bluuebunny/crossref_metadata_2025 huggingface dataset:
The relationship between tropospheric wave forcing and tropical lower stratospheric water vapor
Authors: Dhomse S. , Weber M. , Burrows J.
Published: April 2010

Abstract. The compact relationship between stratospheric temperatures (as well as ozone) and tropospheric generated planetary wave activity have been widely discussed. Higher wave activity leads to a strengthening of the Brewer-Dobson (BD) circulation, which results in warmer/colder temperatures in the polar/tropical stratosphere. The influence of this wave activity on stratospheric water vapor (WV) is not yet well explored primarily due to lack of high quality long term data sets. Using WV data from HALOE and SAGE II, an anti-correlation between planetary wave driving (here expressed by the mid-latitude eddy heat flux at 50 hPa added from both hemispheres) and tropical lower stratospheric (TLS) WV has been found. This appears to be the most direct manifestation of the inter-annual variability of the known relationship between ascending motion in the tropical stratosphere (due to rising branch of the BD circulation) and the amount of the WV entering into the stratosphere from the tropical tropopause layer. A decrease in planetary wave activity in the mid-nineties is probably responsible for the increasing trends in stratospheric WV until late 1990s. After 2000 a sudden decrease in lower stratospheric WV has been reported and was observed by different satellite instruments such as HALOE, SAGE II and POAM III indicating that the lower stratosphere has become drier since then. This is consistent with a sudden rise in the combined mid-latitude eddy heat flux with nearly equal contribution from both hemispheres. The low water vapor and enhanced strength of the Brewer-Dobson circulation has persisted until now. It is estimated that the strengthening of the BD circulation after 2000 contributed to a 0.7 K cooling in the TLS.
Comparison of Box-Air-Mass-Factors and Radiances for Multiple-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) Geometries calculated from different UV/visible Radiative Transfer Models
Authors: Wagner T. , Burrows J. P. , Deutschmann T. , Dix B. , von Friedeburg C. , Frieß U. , Hendrick F. , Heue K.-P. , Irie H. , Iwabuchi H. , Kanaya Y. , Keller J. , McLinden C. A. , Oetjen H. , Palazzi E. , Petritoli A. , Platt U. , Postylyakov O. , Pukite J. , Richter A. , van Roozendael M. , Rozanov A. , Rozanov V. , Sinreich R. , Sanghavi S. , Wittrock F.
Published: April 2010

Abstract. The results of a comparison exercise of radiative transfer models (RTM) of various international research groups for Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) viewing geometry are presented. In contrast to previous comparison exercises, box-air-mass-factors (box-AMFs) for various atmospheric height layers were modelled, which describe the sensitivity of the measurements as a function of altitude. In addition, radiances were calculated allowing the identification of potential errors, which might be overlooked if only AMFs are compared. Accurate modelling of radiances is also a prerequisite for the correct interpretation of satellite observations, for which the received radiance can strongly vary across the large ground pixels, and might be also important for the retrieval of aerosol properties as a future application of MAX-DOAS. The comparison exercises included different wavelengths and atmospheric scenarios (with and without aerosols). The results were systematically investigated with respect to their dependence on the telescope's elevation angle and the azimuth angle. For both dependencies, a strong and systematic influence of aerosol scattering was found indicating that from MAX-DOAS observations also information on atmospheric aerosols can be retrieved. During the various iterations of the exercises, the results from all models showed a substantial convergence, and the final data sets agreed for most cases within about 5%. Larger deviations were found for cases with low atmospheric optical depth, for which the photon path lengths along the line of sight of the instrument can become very large. The differences occurred between models including full spherical geometry and those using only plane parallel approximation indicating that the correct treatment of the Earth's sphericity becomes indispensable. The modelled box-AMFs constitute an universal data base for the calculation of arbitrary (total) AMFs by simple convolution with a given trace gas concentration profile. Together with the modelled radiances and the specified settings for the various exercises, they can serve as test cases for future RTM developments.
Chemical ozone loss in the Arctic winter 1991–1992
Authors: Tilmes S. , Müller R. , Salawitch R. J. , Schmidt U. , Webster C. R. , Oelhaf H. , Russell III J. M. , Camy-Peyret C. C.
Published: April 2010

