The Effect of Varying Engine Conditions on Unregulated VOC Diesel Exhaust Emissions

An extensive set of measurements were performed to investigate the effect of different engine conditions (i.e. load, speed, temperature, "driving scenarios") and emission control devices (with/without diesel oxidative catalyst, DOC) on the composition and abundance of unregulated exhaust gas emissions from a light-duty diesel engine. Exhaust emissions were introduced into an atmospheric chamber and measured using thermal desorption comprehensive two-dimensional gas chromatography coupled to a flame ionisation detector (TD-GC×GC-FID). In total, 16 individual and 8 groups of volatile organic compounds (VOCs) were measured in the exhaust gas, ranging from volatile to intermediate volatility. The total speciated VOC (∑SpVOC) emission rates varied significantly with different engine conditions, ranging from 70 to 9268 milligrams of VOC mass per kilogram of fuel burnt (mg kg-1). ∑SpVOC emission rates generally decreased with increasing engine load and temperature, and to a lesser degree, engine speed. The exhaust gas composition changed as a result of two main influencing factors, the DOC hydrocarbon (HC) removal efficiency and engine combustion efficiency. Increased DOC HC removal efficiency and engine combustion efficiency resulted in a greater percentage contribution of the C7 to C12 branched aliphatics and C7 to C12 n-alkanes, respectively, to the ∑SpVOC emission rate. The investigated DOC removed 46 ± 10 % of the ∑SpVOC emissions, with removal efficiencies of 83 ± 3 % for the single-ring aromatics and 39 ± 12 % for the aliphatics (branched and straight-chain). The DOC aliphatic removal efficiency generally decreased with increasing carbon chain length. The emission factors of n-nonane to n-tridecane were compared with on-road diesel emissions from a highway tunnel in Oakland California. Comparable emission factors were from experiments with relatively high engine loads and speeds, engine conditions which are consistent with the driving conditions of the on-road diesel vehicles. Emission factors from low engine loads and speeds (e.g. cold-start) showed no agreement with the on-road diesel emissions as expected, with the emission factors observed to be 2 to 8 times greater. To our knowledge, this is the first study which has explicitly discussed the effect of the DOC HC removal efficiency and combustion efficiency on the exhaust gas composition. With further work, compositional differences in exhaust gas emissions as a function of engine temperature, could be implemented into air-quality models, resulting in improved refinement and better understanding of diesel exhaust emissions on local air quality.