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Influence of convective transport on tropospheric ozone and its precursors in a chemistry-climate model

The impact of convection on tropospheric O3 and its precursors has been examined in a coupled chemistry-climate model. There are two ways that convection affects O3. First, convection affects O3 by vertical mixing of O3 itself. Convection lifts lower tropospheric air to regions where the O3 lifetime is longer, whilst mass-balance subsidence mixes O3-rich upper tropospheric (UT) air downwards to regions where the O3 lifetime is shorter. This tends to decrease UT O3 and the overall tropospheric column of O3. Secondly, convection affects O3 by vertical mixing of O3 precursors. This affects O3 chemical production and destruction. Convection transports isoprene and its degradation products to the UT where they interact with lightning NOx to produce PAN, at the expense of NOx. In our model, we find that convection reduces UT NOx through this mechanism; convective down-mixing also flattens our imposed profile of lightning emissions, further reducing UT NOx. Over tropical land, which has large lightning NOx emissions in the UT, we find convective lofting of NOx from surface sources appears relatively unimportant. Despite UT NOx decreases, UT O3 production increases as a result of UT HOx increases driven by isoprene oxidation chemistry. However, UT O3 tends to decrease, as the effect of convective overturning of O3 itself dominates over changes in O3 chemistry. Convective transport also reduces UT O3 in the mid-latitudes resulting in a 13% decrease in the global tropospheric O3 burden. These results contrast with an earlier study that uses a model of similar chemical complexity. Differences in convection schemes as well as chemistry schemes – in particular isoprene-driven changes are the most likely causes of such discrepancies. Further modelling studies are needed to constrain this uncertainty range.
Transport and chemical transformations influenced by shallow cumulus over land

The distribution and evolution of reactive species in a boundary layer characterized by the presence of shallow cumulus over land is studied by means of two large-eddy simulation models: the NCAR and WUR codes. The study focuses on two physical processes that can influence the chemistry: the enhancement of the vertical transport by the buoyant convection associated with cloud formation and the perturbation of the photolysis rates below, in and above the clouds. It is shown that the dilution of the reactant mixing ratio caused by the deepening of the atmospheric boundary layer is an important process and that it can decrease reactant mixing ratios by 10 to 50 percent compared to very similar conditions but with no cloud formation. Additionally, clouds transport chemical species to higher elevations in the boundary layer compared to the case with no clouds which influences the reactant mixing ratios of the nocturnal residual layers following the collapse of the daytime boundary layer. Estimates of the rate of reactant transport based on the calculation of the integrated flux divergence range from to −0.2 ppb hr-1 to −1 ppb hr-1, indicating a net loss of sub-cloud layer air transported into the cloud layer. A comparison of this flux to a parameterized mass flux shows good agreement in mid-cloud, but at cloud base the parameterization underestimates the mass flux. Scattering of radiation by cloud drops perturbs photolysis rates. It is found that these perturbed photolysis rates substantially (10–40%) affect mixing ratios locally (spatially and temporally), but have little effect on mixing ratios averaged over space and time. We find that the ultraviolet radiance perturbation becomes more important for chemical transformations that react with a similar order time scale as the turbulent transport in clouds. Finally, the detailed intercomparison of the LES results shows very good agreement between the two codes when considering the evolution of the reactant mean, flux and (co-)variance vertical profiles.
Horizontal and vertical profiles of ozone, carbon monoxide, non-methane hydrocarbons and dimethyl sulphide near the Mace Head observatory, Ireland