Abstract. Chemical ozone loss in winter 1991–1992 is recalculated based on observations of the HALOE satellite instrument, ER-2 aircraft measurements and balloon data. HALOE satellite observations are shown to be reliable in the lower stratosphere below 400 K, at altitudes where profiles are most likely disturbed by the enhanced sulfate aerosols, as a result of the Mt. Pinatubo eruption in June 1991. Very large chemical ozone loss was observed below 400 K from Kiruna balloon observations between December and March 1992. Additionally, for the two winters after the Mt. Pinatubo eruption, HALOE satellite observations show a stronger extent of chemical ozone loss at lower altitudes compared to other Arctic winter between 1991 and 2003. In stipe of already occurring deactivation of chlorine in March 1992, Mipas-B and LPMA balloon observations indicate still chlorine activation at lower altitudes, consistent with observed chemical ozone loss occurring between February and March and April. Enhanced chemical ozone loss in the Arctic winter 1991–1992 as calculated in earlier studies is corroborated here.
Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes
Authors: Ng N. L. , Chhabra P. S. , Chan A. W. H. , Surratt J. D. , Kroll J. H. , Kwan A. J. , McCabe D. C. , Wennberg P. O. , Sorooshian A. , Murphy S. M. , Dalleska N. F. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.
The high Arctic in extreme winters: vortex, temperature, and MLS and ACE-FTS trace gas evolution
Authors: Manney G. L. , Daffer W. H. , Strawbridge K. B. , Walker K. A. , Boone C. D. , Bernath P. F. , Kerzenmacher T. , Schwartz M. J. , Strong K. , Sica R. J. , Krüger K. , Pumphrey H. C. , Froidevaux L. , Lambert A. , Santee M. L. , Livesey N. J. , Remsberg E. E. , Mlynczak M. G. , Russell III J. R.
Published: April 2010

Abstract. The first three Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns at Eureka (80° N, 86° W) were during two extremes of Arctic winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry, and Aura Microwave Limb Sounder (MLS), with meteorological analyses and Eureka lidar and radiosonde temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport and chemistry, and to provide a context for interpretation of campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, above where it could be accurately represented in the meteorological analyses. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with Eureka radiosondes, and with lidar data up to 50–60 km. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex during the 2004 and 2006 Eureka campaigns compared to that in 2005.
Formation and characteristics of ions and charged aerosol particles in a native Australian Eucalypt forest
Authors: Suni T. , Kulmala M. , Hirsikko A. , Bergman T. , Laakso L. , Aalto P. P. , Leuning R. , Cleugh H. , Zegelin S. , Hughes D. , van Gorsel E. , Kitchen M. , Vana M. , Hõrrak U. , Mirme S. , Mirme A. , Twining J. , Tadros C.
Published: April 2010

Abstract. Biogenic aerosol formation is likely to contribute significantly to the global aerosol load. In recent years, new-particle formation (NPF) has been observed in various ecosystems around the world but hardly any measurements have taken place in the terrestrial Southern Hemisphere. Here, we report the first results of atmospheric ion and charged particle concentrations as well as of NPF in a Eucalypt forest in Tumbarumba, South-East Australia, from July 2005 to October 2006. The measurements were carried out with an Air Ion Spectrometer (AIS) with a size range from 0.34 to 40 nm. Daytime aerosol formation took place on 52% of days with acceptable data. Median growth rates (GR) for negative/positive 1.3–3 nm particles were 2.29/2.02 nmh−1; for 3–7 nm particles 3.04/2.94 nmh−1; and for 7–20 nm particles 7.13/5.62 nmh−1, respectively. Intermediate ion growth rates were highest when the wind was blowing from the direction of the native Eucalypt forest, suggesting that the Eucalypts were the strongest source of condensable vapours. Average cluster ion (0.34 to 1.8 nm) concentrations were very high, 2400/1700 cm−3 for negative/positive ions compared to other measurements around the world. These high concentrations are probably the result of the strong radon efflux from the soils around the Tumbarumba field site. Furthermore, comparison between nighttime and daytime concentrations supported the view that cluster ions are produced close to the surface within the boundary layer also at night but that large ions are mostly produced in daytime. Finally, a previously unreported phenomenon, nocturnal aerosol formation, appeared on 32% of the analysed nights but was clustered almost entirely within six months from summer to autumn in 2006. From January to May, nocturnal formation was 2.5 times as frequent as daytime formation. Therefore, it appears that in summer and autumn, nocturnal production was the major mechanism for aerosol formation in Tumbarumba.
Growth rates of stratospheric HCFC-22
Authors: Moore D. P. , Remedios J. J.
Published: April 2010

