Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended

Modelling the global tropospheric ozone budget : exploring the variability in current models.

What are the largest uncertainties in modelling ozone in the troposphere, and how do they affect the calculated ozone budget? Published chemistry-transport model studies of tropospheric ozone differ significantly in their conclusions regarding the importance of the key processes controlling the ozone budget: influx from the stratosphere, chemical processing and surface deposition. This study surveys ozone budgets from previous studies and demonstrates that about two thirds of the increase in ozone production seen between early assessments and more recent model intercomparisons can be accounted for by increased precursor emissions. Model studies using recent estimates of emissions compare better with ozonesonde measurements than studies using older data, and the tropospheric burden of ozone is closer to that derived here from measurement climatologies, 335±10 Tg. However, differences between individual model studies remain large and cannot be explained by surface precursor emissions alone; cross-tropopause transport, wet and dry deposition, humidity, and lightning also make large contributions. The importance of these processes is examined here using a chemistry-transport model to investigate the sensitivity of the calculated ozone budget to different assumptions about emissions, physical processes, meteorology and model resolution. The budget is particularly sensitive to the magnitude and location of lightning NOx emissions, which remain poorly constrained; the 3–8 TgN/yr range in recent model studies may account for a 10% difference in tropospheric ozone burden and a 1.4 year difference in CH4 lifetime. Differences in humidity and dry deposition account for some of the variability in ozone abundance and loss seen in previous studies, with smaller contributions from wet deposition and stratospheric influx. At coarse model resolutions stratospheric influx is systematically overestimated and dry deposition is underestimated; these differences are 5–8% at the 300–600 km grid-scales investigated here, similar in magnitude to the changes induced by interannual variability in meteorology. However, a large proportion of the variability between models remains unexplained, suggesting that differences in chemical mechanisms and dynamical schemes have a large impact on the calculated ozone budget, and these should be the target of future model intercomparisons

Chemical transport model ozone simulations for spring 2001 over the western Pacific: Regional ozone production and its global impacts

The spatial and temporal variation in ozone production over major source regions in East Asia during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) measurement campaign in spring 2001 is assessed using a global chemical transport model. There is a strong latitudinal gradient in ozone production in springtime, driven by regional photochemistry, which rapidly diminishes as the season progresses. The great variability in meteorological conditions characteristic of East Asia in springtime leads to large daily variability in regional ozone formation, but we find that it has relatively little impact on the total global production. We note that transport processes effectively modulate and thus stabilize total ozone production through their influence over its location. However, the impact on the global ozone burden, important for assessing the effects of precursor emissions on tropospheric oxidizing capacity and climate, is sensitive to local meteorology through the effects of location on chemical lifetime. Stagnant, anticyclonic conditions conducive to substantial boundary layer ozone production typically allow little lifting of precursors into the free troposphere where greater ozone production could occur, and the consequent shorter chemical lifetime for ozone leads to relatively small impacts on global ozone. Conversely, cyclonic conditions with heavy cloud cover suppressing regional ozone production are often associated with substantial cloud convection, enhancing subsequent production in the free troposphere where chemical lifetimes are longer, and the impacts on global ozone are correspondingly greater. We find that ozone formation in the boundary layer and free troposphere outside the region of precursor emissions dominates total gross production from these sources in springtime, and that it makes a big contribution to the long range transport of ozone, which is greatest in this season

The Deep Water Abundance on Jupiter: New Constraints from Thermochemical Kinetics and Diffusion Modeling

We have developed a one-dimensional thermochemical kinetics and diffusion model for Jupiter's atmosphere that accurately describes the transition from the thermochemical regime in the deep troposphere (where chemical equilibrium is established) to the quenched regime in the upper troposphere (where chemical equilibrium is disrupted). The model is used to calculate chemical abundances of tropospheric constituents and to identify important chemical pathways for CO-CH4 interconversion in hydrogen-dominated atmospheres. In particular, the observed mole fraction and chemical behavior of CO is used to indirectly constrain the Jovian water inventory. Our model can reproduce the observed tropospheric CO abundance provided that the water mole fraction lies in the range (0.25-6.0) x 10^-3 in Jupiter's deep troposphere, corresponding to an enrichment of 0.3 to 7.3 times the protosolar abundance (assumed to be H2O/H2 = 9.61 x 10^-4). Our results suggest that Jupiter's oxygen enrichment is roughly similar to that for carbon, nitrogen, and other heavy elements, and we conclude that formation scenarios that require very large (>8 times solar) enrichments in water can be ruled out. We also evaluate and refine the simple time-constant arguments currently used to predict the quenched CO abundance on Jupiter, other giant planets, and brown dwarfs.Comment: 42 pages, 7 figures, 4 tables, with note added in proof. Accepted for publication in Icarus [in press

