements have been made using a Wager 650CP full flow exhaust opacity meter. Opacity measurements were taken while the vehicles were operated over transient driving cycles on a chassis dynamometer using the West Virginia University (WVU) Transportable Heavy Duty Vehicle Emissions Testing Laboratories. Data were gathered from Detroit Diesel, Cummins, Caterpillar, and Navistar heavy-duty (HD) diesel engines. Driving cycles used were the Central Business District (CBD) cycle, the WVU 5-Peak Truck cycle, the WVU 5-Mile route, and the New York City Bus (NYCB) cycle. Continuous opacity measurements, integrated over the entire driving cycle, were compared to total integrated PM mass. In addition, the truck was subjected to repeat snap-acceleration tests, and PM was collected for a composite of these snap-acceleration tests. Additional data were obtained from a fleet of 1996 New Flyer buses in Flint, MI, equipped with electronically controlled Detroit Diesel Series 50 engines. Again, continuous opacity, regulated gaseous emissions, and PM were measured. The relationship between continuous carbon monoxide (CO) emissions and continuous opacity was noted. In identifying the level of PM emissions in transient diesel engine operation, it is suggested that CO emissions may prove to be a useful indicator and may be used to apportion total PM on a continuous basis over a transient cycle. The projected continuous PM data will prove valuable in future mobile source inventory prediction.     

Sulfate Emissions from Catalyst-Equipped Automobiles on the Highway

Abstract

A systematic investigation of solid and gaseous atmospheric emissions from some coke-oven batteries of one of Europe’s largest integrated steel factory (Taranto, Italy) has been carried out. In air monitoring samples, polycyclic aromatic hydrocarbons (PAHs) were consistently detected at concentrations largely exceeding threshold limit values. By means of PAHs speciation profile and benzo (a)pyrene (BaP) equivalent dispersion modeling from diffuse sources, the study indicated that serious health risks exist not only in working areas, but also in a densely populated residential district near the factory.     

The Effects of Repairs on Tailpipe Emissions for On-Board Diagnostics II-Equipped Vehicles with the Malfunction Indicator Light Illuminated

Abstract

A total of 77 On-Board Diagnostics II (OBDII)-equipped vehicles with illuminated malfunction indicator lights (MILs) and non-evaporative codes were tested before and after repair. The test cycles included the Federal Test Procedure (FTP), IM240, and steady-state cycles. A total of 17 vehicles were found with emissions greater than 1.5 times their respective FTP emissions standards. Repair of these vehicles resulted in dramatic reductions in overall emissions for all the cycles. A majority of the remaining vehicles were found to have emissions below the certification standard for the FTP both before and after repair. Repairs for the vehicles with emissions <1.5 times the standard resulted in some smaller but quantifiable emission reductions over the FTP and IM240 but larger reductions over the steady-state driving tests. Misfires, bad oxygen sensors, and exhaust gas recirculation (EGR) problems were the most common non-evaporative causes for triggering the MIL. The results show some fundamental differences between identifying malfunctioning vehicles using OBDII as opposed to more traditional dynamometer tests. In particular, for many systems, OBDII identifies components that are operating outside their design specification rather than for a specific emissions threshold.     

Effects of Operating Variables on PAH Emissions and Mutagenicity of Emissions from Woodstoves

As part of the Integrated Air Cancer Project, the U.S. Environmental Protection Agency (EPA) has conducted field emission measurement programs in Raleigh, North Carolina, and Boise, Idaho, to identify the potential mutagenic Impact of residential wood burning and motor vehicles on ambient and indoor air. These studies included the collection of emission samples from chimneys serving wood burning appliances. Parallel projects were undertaken in Instrumented woodstove test laboratories to quantify woodstove emissions during operations typical of in-house usage but under more controlled conditions.

Three woodstoves were operated In test laboratories over a range of burnrates, burning eastern oak, southern yellow pine, or western white pine. Two conventional stoves were tested at an altitude of 90 m. One of the conventional stoves and a catalytic stove were tested at an altitude of 825 m.

Decreasing burnrate increased total paniculate emissions from the conventional stoves while the catalytic stove's total particulate emissions were unaffected. There was no correlation of total particulate emissions with altitude whereas total polynuclear aromatic hydrocarbon (PAH) emissions were higher at the lower altitude. Mutagenicity of the catalytic stove emissions was higher than emissions from the conventional stove. Emissions from burning pine were more mutagenic than emissions from oak.     

Turbulent Diffusion Behind Vehicles: Effect of Traffic Speed on Pollutant Concentrations

Recent theoretical and experimental investigations Indicate that turbulent diffusion behind moving vehicles Is Influenced by the speed of the vehicle. Vertical wake induced turbulent diffusion, explicitly treated in the numerical ROADWAY model, is proportional to the square of the wind speed relative to the moving vehicle. Hence, the model predictions of turbulent mixing and pollutant concentrations on and downwind of a roadway are dependent upon the traffic speed. It Is expected from theoretical considerations that the effect of vehicle speed on pollutant concentrations will be more significant during stable atmospheric conditions, because in neutral and unstable conditions the vehicle-wake turbulence is quickly masked by the ambient turbulence. In this study, experimental data are utilized to evaluate the theoretical predictions of the effects of traffic speed on the ambient pollutant concentrations. The effects of vehicle speed upon ambient concentrations are investigated through wind tunnel experiments and field studies that used dual tracers. Consistent with predictions of the ROADWAY model, data obtained near the Long Island Expressway indicate that the influence of traffic speed on the ambient pollutant concentrations Is not significant during unstable and neutral conditions. The Long Island experiment did not provide sufficient field data to assess the model predictions of the traffic speed effect during stable atmospheric conditions.     

