Isocyanic acid (HNCO) is a well‐known air pollutant that affects human health. Biomass burning, smoking, and combustion engines are known HNCO sources, but recent studies suggest that secondary production in the atmosphere may also occur. We directly observed photochemical production of HNCO from the oxidative aging of diesel exhaust during the Diesel Exhaust Fuel and Control experiments at Colorado State University using acetate ionization time‐of‐flight mass spectrometry. Emission ratios of HNCO were enhanced, after 1.5 days of simulated atmospheric aging, from 50 to 230 mg HNCO/kg fuel at idle engine operating conditions. Engines operated at higher loads resulted in less primary and secondary HNCO formation, with emission ratios increasing from 20 to 40 mg HNCO/kg fuel under 50% load engine operating conditions. These results suggest that photochemical sources of HNCO could be more significant than primary sources in urban areas.

Immersion‐mode ice‐nucleating particle (INP) concentrations from an off‐road diesel engine were measured using a continuous‐flow diffusion chamber at −30°C. Both petrodiesel and biodiesel were utilized, and the exhaust was aged up to 1.5 photochemically equivalent days using an oxidative flow reactor. We found that aged and unaged diesel exhaust of both fuels is not likely to contribute to atmospheric INP concentrations at mixed‐phase cloud conditions. To explore this further, a new limit‐of‐detection parameterization for ice nucleation on diesel exhaust was developed. Using a global‐chemical transport model, potential black carbon INP (INPBC) concentrations were determined using a current literature INPBC parameterization and the limit‐of‐detection parameterization. Model outputs indicate that the current literature parameterization likely overemphasizes INPBC concentrations, especially in the Northern Hemisphere. These results highlight the need to integrate new INPBC parameterizations into global climate models as generalized INPBC parameterizations are not valid for diesel exhaust.

Organic acids have primary and secondary sources in the atmosphere, impact ecosystem health, and are useful metrics for identifying gaps in organic oxidation chemistry through model-measurement comparisons. We photooxidized (OH oxidation) primary emissions from diesel and biodiesel fuel types under two engine loads in an oxidative flow reactor. formic, butyric, and propanoic acids, but not methacrylic acid, have primary and secondary sources. Emission factors for these gas-phase acids varied from 0.3-8.4 mg kg fuel. Secondary chemistry enhanced these emissions by 1.1 (load) to 4.4 (idle) × after two OH-equivalent days. The relative enhancement in secondary organic acids in idle versus loaded conditions was due to increased precursor emissions, not faster reaction rates. Increased hydrocarbon emissions in idle conditions due to less complete combustion (associated with less oxidized gas-phase molecules) correlated to higher primary organic acid emissions. The lack of correlation between organic aerosol and organic acid concentrations downstream of the flow reactor indicates that the secondary products formed on different oxidation time scales and that despite being photochemical products, organic acids are poor tracers for secondary organic aerosol formation from diesel exhaust. Ignoring secondary chemistry from diesel exhaust would lead to underestimates of both organic aerosol and gas-phase organic acids.

Forests can be both sources and sinks of volatile organic compounds to the atmosphere. The role that forests play in controlling organic acid concentrations remains poorly understood with multiple model-measurement comparisons reporting missing sources of formic acid. We conducted seasonal measurements of concentrations and eddy covariance fluxes of oxidized volatile organic compounds over a ponderosa pine forest in Colorado in 2016. Diel concentration profiles show mid-day maxima, consistent with previous studies. We observed persistent but variable upward fluxes of formic, propionic, methacrylic, and butyric acids from the pine forest during all seasons. Formic acid concentrations and fluxes were ∼10 times higher than the other organic acids with daytime exchange velocities on the order of 4–6 cm s–1. The other organic acids had similar exchange velocities as formic acid in the warmer seasons and much smaller exchange velocities in the colder seasons. The upward fluxes for all organic acids increased exponentially with temperature. The observed net upward flux demonstrated that dry deposition was smaller than ecosystem sources of the organic acids. Primary emissions from soil and pine trees were small, in contrast to estimates of in-canopy chemistry. Our study points to an underestimated ecosystem source of organic acids (e.g., in-canopy chemistry of large or multifunctional terpenoids), an overestimated dry deposition sink (potentially due to the arid environment), and/or an unresolved sink of organic acids in the upper boundary layer. Forests are potentially large sources of atmospheric organic acids in warmer seasons but further investigation into dry deposition mechanisms and in-canopy chemistry is warranted.

Diesel engines are important sources of fine particle pollution in urban environments, but their contribution to the atmospheric formation of secondary organic aerosol (SOA) is not well constrained. We investigated direct emissions of primary organic aerosol (POA) and photochemical production of SOA from a diesel engine using an oxidation flow reactor (OFR). In less than a day of simulated atmospheric aging, SOA production exceeded POA emissions by an order of magnitude or more. Efficient combustion at higher engine loads coupled to the removal of SOA precursors and particle emissions by aftertreatment systems reduced POA emission factors by an order of magnitude and SOA production factors by factors of 2-10. The only exception was that the retrofitted aftertreatment did not reduce SOA production at idle loads where exhaust temperatures were low enough to limit removal of SOA precursors in the oxidation catalyst. Use of biodiesel resulted in nearly identical POA and SOA compared to diesel. The effective SOA yield of diesel exhaust was similar to that of unburned diesel fuel. While OFRs can help study the multiday evolution, at low particle concentrations OFRs may not allow for complete gas/particle partitioning and bias the potential of precursors to form SOA.