The distribution of trace gases upwind and above the Mace Head Atmospheric Research Station, Ireland has been determined using measurements made from aircraft. The observations indicate excellent agreement between most non-methane hydrocarbons, dimethyl sulphide (DMS) and ozone measured at the surface, at 390 m overhead and in upwind boundary layer regions of the coastal Atlantic. Vertical profiles above the observatory indicated that local convective events result in a marine influence being detected at 3 km and above. The observation of isoprene from maritime sources at these levels was indicative of very rapid uplift on the hour timescale. Measurements of trace gases were also made directly upwind of the observatory over coastal regions and as far as the deep open ocean beyond the continental shelf. A maximum of 240 pptV DMS was observed in the boundary layer near to the shelf region, declining to a concentration of around 40 pptV at the coastline. The upwelling of nutrient rich waters at the ocean shelf location may be a possible explanation for the high abundance of DMS in these regions. The observations suggest that this region, some 150–200 km from the observatory, would under these environmental conditions have a major influence in the determining the DMS observed on-shore. The spatial distribution of ethene within boundary layer over coastal and deep waters differed significantly from DMS with an almost uniform abundance over all ocean regions.
A global off-line model of size-resolved aerosol microphysics: II. Identification of key uncertainties

We use the new GLOMAP model of global aerosol microphysics to investigate the sensitivity of modelled sulfate and sea salt aerosol properties to uncertainties in the driving microphysical processes and compare these uncertainties with those associated with aerosol and precursor gas emissions. Overall, we conclude that uncertainties in microphysical processes have a larger effect on global sulfate and sea salt derived condensation nuclei (CN) and cloud condensation nuclei (CCN) concentrations than uncertainties in present-day sulfur emissions. Our simulations suggest that uncertainties in predicted sulfate and sea salt CCN abundances due to poorly constrained microphysical processes are likely to be of a similar magnitude to long-term changes in sulfate and sea salt CCN due to changes in anthropogenic emissions. A microphysical treatment of the global sulfate aerosol allows the uncertainty in climate-relevant aerosol properties to be attributed to specific processes in a way that has not been possible with simpler aerosol schemes. In particular we conclude that: (1) changes in the binary H2SO4-H2O nucleation rate and condensation rate of gaseous H2SO4 cause a shift in the vertical location of the upper tropospheric CN layer by as much as 3 km, while the shape of the CN profile is essentially pre-served (2) uncertainties in the binary H2SO4-H2O nucleation rate have a relatively insignificant effect on marine boundary layer (MBL) aerosol properties; (3) emitting a fraction of anthropogenic SO2 as particulates (to represent production of sulfate particles in power plant plumes below the scale of the model grid (which is of the order of 300 km)) has the potential to change the global mean MBL sulfate-derived CN concentrations by up to 72%, and changes of up to a factor 20 can occur in polluted continental regions; (4) predicted global mean MBL sulfate and sea salt CCN concentrations change by 10 to 60% when several microphysical processes are changed within reasonable uncertainty ranges; (5) sulfate and sea salt derived CCN concentrations are particularly sensitive to primary particle emissions, with global mean MBL sulfate and sea salt CCN changing by up to 27% and local concentrations over continental regions changing by more than 100% when the percentage of anthropogenic SO2 emitted as particulates is changed from 0 to 5%; (6) large changes in sea spray flux have insignificant effects on global sulfate aerosol except when the mass accommodation coefficient of sulfuric acid on the salt particles is set unrealistically low.
Simulating aerosol microphysics with the ECHAM/MADE GCM – Part I: Model description and comparison with observations

The aerosol dynamics module MADE has been coupled to the general circulation model ECHAM4 to simulate the chemical composition, number concentration, and size distribution of the global submicrometer aerosol. The present publication describes the new model system ECHAM4/MADE and presents model results in comparison with observations. The new model is able to simulate the full life cycle of particulate matter and various gaseous particle precursors including emissions of primary particles and trace gases, advection, convection, diffusion, coagulation, condensation, nucleation of sulfuric acid vapor, aerosol chemistry, cloud processing, and size-dependent dry and wet deposition. Aerosol components considered are sulfate (SO4), ammonium (NH4), nitrate (NO3), black carbon (BC), particulate organic matter (POM), sea salt, mineral dust, and aerosol liquid water. The model is numerically efficient enough to allow long term simulations, which is an essential requirement for application in general circulation models. Since the current study is focusing on the submicrometer aerosol, a coarse mode is not being simulated. The model is run in a passive mode, i.e. no feedbacks between the MADE aerosols and clouds or radiation are considered yet. This allows the investigation of the effect of aerosol dynamics, not interfered by feedbacks of the altered aerosols on clouds, radiation, and on the model dynamics. In order to evaluate the results obtained with this new model system, calculated mass concentrations, particle number concentrations, and size distributions are compared to observations. The intercomparison shows, that ECHAM4/MADE is able to reproduce the major features of the geographical patterns, seasonal cycle, and vertical distributions of the basic aerosol parameters. In particular, the model performs well under polluted continental conditions in the northern hemispheric lower and middle troposphere. However, in comparatively clean remote areas, e.g. in the upper troposphere or in the southern hemispheric marine boundary layer, the current model version tends to underestimate particle number concentrations.
The uptake of SO2 on Saharan dust: a flow tube study

