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Two methods of sampling exhaust emissions are typically used for characterizing emissions from diesel engines: total dilution which uses a constant volume sampling (CVS) system and partial flow dilution which relies on proportionally diluting a small part from the main exhaust stream. The CVS dilutes the entire exhaust flow to a constant volumetric flowrate which allows for proportional sampling of the exhaust species during transient engine operation. For partial dilution sampling during transient engine operation, obtaining a proportional sample is more rigorous and dilution of the extracted sample must be continuously changed throughout the cycle in order for the extracted sample flowrate to be proportional to the continuously changing exhaust flow. Typically, regulated emissions measured using both methods for an engine platform have shown good correlation. The focus for this work was on the experimental investigation of the two methods for the measurement of unregulated species.

Advanced combustion strategies used to improve efficiency, emissions, and performance in internal combustion engines (IC) alter the chemical composition of engine-out emissions. The characterization of exhaust chemistry from advanced IC engines requires an analytical system capable of measuring a wide range of compounds. For many years, the widely accepted Coordinating Research Council (CRC) Auto/Oil procedure[1,2] has been used to quantify hydrocarbon compounds between C1 and C12 from dilute engine exhaust in Tedlar polyvinyl fluoride (PVF) bags. Hydrocarbons greater than C12+ present the greatest challenge for identification in diesel exhaust. Above C12, PVF bags risk losing the higher molecular weight compounds due to adsorption to the walls of the bag or by condensation of the heavier compounds. This paper describes two specialized exhaust gas sampling and analytical systems capable of analyzing the mid-range (C10 - C24) and the high range (C24+) hydrocarbon in exhaust.

A two-phase study was performed to establish a standard diesel exhaust composition which could be used in the future development of light-duty diesel exhaust aftertreatment. In the first phase, a literature review created a database of diesel engine-out emissions. The database consisted chiefly of data from heavy-duty diesel engines; therefore, the need for an emission testing program for light- and medium-duty engines was identified. A second phase was conducted to provide additional light-duty vehicle emissions data from current technology vehicles. Engine-out diesel exhaust from four 2004 model light-duty vehicles with a variety of engine displacements was collected and analyzed. Each vehicle was evaluated using five steady-state engine operating conditions and two transient test cycles (the Federal Test Procedure and the US06). Regulated emissions were measured along with speciation of both volatile and semi-volatile components of the hydrocarbons.

Newly designed Teflon® O-rings along with XAD-2 resin, stainless steel screens, lock rings, and glass cartridges were used to construct a new semi-volatile organic compounds (SVOC's) sampling device. This new sampling device allows direct and repeated sampling, extraction, and cleaning without ever having to be disassembled or reassembled. This new XAD-2 glass cartridge (X2) was compared with three other sampling methods namely Empore® membrane (EM), hexane impinger (HI), and “Cold Trap” (CT) for SVOC sampling efficiency on diesel engine exhaust emissions. The X2 method showed the highest overall SVOC collection efficiency, followed by the EM and HI methods. The X2 method has higher trapping efficiency for the oxygenates, polycyclic aromatic hydrocarbons (PAH's), alkyl cyclohexanes, and the alkyl aromatics than the other three SVOC sampling methods. The HI method has the highest trapping efficiency for the normal alkanes.

This study compared diesel exhaust emission from four different diesel fuels: a conventional low sulfur D2 diesel (0.03% sulfur, 28% aromatics), California Air Resources Board (CARB) diesel (0.015% sulfur, 8% aromatics), “Swedish” diesel (<0.001% sulfur, 4% aromatics), and a Fischer-Tropsch (F-T) diesel (<0.0001% sulfur, <0.1% aromatics) fuel. The comparison included regulated emissions, hydrocarbon speciation, air toxics, aldehydes and ketones, particle size distribution, and greenhouse gas emissions. Testing was conducted using a Cummins B-Series engine installed both in a heavy light-duty truck operating on a chassis dynamometer and on an engine dynamometer. The chassis driving cycles included city, highway, and aggressive driving operation. Engine dynamometer tests included the U.S. transient cycle.

Two additive blends proposed for improving the flame luminosity in neat methanol fuel were investigated to determine the effect of these additives on the exhaust emissions in a dual-fueled Volkswagen Jetta. The two blends contained 4 percent toluene plus 2 percent indan in methanol and 5 percent cyclopentene plus 5 percent indan in methanol. Each blend was tested for regulated and unregulated emissions as well as a speciation of the exhaust hydrocarbons resulting from use of each fuel. The vehicle exhaust emissions from these two fuel blends were compared to the Coordinating Research Council Auto-Oil national average gasoline (RF-A), M100, and M85 blended from RF-A. Carter Maximum Incremental Reactivity Factors were applied to the speciated hydrocarbon emission results to determine the potential ozone formation for each fuel. Toxic emissions as defined in the 1990 Clean Air Act were also compared for each fuel.

The effects of fuel properties and emission control systems on exhaust hydrocarbon emissions have been studied. Using fourteen fuels with different properties, exhaust hydrocarbon emissions were measured for the two vehicle types with different emission control systems, under body catalyst and closed coupled catalyst, under the Federal Test Procedure. The fuel properties included high and low concentrations of olefins and aromatics as well as high and low T90. In addition, two fuels contained MTBE. The hydrocarbon emissions were discussed from the view point of the ozone reactivity and ozone formation potential. The results show that the high ozone reactivity of exhaust emissions are mainly caused by the olefins and aromatics in fuels. And also, the effects of fuel property change on exhaust emissions for the vehicle with an under body catalyst are more sensitive than the case of the vehicle with a closed coupled catalyst.

Particulate and regulated gaseous emissions were characterized in a feasibility study for a 1994 Ford Taurus Flexible Fuel Vehicle (FFV) operating on five fuels. The five fuels included Federal Reformulated Gasoline (RFG); 85% fuel grade methanol and 15% gasoline (M85); 85% denatured ethanol and 15% gasoline (E85d); liquefied petroleum gas (LPG) meeting HD-5 specifications; and industry average compressed natural gas (CNG). The vehicle was operated fuel-rich to simulate a vehicle operating condition leading to increased production of particulate matter. This simulation was accomplished by using a universal exhaust gas oxygen sensor (UEGO) in connection with an external controller. Appropriate aftermarket conversion kits involving closed-loop control and adaptive learning capabilities allowed operation on the gaseous fuels. Particulate emissions were characterized by total mass and particle size.

This paper reviews the use of additives to improve safety aspects associated with the use of methanol as a motor fuel. A survey of the literature was conducted to determine candidate additives for methanol that produce one or more of the following properties: provide a visible or luminous flame, reduce the potential for skin contact, give a foul or unpleasant taste and odor, and act as an emetic. Candidate additives were reviewed to determine potential effectiveness, cost, east of production, health problems, and effects on vehicle performance. Potential additives include complex hydrocarbon mixtures such as gasoline, alcohol soluble dyes and unpalatable compounds such as denatonium benzoate.

Since the conception of the internal combustion engine, smoky and ill-smelling exhaust was prevalent. Over the last century, significant improvements have been made in improving combustion and in treating the exhaust to reduce these effects. One group of compounds typically found in exhaust, polycyclic aromatic hydrocarbons (PAH), usually occurs at very low concentrations in diesel engine exhaust. Some of these compounds are considered carcinogenic, and most are considered hazardous air pollutants (HAP). Many methods have been developed for sampling, handling, and analyzing PAH. For this study, an improved method for dilute exhaust sampling was selected for sampling the PAH in diesel engine exhaust. This sampling method was used during transient engine operation both with and without aftertreatment to show the effect of aftertreatment.