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Observationally derived transport diagnostics for the lowermost stratosphere and their application to the GMI chemistry and transport model

Transport from the surface to the lowermost stratosphere (LMS) can occur on timescales of a few months or less, making it possible for short-lived tropospheric pollutants to influence stratospheric composition and chemistry. Models used to study this influence must demonstrate the credibility of their chemistry and transport in the upper troposphere and lower stratosphere (UT/LS). Data sets from satellite and aircraft instruments measuring CO, O3, N2O, and CO2 in the UT/LS are used to create a suite of diagnostics for the seasonally-varying transport into and within the lowermost stratosphere, and of the coupling between the troposphere and stratosphere in the extratropics. The diagnostics are used to evaluate a version of the Global Modeling Initiative (GMI) Chemistry and Transport Model (CTM) that uses a combined tropospheric and stratospheric chemical mechanism and meteorological fields from the GEOS-4 general circulation model. The diagnostics derived from N2O and O3 show that the model lowermost stratosphere has realistic input from the overlying high latitude stratosphere in all seasons. Diagnostics for the LMS show two distinct layers. The upper layer begins ~30 K potential temperature above the tropopause and has a strong annual cycle in its composition. The lower layer is a mixed region ~30 K thick near the tropopause that shows no clear seasonal variation in the degree of tropospheric coupling. Diagnostics applied to the GMI CTM show credible seasonally-varying transport in the LMS and a tropopause layer that is realistically coupled to the UT in all seasons. The vertical resolution of the GMI CTM in the UT/LS, ~1 km, is sufficient to realistically represent the extratropical tropopause layer. This study demonstrates that the GMI CTM has the transport credibility required to study the impact of tropospheric emissions on the stratosphere.
Development of the adjoint of GEOS-Chem

We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate – ammonium – nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The accuracy of the adjoint model is extensively verified by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances. We explore the robustness of these results, noting how discontinuities in the advection routine hinder, but do not entirely preclude, the use of such comparisons for validation of the adjoint model. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors.
Aerosol climatology: on the discrimination of aerosol types over four AERONET sites

Aerosols have a significant regional and global effect on climate, which is about equal in magnitude but opposite in sign to that of greenhouse gases. Nevertheless, the aerosol climatic effect changes strongly with space and time because of the large variability of aerosol physical and optical properties, which is due to the variety of their sources, which are natural, and anthropogenic, and their dependence on the prevailing meteorological and atmospheric conditions. Characterization of aerosol properties is of major importance for the assessment of their role for climate. In the present study, 3-year AErosol RObotic NETwork (AERONET) data from ground-based sunphotometer measurements are used to establish climatologies of aerosol optical depth (AOD) and Ångström exponent α in several key locations of the world, characteristic of different atmospheric environments. Using daily mean values of AOD at 500 nm (AOD500) and Ångström exponent at the pair of wavelengths 440 and 870 nm (α 440–870), a discrimination of the different aerosol types occurring in each location is achieved. For this discrimination, appropriate thresholds for AOD500 and α 440–870 are applied. The discrimination of aerosol types in each location is made on an annual and seasonal basis. It is shown that a single aerosol type in a given location can exist only under specific conditions (e.g. intense forest fires or dust outbreaks), while the presence of well-mixed aerosols is the accustomed situation. Background clean aerosol conditions (AOD500<0.06) are mostly found over remote oceanic surfaces occurring on average in ~56.7% of total cases, while this situation is quite rare over land (occurrence of 3.8–13.7%). Our analysis indicates that these percentages change significantly from season to season. The spectral dependence of AOD exhibits large differences between the examined locations, while it exhibits a strong annual cycle.
Application of synchrotron radiation for measurement of iron red-ox speciation in atmospherically processed aerosols

In this study, ambient atmospheric particulate matter samples were collected using a size-resolved impactor sampler from three urban sites. The purpose of this study is to gain a better understanding of transformations of aerosol-bound iron as it is processed in the atmosphere. Thus, the aerosol samples were artificially aged to represent long-term transport (10 to 40 days) or short-term transport (1 to 10 days) and were measured for iron at several time points. At each time point, iron was measured in each size fraction using three different techniques; 1) inductively coupled plasma-mass spectrometry (ICPMS) for total iron, 2) x-ray absorbance near edge structure (XANES) spectroscopy for the measurement of total Fe(II) and Fe(III), and 3) a wet-chemical method to measure soluble Fe(II) and Fe(III). Prior to aging, the XANES spectroscopy results show that a majority (>60% for each size fraction) of the total iron in the PM is in the form of Fe(III). Fe(III) was shown to be a significant fraction of the soluble iron (sometimes >50%), but the relative significance of Fe(III) was found to vary depending on the site. Overall, the total soluble iron depended on the sampling site, but values ranged from less than 1% up to about 20% of the total iron. Over the course of the 40 day aging period, we found moderate changes in the relative Fe(II)/Fe(III) content. A slight increase was noted in the coarse (>2.5 µm) fraction and a slight decrease in the 0.25 to 0.5 µm fraction. The soluble fraction generally showed (excepting one day) a decrease of soluble Fe(II) prior to 10 days of aging, followed by a relatively constant concentration. In the short-term transport condition, we found that the sub-micron fraction of soluble Fe(II) spikes at 1 to 3 days of aging, then decreases to near the initial value at around 6 to 10 days. Very little change in soluble Fe(II) was observed in the super-micron fraction.
On the diurnal variability of particle properties related to light absorbing carbon in Mexico City