Abstract. The Michelson Interferometer for Passive Atmospheric Sounding onboard ENVISAT (MIPAS-E) offers the opportunity to detect and spectrally resolve many atmospheric minor constituents affecting atmospheric chemistry. In this paper, we describe an algorithm produced to retrieve HCFC–22 profiles from MIPAS-E measurements made in 2003 and present results from this scheme between 300 and 50 mb. By comparison with ATMOS (AT–3) version 3 data, we find a mean Northern Hemisphere mid-latitude (20–50° N) HCFC–22 growth rate between 1994 and 2003 of 5.4±0.7 pptv/yr in the lower stratosphere (LS) and a mean LS Southern Hemisphere growth rate (60–80°S) of 6.0±0.7 pptv/yr in the same period. We test the feasibility of using a global data set to estimate the chemical lifetime of HCFC–22 in the LS and we derive this for two regions; 20–50° N (259±38 years) and 60–80° S (288±34 years). From these data we note a global LS lifetime of 274±25 years, significantly longer than previous estimates.
Effects of model chemistry and data biases on stratospheric ozone assimilation
Authors: Coy L. , Allen D. R. , Eckermann S. D. , McCormack J. P. , Stajner I. , Hogan T. F.
Published: April 2010

Abstract. The innovations or observation minus forecast (O−F) residuals produced by a data assimilation system provide a convenient metric of evaluating global analyses. In this study, O–F statistics from the Global Ozone Assimilation Testing System (GOATS) are used to examine how ozone assimilation products and their associated O−F statistics depend on input data biases and ozone photochemistry parameterizations (OPP). All the GOATS results shown are based on a 6-h forecast and analysis cycle using observations from SBUV/2 (Solar Backscatter UltraViolet instrument-2) during September–October 2002. Results show that zonal mean ozone analyses are more independent of observation biases and drifts when using an OPP, while the mean ozone O−Fs are more sensitive to observation drifts when using an OPP. In addition, SD O−Fs (standard deviations) are reduced in the upper stratosphere when using an OPP due to a reduction of forecast model noise and to increased covariance between the forecast model and the observations. Experiments that changed the OPP reference state to match the observations by using an "adaptive" OPP scheme reduced the mean ozone O−Fs at the expense of zonal mean ozone analyses being more susceptible to data biases and drifts. Additional experiments showed that the upper boundary of the ozone DAS can affect the quality of the ozone analysis and therefore should be placed well above (at least a scale height) the region of interest.
Technical note: a new day- and night-time Meteosat Second Generation Cirrus Detection Algorithm MeCiDA
Authors: Krebs W. , Mannstein H. , Bugliaro L. , Mayer B.
Published: April 2010

Abstract. A new cirrus detection algorithm for the Spinning Enhanced Visible and Infra-Red Imager (SEVIRI) aboard the geostationary Meteosat Second Generation (MSG), MeCiDA, is presented. The algorithm uses the seven infrared channels of SEVIRI and thus provides a consistent scheme for cirrus detection at day and night. MeCiDA combines morphological and multi-spectral threshold tests and detects optically thick and thin ice clouds. The thresholds were determined by a comprehensive theoretical study using radiative transfer simulations for various atmospheric situations as well as by manually evaluating actual satellite observations. The retrieved cirrus masks have been validated by comparison with the Moderate Resolution Imaging Spectroradiometer (MODIS) Cirrus Reflection Flag. To study possible seasonal variations in the performance of the algorithm, one scene per month of the year 2004 was randomly selected and compared with the standard MODIS cirrus product. 81% of the pixels were classified identically by both algorithms. On average, MeCiDA detected 60% of the MODIS cirrus. A lower detection efficiency is to be expected for MeCiDA, as the spatial resolution of MODIS is considerably better and as we used only the thermal infrared channels in contrast to the MODIS algorithm which uses infrared and visible radiances. The advantage of MeCiDA compared to retrievals for polar orbiting instruments or previous geostationary satellites is that it allows to derive quantitative data every 15 min, 24 h a day. This high temporal resolution allows the study of diurnal variations and life cycle aspects. MeCiDA is fast enough for near real-time applications.
Observations of the effects of temperature on atmospheric HNO3, ∑ANs, ∑PNs, and NOx: evidence for a temperature dependent HOx source
Authors: Day D. A. , Wooldridge P. J. , Cohen R. C.
Published: April 2010