The impact of the 1783-1784 AD Laki eruption on global aerosol formation processes and cloud condensation nuclei

The 1783–1784 AD Laki flood lava eruption commenced on 8 June 1783 and released 122 Tg of sulphur dioxide gas over the course of 8 months into the upper troposphere and lower stratosphere above Iceland. Previous studies have examined the impact of the Laki eruption on sulphate aerosol and climate using general circulation models. Here, we study the impact on aerosol microphysical processes, including the nucleation of new particles and their growth to cloud condensation nuclei (CCN) using a comprehensive Global Model of Aerosol Processes (GLOMAP). Total particle concentrations in the free troposphere increase by a factor ~16 over large parts of the Northern Hemisphere in the 3 months following the onset of the eruption. Particle concentrations in the boundary layer increase by a factor 2 to 5 in regions as far away as North America, the Middle East and Asia due to long-range transport of nucleated particles. CCN concentrations (at 0.22% supersaturation) increase by a factor 65 in the upper troposphere with maximum changes in 3-month zonal mean concentrations of ~1400 cm<sup>−3</sup> at high northern latitudes. 3-month zonal mean CCN concentrations in the boundary layer at the latitude of the eruption increase by up to a factor 26, and averaged over the Northern Hemisphere, the eruption caused a factor 4 increase in CCN concentrations at low-level cloud altitude. The simulations show that the Laki eruption would have completely dominated as a source of CCN in the pre-industrial atmosphere. The model also suggests an impact of the eruption in the Southern Hemisphere, where CCN concentrations are increased by up to a factor 1.4 at 20° S. Our model simulations suggest that the impact of an equivalent wintertime eruption on upper tropospheric CCN concentrations is only about one-third of that of a summertime eruption. The simulations show that the microphysical processes leading to the growth of particles to CCN sizes are fundamentally different after an eruption when compared to the unperturbed atmosphere, underlining the importance of using a fully coupled microphysics model when studying long-lasting, high-latitude eruptions

Optical-microphysical Properties of Saharan Dust Aerosols and Composition Relationship Using a Multi-wavelength Raman Lidar, in Situ Sensors and Modelling: a Case Study Analysis

A strong Saharan dust event that occurred over the city of Athens, Greece (37.9° N, 23.6° E) between 27 March and 3 April 2009 was followed by a synergy of three instruments: a 6-wavelength Raman lidar, a CIMEL sun-sky radiometer and the MODIS sensor. The BSC-DREAM model was used to forecast the dust event and to simulate the vertical profiles of the aerosol concentration. Due to mixture of dust particles with low clouds during most of the reported period, the dust event could be followed by the lidar only during the cloud-free day of 2 April 2009. The lidar data obtained were used to retrieve the vertical profile of the optical (extinction and backscatter coefficients) properties of aerosols in the troposphere. The aerosol optical depth (AOD) values derived from the CIMEL ranged from 0.33-0.91 (355 nm) to 0.18-0.60 (532 nm), while the lidar ratio (LR) values retrieved from the Raman lidar ranged within 75-100 sr (355 nm) and 45-75 sr (532 nm). Inside a selected dust layer region, between 1.8 and 3.5 km height, mean LR values were 83 ± 7 and 54 ± 7 sr, at 355 and 532 nm, respectively, while the Ångström-backscatter-related (ABR 355/532) and Ångström-extinction-related (AER 355/532) were found larger than 1 (1.17 ± 0.08 and 1.11 ± 0.02, respectively), indicating mixing of dust with other particles. Additionally, a retrieval technique representing dust as a mixture of spheres and spheroids was used to derive the mean aerosol microphysical properties (mean and effective radius, number, surface and volume density, and mean refractive index) inside the selected atmospheric layers. Thus, the mean value of the retrieved refractive index was found to be 1.49( ± 0.10) + 0.007( ± 0.007)i, and that of the effective radiuses was 0.30 ± 0.18 μm. The final data set of the aerosol optical and microphysical properties along with the water vapor profiles obtained by Raman lidar were incorporated into the ISORROPIA II model to provide a possible aerosol composition consistent with the retrieved refractive index values. Thus, the inferred chemical properties showed 12-40% of dust content, sulfate composition of 16-60%, and organic carbon content of 15-64%, indicating a possible mixing of dust with haze and smoke. PM10 concentrations levels, PM10 composition results and SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray) analysis results on sizes and mineralogy of particles from samples during the Saharan dust transport event were used to evaluate the retrieval

Patterns of CO2 and radiocarbon across high northern latitudes during International Polar Year 2008

