bluuebunny/crossref_metadata_2025 huggingface dataset:
The importance of meteorological scales to forecast air pollution scenarios on coastal complex terrain
Authors: Palau J. L. , Pérez-Landa G. , Diéguez J. J. , Monter C. , Millán M. M.
Published: April 2010

Abstract. Some of the meteorological approaches commonly considered in urban air pollution models do not take into account the importance of the smaller scales in the meteorology of complex-terrain coastal sites. The aim of this work is to estimate the impact of using the proper meteorological scales when simulating the behaviour of the pollutant concentrations emitted in the lower layers over coastal complex terrain areas. The availability of experimental measurements of a power plant plume near the Castellón conurbation (on the Spanish Mediterranean coast) has allowed us to use this plume as a tracer of opportunity of the lower atmosphere to check the results of a simulation exercise using the RAMS mesoscale model coupled to the HYPACT particle model. The results obtained show that in a complex-terrain coastal site, because of the strong effect of the meteorological interactions between the different scales on the integral advection and the turbulent dispersion of pollutants, using an inadequate scale to solve the meteorology can result in a very big gap in the simulation of lower-layer pollutant behaviour at urban scales.
Technical note: A stratospheric climatology for O3, H2O, CH4, NOx, HCl and HF derived from HALOE measurements
Authors: Grooß J.-U. , Russell James M.
Published: April 2010

Abstract. The Halogen Occultation Experiment (HALOE) on board the Upper Atmosphere Research Satellite (UARS) has observed mixing ratios of important trace species in the stratosphere for more than a decade since 1991. Here we present a climatology for the stratosphere compiled from HALOE O3, H2O, CH4, NOx, HCl, and HF data for the period from 1991 to 2002. In this approach, the data are averaged over equivalent latitude instead of latitude in order to correctly reproduce the gradients at the transport barriers like the polar vortex edge. The climatology is compiled for 5 degree equivalent latitude bins. Seasonal dependence is taken into account by choosing intervals of one month. The climatology is available as an electronic supplement.
On the isolation of elemental carbon (EC) for micro-molar 14C accelerator mass spectrometry: development of a hybrid reference material for 14C-EC accuracy assurance, and a critical evaluation of the thermal optical kinetic (TOK) EC isolation procedure
Authors: Currie L. A. , Kessler J. D.
Published: April 2010

Abstract. The primary objective of the research reported here has been the development of a hybrid reference material (RM) to serve as a test of accuracy for elemental carbon (EC) isotopic (14C) speciation measurements. Such measurements are vital for the quantitative apportionment of fossil and biomass sources of "soot" (EC), the tracer of fire that has profound effects on health, atmospheric visibility, and climate. Previous studies of 14C-EC measurement quality, carried out with NIST SRM 1649a (Urban Dust), showed a range of results, but since the "truth" was not known for this natural matrix RM, one had to rely on isotopic-chemical consistency evidence (14C in PAH, EC) of measurement validity (Currie et al., 2002). Components of the new Hybrid RM (DiesApple), however, have known 14C and EC composition, and they are nearly orthogonal (isotopically and chemically). NIST SRM 2975 (Forklift Diesel Soot) has little or no 14C, and its major compositional component is EC; SRM 1515 (Apple Leaves) has the 14C content of biomass-C, and it has little or no EC. Thus, the Hybrid RM can serve as an absolute isotopic test for the absence of EC-mimicking pyrolysis-C (char) from SRM 1515 in the EC isolate of the Hybrid RM, as well as a test for conservation of its dominant soot fraction throughout the isolation procedure. The secondary objective was to employ the Hybrid RM for the comparative evaluation of the thermal optical kinetic (TOK) and thermal optical transmission (TOT) methods for the isolation of EC for micro-molar carbon accelerator mass spectrometry (AMS). As part of this process, the relatively new TOK method was subjected to a critical evaluation and significant development. Key findings of our study are: (1) both methods exhibited biomass-C "leakage"; for TOT, the EC fraction isolated for AMS contained about 8% of the original biomass-C; for TOK, the refractory carbon (RC) isolated contained about 3% of the original biomass-C.; (2) the initial isothermal oxidation stage of the TOK method substantially reduced the transfer of artifact char to the RC fraction, improving isolation capabilities; (3) the Hybrid RM was not equal to the sum of its parts, with matrix interactions inducing premature loss of EC which, however, could be quantified and minimized; (4) the three-stage TOK method provided a superior capability for carbonate quantification at the sub-micromolar level, with "reagent-free" removal of carbonate-C from EC – essential for low-level EC-14C AMS.
Global carbon monoxide vertical distributions from spaceborne high-resolution FTIR nadir measurements
Authors: Barret B. , Turquety S. , Hurtmans D. , Clerbaux C. , Hadji-Lazaro J. , Bey I. , Auvray M. , Coheur P.-F.
Published: April 2010