Abstract. We describe observations of atmospheric reactive nitrogen compounds including NO, NO2, total peroxy nitrates, total alkyl nitrates, and HNO3 and their correlation with temperature. The measurements were made at a rural location 1315 m a.s.l. on the western slope of the Sierra Nevada Mountains in California during summer of 2001. The ratio of HNO3 to its source molecule, NO2, and the ratio of HNO3 to all other higher oxides of nitrogen (NOz) all increase with increasing temperature. Analysis of these increases suggests they are due to a steep increase in OH of between a factor of 2 and 3 over the range 18–32°C. Total peroxy nitrates decrease and total alkyl nitrates increase over the same temperature range. The decrease in the total peroxy nitrates is shown to be much less than expected if the rate of thermal decomposition were the sole important factor and to be consistent with the increase in OH inferred from the temperature trends in the HNO3/NO2 ratio.
Impact of climate change on tropospheric ozone and its global budgets
Authors: Zeng G. , Pyle J. A. , Young P. J.
Published: April 2010

Abstract. We present the chemistry-climate model UM_CAM in which a relatively detailed tropospheric chemical module has been incorporated into the UK Met Office's Unified Model version 4.5. We obtain good agreements between the modelled ozone/nitrogen species and a range of observations including surface ozone measurements, ozone sonde data, and some aircraft campaigns. Four 2100 calculations assess model responses to projected changes of anthropogenic emissions (SRES A2), climate change (due to doubling CO2), and idealised climate change associated changes in biogenic emissions (i.e. 50% increase of isoprene emission and doubling emissions of soil-NOx). The global tropospheric ozone burden increases significantly for all the 2100 A2 simulations, with the largest response caused by the increase of anthropogenic emissions. Climate change has diverse impacts on O3 and its budgets through changes in circulation and meteorological variables. Increased water vapour causes a substantial ozone reduction especially in the tropical lower troposphere (>10 ppbv reduction over the tropical ocean). On the other hand, an enhanced stratosphere-troposphere exchange of ozone, which increases by 80% due to doubling CO2, contributes to ozone increases in the extratropical free troposphere which subsequently propagate to the surface. Projected higher temperatures favour ozone chemical production and PAN decomposition which lead to high surface ozone levels in certain regions. Enhanced convection transports ozone precursors more rapidly out of the boundary layer resulting in an increase of ozone production in the free troposphere. Lightning-produced NOx increases by about 22% in the doubled CO2 climate and contributes to ozone production. The response to the increase of isoprene emissions shows that the change of ozone is largely determined by background NOx levels: high NOx environment increases ozone production; isoprene emitting regions with low NOx levels see local ozone decreases, and increase of ozone levels in the remote region due to the influence of PAN chemistry. The calculated ozone changes in response to a 50% increase of isoprene emissions are in the range of between –8 ppbv to 6 ppbv. Doubling soil-NOx emissions will increase tropospheric ozone considerably, with up to 5 ppbv in source regions.
Balloon-borne radiometer measurement of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years
Authors: Toohey M. , Quine B. M. , Strong K. , Bernath P. F. , Boone C. D. , Jonsson A. I. , McElroy C. T. , Walker K. A. , Wunch D.
Published: April 2010

Abstract. Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and global optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. This suggests that, to within the errors of the 1990 measurements, there has been no significant change in the HNO3 summer mid-latitude profile.
Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic
Authors: Cavender A. E. , Biesenthal T. A. , Bottenheim J. W. , Shepson P. B.
Published: April 2010

Abstract. Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack) to correctly simulate the VOC chemistry of the Arctic, and that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events.
Normal mode Rossby waves and their effects on chemical composition in the late summer stratosphere
Authors: Pendlebury D. , Shepherd T. G. , Pritchard M. , McLandress C.
Published: April 2010