The mass of light absorbing carbon (LAC) in individual, internally mixed aerosol particles was measured with the Single Particle Soot Photometer (SP2) in April of 2003 and 2005 and evaluated with respect to concentrations of carbon monoxide (CO), particle bound polycyclic aromatic hydrocarbons (PPAH) and condensation nuclei (CN). The LAC and CO have matching diurnal trends that are linked to traffic patterns and boundary layer growth. The PPAH reaches a maximum at the same time as CO and LAC but returns rapidly back to nighttime values within three hours of the peak. The number of particles containing LAC ranges between 10% to 40% of all particles between 150 nm and 650 nm and the mass is between 5% and 25% of the total mass in this size range. The average LAC equivalent mass diameter varies between 160 and 230 nm and the thinnest coating of non-light absorbing material is observed during periods of maximum LAC mass. The coating varies between 10 nm and 30 nm during the day, but is a strong function of particle size. The mass absorption cross sections, σabs, derived from the SP2, are 5.0±0.2 m2g−1 and 4.8±0.2 m2g−1, dependent on the optical model used to describe LAC mixtures. The LAC contributes up to 50% of the total light extinction in the size range from 100 nm to 400 nm. The estimated emission rate of LAC is 1200 metric tons per year in Mexico City, based upon the SP2 measurements and correlations between LAC and CO.
Impact of an improved shortwave radiation scheme in the MAECHAM5 General Circulation Model

In order to improve the representation of ozone absorption in the stratosphere of the MAECHAM5 general circulation model, the spectral resolution of the shortwave radiation parameterization used in the model has been increased from 4 to 6 bands. Two 20-years simulations with the general circulation model have been performed, one with the standard and the other with the newly introduced parameterization respectively, to evaluate the temperature and dynamical changes arising from the two different representations of the shortwave radiative transfer. In the simulation with the increased spectral resolution in the radiation parameterization, a significant warming of almost the entire model domain is reported. At the summer stratopause the temperature increase is about 6 K and alleviates the cold bias present in the model when the standard radiation scheme is used. These general circulation model results are consistent both with previous validation of the radiation scheme and with the offline clear-sky comparison performed in the current work with a discrete ordinate 4 stream scattering line by line radiative transfer model. The offline validation shows a substantial reduction of the daily averaged shortwave heating rate bias (1–2 K/day cooling) that occurs for the standard radiation parameterization in the upper stratosphere, present under a range of atmospheric conditions. Therefore, the 6 band shortwave radiation parameterization is considered to be better suited for the representation of the ozone absorption in the stratosphere than the 4 band parameterization. Concerning the dynamical response in the general circulation model, it is found that the reported warming at the summer stratopause induces stronger zonal mean zonal winds in the middle atmosphere. These stronger zonal mean zonal winds thereafter appear to produce a dynamical feedback that results in a dynamical warming (cooling) of the polar winter (summer) mesosphere, caused by an increased downward (upward) circulation in the winter (summer) hemisphere. In addition, the comparison of the two simulations performed with the general circulation model shows that the increase in the spectral resolution of the shortwave radiation and the associated changes in the cloud optical properties result in a warming (0.5–1 K) and moistening (3%–12%) of the upper tropical troposphere. By comparing these modeled differences with previous works, it appears that the reported changes in the solar radiation scheme contribute to improve the model mean temperature also in the troposphere.
Diurnal variation of upper tropospheric humidity and its relations to convective activities over tropical Africa