Abstract. This paper presents the first global distributions of CO vertical profiles retrieved from a thermal infrared FTS working in the nadir geometry. It is based on the exploitation of the high resolution and high quality spectra measured by the Interferometric Monitor of Greenhouse gases (IMG) which flew onboard the Japanese ADEOS platform in 1996-1997. The retrievals are performed with an algorithm based on the Optimal Estimation Method (OEM) and are characterized in terms of vertical sensitivity and error budget. It is found that most of the IMG measurements contain between 1.5 and 2.2 independent pieces of information about the vertical distribution of CO from the lower troposphere to the upper troposphere-lower stratosphere (UTLS). The retrievals are validated against coincident NOAA/CMDL in situ surface measurements and NDSC/FTIR total columns measurements. The retrieved global distributions of CO are also found to be in good agreement with the distributions modeled by the GEOS-CHEM 3D CTM, highlighting the ability of IMG to capture the horizontal as well as the vertical structure of the CO distributions.
The mean meridional circulation and midlatitude ozone buildup
Authors: Nikulin G. , Karpechko A.
Published: April 2010

Abstract. The wintertime ozone buildup over the Northern Hemisphere (NH) midlatitudes and its connection with the mean meridional circulation in the stratosphere are examined statistically on a monthly basis from October to March (1980–2002). The ozone buildup begins locally in October with positive total ozone tendencies over the North Pacific, which spread eastward and westward in November and finally cover all midlatitudes in December. The local onset of the buildup in October is not evident in zonal mean ozone tendency, which is close to zero. From November to March, zonal mean total ozone tendency (50°–60° N) shows a strong correlation (|r|=0.7) with several zonal mean parameters associated to the mean meridional circulation, namely: eddy heat flux, temperature tendency, the vertical residual velocity and the residual streamfunction. At the same time, on the latitude-altitude cross section, correlation patterns between ozone tendency and widely used eddy heat flux are not uniform during winter. The strongest correlations are located equatorward (almost throughout the stratosphere) or poleward (only in the lower stratosphere) of the edge of the polar vortex. Such distribution may depend on the existence of the midlatitude and polar waveguides which defined refraction of upward propagating waves from the troposphere either to the midlatitude stratosphere or to the polar stratosphere. As a consequence of the nonuniform correlation patterns, heat flux averaged over the common region 45°–75° N, 100 hPa is not always an optimum proxy for statistical models describing total ozone variability in midlatitudes. Other parameters approximating the strength of the mean meridional circulation have more uniform and stable correlation patterns with ozone tendency during winter. We show that the NH midlatitude ozone buildup has a stable statistical relationship with the mean meridional circulation in all months from October to March and half of the interannual variability in monthly ozone tendencies can be explained by applying different proxies of the mean meridional circulation.
Daily CO2 flux estimates over Europe from continuous atmospheric measurements: 1, inverse methodology
Authors: Peylin P. , Rayner P. J. , Bousquet P. , Carouge C. , Hourdin F. , Heinrich P. , Ciais P. ,   AEROCARB contributors
Published: April 2010