Abstract. During past MANTRA campaigns, ground-based measurements of several long-lived chemical species have revealed quasi-periodic fluctuations on time scales of several days. These fluctuations could confound efforts to detect long-term trends from MANTRA, and need to be understood and accounted for. Using the Canadian Middle Atmosphere Model, we investigate the role of dynamical variability in the late summer stratosphere due to normal mode Rossby waves and the impact of this variability on fluctuations in chemical species. Wavenumber~1, westward travelling waves are considered with average periods of 5, 10 and 16 days. Time-lagged correlations between the temperature and nitrous oxide, methane and ozone fields are calculated in order to assess the possible impact of these waves on the chemical species, although transport may be the dominant effect. Using Fourier-wavelet decomposition and correlating the fluctuations between the temperature and chemical fields, we determine that variations in the chemical species are well-correlated with the 5-day wave and the 10-day wave between 30 and 60 km. Interannual variability of the waves is also examined.
Validation of 525 nm and 1020 nm aerosol extinction profiles derived from ACE imager data: comparisons with GOMOS, SAGE II, SAGE III, POAM III, and OSIRIS
Authors: Vanhellemont F. , Tetard C. , Bourassa A. , Fromm M. , Dodion J. , Fussen D. , Brogniez C. , Gilbert K. L. , Turnbull D. N. , Bernath P. , Boone C. , Walker K. A.
Published: April 2010

Abstract. The Canadian ACE (Atmospheric Chemistry Experiment) mission is dedicated to the retrieval of a large number of atmospheric trace gas species using the solar occultation technique in the infrared and UV/visible spectral domain. However, two additional solar disk imagers (at 525 nm and 1020 nm) were added for a number of reasons, including the retrieval of aerosol and cloud products. In this paper, we present the first validation results for these imager aerosol/cloud optical extinction coefficient profiles, by intercomparison with profiles derived from measurements performed by 3 solar occultation instruments (SAGE II, SAGE III, POAM III), one stellar occultation instrument (GOMOS) and one limb sounder (OSIRIS). The results indicate that the ACE imager profiles are of good quality in the upper troposphere/lower stratosphere, although the aerosol extinction for the visible channel at 525 nm contains a significant negative bias at higher altitudes, while the profiles are systematically too high at 1020 nm. Both problems are probably related to ACE imager instrumental issues.
Comparison of satellite limb-sounding humidity climatologies of the uppermost tropical troposphere
Authors: Ekström M. , Eriksson P. , Read W. G. , Murtagh D. P.
Published: April 2010

Abstract. Humidity climatologies of the tropical uppermost troposphere from satellite limb emission measurements have been compared. Four instruments are considered; UARS-MLS, Odin-SMR, and Aura-MLS operating in the microwave region, and MIPAS in the IR region. A reference for the comparison is obtained by MOZAIC in-situ measurements. The upper tropospheric humidity products were compared on basis of their empirical probability density functions and seasonally averaged horizontal fields at two altitude layers, 12 and 15 km. The probability density functions of the microwave datasets were found to be in very good agreement with each other, and are also consistent with MOZAIC. The average seasonal humidities differ with less than 10%RHi between the instruments, indicating that stated measurement accuracies of 20–30% are conservative estimates. The systematic uncertainty in Odin-SMR data due to cloud correction was also independently estimated to be 10%RHi. MIPAS humidity profiles were found to suffer from cloud contamination, with only 30% of the measurements reaching into the upper troposphere, but under clear-sky conditions there is a good agreement between MIPAS, Odin-SMR and Aura-MLS. Odin-SMR and the two MLS datasets can be treated as independent, being based on different underlying spectroscopy and technology. The good agreement between the microwave limb-sounders, and MOZAIC, is therefore an important step towards understanding the upper tropospheric humidity. The found accuracy of 10%RHi is approaching the level required to validate climate modelling of the upper troposphere humidity. The comparison of microwave and IR also stresses that microwave limb-sounding is necessary for a complete view of the upper troposphere.
Vertical distribution of ozone and VOCs in the low boundary layer of Mexico City
Authors: Velasco E. , Márquez C. , Bueno E. , Bernabé R. M. , Sánchez A. , Fentanes O. , Wöhrnschimmel H. , Cárdenas B. , Kamilla A. , Wakamatsu S. , Molina L. T.
Published: April 2010

Abstract. The evolution of ozone 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 ozone 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 a simple picture of nighttime trapping of ozone in an upper residual layer and of VOCs in a shallow unstable layer above the ground. After sunrise an ozone balance is determined by photochemical production, entrainment from the upper residual layer and destruction by titration with NO, delaying the ground-level ozone 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.
Technical Note: Determination of formaldehyde mixing ratios in polluted air with PTR-MS: laboratory experiments and field measurements
Authors: Inomata S. , Tanimoto H. , Kameyama S. , Tsunogai U. , Irie H. , Kanaya Y. , Wang Z.
Published: April 2010

