Emission of formic and acetic acids from two Colorado soils.

A 'missing source' of atmospheric formic acid is consistently observed during model-measurement comparisons, and evidence from multiple environments suggests a near-surface source. Soil emissions are considered to be a small formic acid source, but estimates are based on a single study from a tropical site. Here, we investigate soil emissions of organic acids from two soils - a ponderosa pine forest (Manitou Experimental Forest Observatory), and a managed lawn (Colorado State University) using a laboratory chamber. Both soils are a source of formic and acetic acids. Under ambient conditions, formic acid emissions are 0.11 (pine forest) and 0.15 (lawn) nmol m-2 s-1, and acetic acid emissions are 0.05 (pine forest) and 0.71 (lawn) nmol m-2 s-1. Only acetic acid emissions from the forest site correlate with CO2 fluxes, but all formic and acetic acid emissions increase exponentially with temperature. Increasing soil moisture only enhances acetic acid emissions from the forest. Considering this temperature and moisture dependence, we hypothesize that while equilibrium partitioning may contribute to the forest emissions, organic acid emissions from the lawn are likely driven by microbial activity. Lactic acid was emitted from both soils, but not quantified. The observed formic acid emissions are higher than previous measurements, but still low enough that soils are unlikely the 'missing source' of atmospheric organic acids, although the variability in the soil source is substantial. We contrast observations to previous parameterizations used in models, and present recommendations for modified parameterizations for formic and acetic acid emission.

Primary and Secondary Sources of Gas-Phase Organic Acids from 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-1 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.