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Balloon water vapour in situ and remote measurements in the tropical upper troposphere and lower stratosphere (UTLS) obtained during the HIBISCUS campaign around 20° S in Brazil in February–March 2004 using a tunable diode laser (μSDLA), a surface acoustic wave (SAW) and a Vis-NIR solar occultation spectrometer (SAOZ) on a long duration balloon, have been used for evaluating the performances of satellite borne remote water vapour instruments available at the same latitude and measurement period. In the stratosphere, HALOE displays the best precision (2.5%), followed by SAGE II (7%), MIPAS (10%), SAOZ (20–25%) and SCIAMACHY (35%), all of which show approximately constant H<sub>2</sub>O mixing ratios between 20–25 km. Compared to HALOE of ±10% accuracy between 0.1–100 hPa, SAGE II and SAOZ show insignificant biases, MIPAS is wetter by 10% and SCIAMACHY dryer by 20%. The currently available GOMOS profiles of 25% precision show a positive vertical gradient in error for identified reasons. Compared to these, the water vapour of the Reprobus Chemistry Transport Model, forced at pressures higher than 95 hPa by the ECMWF analyses, is dryer by about 1 ppmv (20%). <br><br> In the lower stratosphere between 16–20 km, most notable features are the steep degradation of MIPAS precision below 18 km, and the appearance of biases between instruments far larger than their quoted total uncertainty. HALOE and SAGE II (after spectral adjustment for reducing the bias with HALOE at northern mid-latitudes) both show decreases of water vapour with a minimum at the tropopause not seen by other instruments or the model, possibly attributable to an increasing error in the HALOE altitude registration. Between 16–18 km where the water vapour concentration shows little horizontal variability, and where the μSDLA balloon measurements are not perturbed by outgassing, the average mixing ratios reported by the remote sensing instruments are substantially lower than the 4–5 ppmv observed by the μSDLA. Differences between μSDLA and HALOE and SAGE II (of the order of −2 ppmv), SCIAMACHY, MIPAS and GOMOS (−1 ppmv) and SAOZ (−0.5 ppmv), exceed the 10% uncertainty of μSDLA, implying larger systematic errors than estimated for the various instruments. <br><br> In the upper troposphere, where the water vapour concentration is highly variable, AIRS v5 appears to be the most consistent within its 25% uncertainty with balloon in-situ measurements as well as ECMWF. Most of the remote measurements show less reliability in the upper troposphere, losing sensitivity possibly because of absorption line saturation in their spectral ranges (HALOE, SAGE II and SCIAMACHY), instrument noise exceeding 100% (MIPAS) or imperfect refraction correction (GOMOS). An exception is the SAOZ-balloon, employing smaller H<sub>2</sub>O absorption bands in the troposphere.
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In order to study the spatial and temporal variations of the emissions of greenhouse gases and of their precursors, we developed a data assimilation system and applied it to infer emissions of CH<sub>4</sub>, CO and H<sub>2</sub> for one year. It is based on an atmospheric chemical transport model and on a simplified scheme for the oxidation chain of hydrocarbons, including methane, formaldehyde, carbon monoxide and molecular hydrogen together with methyl chloroform. The methodology is exposed and a first attempt at evaluating the inverted fluxes is made. Inversions of the emission fluxes of CO, CH<sub>4</sub> and H<sub>2</sub> and concentrations of HCHO and OH were performed for the year 2004, using surface concentration measurements of CO, CH<sub>4</sub>, H<sub>2</sub> and CH<sub>3</sub>CCl<sub>3</sub> as constraints. Independent data from ship and aircraft measurements and satellite retrievals are used to evaluate the results. The total emitted mass of CO is 30% higher after the inversion, due to increased fluxes by up to 35% in the Northern Hemisphere. The spatial distribution of emissions of CH<sub>4</sub> is modified by a decrease of fluxes in boreal areas up to 60%. The comparison between mono- and multi-species inversions shows that the results are close at a global scale but may significantly differ at a regional scale because of the interactions between the various tracers during the inversion.