The uptake of SO2 onto Saharan mineral dust from the Cape Verde Islands was investigated using a coated wall flow tube coupled to a mass spectrometer. The rate of loss of SO2 to the dust coating was measured and uptake coefficients were determined using the measured BET surface area of the sample. The uptake of SO2, with an initial concentration between (2-40)x1010molecule cm-3 (0.62-12 µTorr), was found to be strongly time dependent over the first few hundred seconds of an experiment, with an initial uptake γ0,BET of (6.6±0.8)x10-5 (298 K), declining at longer times. The amount of SO2 adsorbed on the dust samples was measured over a range of SO2 concentrations and mineral dust loadings. The uptake of SO2 was found to be up to 98% irreversible over the timescale of these investigations. Experiments were also performed at 258 K, at a relative humidity of 27% and at 298 K in the presence of ozone. The initial uptake and the amount of SO2 taken up per unit area of BET dust surface was the same within error, irrespective of the conditions used; however the presence of ozone reduced the amount of SO2 released back into the gas-phase per unit area once exposure of the surface ended. Multiple uptakes to the same surface revealed a loss of surface reactivity, which did not return if the samples were exposed to gas-phase water, or left under vacuum overnight. A mechanism which accounts for the observed uptake behaviour is proposed and numerically modelled, allowing quantitative estimates of the rate and amount of SO2 removal in the atmosphere to be estimated. Removal of SO2 by mineral dust is predicted to be significant at high dust loadings.
The use of tunnel concentration profile data to determine the ratio of NO2/NOx directly emitted from vehicles

Recently, it is reported that primary vehicular NO2/NOx ratio to be 10–30% and primary vehicular NO2 has raised much interest and concern in the control of NO2 in urban areas. In this study, primary vehicular NO2/NOx ratio in Hong Kong was investigated based on intensive long tunnel (3.7–4 km in length) experiments where concentration profiles of air pollutants along the entire lengths of the tunnels were obtained. Long tunnels were selected because of the inherent low O3 concentrations in the partially enclosed environment. In addition the concentrations of pollutants from vehicles are high. Thus, the NO2 measured inside long tunnels would be more representative of the primary NO2 emitted by vehicles and contribution due to atmospheric transformation would be limited. This dataset was supported by a long-term on-road air quality dataset (June 2002–August 2003). Both datasets were obtained using the Mobile Real-time Air Monitoring Platform (MAP). The primary on-road vehicular NO2/NOx ratio was less than 2%, detected in the mid sections of tunnels investigated, where O3 concentration was at a minimum. In sections of the tunnels (entrance and exit) where O3 concentrations were relatively high, the NO2/NOx ratio could be as high as 19%. Long-term (annual average) on-road air quality data in open air yielded NO2/NOx ratios up to 28%. Thus, it is apparent that directly emitted NO2 from vehicles is not significant in atmospheric NO2 concentration. A simple model was used to segregate the contribution of background NO2 and transformed NO2 measured in vehicle plumes.
A look at aerosol formation using data mining techniques