Abstract. This paper presents an inverse method for inferring trace gas fluxes at high temporal (daily) and spatial (model grid) resolution from continuous atmospheric concentration measurements. The method is designed for regional applications and for use in intensive campaigns. We apply the method to a one month inversion of fluxes over Europe. We show that the information added by the measurements depends critically on the smoothness constraint assumed among the source components. We show that the initial condition affects the inversion for 20 days, provided one has enough observing sites to constrain regional fluxes. We show that the impact of the far-field fluxes grows throughout the inversion and hence a reasonable global flux field is a prerequisite for a regional inversion.
Simulating aerosol microphysics with the ECHAM/MADE GCM – Part I: Model description and comparison with observations
Authors: Lauer A. , Hendricks J. , Ackermann I. , Schell B. , Hass H. , Metzger S.
Published: April 2010

Abstract. The aerosol dynamics module MADE has been coupled to the general circulation model ECHAM4 to simulate the chemical composition, number concentration, and size distribution of the global submicrometer aerosol. The present publication describes the new model system ECHAM4/MADE and presents model results in comparison with observations. The new model is able to simulate the full life cycle of particulate matter and various gaseous particle precursors including emissions of primary particles and trace gases, advection, convection, diffusion, coagulation, condensation, nucleation of sulfuric acid vapor, aerosol chemistry, cloud processing, and size-dependent dry and wet deposition. Aerosol components considered are sulfate (SO4), ammonium (NH4), nitrate (NO3), black carbon (BC), particulate organic matter (POM), sea salt, mineral dust, and aerosol liquid water. The model is numerically efficient enough to allow long term simulations, which is an essential requirement for application in general circulation models. Since the current study is focusing on the submicrometer aerosol, a coarse mode is not being simulated. The model is run in a passive mode, i.e. no feedbacks between the MADE aerosols and clouds or radiation are considered yet. This allows the investigation of the effect of aerosol dynamics, not interfered by feedbacks of the altered aerosols on clouds, radiation, and on the model dynamics. In order to evaluate the results obtained with this new model system, calculated mass concentrations, particle number concentrations, and size distributions are compared to observations. The intercomparison shows, that ECHAM4/MADE is able to reproduce the major features of the geographical patterns, seasonal cycle, and vertical distributions of the basic aerosol parameters. In particular, the model performs well under polluted continental conditions in the northern hemispheric lower and middle troposphere. However, in comparatively clean remote areas, e.g. in the upper troposphere or in the southern hemispheric marine boundary layer, the current model version tends to underestimate particle number concentrations.
A look at aerosol formation using data mining techniques
Authors: Hyvönen S. , Junninen H. , Laakso L. , Dal Maso M. , Grönholm T. , Bonn B. , Keronen P. , Aalto P. , Hiltunen V. , Pohja T. , Launiainen S. , Hari P. , Mannila H. , Kulmala M.
Published: April 2010

Abstract. Atmospheric aerosol particle formation is frequently observed throughout the atmosphere, but despite various attempts of explanation, the processes behind it remain unclear. In this study data mining techniques were used to find the key parameters needed for atmospheric aerosol particle formation to occur. A dataset of 8 years of 80 variables collected at the boreal forest station (SMEAR II) in Southern Finland was used, incorporating variables such as radiation, humidity, SO2, ozone and present aerosol surface area. This data was analyzed using clustering and classification methods. The aim of this approach was to gain new parameters independent of any subjective interpretation. This resulted in two key parameters, relative humidity and preexisting aerosol particle surface (condensation sink), capable in explaining 88% of the nucleation events. The inclusion of any further parameters did not improve the results notably. Using these two variables it was possible to derive a nucleation probability function. Interestingly, the two most important variables are related to mechanisms that prevent the nucleation from starting and particles from growing, while parameters related to initiation of particle formation seemed to be less important. Nucleation occurs only with low relative humidity and condensation sink values. One possible explanation for the effect of high water content is that it prevents biogenic hydrocarbon ozonolysis reactions from producing sufficient amounts of low volatility compounds, which might be able to nucleate. Unfortunately the most important biogenic hydrocarbon compound emissions were not available for this study. Another effect of water vapour may be due to its linkage to cloudiness which may prevent the formation of nucleating and/or condensing vapours. A high number of preexisting particles will act as a sink for condensable vapours that otherwise would have been able to form sufficient supersaturation and initiate the nucleation process.
Measurements of tropospheric NO2 with an airborne multi-axis DOAS instrument
Authors: Wang P. , Richter A. , Bruns M. , Rozanov V. V. , Burrows J. P. , Heue K.-P. , Wagner T. , Pundt I. , Platt U.
Published: April 2010