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Two 40-year meteorological datasets are used to drive the Model of Ozone and Related Tracers chemical transport model, version 2 (MOZART2) in hindcast simulations. One dataset is from the National Center for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis, the second dataset uses meteorology from the Community Atmosphere Model (CAM3) forced with observed interannually varying sea surface temperatures. All emissions, except those from lightning are annually constant. Analysis of these simulations focuses on the period between 1979–1999, due to meteorological discontinuities in the NCEP reanalysis during the 1970s. The meteorology using CAM3 captures observed trends in temperature and water vapor; the simulation using NCEP meteorology does not. This paper examines the regional and global interannual variability of various chemical and meteorological fields: CO, OH, O<sub>3</sub> and HNO<sub>3</sub>, the surface photolysis rate of NO<sub>2</sub> (as a proxy for overhead cloudiness), lightning NO emissions, water vapor, planetary boundary layer height, and temperature. The variability due to changes in emissions is not considered in this analysis. In both the NCEP and CAM3 simulations the relative variability of CO, OH, O<sub>3</sub> and HNO<sub>3</sub> are qualitatively similar, with variability maxima both in the tropics and the high latitudes. Locally, relative variability generally ranges between 3 and 10%; globally the tropospheric variability generally ranges from half to one percent, but can be higher. For most fields the leading global Empirical Orthogonal Function explains approximately 10% of the variability and correlates significantly with El Niño. In both simulations the first principal component of a multiple tracer, globally averaged analysis shows a strong coupling between surface temperature, measures of the hydrological cycle, CO and OH, but is not correlated with El Niño. In both simulations we examine the global response of the selected variables to changes in global surface temperature, and compare with a climate simulation over the 21st century.
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A high resolution regional chemistry-transport model has been used to study the distribution of exposure-plant response index (AOT40, Accumulated exposure Over a Threshold of 40 ppb, expressed as ppb h) over the Indian geographical region for the year 2003 as case study. The directives on ozone pollution in ambient air provided by United Nations Economic Commission for Europe (UNECE) and World Health Organization (WHO) for vegetation protection (AOT40) have been used to assess the air quality. A substantial temporal and spatial variation in AOT40 values has been observed across the Indian region. Large areas of India show ozone values above the AOT40 threshold limit (3000 ppb h for 3 months). Simulated AOT40 values are found to be substantially higher throughout the year over the most fertile Indo-Gangetic plains than the other regions of India, which can have an adverse effect on plants and vegetation in this region. The observed monthly AOT40 values reported from an Indian station, agree reasonably well with model simulated results. There is an underestimation of AOT40 in the model results during the periods of highest ozone concentration from December to March. We find that the simulated AOT40 target values for protection of vegetation is exceeded even in individual months, especially during November to April. Necessary and effective emission reduction strategies are therefore required to be developed in order to curb the surface level ozone pollution to protect the vegetation from further damage in India whose economy is highly dependent on agricultural sector and may influence the global balance.
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A series of aggressive measures was launched by the Chinese government to reduce pollutant emissions from Beijing and surrounding areas during the Olympic Games. Observations at Miyun, a rural site 100 km downwind of the Beijing urban center, show significant decreases in concentrations of O<sub>3</sub>, CO, NO<sub>y</sub>, and SO<sub>2</sub> during August 2008, relative to August 2006–2007. The mean daytime mixing ratio of O<sub>3</sub> was lower by about 15 ppbv, reduced to 50 ppbv, in August 2008. The relative reductions in daytime SO<sub>2</sub>, CO, and NO<sub>y</sub> were 61%, 25%, and 21%, respectively. Changes in SO<sub>2</sub> and in species correlations from 2007 to 2008 indicate that emissions of SO<sub>2</sub>, CO, and NO<sub>x</sub> were reduced at least by 60%, 32%, and 36%, respectively, during the Olympics. Analysis of meteorological conditions and interpretation of observations using a chemical transport model suggest that although the day-to-day variability in ozone is driven mostly by meteorology, the reduction in emissions of ozone precursors associated with the Olympic Games had a significant contribution to the observed decrease in O<sub>3</sub> during August 2008, accounting for 80% of the O<sub>3</sub> reduction for the month as a whole and 45% during the Olympics Period (8–24 August). The model predicts that emission restrictions such as those implemented during the Olympics can affect O<sub>3</sub> far beyond the Beijing urban area, resulting in reductions in boundary layer O<sub>3</sub> of 2–10 ppbv over a large region of the North China Plain and Northeastern China.
