Intermediate volatility organic compound (IVOC) emissions from a large cargo vessel were characterized under realworld operating conditions using an on-board measurement system. Test ship fuel-based emission factors (EFs) of total IVOCs were determined for two fuel types and seven operating conditions. The average total IVOC EF was 1003 ± 581 mg•kg-fuel −1 , approximately 0.76 and 0.29 times the EFs of primary organic aerosol (POA) emissions from low-sulfur fuel (LSF, 0.38 wt % S) and high-sulfur fuel (HSF, 1.12 wt % S), respectively. The average total IVOC EF from LSF was 2.4 times that from HSF. The average IVOC EF under low engine load (15%) was 0.5−1.6 times higher than those under 36%−74% loads. An unresolved complex mixture (UCM) contributed 86.1 ± 1.9% of the total IVOC emissions. Ship secondary organic aerosol (SOA) production was estimated to be 546.5 ± 284.1 mg•kg-fuel −1 ; IVOCs contributed 98.9 ± 0.9% of the produced SOA on average. Fuel type was the dominant determinant of ship IVOC emissions, IVOC volatility distributions, and SOA production. The ship emitted more IVOC mass, produced higher proportions of volatile organic components, and produced more SOA mass when fueled with LSF than when fueled with HSF. When reducing ship POA emissions, more attention should be paid to commensurate control of ship SOA formation potential.

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Abstract. An observation-based model coupled to the Master Chemical Mechanism (V3.3.1) and constrained by a full suite of observations was developed to study atmospheric oxidation capacity (AOC), OH reactivity, OH chain length and HOx (=OH+HO2) budget for three different ozone (O3) concentration levels in Shanghai, China. Five months of observations from 1 May to 30 September 2018 showed that the air quality level is lightly polluted or worse (Ambient Air Quality Index, AQI, of > 100) for 12 d, of which ozone is the primary pollutant for 10 d, indicating ozone pollution was the main air quality challenge in Shanghai during summer of 2018. The levels of ozone and its precursors, as well as meteorological parameters, revealed the significant differences among different ozone levels, indicating that the high level of precursors is the precondition of ozone pollution, and strong radiation is an essential driving force. By increasing the input JNO2 value by 40 %, the simulated O3 level increased by 30 %–40 % correspondingly under the same level of precursors. The simulation results show that AOC, dominated by reactions involving OH radicals during the daytime, has a positive correlation with ozone levels. The reactions with non-methane volatile organic compounds (NMVOCs; 30 %–36 %), carbon monoxide (CO; 26 %–31 %) and nitrogen dioxide (NO2; 21 %–29 %) dominated the OH reactivity under different ozone levels in Shanghai. Among the NMVOCs, alkenes and oxygenated VOCs (OVOCs) played a key role in OH reactivity, defined as the inverse of the OH lifetime. A longer OH chain length was found in clean conditions primarily due to low NO2 in the atmosphere. The high level of radical precursors (e.g., O3, HONO and OVOCs) promotes the production and cycling of HOx, and the daytime HOx primary source shifted from HONO photolysis in the morning to O3 photolysis in the afternoon. For the sinks of radicals, the reaction with NO2 dominated radical termination during the morning rush hour, while the reactions of radical–radical also contributed to the sinks of HOx in the afternoon. Furthermore, the top four species contributing to ozone formation potential (OFP) were HCHO, toluene, ethylene and m/p-xylene. The concentration ratio (∼23 %) of these four species to total NMVOCs is not proportional to their contribution (∼55 %) to OFP, implying that controlling key VOC species emission is more effective than limiting the total concentration of VOC in preventing and controlling ozone pollution.

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Chamber experiments, exhaust collection, and in-situ sampling were employed to study the emission profiles of volatile organic compounds (VOCs) from solvent use, specifically indoor paint, auto paint, furniture paint, and print ink, which are of significant importance with regard to VOC emissions in Shanghai. The results showed that there were some differences among these VOC source profiles of the emissions associated with different solvents. On the one hand, for emissions from imported indoor solvents, ~50% of the total mass concentration was contributed by aromatics, and ~30% by alkanes. On the other hand, VOC source profiles from domestic indoor paint, furniture paint, and auto paint were similar in the sense that aromatics made a much larger contribution to total VOCs, specifically, 98% for domestic indoor paint, 80%-93% for the other two, and C8-C9 aromatics accounted for ~70% of total VOCs. For VOCs from printing, C2-C5 species dominated by more than 50%, followed by C8-C9 aromatics. VOCs from the use of different solvents presented different chemical reactivities. Among the four solvents listed above, the average OH loss rate constant (k-avg) and maximum incremental reactivity (MIR-avg) of VOCs from printing were the lowest, with values of 8.2 × 10 -12 cm 3 /molecule/s and 2.9 g(O 3 )/g(VOC), respectively. For VOCs from painting, the average reactivity was twice that of VOCs from printing, and its value of MIR-avg was 4.7-6.3 g(O 3 )/g(VOC). There are significant variations in the VOC source profiles related to solvent use in different studies. The representativeness of the solvents studied and the VOC samples collected should thus be more closely examined. The accuracy of VOC source profiles related to solvent use is highly dependent on location and sampling frequency.