Diurnal variations of upper tropospheric humidity (UTH) as well as middle tropospheric humidity (MTH) were examined in conjunction with the diurnal cycle of convection over tropical Africa and the adjacent tropical Atlantic Ocean using Meteosat-8 measurements. Cloud and humidity features were also tracked to document the diurnal variations of humidity and clouds in the Lagrangian framework. A distinct diurnal variation of UTH (and MTH) is noted over regions where tropical deep convective cloud systems are commonly observed. The amplitude of the UTH diurnal variation is larger over land, while its variations over convectively inactive subtropical regions are much smaller. The diurnal variation of UTH tends to reach a maximum during nighttime over land, lagging deep convection and high cloud whose maxima occurred in the late afternoon and evening, respectively. It was revealed that these diurnal variations over the African continent are likely associated with continental-scale daytime solar heating and topography, in which topographically-induced signals develop earlier around the mid-afternoon and merge into stronger and broader continental-scale convection clusters later, forming a precipitation maximum in the late afternoon. It was also revealed that advection effect on the diurnal variation appears to be insignificant.
Simulating organic species with the global atmospheric chemistry general circulation model ECHAM5/MESSy1: a comparison of model results with observations

The atmospheric-chemistry general circulation model ECHAM5/MESSy1 is evaluated with observations of different organic ozone precursors. This study continues a prior analysis which focused primarily on the representation of atmospheric dynamics and ozone. We use the results of the same reference simulation and apply a statistical analysis using data from numerous field campaigns. The results serve as a basis for future improvements of the model system. ECHAM5/MESSy1 generally reproduces the spatial distribution and the seasonal cycle of carbon monoxide (CO) very well. However, for the background in the Northern Hemisphere we obtain a negative bias (mainly due to an underestimation of emissions from fossil fuel combustion), and in the high latitude Southern Hemisphere a yet unexplained positive bias. The model results agree well with observations of alkanes, whereas severe problems in the simulation of alkenes and isoprene are present. For oxygenated compounds the results are ambiguous: The model results are in good agreement with observations of formaldehyde, but systematic biases are present for methanol and acetone. The discrepancies between the model results and the observations are explained (partly) by means of sensitivity studies.
Ground-based measurements of tropospheric and stratospheric bromine monoxide above Nairobi (1° S, 36° E)

Ground based observations of stratospheric and tropospheric bromine monoxide, BrO, from a multi axial differential optical absorption spectrometer, MAXDOAS, located at the UNEP/UNON site in Nairobi (1° S, 36° E) are presented for the year 2003. Differences in BrO slant column densities at 90° and 80° solar zenith angle retrieved from the zenith-sky measurements are used to study stratospheric BrO. They show only small variations with season, as expected for the small seasonality in stratospheric Bry and NO2 in this region. A pronounced diurnal variation can be observed, the average value for the morning being 1.3×1014 molecules/cm2 and for the evening 1.5×1014 molecules/cm2. The measurements are compared with simulations from a one-dimensional photochemical stacked box model which is coupled with a radiative transfer model to allow direct comparisons between the observations and the model calculations. In general the model reproduces the measurements very well. The differences in the absolute values are 15% for the evening and 20% for the morning which is within the limits of the combined uncertainties. Both seasonality and diurnal variation are well reproduced by the model. A sensitivity study shows that inclusion of the reaction BrONO2 + O(3P) significantly improves the agreement between model calculations and measurements, indicating an important role of this reaction in the stratosphere near to the equator. Tropospheric BrO columns and profile information is derived from the combined results obtained in the different viewing directions for the average over several clear days. The resulting tropospheric BrO columns are in the range of 4–7.5×1012 molecules/cm2 which is significant but lower than in previous studies at mid and high latitudes. The vertical distribution of the tropospheric BrO peaks at about 3 km indicating the absence of local sources at this high altitude site.
Size-segregated mass distributions of aerosols over Eastern Mediterranean: seasonal variability and comparison with AERONET columnar size-distributions

This work provides long-term (2004–2006) size segregated measurements of aerosol mass at a remote coastal station in the southern Europe, with the use of size-selective samplings (SDI impactor). Seven distinct modes were identified in the range 0–10 µm and the dominant were the "Accumulation 1" (0.25–0.55 µm) and the "Coarse 2" (3–7 µm) modes. The seasonal characteristics of each mode were thoroughly studied and different sources for submicron and supermicron particles were identified, the first being related to local/regional and transported pollution with maximum in summer and the latter to dust from deserted areas in Northern Africa maximizing in spring. On average, PM2.5 and PM1 accounted for 60% and 40% of PM10 mass, respectively.The representativity of the ground-based measurements for the total column was also investigated by comparing the measured aerosol mass distributions with the AERONET volume size distribution data. Similar seasonal patterns were revealed and AERONET was found adequate for the estimation of background levels of both fine and coarse particles near surface, with certain limitations in the case of pollution or dust abrupt episodes due to its low temporal coverage.