Abstract. Formaldehyde (HCHO), the most abundant carbonyl compound in the atmosphere, is generated as an intermediate product in the oxidation of nonmethane hydrocarbons. Proton transfer reaction mass spectrometry (PTR-MS) has the capability to detect HCHO from ion signals at m/z 31 with high time-resolution. However, the detection sensitivity is low compared to other detectable species, and is considerably affected by humidity, due to back reactions between protonated HCHO and water vapor prior to analysis. We performed a laboratory calibration of HCHO by PTR-MS and examined the detection sensitivity and humidity dependence at various field strengths. Subsequently, we deployed the PTR-MS instrument in a field campaign at Mount Tai in China in June 2006 to measure HCHO in various meteorological and photochemical conditions; we also conducted intercomparison measurements by Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). Correction of interference in the m/z 31 signals by fragments from proton transfer reactions with methyl hydroperoxide, methanol, and ethanol greatly improves agreement between the two methods, giving the correlation [HCHO]MAX-DOAS = (0.99±0.16) [HCHO]PTR-MS + (0.02±0.38), where error limits represent 95% confidence levels.
Cospectral analysis of high frequency signal loss in eddy covariance measurements
Authors: Wolf A. , Laca E. A.
Published: April 2010

Abstract. The cospectra of momentum (M), sensible heat (H), latent heat (LE), and carbon dioxide (Fc) fluxes measured by eddy covariance (EC) over a shortgrass steppe are calculated for over 800 time intervals spanning a range of wind, surface heating, evaporative, and photosynthetic conditions. The power spectrum of the vertical wind clearly shows that the inertial subrange is not sufficiently captured. The cospectra of the different fluxes show that the lack of measurement resolution in the high frequency results in a loss of flux, especially as stability approaches neutral. A procedure is outlined to use statistics from the cospectrum to estimate the amount of high-frequency flux that remains unmeasured for each time interval. The greatest loss of flux was for H (14% on average for 0>z/L>0.001 where z/L is the dimensionless stability), consistent with other studies which indicate temperature fluctuations actively produce turbulence at high frequencies. LE and Fc showed less than half as much loss of flux as H. This differential loss of flux has direct implications for addressing energy balance closure in EC studies, as well as reconciling biases of fluxes measured by EC with the Modified Bowen Ratio technique. It is recommended that the cospectra of fluxes be examined while setting the height of instrumentation in order to insure that high frequency eddies are resolved.
Application of synchrotron radiation for measurement of iron red-ox speciation in atmospherically processed aerosols
Authors: Majestic B. J. , Schauer J. J. , Shafer M. M.
Published: April 2010

Abstract. In this study, ambient atmospheric particulate matter (PM) 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 18% 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. These results show that changes in the soluble iron fraction occur within the lifetime of urban aerosols (1–3 days) and, therefore, atmospheric processing can have a large effect on human exposure to soluble iron.
Retrieval of global upper tropospheric and stratospheric formaldehyde (H2CO) distributions from high-resolution MIPAS-Envisat spectra
Authors: Steck T. , Glatthor N. , von Clarmann T. , Fischer H. , Flaud J. M. , Funke B. , Grabowski U. , Höpfner M. , Kellmann S. , Linden A. , Perrin A. , Stiller G. P.
Published: April 2010

Abstract. The Fourier transform spectrometer MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) on Envisat measures infrared emission of the Earth's atmosphere in a limb viewing mode. High spectral resolution measurements of MIPAS are sensitive to formaldehyde from the upper troposphere to the stratopause. Formaldehyde single profile retrieval is formally possible, however with a large noise error (more than 60%), which is the dominant error source. The number of degrees of freedom for single profile retrieval ranges from 2 to 4.5 depending on latitude and number of cloud-free tangent altitudes. Calculation of zonal mean values for 30 days of data during 8 September 2003 and 1 December 2003 reduces the noise induced error by a factor of 20 or more. In the upper tropical troposphere zonal mean values of about 70 parts per trillion by volume (pptv) were found, which have been attributed to biomass burning emissions. In the stratosphere, formaldehyde values are determined by photochemical reactions. In the upper tropical stratosphere, formaldehyde zonal mean maximum values can reach 130 pptv. Diurnal variations in this region can be up to 50 pptv. Comparisons with other satellite instruments show generally good agreement in the region of upper troposphere and lower stratosphere as well as in the upper stratosphere.
Hygroscopicity of the submicrometer aerosol at the high-alpine site Jungfraujoch, 3580 m a.s.l., Switzerland
Authors: Sjogren S. , Gysel M. , Weingartner E. , Alfarra M. R. , Duplissy J. , Cozic J. , Crosier J. , Coe H. , Baltensperger U.
Published: April 2010

