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We have used high spectral resolution spectroscopic measurements from the MIPAS instrument on the Envisat satellite to simultaneously retrieve vertical profiles of H<sub>2</sub>O and HDO in the stratosphere and uppermost troposphere. Variations in the deuterium content of water are expressed in the common δ notation, where δD is the deviation of the Deuterium/Hydrogen ratio in a sample from a standard isotope ratio. A thorough error analysis of the retrievals confirms that reliable δD data can be obtained up to an altitude of ~45 km. Averaging over multiple orbits and thus over longitudes further reduces the random part of the error. The absolute total error of averaged δD is between 36‰ and 111‰. With values lower than 42‰ the total random error is significantly smaller than the natural variability of δD. The data compare well with previous investigations. The MIPAS measurements now provide a unique global data set of high-quality δD data that will provide novel insight into the stratospheric water cycle.
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The strength of the stratospheric wave driving during northern winter is often quantified by the January–February mean poleward eddy heat flux at 100 hPa, averaged over 40°–80° N (or a similar area and period). Despite the dynamical and chemical relevance of the wave driving, the causes for its variability are still not well understood. In this study, ERA-40 reanalysis data for the period 1979–2002 are used to examine several factors that significantly affect the interannual variability of the wave driving. The total poleward heat flux at 100 hPa is poorly correlated with that in the troposphere, suggesting a decoupling between 100 hPa and the troposphere. However, the individual zonal wave-1 and wave-2 contributions to the wave driving at 100 hPa do exhibit a significant coupling with the troposphere, predominantly their stationary components. The stationary wave-1 contribution to the total wave driving significantly depends on the latitude of the stationary wave-1 source in the troposphere. The results suggest that this dependence is associated with the varying ability of stationary wave-1 activity to enter the tropospheric waveguide at mid-latitudes. The wave driving anomalies are separated into three parts: one part due to anomalies in the zonal correlation coefficient between the eddy temperature and eddy meridional wind, another part due to anomalies in the zonal eddy temperature amplitude, and a third part due to anomalies in the zonal eddy meridional wind amplitude. It is found that year-to-year variability in the zonal correlation coefficient between the eddy temperature and the eddy meridional wind is the most dominant factor in explaining the year-to-year variability of the poleward eddy heat flux.
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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 NO<sub>x</sub> 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 CH<sub>4</sub> 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.
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The seasonal variability and the interannual variance explained by ENSO and NAO to cirrus cloud cover (CCC) are examined during the twenty-year period 1984–2004. CCC was found to be significantly correlated with vertical velocities and relative humidity from ECMWF/ERA40 in the tropics (correlations up to −0.7 and +0.7 at some locations, respectively) suggesting that variations in large-scale vertical winds and relative humidity fields can be the origin of up to half of the local variability in CCC over these regions. These correlations reflect mostly the seasonal cycle. Although the annual cycle is dominant in all latitudes and longitudes, peaking over the tropics and subtropics, its amplitude can be exceeded during strong El Nino/La Nina events. Over the eastern tropical Pacific Ocean the interannual variance of CCC which can be explained by ENSO is about 6.8% and it is ~2.3 times larger than the amplitude of the annual cycle. Natural long-term trends in the tropics are generally small (about −0.3% cloud cover per decade) and possible manmade trends in those regions are also small. The contributions of NAO and QBO to the variance of CCC in the tropics are also small. In the northern mid-latitudes, on the other hand, the effect of NAO is more significant and can be very important regionally. Over northern Europe and the eastern part of the North Atlantic Flight Corridor (NAFC) there is a small positive correlation between CCC and NAO index during the wintertime of about 0.3. In this region, the interannual variance of CCC explained by NAO is 2.6% and the amplitude of the annual cycle is 3.1%. Long-term trends over this region are about +1.6% cloud cover per decade and compare well with the observed manmade trends over congested air traffic regions in Europe and the North Atlantic as have been evidenced from earlier findings.
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Three independent datasets of Radiation Budget at the top of the atmosphere (TOA) spanning two decades are compared: the Scanner Narrow Field of View data (from ERBE, ScaRaB, and CERES instruments, 1985–2005), the ERBS Nonscanner Wide Field of View data (1985–1998) and the simulated broadband fluxes from the International Satellite Cloud Climatology Project (ISCCP-FD, 1983–2004). The analysis concerns the shortwave (SW) reflected flux, the longwave (LW) emitted flux and the net flux at the Top Of the Atmosphere (TOA) over Africa and the surrounding oceans (45° S–45° N/60° W–60° E), a region particularly impacted by climate variability. For each month, local anomalies are computed with reference to the average over this large region, and their differences between the 2002–2005 and 1985–1989 periods are analysed. These anomalies are, for a large part, independent on the general observed trends (about 2.5 W m<sup>−2</sup> per decade), which may be affected by possible calibration drifts. Although the regional flux anomalies can be related to calibration through the scene identification and the choice of the anisotropy correction, this effect is limited if the calibration drifts remains reasonable. Large inter-annual variations are observed locally. Over a part of the South East Atlantic (35°–10° S/10° W–10° E), including the marine low cloud area off Angola, there is a decrease of the yearly means of net flux estimated to 2.2, 3 and 6 W m<sup>−2</sup> respectively for the Scanner, Nonscanner and ISCPP-FD data. Over a narrow strip of the Sahel Zone, the net flux increases by about 5 W m<sup>−2</sup>. We believe that these observations are real. They could be due to the impact of calibration drift but only if the drifts were significant (>4%) and correlated between the datasets, which is highly improbable.
