• Energy Research

Humic-like substances (HULIS), known for their substantial impact on the atmosphere, are identified in marine diesel engine emissions obtained from five different fuels at two engine loads simulating real world scenarios as well as the application of wet sulfur scrubbers. The HULIS chemical composition is characterized by electrospray ionization (ESI) ultrahigh resolution mass spectrometry and shown to contain partially oxidized alkylated polycyclic aromatic compounds as well as partially oxidized aliphatic compounds, both including abundant nitrogen- and sulfur-containing species, and clearly different to HULIS emitted from biomass burning. Fuel properties such as sulfur content and aromaticity as well as the fuel combustion efficiency and engine mode are reflected in the observed HULIS composition. When the marine diesel engine is operated below the optimum engine settings, e.g., during maneuvering in harbors, HULIS-C emission factors are increased (262-893 mg kg-1), and a higher number of HULIS with a shift toward lower degree of oxidation and higher aromaticity is detected. Additionally, more aromatic and aliphatic CHOS compounds in HULIS were detected, especially for high-sulfur fuel combustion. The application of wet sulfur scrubbers decreased the HULIS-C emission factors by 4-49% but also led to the formation of new HULIS compounds. Overall, our results suggest the consideration of marine diesel engines as a relevant regional source of HULIS emissions.

We establish laboratory-photochemical ageing in the 1800 m3 environmental chamber “PHOTO-LAC” to study the atmospheric processing of dense wildfire plumes.

Humic-like substances (HULIS) account for a major redox-active fraction of biomass burning organic aerosols (BBOA). During atmospheric transport, fresh acidic BB-HULIS in droplets and humid aerosols are subject to neutralization and pH-modified aging process. In this study, solutions containing HULIS isolated from wood smoldering emissions were first adjusted with NaOH and NH3 to pH values in the range of 3.6-9.0 and then aged under oxic dark conditions. Evolution of HULIS oxidative potential (OP) and total peroxide content (equivalent H2O2 concentration, H2O2eq) were measured together with the changes in solution absorbance and chemical composition. Notable immediate responses such as peroxide generation, HULIS autoxidation, and an increase in OP and light absorption were observed under alkaline conditions. Initial H2O2eq, OP, and absorption increased exponentially with pH, regardless of the alkaline species added. Dark aging further oxidized the HULIS and led to pH-dependent toxic and chemical changes, exhibiting an alkaline-facilitated initial increase followed by a decrease of OP and H2O2eq. Although highly correlated with HULIS OP, the contributions of H2O2eq to OP are minor but increased both with solution pH and dark aging time. Alkalinity-assisted autoxidation of phenolic compounds and quinoids with concomitant formation of H2O2 and other alkalinity-favored peroxide oxidation reactions are proposed here for explaining the observed HULIS OP and chemical changes in the dark. Our findings suggest that alkaline neutralization of fresh BB-HULIS represents a previously overlooked peroxide source and pathway for modifying aerosol redox-activity and composition. Additionally, these findings imply that the lung fluid neutral environment can modify the OP and peroxide content of inhaled BB-HULIS. The results also suggest that common separation protocols of HULIS using base extraction methods should be treated with caution when evaluating and comparing their composition, absorption, and relative toxicity.