A one‐dimensional canopy model was used to quantify the impact of photochemistry in modifying biosphere‐atmosphere exchange of trace gases. Canopy escape efficiencies, defined as the fraction of emission that escapes into the well‐mixed boundary layer, were calculated for reactive terpene species. The modeled processes of emission, photochemistry, diffusive transport, and deposition were highly constrained based on intensive observations collected in a Loblolly Pine plantation at Duke Forest, North Carolina, during the CELTIC field study. Canopy top fluxes for isoprene and α,β‐pinene were not significantly altered by photochemistry as calculated escape efficiencies were greater than 0.90 for both species. β‐caryophyllene emission and photochemistry were added to the canopy model as a surrogate for the reactive sesquiterpene class of species. β‐caryopyllene escape efficiencies of 0.30 were calculated for midday summertime conditions. Urbanization scenarios were also performed to assess the impact of pollution on modifying biosphere‐atmosphere exchange. Modest changes in escape efficiencies were calculated for a wide range of anthropogenic hydrocarbon and NO_x mixing ratios suggesting a simple parameterization of escape efficiency in terms of grid cell NO_x may be possible for incorporating the impact of canopy scale photochemistry within biogenic emission processing systems for regional air quality and climate models. The inferred magnitude of sesquiterpene ozonolysis reactions has important implications on both daytime and nighttime radical formation in the canopy.

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R² = 64–96%) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr⁻¹ that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Whole-system fluxes of isoprene from a moist acidic tundra ecosystem and leaf-level emission rates of isoprene from a common species (Salix pulchra) in that same ecosystem were measured during three separate field campaigns. The field campaigns were conducted during the summers of 2005, 2010 and 2011 and took place at the Toolik Field Station (68.6° N, 149.6° W) on the north slope of the Brooks Range in Alaska, USA. The maximum rate of whole-system isoprene flux measured was over 1.2 mg C m⁻² h⁻¹ with an air temperature of 22 °C and a PAR level over 1500 μmol m⁻² s⁻¹. Leaf-level isoprene emission rates for S. pulchra averaged 12.4 nmol m⁻² s⁻¹ (27.4 μg C gdw⁻¹ h⁻¹) extrapolated to standard conditions (PAR = 1000 μmol m⁻² s⁻¹ and leaf temperature = 30 °C). Leaf-level isoprene emission rates were well characterized by the Guenther algorithm for temperature with published coefficients, but less so for light. Chamber measurements from a nearby moist acidic tundra ecosystem with little S. pulchra emitted significant amounts of isoprene, but at lower rates (0.45 mg C m⁻² h⁻¹) suggesting other significant isoprene emitters. Comparison of our results to predictions from a global model found broad agreement, but a detailed analysis revealed some significant discrepancies. An atmospheric chemistry box model predicts that the observed isoprene emissions have a significant impact on Arctic atmospheric chemistry, including a reduction of hydroxyl radical (OH) concentrations. Our results support the prediction that isoprene emissions from Arctic ecosystems will increase with global climate change.