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We present ozone measurements of the Global Atmospheric Sampling Program (GASP) performed from four commercial and one research aircraft in the late 1970s to compare them with respective measurements of the ongoing MOZAIC project. Multi-annual averages of UT/LS ozone were built using the aircraft data sets (1975–1979 and 1994–2001), and long-term changes between the 1970s and 1990s were derived by comparison. The data were binned relative to the dynamical tropopause to separate between UT and LS air masses. LS data were analysed using equivalent latitudes. In the UT, pronounced increases of 20–40% are found over the Middle East and South Asia in the spring and summer seasons. Increases are also found over Japan, Europe, and the eastern parts of the United States depending on season. LS ozone over northern mid- and high latitudes was found to be lower in the 1990s compared to the 1970s in all seasons of the year. In addition, a comparison with long-term changes deduced from ozonesondes is presented. The early 1970s European Brewer-Mast (BM) sonde data agree with GASP within the range of uncertainty (UT) or measured slightly less ozone (LS). In contrast, the 1990s BM sensors show consistently and significantly higher UT/LS ozone values than MOZAIC. This unequal behaviour of aircraft/sonde comparisons in the 1970s and 1990s leads to differences in the estimated long-term changes over Europe: while the comparison between GASP and MOZAIC indicates ozone changes of −5% to 10% over Europe, the sondes suggest a much larger increase of 10%–35% depending on station and season, although statistical significance is not conclusive due to data sample limitations. In contrast to the BM sondes, the Electrochemical Cell (ECC) sonde at Wallops Island, USA, measured higher UT ozone than both GASP and MOZAIC. Hence, long-term changes from GASP/MOZAIC agree within the range of uncertainty with the changes deduced from Wallops Island.
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A retrieval algorithm that uses a statistical strategy based on dimension reduction is proposed. The methodology and details of the implementation of the new algorithm are presented and discussed. The algorithm has been applied to high resolution spectra measured by the Infrared Atmospheric Sounding Interferometer instrument to retrieve atmospheric profiles of temperature, water vapour and ozone. The performance of the inversion strategy has been assessed by comparing the retrieved profiles to the ones obtained by co-locating in space and time profiles from the European Centre for Medium-Range Weather Forecasts analysis.
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Mixing ratio measurements of atmospheric tracers like CO<sub>2</sub> can be used to estimate regional surface-air tracer fluxes using inverse methods, involving a numerical transport model. Currently available transport models are either global but rather coarse, or more accurate but only over a limited spatial and temporal domain. To obtain higher-resolution flux estimates within a region of interest, existing studies use zoomed or coupled models. The two-step scheme developed here uses global and regional models sequentially in separate inversion steps, coupled only via the data vector. This provides a nested atmospheric inversion scheme without the necessity of a direct coupled model implementation. For example, the scheme allows an easy nesting of Lagrangian models with their potential of very high resolution into global inversions based on Eulerian models.
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Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.
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Ozone is an important atmospheric constituent due to its role as both a greenhouse gas and an oxidant. Recent measurements in the Mount Everest region indicate the presence of ozone at elevations from 5000 to 9000 m a.s.l. that are the result of both stratospheric and tropospheric sources. Here we examine the temporal variability in the surface ozone concentration measurements from the ABC-Pyramid Observatory in the Mount Everest region during 2006 and compare it to the total column ozone data from the OMI instrument as well as meteorological fields from the ECMWF Interim Reanalysis. Both the surface ozone at and the total column ozone over the ABC-Pyramid Observatory site have maxima in the pre-monsoon period. We show that during this period, there is a statistically significant correlation between the two suggesting that the stratosphere was an important contributor to the high levels of ozone observed during the period. There was a hiatus in the monsoon in June that resulted in a return of westerlies over northern Indian and southern Tibet and as a result, the aforementioned correlation extended into June. No such correlation exists during the monsoon and post-monsoon periods. Spatial correlation maps between the surface ozone and total column ozone as well as meteorological fields from the ECMWF Interim Reanalysis support the contention that there is a significant stratospheric contribution in the pre-monsoon period that is absent during and after the monsoon.
