Nitrogen is a major nutrient in terrestrial ecosystems and an important catalyst in tropospheric photochemistry. Over the last century human activities have dramatically increased inputs of reactive nitrogen (Nr, the combination of oxidized, reduced, and organically bound nitrogen) to the Earth system (Figure 1). Nitrogen cycle perturbations have compromised air quality and human health, acidified ecosystems, and degraded and eutrophied lakes and coastal estuaries [Vitousek et al., 1997a, 1997b; Rabalais, 2002; Howarth et al., 2003; Townsend et al., 2003; Galloway et al., 2004]. Increased Nr affects global climate. Use of agricultural fertilizers such as ammonium nitrate leads to increased soil production of nitrous oxide (N2O), which has 320 times the global warming potential of carbon dioxide (CO2). Emission of nitrogen oxides (NOx = nitric oxide, NO + nitrogen dioxide, NO2) from fossil fuel burning leads to increases in tropospheric ozone, another greenhouse gas. Ozone is phytotoxic, and may reduce terrestrial CO2 sequestration. To predict the effects of nitrogen cycling changes under changing climatic conditions, there needs to be a better understanding of the global nitrogen budget.

Three weeks of summertime surface-based chemical and meteorological observations at Sable Island, Nova Scotia, during the North Atlantic Regional Experiment (NARE) 1993 summer intensive are used to study instantaneous photochemical production and loss rates of ozone by means of a numerical photochemical model. Results are most sensitive to the averaging scheme of data used to constrain the model and the ambient variability of the measurements. Model simulations driven by a time series of 5 min averaged data, most representative of the chemistry at the site, yield an average net photochemical ozone production of 3.6 ppbv/d. Estimates of net ozone production designed to filter out local sources, by using 1000-1400 LT median values of observations to drive the model and by excluding short-lived hydrocarbons, give values ranging from 1 to 4 ppbv/d. These positive values of net ozone production within the marine boundary layer over Sable Island demonstrate the impact of polluted continental plumes on the background photochemistry of the region during the intensive. The dominant ambient variables controlling photochemical production and loss rates of zone at the site during the measurement campaign appear to be levels of nitrogen oxides, ozone, nonmethane hydrocarbons, and solar intensity determined by cloud cover. The model partitioning of nitrogen oxides agrees for the most part with measurements, lending credence to calculated photochemical production and loss rates of ozone as well as inferred levels of peroxy radicals not measured at the site. Discrepancies, however, often occur during episodes of intermittent cloud cover, fog, and rain, suggesting the influence of cloud processes on air masses reaching the site.

Vegetation emits large quantities of biogenic volatile organic compounds (BVOC). At remote sites, these compounds are the dominant precursors to ozone and secondary organic aerosol (SOA) production, yet current field studies show that atmospheric models have difficulty in capturing the observed HOx cycle and concentrations of BVOC oxidation products. In this manuscript, we simulate BVOC chemistry within a forest canopy using a one-dimensional canopy-chemistry model (Canopy Atmospheric CHemistry Emission model; CACHE) for a mixed deciduous forest in northern Michigan during the CABINEX 2009 campaign. We find that the base-case model, using fully-parameterized mixing and the simplified biogenic chemistry of the Regional Atmospheric Chemistry Model (RACM), underestimates daytime in-canopy vertical mixing by 50-70% and by an order of magnitude at night, leading to discrepancies in the diurnal evolution of HO x, BVOC, and BVOC oxidation products. Implementing observed micrometeorological data from above and within the canopy substantially improves the diurnal cycle of modeled BVOC, particularly at the end of the day, and also improves the observation-model agreement for some BVOC oxidation products and OH reactivity. We compare the RACM mechanism to a version that includes the Mainz isoprene mechanism (RACM-MIM) to test the model sensitivity to enhanced isoprene degradation. RACM-MIM simulates higher concentrations of both primary BVOC (isoprene and monoterpenes) and oxidation products (HCHO, MACR+MVK) compared with RACM simulations. Additionally, the revised mechanism alters the OH concentrations and increases HO 2. These changes generally improve agreement with HO x observations yet overestimate BVOC oxidation products, indicating that this isoprene mechanism does not improve the representation of local chemistry at the site. Overall, the revised mechanism yields smaller changes in BVOC and BVOC oxidation product concentrations and gradients than improving the parameterization of vertical mixing with observations, suggesting that uncertainties in vertical mixing parameterizations are an important component in understanding observed BVOC chemistry. © 2012 Author(s).