Abstract. Data from measurements of hygroscopic growth of submicrometer aerosol with a hygroscopicity tandem differential mobility analyzer (HTDMA) during four campaigns at the high alpine research station Jungfraujoch, Switzerland, are presented. The campaigns took place during the years 2000, 2002, 2004 and 2005, each lasting approximately one month. In parallel, size resolved chemical composition measurements with an aerosol mass spectrometer were performed. A hygroscopic closure was done with the composition data using the Zdanovskii-Stokes-Robinson relation. In general, a good agreement between measured and modeled data was found, with some discrepancies caused by instrumental noise at low aerosol loadings. Hygroscopic growth factors (GF, i.e. the relative change in particle diameter from dry diameter, D0, to diameter measured at higher relative humidity, RH) are presented for three distinct air mass types, namely for: 1) free tropospheric winter conditions, 2) planetary boundary layer influenced air masses (during a summer period) and 3) Saharan dust events (SDE). The GF values at 85% RH (D0=100 nm) were 1.40±0.11 and 1.29±0.08 for the first two situations while for SDE a bimodal GF distribution was often found. No phase changes were observed when the RH was varied between 10–90%, and the continuous water uptake could be well described with a single-parameter empirical model. The frequency distributions of the average hygroscopic growth factors and the width of the retrieved growth factor distributions (indicating whether the aerosol is internally or externally mixed) are presented, which can be used for modeling purposes.
Chemical Isolation in the Asian monsoon anticyclone observed in Atmospheric Chemistry Experiment (ACE-FTS) data
Authors: Park M. , Randel W. J. , Emmons L. K. , Bernath P. F. , Walker K. A. , Boone C. D.
Published: April 2010

Abstract. Evidence of chemical isolation in the Asian monsoon anticyclone is presented using chemical constituents obtained from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer instrument during summer (June–August) of 2004–2006. Carbon monoxide (CO) shows a broad maximum over the monsoon anticyclone region in the upper troposphere and lower stratosphere (UTLS); these enhanced CO values are associated with air pollution transported upward by convection, and confined by the strong anticyclonic circulation. Profiles inside the anticyclone show enhancement of tropospheric tracers CO, HCN, C2H6, and C2H2 between ~12 to 20 km, with maxima near 13–15 km. Strong correlations are observed among constituents, consistent with sources from near-surface pollution and biomass burning. Stratospheric tracers (O3, HNO3 and HCl) exhibit decreased values inside the anticyclone between ~12–20 km. These observations are further evidence of transport of lower tropospheric air into the UTLS region, and isolation of air within the anticyclone. The relative enhancements of tropospheric species inside the anticyclone are closely related to the photochemical lifetime of the species, with strongest enhancement for shorter lived species. Vertical profiles of the ratio of C2H2/CO (used to measure the relative age of air) suggest relatively rapid transport of fresh emissions up to tropopause level inside the anticyclone.
Influence of particle size and chemistry on the cloud nucleating properties of aerosols
Authors: Quinn P. K. , Bates T. S. , Coffman D. J. , Covert D. S.
Published: April 2010

Abstract. The ability of an aerosol particle to act as a cloud condensation nuclei (CCN) is a function of the size of the particle, its composition and mixing state, and the supersaturation of the cloud. In-situ data from field studies provide a means to assess the relative importance of these parameters. During the 2006 Texas Air Quality – Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS-GoMACCS), the NOAA RV Ronald~H.~Brown encountered a wide variety of aerosol types ranging from marine near the Florida panhandle to urban and industrial in the Houston-Galveston area. These varied sources provided an opportunity to investigate the role of aerosol sources, chemistry, and size in the activation of particles to form cloud droplets. Measurements were made of CCN concentrations, aerosol chemical composition in the size range relevant for particle activation, and aerosol size distributions. Variability in aerosol composition was parameterized by the mass fraction of Hydrocarbon-like Organic Aerosol (HOA) for particle diameters less than 200 nm (vacuum aerodynamic). The HOA mass fraction in this size range was lowest for marine aerosol and highest for aerosol sampled close to anthropogenic sources. Combining all data from the experiment reveals that composition (defined by HOA mass fraction) explains 40% of the variance in the critical diameter for particle activation at 0.44% supersaturation (S). Correlations between HOA mass fraction and aerosol mean diameter show that these two parameters are essentially independent of one another for this data set. We conclude that, based on the variability of the HOA mass fraction observed during TexAQS-GoMACCS, composition played a significant role in determining the fraction of particles that could activate to form cloud droplets. In addition, we estimate the error that results in calculated CCN concentrations if the HOA mass fraction is neglected (i.e., a fully soluble composition of (NH4)2SO4 is assumed) for the range of mass fractions and mean diameters observed during the experiment. This error is then related to the source of the aerosol. At 0.22 and 0.44% S, the error is considerable (>50%) for anthropogenic aerosol sampled near the source region as this aerosol had, on average, a high HOA mass fraction in the sub-200 nm diameter size range (vacuum aerodynamic). The error is lower for aerosol distant from anthropogenic source regions as it had a lower HOA mass fraction. Hence, the percent error in calculated CCN concentration is larger for organic-rich aerosol sampled near the source and smaller for aerosol sampled away from sources of anthropogenic particulate organic matter (POM).
Impacts of the solar eclipse of 29 March 2006 on the surface ozone and nitrogen dioxide concentrations at Athens, Greece
Authors: Tzanis C. , Varotsos C. , Viras L.
Published: April 2010

