HONO Measurement by Catalytic Conversion to NO on Nafion Surfaces.

A selective catalytic converter has been developed to quantify nitrous acid (HONO), a photochemical precursor to NO and OH radicals that drives the formation of ozone and other pollutants in the troposphere. The converter is made from a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion) that was found to convert HONO to NO with unity yield under specific conditions. When coupled to a commercially available NOx (=NO + NO2) chemiluminescence (CL) analyzer, the system measures HONO with a limit of detection as low as 64 parts-per-trillion (ppt) (1 min average) in addition to NOx. The converter is selective for HONO when tested against other common gas-phase reactive nitrogen species, although loss of O3 on Nafion is a potential interference. The sensitivity and selectivity of this method allow for accurate measurement of atmospherically relevant concentrations of HONO. This was demonstrated by good agreement between HONO measurements made with the Nafion-CL method and those made with chemical ionization mass spectrometry in a simulation chamber and in indoor air. The observed reactivity of HONO on Nafion also has significant implications for the accuracy of CL NOx analyzers that use Nafion to remove water from sampling lines.

Microbial mechanisms and ecosystem flux estimation for aerobic NOy emissions from deciduous forest soils.

Reactive nitrogen oxides (NOy; NOy = NO + NO2 + HONO) decrease air quality and impact radiative forcing, yet the factors responsible for their emission from nonpoint sources (i.e., soils) remain poorly understood. We investigated the factors that control the production of aerobic NOy in forest soils using molecular techniques, process-based assays, and inhibitor experiments. We subsequently used these data to identify hotspots for gas emissions across forests of the eastern United States. Here, we show that nitrogen oxide soil emissions are mediated by microbial community structure (e.g., ammonium oxidizer abundances), soil chemical characteristics (pH and C:N), and nitrogen (N) transformation rates (net nitrification). We find that, while nitrification rates are controlled primarily by chemoautotrophic ammonia-oxidizing archaea (AOA), the production of NOy is mediated in large part by chemoautotrophic ammonia-oxidizing bacteria (AOB). Variation in nitrification rates and nitrogen oxide emissions tracked variation in forest communities, as stands dominated by arbuscular mycorrhizal (AM) trees had greater N transformation rates and NOy fluxes than stands dominated by ectomycorrhizal (ECM) trees. Given mapped distributions of AM and ECM trees from 78,000 forest inventory plots, we estimate that broadleaf forests of the Midwest and the eastern United States as well as the Mississippi River corridor may be considered hotspots of biogenic NOy emissions. Together, our results greatly improve our understanding of NOy fluxes from forests, which should lead to improved predictions about the atmospheric consequences of tree species shifts owing to land management and climate change.

Nitrogen cycling microbiomes are structured by plant mycorrhizal associations with consequences for nitrogen oxide fluxes in forests.

Volatile nitrogen oxides (N2 O, NO, NO2 , HONO, …) can negatively impact climate, air quality, and human health. Using soils collected from temperate forests across the eastern United States, we show microbial communities involved in nitrogen (N) cycling are structured, in large part, by the composition of overstory trees, leading to predictable N-cycling syndromes, with consequences for emissions of volatile nitrogen oxides to air. Trees associating with arbuscular mycorrhizal (AM) fungi promote soil microbial communities with higher N-cycle potential and activity, relative to microbial communities in soils dominated by trees associating with ectomycorrhizal (ECM) fungi. Metagenomic analysis and gene expression studies reveal a 5 and 3.5 times greater estimated N-cycle gene and transcript copy numbers, respectively, in AM relative to ECM soil. Furthermore, we observe a 60% linear decrease in volatile reactive nitrogen gas flux (NOy  ≡ NO, NO2 , HONO) as ECM tree abundance increases. Compared to oxic conditions, gas flux potential of N2 O and NO increase significantly under anoxic conditions for AM soil (30- and 120-fold increase), but not ECM soil-likely owing to small concentrations of available substrate ( NO 3 - ) in ECM soil. Linear mixed effects modeling shows that ECM tree abundance, microbial process rates, and geographic location are primarily responsible for variation in peak potential NOy flux. Given that nearly all tree species associate with either AM or ECM fungi, our results indicate that the consequences of tree species shifts associated with global change may have predictable consequences for soil N cycling.

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy.

Formic acid (HCOOH) is among the most abundant carboxylic acids in the atmosphere, but its budget is poorly understood. We present eddy flux, vertical gradient, and soil chamber measurements from a mixed forest and apply the data to better constrain HCOOH source/sink pathways. While the cumulative above-canopy flux was downward, HCOOH exchange was bidirectional, with extended periods of net upward and downward flux. Net above-canopy fluxes were mostly upward during warmer/drier periods. The implied gross canopy HCOOH source corresponds to 3% and 38% of observed isoprene and monoterpene carbon emissions and is 15× underestimated in a state-of-science atmospheric model (GEOS-Chem). Gradient and soil chamber measurements identify the canopy layer as the controlling source of HCOOH or its precursors to the forest environment; below-canopy sources were minor. A correlation analysis using an ensemble of marker volatile organic compounds suggests that secondary formation, not direct emission, is the major source driving ambient HCOOH.