Atmospheric aerosol particle formation is frequently observed throughout the atmosphere, but despite various attempts of explanation, the processes behind it remain unclear. In this study data mining techniques were used to find the key parameters needed for atmospheric aerosol particle formation to occur. A dataset of 8 years of 80 variables collected at the boreal forest station (SMEAR II) in Southern Finland was used, incorporating variables such as radiation, humidity, SO2, ozone and present aerosol surface area. This data was analyzed using clustering and classification methods. The aim of this approach was to gain new parameters independent of any subjective interpretation. This resulted in two key parameters, relative humidity and preexisting aerosol particle surface (condensation sink), capable in explaining 88% of the nucleation events. The inclusion of any further parameters did not improve the results notably. Using these two variables it was possible to derive a nucleation probability function. Interestingly, the two most important variables are related to mechanisms that prevent the nucleation from starting and particles from growing, while parameters related to initiation of particle formation seemed to be less important. Nucleation occurs only with low relative humidity and condensation sink values. One possible explanation for the effect of high water content is that it prevents biogenic hydrocarbon ozonolysis reactions from producing sufficient amounts of low volatility compounds, which might be able to nucleate. Unfortunately the most important biogenic hydrocarbon compound emissions were not available for this study. Another effect of water vapour may be due to its linkage to cloudiness which may prevent the formation of nucleating and/or condensing vapours. A high number of preexisting particles will act as a sink for condensable vapours that otherwise would have been able to form sufficient supersaturation and initiate the nucleation process.
A method for detecting the presence of organic fraction in nucleation mode sized particles

New particle formation and growth has a very important role in many climate processes. However, the overall knowlegde of the chemical composition of atmospheric nucleation mode (particle diameter, d<20 nm) and the lower end of Aitken mode particles (d≤50 nm) is still insufficient. In this work, we have applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to shed light on the presence of an organic fraction in the nucleation mode size class in different atmospheric environments. The basic principle of the organic fraction detection is based on our laboratory UFO-TDMA measurements with organic and inorganic compounds. Our laboratory measurements indicate that the usefulness of the UFO-TDMA in the field experiments would arise especially from the fact that atmospherically the most relevant inorganic compounds do not grow in subsaturated ethanol vapor, when particle size is 10 nm in diameter and saturation ratio is about 86% or below it. Furthermore, internally mixed particles composed of ammonium bisulfate and sulfuric acid with sulfuric acid mass fraction ≤33% show no growth at 85% saturation ratio. In contrast, 10 nm particles composed of various oxidized organic compounds of atmospheric relevance are able to grow in those conditions. These discoveries indicate that it is possible to detect the presence of organics in atmospheric nucleation mode sized particles using the UFO-TDMA method. In the future, the UFO-TDMA is expected to be an important aid to describe the composition of atmospheric newly-formed particles.
Carbon monoxide, methane and carbon dioxide columns retrieved from SCIAMACHY by WFM-DOAS: year 2003 initial data set

The near-infrared nadir spectra measured by SCIAMACHY on-board ENVISAT contain information on the vertical columns of important atmospheric trace gases such as carbon monoxide (CO), methane (CH4), and carbon dioxide (CO2). The scientific algorithm WFM-DOAS has been used to retrieve this information. For CH4 and CO2 also column averaged mixing ratios (XCH4 and XCO2) have been determined by simultaneous measurements of the dry air mass. All available spectra of the year 2003 have been processed. We describe the algorithm versions used to generate the data (v0.4; for methane also v0.41) and show comparisons of monthly averaged data over land with global measurements (CO from MOPITT) and models (for CH4 and CO2). We show that elevated concentrations of CO resulting from biomass burning have been detected in reasonable agreement with MOPITT. The measured XCH4 is enhanced over India, south-east Asia, and central Africa in September/October 2003 in line with model simulations, where they result from surface sources of methane such as rice fields and wetlands. The CO2 measurements over the Northern Hemisphere show the lowest mixing ratios around July in qualitative agreement with model simulations indicating that the large scale pattern of CO2 uptake by the growing vegetation can be detected with SCIAMACHY. We also identified potential problems such as a too low inter-hemispheric gradient for CO, a time dependent bias of the methane columns on the order of a few percent, and a few percent too high CO2 over parts of the Sahara.