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 %.     

Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Idle Emissions from Heavy-Duty Diesel Vehicles: Review and Recent Data

Abstract

Heavy-duty diesel vehicle idling consumes fuel and reduces atmospheric quality, but its restriction cannot simply be proscribed, because cab heat or air-conditioning provides essential driver comfort. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from the West Virginia University transient engine test cell, the E-55/59 Study and the Gasoline/Diesel PM Split Study. It covered 75 heavy-duty diesel engines and trucks, which were divided into two groups: vehicles with mechanical fuel injection (MFI) and vehicles with electronic fuel injection (EFI). Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NO_x), particulate matter (PM), and carbon dioxide (CO₂) have been reported. Idle CO₂ emissions allowed the projection of fuel consumption during idling. Test-to-test variations were observed for repeat idle tests on the same vehicle because of measurement variation, accessory loads, and ambient conditions. Vehicles fitted with EFI, on average, emitted [~20 g/hr of CO, 6 g/hr of HC, 86 g/hr of NO_x, 1 g/hr of PM, and 4636 g/hr of CO₂ during idle. MFI equipped vehicles emitted ~35 g/hr of CO, 23 g/hr of HC, 48 g/hr of NO_x, 4 g/hr of PM, and 4484 g/hr of CO₂, on average, during idle. Vehicles with EFI emitted less idleCO, HC, and PM, which could be attributed to the efficient combustion and superior fuel atomization in EFI systems. Idle NO_x, however, increased with EFI, which corresponds with the advancing of timing to improve idle combustion. Fuel injection management did not have any effect on CO₂ and, hence, fuel consumption. Use of air conditioning without increasing engine speed increased idle CO₂, NO_x, PM, HC, and fuel consumption by 25% on average. When the engine speed was elevated from 600 to 1100 revolutions per minute, CO₂ and NO_x emissions and fuel consumption increased by >150%, whereas PM and HC emissions increased by ~100% and 70%, respectively. Six Detroit Diesel Corp. (DDC) Series 60 engines in engine test cell were found to emit less CO, NO_x, and PM emissions and consumed fuel at only 75%of the level found in the chassis dynamometer data. This is because fan and compressor loads were absent in the engine test cell.     

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.     

The Effect of Ethanol Fuel on the Emissions of Vehicles over a Wide Range of Temperatures

ABSTRACT

The emissions from a fleet of 11 vehicles, including three from the State of Alaska, were tested at 75, 0, and -20 °F with base gasolines and E10 gasolines, that is, gasolines with 10% by volume ethanol added. The data for the changes in emissions for the test run at 75 °F are included, since most other studies on the effects of E10 gasoline on emissions were run at that temperature. The three Alaskan vehicles were also tested at 20 °F. The testing followed the Federal Test Procedure, and regulated emissions—CO, total hydrocarbons (THC), and nitrogen oxides (NO_x)—CO₂, speciated organics, and fuel economy were measured. A total of 490 FTP tests were run. The data obtained indicated that with most vehicles, at the temperatures tested, improvements in both CO and THC emissions were obtained with the use of E10 fuel. At the lowest temperature used, -20 °F, most vehicles had an increase in NO emissions with the use of E10 fuel. At the other temperatures, however, more vehicles showed a decrease in NO_x emissions with the use of E10. With all vehicles at all temperatures tested, the emissions of acetaldehyde increased significantly when E10 fuel was used. The highest increase was about 8 to 1. Benzene, formaldehyde, and 1,3 butadiene showed both increases and decreases in the emissions when using E10 fuel. Unexpected results were obtained with the fuel economy, with about half of the tests showing an increase in fuel economy with the use of E10 fuel.     

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.     

Idle Emissions from Heavy-Duty Diesel and Natural Gas Vehicles at High Altitude

ABSTRACT

Idle emissions of total hydrocarbon (THC), CO, NO_x, and particulate matter (PM) were measured from 24 heavy-duty diesel-fueled (12 trucks and 12 buses) and 4 heavy-duty compressed natural gas (CNG)-fueled vehicles. The volatile organic fraction (VOF) of PM and aldehyde emissions were also measured for many of the diesel vehicles. Experiments were conducted at 1609 m above sea level using a full exhaust flow dilution tunnel method identical to that used for heavy-duty engine Federal Test Procedure (FTP) testing. Diesel trucks averaged 0.170 g/min THC, 1.183 g/min CO, 1.416 g/min NO_x, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NO_x, and 0.048 g/min PM.

Results are compared to idle emission factors from the MOBILE5 and PART5 inventory models. The models significantly (45-75%) overestimate emissions of THC and CO in comparison with results measured from the fleet of vehicles examined in this study. Measured NO_x emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NO_x emissions increased with Health and Environment; June 30, 1999 (available from the authors).     

Toxic Emissions from Mobile Sources: A Total Fuel-Cycle Analysis for Conventional and Alternative Fuel Vehicles

ABSTRACT

Mobile sources are among the largest contributors of four hazardous air pollutants—benzene, 1,3-butadiene, acetal-dehyde, and formaldehyde—in urban areas. At the same time, federal and state governments are promoting the use of alternative fuel vehicles as a means to curb local air pollution. As yet, the impact of this movement toward alternative fuels with respect to toxic emissions has not been well studied. The purpose of this paper is to compare toxic emissions from vehicles operating on a variety of fuels, including reformulated gasoline (RFG), natural gas, ethanol, methanol, liquid petroleum gas (LPG), and electricity. This study uses a version of Argonne National Laboratory's Greenhouse Gas, Regulated Emissions, and Energy Use in Transportation (GREET) model, appropriately modified to estimate toxic emissions. The GREET model conducts a total fuel-cycle analysis that calculates emissions from both downstream (e.g., operation of the vehicle) and upstream (e.g., fuel production and distribution) stages of the fuel cycle. We find that almost all of the fuels studied reduce 1,3-buta-diene emissions compared with conventional gasoline (CG). However, the use of ethanol in E85 (fuel made with 85% ethanol) or RFG leads to increased acetaldehyde emissions, and the use of methanol, ethanol, and compressed natural gas (CNG) may result in increased formaldehyde emissions. When the modeling results for the four air toxics are considered together with their cancer risk factors, all the fuels and vehicle technologies show air toxic emission reduction benefits.     

Gaseous Emissions from Vehicles in a Traffic Tunnel in Vancouver,British Columbia

ABSTRACT

In August 1995, measurements of CO, NO_x, speciated nonmethane hydrocarbons (NMHC), and CO₂ were made in Vancouver's Cassiar Connector, a 730-m-long level-grade highway traffic tunnel. Two characteristics of the Vancouver setting are the presence of many propane vehicles and a mandatory inspection and maintenance (I/M) program. Although the driving conditions and vehicle fleets are otherwise outwardly similar to those of recent Tuscarora-tunnel studies, CO/NO ratios at the Cassiar Connector are significantly lower than those measured at Tuscarora. The Cassiar measurements are consistent with the MOBILE5A mobile emissions model predictions. The Canadian version of MOBILE5A—known as MOBILE5C—gives nearly identical results, indicating that differences in Canadian and U.S. emission standards cannot explain differences between Cassiar and U.S. tunnels. Considering the modeling results as well as measured ethene/acetylene ratios indicative of noncatalyst vehicles, it appears that vehicle deterioration remains the major issue in in-use vehicle emissions—even in Vancouver, where there is a mandatory loaded-mode I/M program.     

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.     

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.