High-resolution in situ CO2 measurements were conducted aboard the NASA DC-8 aircraft during the ARCTAS/POLARCAT field campaign, a component of the wider 2007-2008 International Polar Year activities. Data were recorded during large-scale surveys spanning the North American sub-Arctic to the North Pole from 0.04 to 12 km altitude in spring and summer of 2008. Influences on the observed CO2 concentrations were investigated using coincident CO, black carbon, CH3CN, HCN, O3, C2Cl4, and Δ14CO2 data, and the FLEXPART model. In spring, the CO2 spatial distribution from 55̊N to 90̊N was largely determined by the long-range transport of air masses laden with Asian anthropogenic pollution intermingled with Eurasian fire emissions evidenced by the greater variability in the mid-to-upper troposphere. At the receptor site, the enhancement ratios of CO2 to CO in pollution plumes ranged from 27 to 80 ppmv ppmv-1 with the highest anthropogenic content registered in plumes sampled poleward of 80̊N. In summer, the CO2 signal largely reflected emissions from lightning-ignited wildfires within the boreal forests of northern Saskatchewan juxtaposed with uptake by the terrestrial biosphere. Measurements within fresh fire plumes yielded CO2 to CO emission ratios of 4 to 16 ppmv ppmv-1 and a mean CO2 emission factor of 1698 ± 280 g kg-1 dry matter. From the 14C in CO2 content of 48 whole air samples, mean spring (46.6 ± 4.4%) and summer (51.5 ± 5%) D14CO2 values indicate a 5%seasonal difference. Although the northern midlatitudes were identified as the emissions source regions for the majority of the spring samples, depleted Δ14CO2 values were observed in <1% of the data set. Rather, ARCTAS Δ14CO2 observations (54%) revealed predominately a pattern of positive disequilibrium (1-7%) with respect to background regardless of season owing to both heterotrophic respiration and fire-induced combustion of biomass. Anomalously enriched Δ14CO2 values (101-262%) measured in emissions from Lake Athabasca and Eurasian fires speak to biomass burning as an increasingly important contributor to the mass excess in Δ14CO2 observations in a warming Arctic, representing an additional source of uncertainty in the quantification of fossil fuel CO2

Analysis and quantification of the diversities of aerosol life cycles within AeroCom

Simulation results of global aerosol models have been assembled in the framework of the AeroCom intercomparison exercise. In this paper, we analyze the life cycles of dust, sea salt, sulfate, black carbon and particulate organic matter as simulated by sixteen global aerosol models. The diversities among the models for the sources and sinks, burdens, particle sizes, water uptakes, and spatial dispersals have been established. These diversities have large consequences for the calculated radiative forcing and the aerosol concentrations at the surface. The AeroCom all-models-average emissions are dominated by the mass of sea salt (SS), followed by dust (DU), sulfate (SO_4), particulate organic matter (POM), and finally black carbon (BC). Interactive parameterizations of the emissions and contrasting particles sizes of SS and DU lead generally to higher diversities of these species, and for total aerosol. The lower diversity of the emissions of the fine aerosols, BC, POM, and SO_4, is due to the use of similar emission inventories, and does therefore not necessarily indicate a better understanding of their sources. The diversity of SO_4-sources is mainly caused by the disagreement on depositional loss of precursor gases and on chemical production. The diversities of the emissions are passed on to the burdens, but the latter are also strongly affected by the model-specific treatments of transport and aerosol processes. The burdens of dry masses decrease from largest to smallest: DU, SS, SO_4, POM, and BC. The all-models-average residence time is shortest for SS with about half a day, followed by S_O4 and DU with four days, and POM and BC with six and seven days, respectively. The wet deposition rate is controlled by the solubility and increases from DU, BC, POM to SO_4 and SS. It is the dominant sink for SO_4, BC, and POM, and contributes about one third to the total removal rate coefficients of SS and DU species. For SS and DU we find high diversities for the removal rate coefficients and deposition pathways. Models do neither agree on the split between wet and dry deposition, nor on that between sedimentation and turbulent dry Deposition. We diagnose an extremely high diversity for the uptake of ambient water vapor that influences the particle size and thus the sink rate coefficients. Furthermore, we find little agreement among the model results for the partitioning of wet removal into scavenging by convective and stratiform rain. Large differences exist for aerosol dispersal both in the vertical and in the horizontal direction. In some models, a minimum of total aerosol concentration is simulated at the surface. Aerosol dispersal is most pronounced for SO4 and BC and lowest for SS. Diversities are higher for meridional than for vertical dispersal, they are similar for a given species and highest for SS and DU. For these two components we do not find a correlation between vertical and meridional aerosol dispersal. In addition the degree of dispersals of SS and DU is not related to their residence times. SO_4, BC, and POM, however, show increased meridional dispersal in models with larger vertical dispersal, and dispersal is larger for longer simulated residence times