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 15 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 20 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 25 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 30 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 t he Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2017-603 Manuscript under review for journal Atmos. Chem. Phys. 2 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.