Abstract. The behavior of surface ozone and nitrogen dioxide concentration as well as the variations in various meteorological parameters before, during and after the total solar eclipse of 29 March 2006 has been examined. This analysis is based on measurements performed at four stations located in the greater Athens basin in Greece. The experimental data demonstrated that the solar eclipse phenomenon affects the surface ozone and nitrogen dioxide concentrations as well as the temperature, the relative humidity and the wind speed near the ground. The reduction of the solar ultraviolet radiation at 312 and 365 nm reached 97% and 93% respectively, while the air temperature dropped, the relative humidity increased and the wind speed decreased. The percentage change (decrease) of surface ozone concentration was maximized one hour after the maximum phase of the eclipse due to the decreased efficiency of the photochemical ozone formation. The surface nitrogen dioxide concentration increased and the time lag of the nitrogen dioxide response to the solar eclipse was found to be different for each station. A plausible cause for the increase in NO2 concentration may be the conversion of NO to NO2 through reaction with pre-existing O3 along with the low photolysis rates of NO2 as a consequence of the decreased solar radiation during the solar eclipse event.In general, the time response to the eclipse phenomenon was different for each of the aforementioned parameters.
Black carbon record based on a shallow Himalayan ice core and its climatic implications
Authors: Ming J. , Cachier H. , Xiao C. , Qin D. , Kang S. , Hou S. , Xu J.
Published: April 2010

Abstract. A continuous measurement for black carbon conducted on a shallow ice core extracted from the East Rongbuk glacier beside Mt. Qomolangma recovers the first historical record of black carbon 13 deposition in the past ~50 years in the high Asian cryosphere. Fast increasing trend of BC concentration is revealed since the mid-1990s. Backward air trajectory analysis indicates that South Asia's emission has significant impacts on the BC deposition in the East Rongbuk glacier. The estimated atmospheric BC concentration over the East Rongbuk glacier is about 80 ngC m−3. This suggests black carbon from South Asia's emission might penetrate into the Tibetan Plateau by 18 climbing over the elevated Himalayas. Considering the consequent extra solar radiative absorption over the glacier, it is suggested that this amplitude of BC concentration in the atmosphere over the Himalayas could not be neglected when assessing the warming effect on the surface of the glaciers on the Himalayas.
Extreme associated functions: optimally linking local extremes to large-scale atmospheric circulation structures
Authors: Panja D. , Selten F. M.
Published: April 2010

Abstract. We present a new statistical method to optimally link local weather extremes to large-scale atmospheric circulation structures. The method is illustrated using July–August daily mean temperature at 2 m height (T2m) time-series over the Netherlands and 500 hPa geopotential height (Z500) time-series over the Euroatlantic region of the ECMWF reanalysis dataset (ERA40). The method identifies patterns in the Z500 time-series that optimally describe, in a precise mathematical sense, the relationship with local warm extremes in the Netherlands. Two patterns are identified; the most important one corresponds to a blocking high pressure system leading to subsidence and calm, dry and sunny conditions over the Netherlands. The second one corresponds to a rare, easterly flow regime bringing warm, dry air into the region. The patterns are robust; they are also identified in shorter subsamples of the total dataset. The method is generally applicable and might prove useful in evaluating the performance of climate models in simulating local weather extremes.