Abstract. The AMAXDOAS instrument is an airborne multi-axis DOAS instrument covering the spectral range from 300 to 600 nm. During one flight of the SCIAVALUE campaign on 19 March 2003, the AMAXDOAS onboard the DLR Falcon detected tropospheric NO2 over Europe under both cloudy and cloud free conditions. By combining the measurements in nadir and zenith direction, and analysing the spectra in the UV and the visible spectral region, information was derived on where the bulk of the observed NO2 was located. Vertical columns of up to 5.7x1016 molec cm-2 were observed close to Frankfurt, with a distribution peaking in the boundary layer and in good agreement with surface measurements. On several occasions, strong tropospheric NO2 signals were also detected when flying above clouds. The ratio of zenith and nadir measurements indicates that the NO2 observed was located within the cloud, and assuming the same profile as for the cloud free situation the NO2 vertical column was estimated to be 5.0x1016 molec cm-2. The results are relevant for the retrieval of tropospheric NO2 columns from space-borne instruments in cloudy situations.
Sensitivity of Global Modeling Initiative chemistry and transport model simulations of radon-222 and lead-210 to input meteorological data
Authors: Considine D. B. , Bergmann D. J. , Liu H.
Published: April 2010

Abstract. We have used the Global Modeling Initiative chemistry and transport model to simulate the radionuclides radon-222 and lead-210 using three different sets of input meteorological information: 1. Output from the Goddard Space Flight Center Global Modeling and Assimilation Office GEOS-STRAT assimilation; 2. Output from the Goddard Institute for Space Studies GISS II' general circulation model; and 3. Output from the National Center for Atmospheric Research MACCM3 general circulation model. We intercompare these simulations with observations to determine the variability resulting from the different meteorological data used to drive the model, and to assess the agreement of the simulations with observations at the surface and in the upper troposphere/lower stratosphere region. The observational datasets we use are primarily climatologies developed from multiple years of observations. In the upper troposphere/lower stratosphere region, climatological distributions of lead-210 were constructed from ~25 years of aircraft and balloon observations compiled into the US Environmental Measurements Laboratory RANDAB database. Taken as a whole, no simulation stands out as superior to the others. However, the simulation driven by the NCAR MACCM3 meteorological data compares better with lead-210 observations in the upper troposphere/lower stratosphere region. Comparisons of simulations made with and without convection show that the role played by convective transport and scavenging in the three simulations differs substantially. These differences may have implications for evaluation of the importance of very short-lived halogen-containing species on stratospheric halogen budgets.
Kinetics and mechanism of the uptake of N2O5 on mineral dust at 298 K
Authors: Seisel S. , Börensen C. , Vogt R. , Zellner R.
Published: April 2010

Abstract. The heterogeneous reaction of N2O5 with mineral (Saharan) dust has been studied at T=298 K using a combination of Knudsen and DRIFTS cells for kinetic and product investigations, respectively. The initial uptake coefficient has been determined to be γ=(8.0±0.3)·10−2. This uptake slowly saturates into a steady state uptake of γ=(1.3±0.3)·10−2 suggesting that reaction of N2O5 with the mineral dust surface and hydrolysis of N2O5 on the surface take place simultaneously. Both uptake coefficients have been calculated on the basis of the geometric (projected) surface area of the sample and must therefore be regarded as upper limits. In addition, the product investigations show that N2O5 is irreversibly taken up to form nitrate on the surface. Recent model calculations suggest that the uptake rates of N2O5 on Saharan dust which we measured may be large enough to influence the photo-oxidant budget of the atmosphere.
On the changing seasonal cycles and trends of ozone at Mace Head, Ireland
Authors: Carslaw D. C.
Published: April 2010