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Iodine is an essential trace element for all mammals and may also influence climate through new aerosol formation. Atmospheric bromine cycling is also important due to its well-known ozone depletion capabilities. Despite precipitation being the ultimate source of iodine in the terrestrial environment, the processes effecting its distribution, speciation and transport are relatively unknown. The aim of this study was to determine the effect of orographically induced precipitation on iodine concentrations in snow and also to quantify the inorganic and organic iodine and bromine species. Snow samples were collected over an altitude profile (~840 m) from the northern Black Forest and were analysed by ion-chromatography - inductively coupled plasma mass spectrometry (IC-ICP-MS) for iodine and bromine species and trace metals (ICP-MS). All elements and species concentrations in snow showed significant (<i>r</i><sup>2</sup>>0.65) exponential decrease relationships with altitude despite the short (5 km) horizontal distance of the transect. In fact, total iodine more than halved (38 to 13 nmol/l) over the 840 m height change. The results suggest that orographic lifting and subsequent precipitation has a major influence on iodine concentrations in snow. This orographically induced removal effect may be more important than lateral distance from the ocean in determining iodine concentrations in terrestrial precipitation. The microphysical removal process was common to all elements indicating that the iodine and bromine are internally mixed within the snow crystals. We also show that organically bound iodine is the dominant iodine species in snow (61–75%), followed by iodide. Iodate was only found in two samples despite a detection limit of 0.3 nmol/l. Two unknown but most likely anionic organo-I species were also identified in IC-ICP-MS chromatograms and comprised 2–10% of the total iodine. The majority of the bromine was inorganic bromide with a max. of 32% organo-Br.
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The performances of satellite and sondes ozone measuring instruments available in the tropics between 10 and 26 km during the southern hemisphere summer in 2003 and 2004, have been investigated by comparison with series of profiles obtained by solar occultation in the visible Chappuis bands using a SAOZ UV-Vis spectrometer carried by long duration balloons. When compared to SAOZ, systematic positive or negative altitude shifts are observed in the satellite profiles, varying from <50 m for the GOMOS v6.0b stellar occultation instrument, followed by +100/200 m for solar occultation systems (SAGE II v6.2, HALOE v19 above 22 km), but as large as −900 m for the OSIRIS limb viewing system. The ozone relative biases are generally limited, between −4% and +4%, for measurements in the visible Chappuis bands (SAGE II and SAGE III moon v3, GOMOS above 22 km and OSIRIS), the near IR (HALOE above 22 km) and the ozonesondes, but increase to +5.5% (SCIAMACHY IUP v1.63) though still in the visible, and +7% in the mid-IR (MIPAS NL v4.61) and the submillimetric range (SMR v222). Regarding precision, evaluated statistically from the zonal variability of ozone concentration, the best measurements are found to be those of SAGE II (2%), followed by HALOE above 22 km (3–4%), then the ozonesondes, SAGE III moon, SCIAMACHY and OSIRIS (4–5%), GOMOS above 22 km (~6%), MIPAS (8.5%) and finally SMR (16%). Overall, all satellite ozone measurements appear to be of little utility in the tropical troposphere except those of SAGE II (and eventually SAGE III), though low biased by 50% and of limited (50%) precision.
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The properties of atmospheric aerosol particles in Marseille and Athens were investigated. The studies were performed in Marseille, France, during July 2002 and in Athens, Greece, during June 2003. The aerosol size distribution and the formation and growth rates of newly formed particles were characterized using Differential Mobility Particle Sizers. Hygroscopic properties were observed using a Hygroscopic Tandem Differential Mobility Analyzer setup. During both campaigns, the observations were performed at suburban, almost rural sites, and the sites can be considered to show general regional background behavior depending on the wind direction. At both sites there were clear pattern for both aerosol number concentration and hygroscopic properties. Nucleation mode number concentration increased during the morning hours indicating new particle formation, which was observed during more than 30% of the days. The observed formation rate was typically more than 1 cm<sup>−3</sup> s<sup>−1</sup>, and the growth rate was between 1.2–9.9 nm h<sup>−1</sup>. Based on hygroscopicity measurements in Athens, the nucleation mode size increase was due to condensation of both water insoluble and water soluble material. However, during a period of less anthropogenic influence, the growth was to a larger extent due to water insoluble components. When urban pollution was more pronounced, growth due to condensation of water soluble material dominated.
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Data from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO<sub>2</sub>. Measurements of NO<sub>2</sub> from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO<sub>2</sub> concentration during afternoon hours. As expected, this interference correlates well with non-NO<sub>x</sub> reactive nitrogen species (NO<sub>z</sub>) as well as with ambient O<sub>3</sub> concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO<sub>3</sub> to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concentrations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO<sub>2</sub> concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants.
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Strong radar returns at VHF known as Polar Mesospheric Winter Echoes (PMWE) seem to occur during periods of intense ionisation of the mesosphere. Apart from a mechanism to produce such ionisation, viz. solar proton precipitation, other prerequisites have been proposed, such as neutral air turbulence. Here, we employ a medium frequency radar to examine whether the atmospheric state is conducive to the appearance of PMWE; echo power signatures (isolated lower mesospheric echoes – "ILME") are indicators of the necessary ionisation at sufficient depth in the middle atmosphere, and also echo fading times give information on turbulence. We fail to find evidence for causal relationship between ILME and turbulence but suggest that on occasion turbulence may be enhanced related to proton precipitation. The results presented provide a basis for investigating whether turbulence is a prerequisite for PMWE.
