The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.