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Accounting for the effect of horizontal gradients in limb measurements of scattered sunlight

Limb measurements provided by the SCanning Imaging Absorption spectrometer for Atmospheric CHartographY (SCIAMACHY) on the ENVISAT satellite allow retrieving stratospheric profiles of various trace gases on a global scale, among them BrO for the first time. For limb observations in the UV/VIS spectral region the instrument measures scattered light with a complex distribution of light paths: the light is measured at different tangent heights and can be scattered or absorbed in the atmosphere or reflected by the ground. By means of spectroscopy and radiative transfer modelling these measurements can be inverted to retrieve the vertical distribution of stratospheric trace gases. The fully spherical 3-D Monte Carlo radiative transfer model "Tracy-II" is applied in this study. The Monte Carlo method benefits from conceptual simplicity and allows realizing the concept of full spherical geometry of the atmosphere and also its 3-D properties, which is important for a realistic description of the limb geometry. Furthermore it allows accounting for horizontal gradients in the distribution of trace gases. In this study the effect of horizontally inhomogeneous distributions of trace gases along flight/viewing direction on the retrieval of profiles is investigated. We introduce a tomographic method to correct for this effect by combining consecutive limb scanning sequences and utilizing the overlap in their measurement sensitivity regions. It is found that if horizontal inhomogenity is not properly accounted for, typical errors of 20% for NO2 and up to 50% for OClO around the altitude of the profile peak can arise for measurements close to the Arctic polar vortex boundary in boreal winter.
Vertical distribution of ozone and VOCs in the low boundary layer of Mexico City

The evolution of ozone (O3) and 13 volatile organic compounds (VOCs) in the boundary layer of Mexico City was investigated during 2000–2004 to improve our understanding of the complex interactions between those trace gases and meteorological variables, and their influence on the air quality of a polluted megacity. A tethered balloon, fitted with electrochemical and meteorological sondes, was used to obtain detailed vertical profiles of O3 and meteorological parameters up to 1000 m above ground during part of the diurnal cycle (02:00–18:00 h). VOCs samples were collected up to 200 m by pumping air to canisters with a Teflon tube attached to the tether line. Overall, features of these profiles were found to be consistent with the formation of an upper residual layer during nighttime carrying over a fraction of the O3 from the previous day that contributes to the background concentration in surrounding regions. At the same time the release of heat stored in the urban surface forms a shallow unstable layer close to the ground, where the nocturnal emissions are trapped. After sunrise an O3 balance is determined by photochemical production, entrainment from the upper residual layer and destruction by titration with nitric oxide, delaying the ground-level O3 rise by 2 h. The subsequent evolution of the conductive boundary layer and vertical distribution of pollutants are discussed in terms of the energy balance, the presence of turbulence and the atmospheric stability.
Representativeness and climatology of carbon monoxide and ozone at the global GAW station Mt. Kenya in equatorial Africa

