Tracing fuel component carbon in the emissions from diesel engines

The addition of oxygenates to diesel fuel can reduce particulate emissions, but the underlying chemical pathways for the reductions are not well understood. While measurements of particulate matter (PM), unburned hydrocarbons (HC), and carbon monoxide (CO) are routine, determining the contribution of carbon atoms in the original fuel molecules to the formation of these undesired exhaust emissions has proven difficult. Renewable bio-derived fuels (ethanol or bio-diesel) containing a universal distribution of contemporary carbon are easily traced by accelerator mass spectrometry (AMS). These measurements provide general information about the emissions of bio-derived fuels. Another approach exploits synthetic organic chemistry to place ¹⁴C atoms in a specific bond position in a specific fuel molecule. The highly labeled fuel molecule is then diluted in ¹⁴C-free petroleum-derived stock to make a contemporary petroleum fuel suitable for tracing. The specific ¹⁴C atoms are then traced through the combustion event to determine whether they reside in PM, HC, CO, CO₂, or other emission products. This knowledge of how specific molecular structures produce certain emissions can be used to refine chemical-kinetic combustion models and to optimize fuel composition to reduce undesired emissions. Due to the high sensitivity of the technique and the lack of appreciable ¹⁴C in fossil fuels, fuels for AMS experiments can be labeled with modern levels of ¹⁴C and still produce a strong signal. Since the fuel is not radioactive, emission tests can be conducted in any conventional engine lab, dynamometer facility, or on the open road. Published by Elsevier B.V.