SOSA – a new model to simulate the concentrations of organic vapours and sulphuric acid inside the ABL – Part 1: Model description and initial evaluation

Chemistry in the atmospheric boundary layer (ABL) is controlled by complex processes of surface fluxes, flow, turbulent transport, and chemical reactions. We present a new model SOSA (model to simulate the concentration of organic vapours and sulphuric acid) and attempt to reconstruct the emissions, transport and chemistry in the ABL in and above a vegetation canopy using tower measurements from the SMEAR II at Hyytiälä, Finland and available soundings data from neighbouring meteorological stations. Using the sounding data for upper boundary condition and nudging the model to tower measurements in the surface layer we were able to get a reasonable description of turbulence and other quantities through the ABL. As a first application of the model, we present vertical profiles of organic compounds and discuss their relation to newly formed particles

Large methane releases lead to strong aerosol forcing and reduced cloudiness

The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4) levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH) concentrations, while moderately increasing ozone (O3). These changes lead to a 70 % increase in the atmospheric lifetime of methane, and an 18 % decrease in global mean cloud droplet number concentrations (CDNC). The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O3 and CH4-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases

Simulations of atmospheric OH, O-3 and NO3 reactivities within and above the boreal forest

Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO3 and O-3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R similar to 3 s(-1)) followed by NO3 (R similar to 0.07 s(-1)) and O-3 (R similar to 2 x 10 5 s(-1)). The missing OH reactivity was found to be large in accordance with measurements (similar to 65 %) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (similar to 41 %, mainly due to reaction with CO), emitted monoterpenes (similar to 14 %) and oxidised biogenic volatile organic compounds (similar to 44 %). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (similar to 60 %) and inorganic compounds (similar to 37 %, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign (with typical temperatures of 20-25 degrees C) and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady-state reactivity and present the first boreal forest steady-state lifetime of NO3 (113 s). O-3 almost exclusively reacts with inorganic compounds (similar to 91 %, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (similar to 6 %) and monoterpenes (similar to 3 %). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO3 can remove organic molecules at a faster rate during night-time. O-3 competes with OH and NO3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7-8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was un-derestimated.Peer reviewe

Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needleleaf forest

New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Biohydro-atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.Peer reviewe

Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needleleaf forest

New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Biohydro-atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.Peer reviewe

Using a one-and-a-half order closure model of the atmospheric boundary layer for surface flux footprint estimation

A knowledge of the distribution of the contribution of upwind sources to measurements of vertical scalar flux densities is important for the correct interpretation of eddy covariance data. Several approaches have been developed to estimate this so-called footprint function. Here a new approach based on the ensemble-averaged Navier-Stokes equations is presented. Comparisons of numerical results using this approach with results from other studies under a range of environmental conditions show that the model predictions are robust. Moreover, the approach outlined here has the advantage of a potential wide applicability, due to an ability to take into account the heterogeneous nature of underlying surfaces. For example, the model showed that any variations in surface drag, such as must occur in real life heterogeneous canopies, can exert a marked influence of the shape and extent of flux footprints. Indeed, it seems likely that under such circumstances, estimates of surface fluxes will be weighted towards areas of highest foliage density ( and therefore quite likely higher photosynthetic rates) close to the measurement sensor. determined for a mixed coniferous forest in european Russia. A marked asymmetry of the footprint in the crosswind direction was observed, this being especially pronounced for non-uniform plant distributions involving vegetation types with different morphological and physiological properties. The model also found that, other things being equal, the footprint peak for forest soil respiration is typically over twice the distance from the above canopy measurement sensor compared to that for canopy photosynthesis. This result has important consequences for the interpretation of annual ecosystem carbon balances by the eddy covariance method. [References: 54