Emissions from India's transport sector: Statewise synthesis

A decentralized emission inventories are prepared for road transport sector of India in order to design and implement suitable technologies and policies for appropriate mitigation measures. Globalization and liberalization policies of the government in 90's have increased the number of road vehicles nearly 92.6% from 1980–1981 to 2003–2004. These vehicles mainly consume non-renewable fossil fuels, and are a major contributor of green house gases, particularly CO₂ emission. This paper focuses on the statewise road transport emissions (CO₂, CH₄, CO, NO_x, N₂O, SO₂, PM and HC), using region specific mass emission factors for each type of vehicles. The country level emissions (CO₂, CH₄, CO, NO_x, N₂O, SO₂ and NMVOC) are calculated for railways, shipping and airway, based on fuel types. In India, transport sector emits an estimated 258.10 Tg of CO₂, of which 94.5% was contributed by road transport (2003–2004). Among all the states and Union Territories, Maharashtra's contribution is the largest, 28.85 Tg (11.8%) of CO₂, followed by Tamil Nadu 26.41 Tg (10.8%), Gujarat 23.31 Tg (9.6%), Uttar Pradesh 17.42 Tg (7.1%), Rajasthan 15.17 Tg (6.22%) and, Karnataka 15.09 Tg (6.19%). These six states account for 51.8% of the CO₂ emissions from road transport.     

Contaminant Emissions from the Combustion of Fuels

In the past several years the use of cattle feeding lots for preparing cattle for market has developed into a large industry. These installations extend over much of the United States. Our lot, just outside of Memphis, Tennessee, is at present the only one in the area, but we feel that there will be others soon.

The control of odor in the cattle feeder industry is necessary if the operator does not wish to become the target of a nuisance or injunction suit. In one recent trip extending to Texas, then to California and back, numerous lots were inspected and this paper will present various types of odor control measures which were observed. The problem is one which can be controlled, but it is primarily dependent upon the willingness on the part of management to make the effort.

As a by-product of the cattle feeder lot, large quantities of manure are obtained and unless measures are taken to properly store this material, considerable odor can result. We believe that the use of dehydration in connection with the feeder lot will become more and more necessary, and it is our experience that this type of operation requires: 1. Good design of the dehydrating unit, 2. Careful control of the product flow, 3. An understanding of the proper method for storing the manure prior to its dehydration, and 4. Use of odor control methods to keep down those odors which would constitute nuisance to those living nearby. Various methods of odor control will be discussed.     

Fine Particulate Matter Emissions Inventories: Comparisons of Emissions Estimates with Observations from Recent Field Programs

Abstract

Emissions inventories of fine particulate matter (PM_2.5) were compared with estimates of emissions based on data emerging from U.S. Environment Protection Agency Particulate Matter Supersites and other field programs. Six source categories for PM_2.5 emissions were reviewed: on-road mobile sources, nonroad mobile sources, cooking, biomass combustion, fugitive dust, and stationary sources. Ammonia emissions from all of the source categories were also examined. Regional emissions inventories of PM in the exhaust from on-road and nonroad sources were generally consistent with ambient observations, though uncertainties in some emission factors were twice as large as the emission factors. In contrast, emissions inventories of road dust were up to an order of magnitude larger than ambient observations, and estimated brake wear and tire dust emissions were half as large as ambient observations in urban areas. Although comprehensive nationwide emissions inventories of PM_2.5 from cooking sources and biomass burning are not yet available, observational data in urban areas suggest that cooking sources account for approximately 5–20% of total primary emissions (excluding dust), and biomass burning sources are highly dependent on region. Finally, relatively few observational data were available to assess the accuracy of emission estimates for stationary sources. Overall, the uncertainties in primary emissions for PM_2.5 are substantial. Similar uncertainties exist for ammonia emissions. Because of these uncertainties, the design of PM_2.5 control strategies should be based on inventories that have been refined by a combination of bottom-up and top-down methods.     

Real-World In-Use Activity,Fuel Use,and Emissions for Nonroad Construction Vehicles: A Case Study for Excavators

Abstract

A study design was developed and demonstrated for deployment of a portable emission measurement system (PEMS) for excavators. Excavators are among the most commonly used vehicles in construction activities. The PEMS measured nitric oxide, carbon monoxide, hydrocarbons, carbon dioxide, and opacity-based particulate matter. Data collection, screening, processing, and analysis protocols were developed to assure data quality and to quantify variability in vehicle fuel consumption and emissions rates. The development of data collection procedures was based on securing the PEMS while avoiding disruption to normal vehicle operations. As a result of quality assurance, approximately 90% of the attempted measurements resulted in valid data. On the basis of field data collected for three excavators, an average of 50% of the total nitric oxide emissions was associated with 29% of the time of operation, during which the average engine speed and manifold absolute pressure were significantly higher than corresponding averages for all data. Mass per time emission rates during non-idle modes (i.e., moving and using bucket) were on average 7 times greater than for the idle mode. Differences in normalized average rates were influenced more by intercycle differences than intervehicle differences. This study demonstrates the importance of accounting for intercycle variability in real-world in-use emissions to develop more accurate emission inventories. The data collection and analysis methodology demonstrated here is recommended for application to more vehicles to better characterize real-world vehicle activity, fuel use, and emissions for nonroad construction equipment.