The tropics strongly influence the global atmospheric chemistry budget. However, continuous in-situ observations of trace gases are rare especially in equatorial Africa. The WMO Global Atmosphere Watch (GAW) programme aimed to close this gap with the installation of the Mt. Kenya (MKN) baseline station. Here, the first continuous measurements of carbon monoxide (CO) and ozone (O3) at this site covering the period June 2002 to June 2006 are presented. The representativeness of the site was investigated by means of statistical data analysis, air mass trajectory clustering, interpretation of biomass burning variability and evaluation of O3-CO relationships. Because of its location in eastern equatorial Africa, the site was rarely directly influenced by biomass burning emissions, making it suitable for background observations. Located at 3678 m above sea level the night-time (21:00–04:00 UTC) measurements of CO and O3 were in general representative of the free troposphere, while day-time measurements were influenced by atmospheric boundary layer air. Increased night-time concentrations were observed in 25% of all nights and associated with residual layers of increased CO and water vapour in the free troposphere. Six representative flow regimes towards Mt. Kenya were determined: eastern Africa (21% of the time), Arabian Peninsula and Pakistan (16%), northern Africa free tropospheric (6%), northern Indian Ocean and India (17%), south-eastern Africa (18%) and southern India Ocean (21%) flow regimes. The seasonal alternation of these flow regimes was determined by the monsoon circulation and caused a distinct semi-annual cycle of CO with maxima during February (primary) and August (secondary, annually variable) and with minima in April (primary) and November (secondary, annually variable). O3 showed a weaker annual cycle with a minimum in November and a broad summer maximum. Inter-annual variations were explained with differences in southern African biomass burning and transport towards MKN. Although biomass burning had little direct influence on the measurements at MKN it introduces inter-annual variability in the background concentrations of the southern hemisphere that subsequently reaches Kenya. The measurements at MKN were representative of air masses with little photochemical activity as indicated by weak O3-CO correlations, underlining the baseline character of the site. Inter-comparison of O3 at MKN with sounding data from Nairobi revealed a positive offset of the sounding data, most likely due to additional photochemical production of O3 in the Nairobi city plume. Future extensions of the measurement programme will provide better understanding of the atmospheric chemistry of this globally important region.
Long-term solar UV radiation reconstructed by ANN modelling with emphasis on spatial characteristics of input data

Artificial Neural Networks (ANN) are efficient tools to derive solar UV radiation from measured meteorological parameters such as global radiation, aerosol optical depths and atmospheric column ozone. The ANN model has been tested with different combinations of data from the two sites Potsdam and Lindenberg, and used to reconstruct solar UV radiation at eight European sites by more than 100 years into the past. Special emphasis will be given to the discussion of small-scale characteristics of input data to the ANN model. Annual totals of UV radiation derived from reconstructed daily UV values reflect interannual variations and long-term patterns that are compatible with variabilities and changes of measured input data, in particular global dimming by about 1980/1990, subsequent global brightening, volcanic eruption effects such as that of Mt. Pinatubo, and the long-term ozone decline since the 1970s. Patterns of annual erythemal UV radiation are very similar at sites located at latitudes close to each other, but different patterns occur between UV radiation at sites in different latitude regions.
Validation of stratospheric water vapour measurements from the airborne microwave radiometer AMSOS

We present the validation of a water vapour dataset obtained by the Airborne Microwave Stratospheric Observing System AMSOS, a passive microwave radiometer operating at 183 GHz. Vertical profiles are retrieved from spectra by an optimal estimation method. The useful vertical range lies in the upper troposphere up to the mesosphere with an altitude resolution of 8 to 16 km and a horizontal resolution of about 57 km. Flight campaigns were performed once a year from 1998 to 2006 measuring the latitudinal distribution of water vapour from the tropics to the polar regions. The obtained profiles show clearly the main features of stratospheric water vapour in all latitudinal regions. Data are validated against a set of instruments comprising satellite, ground-based, airborne remote sensing and in-situ instruments. It appears that AMSOS profiles have a dry bias of 0 to –20%, when compared to satellite experiments. Also a comparison between AMSOS and in-situ hygrosondes FISH and FLASH have been performed. A matching in the short overlap region in the upper troposphere of the lidar measurements from the DIAL instrument and the AMSOS dataset allowed water vapour profiling from the middle troposphere up to the mesosphere.
Halogenated organic species over the tropical South American rainforest

Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and about 1000 km of pristine tropical rainforest in Suriname and French Guyana (3–6° N, 51–59° W) in October 2005. In the boundary layer (0–1.4 km), maritime air masses, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4–1.0 years) in comparison to the advection times from the coast (1–2 days), emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of time the air spent over land and the respective relationship used to determine net fluxes from the rainforest for one week within the long dry season. Net fluxes from the rainforest ecosystem have been calculated for methyl chloride and chloroform as 9.5 (±3.8 2σ) and 0.35 (±0.15 2σ)μg m-2 h−1, respectively. No significant flux was observed for methyl bromide within the limits of these measurements. The global budget of methyl chloride contains large uncertainties, in particular with regard to a possible source from tropical vegetation. Our measurements are used in a large-scale approach to determine the net flux from a tropical ecosystem to the planetary boundary layer. The obtained global net flux of 1.5 (±0.6 2σ) Tg yr-1 for methyl chloride is at the lower end of current estimates for tropical vegetation sources, which helps to constrain the range of tropical sources and sinks (0.82 to 8.2 Tg yr-1 from tropical plants, 0.03 to 2.5 Tg yr-1 from senescent/dead leaves and a sink of 0.1 to 1.6 Tg yr-1 by soil uptake). Nevertheless, these results show that the contribution of the rainforest ecosystem is the major source in the global budget of methyl chloride. For chloroform, the extrapolated global net flux from tropical ecosystems is 56 (±23 2σ) Gg yr−1, which is of minor importance compared to the total global sources and might be already contained in the soil emission term.
Atmospheric chemistry of trans-CF3CH=CHF: products and mechanisms of hydroxyl radical and chlorine atom initiated oxidation

Smog chamber/FTIR techniques were used to study the products and mechanisms of OH radical and Cl atom initiated oxidation of trans-CF3CH=CHF in 700 Torr of N2/O2 diluent at 295±1 K. Hydroxyl radical initiated oxidation leads to the formation of CF3CHO and HC(O)F in yields which were indistinguishable from 100% and were not dependent on the O2 partial pressure. Chlorine atom initiated oxidation gives HC(O)F, CF3CHO, CF3C(O)Cl, and CF3C(O)CHFCl. The yields of CF3C(O)Cl and CF3C(O)CHFCl increased at the expense of HC(O)F and CF3CHO as the O2 partial pressure was increased over the range 5–700 Torr. The results are discussed with respect to the atmospheric chemistry and environmental impact of trans-CF3CH=CHF.
Intercomparison between aerosol optical properties by a PREDE skyradiometer and CIMEL sunphotometer over Beijing, China

This study compares the aerosol optical and physical properties simultaneously measured by a SKYNET PREDE skyradiometer and AERONET/PHOTONS CIMEL sunphotometer at a location in Beijing, China. Aerosol optical properties (AOP) including the Aerosol Optical Depth (AOD), Angstrom exponent (α), volume size distribution, single scattering albedo (ω) and the complex refractive index were compared. The difference between the two types of instruments was less than 1.3% for the AOD and less than 4% for the single scattering albedo below the wavelength of 670 nm. There is a difference between the volume size distribution patterns derived from two instruments, which is probably due to difference of measurement protocols and inversion algorithms for the respective instruments. AOP under three distinct weather conditions (background, haze, and dust days) over Beijing were compared by using the retrieved skyradiometer and sunphotometer data combined with MODIS satellite results, pyranometer measurements, PM10 measurements, and backtrajectory analysis. The results show that the significant difference of AOP under background, haze, and dust days over Beijing is probably due to different aerosol components under distinct weather conditions.
Ozone prediction based on meteorological variables: a fuzzy inductive reasoning approach

MILAGRO project was conducted in Mexico City during March 2006 with the main objective of study the local and global impact of pollution generated by megacities. The research presented in this paper is framed in MILAGRO project and is focused on the study and development of modeling methodologies that allow the forecasting of daily ozone concentrations. The present work aims to develop Fuzzy Inductive Reasoning (FIR) models using the Visual-FIR platform. FIR offers a model-based approach to modeling and predicting either univariate or multivariate time series. Visual-FIR offers an easy-friendly environment to perform this task. In this research, long term prediction of maximum ozone concentration in the downtown of Mexico City Metropolitan Area is performed. The data were registered every hour and include missing values. Two modeling perspectives are analyzed, i.e. monthly and seasonal models. The results show that the developed models are able to predict the diurnal variation of ozone, including its maximum daily value in an accurate manner.
Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively. Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.