Abstract. A seasonal-trend decomposition technique based on a locally-weighted regression smoothing (Loess) approach has been used to decompose monthly ozone concentrations at Mace Head (Ireland) into trend, seasonal and irregular components. The trend component shows a steady increase from 1990–2004, which is confirmed by statistical testing which shows that ozone concentrations at Mace Head have increased at the p=0.06 level by 0.18±0.04 ppb yr−1. By considering different air mass origins using a trajectory analysis, it has been possible to separate air masses into "polluted" and "unpolluted" origins. The seasonal-trend decomposition technique confirms the different seasonal cycles of these air mass origins with unpolluted air mass maxima in April and polluted air mass maxima in July/August. A detailed consideration of the seasonal component reveals different behaviour depending on the air mass origin. For baseline unpolluted air arriving at Mace Head there has been a gradual increase in the seasonal amplitude, driven by a declining summertime component. The amplitude of the seasonal component of baseline air is controlled by a maximum in April and a minimum in July. For polluted air mass trajectories, there was a substantial reduction in the amplitude of the seasonal component from 1990–1997. However, post-1997 results indicate that the seasonal amplitude in polluted air masses arriving at Mace Head is increasing. Furthermore, there has been a shift in the months controlling the size of the seasonal amplitude in polluted air from a maximum in May and minimum in January in 1990 to a maximum in April and a minimum in July by 2001. This finding suggests that there has been a steadily decreasing influence of polluted air masses arriving from Europe. These air masses have therefore increasingly taken on the attributes of baseline air.
Oxygenated compounds in aged biomass burning plumes over the Eastern Mediterranean: evidence for strong secondary production of methanol and acetone
Authors: Holzinger R. , Williams J. , Salisbury G. , Klüpfel T. , de Reus M. , Traub M. , Crutzen P. J. , Lelieveld J.
Published: April 2010

Abstract. Airborne measurements of acetone, methanol, PAN, acetonitrile (by Proton Transfer Reaction Mass Spectrometry), and CO (by Tunable Diode Laser Absorption Spectroscopy) have been performed during the Mediterranean Intensive Oxidants Study (MINOS August 2001). We have identified ten biomass burning plumes from strongly elevated acetonitrile mixing ratios. The characteristic biomass burning signatures obtained from these plumes reveal secondary production of acetone and methanol, while CO photochemically declines in the plumes. Mean excess mixing ratios - normalized to CO - of 1.8%, 0.20%, 3.8%, and 0.65% for acetone, acetonitrile, methanol, and PAN, respectively, were found. By scaling to an assumed global annual source of 663-807Tg CO, biomass burning emissions of 25-31 and 29-35 Tg/yr for acetone and methanol are estimated, respectively. Our measurements suggest that the present biomass burning contributions of acetone and methanol are significantly underestimated due to the neglect of secondary formation within the plume. Median acetonitrile mixing ratios throughout the troposphere were around 150pmol/mol, in accord with current biomass burning inventories and an atmospheric lifetime of ~6 months.
Using a photochemical model for the validation of NO2 satellite measurements at different solar zenith angles
Authors: Bracher A. , Sinnhuber M. , Rozanov A. , Burrows J. P.
Published: April 2010

Abstract. SCIAMACHY (Scanning Imaging Spectrometer for Atmospheric Chartography) aboard the recently launched Environmental Satellite (ENVISAT) of ESA is measuring solar radiance upwelling from the atmosphere and the extraterrestrial irradiance. Appropriate inversion of the ultraviolet and visible radiance measurements, observed from the atmospheric limb, yields profiles of nitrogen dioxide, NO2, in the stratosphere (SCIAMACHY-IUP NO2 profiles V1). In order to assess their accuracy, the resulting NO2 profiles have been compared with those retrieved from the space borne occultation instruments Halogen Occultation Experiment (HALOE, data version v19) and Stratospheric Aerosol and Gas Experiment II (SAGE II, data version 6.2). As the HALOE and SAGE II measurements are performed during local sunrise or sunset and because NO2 has a significant diurnal variability, the NO2 profiles derived from HALOE and SAGE II have been transformed to those predicted for the solar zenith angles of the SCIAMACHY measurement by using a 1-dimensional photochemical model. The model used to facilitate the comparison of the NO2 profiles from the different satellite sensors is described and a sensitivity ananlysis provided. Comparisons between NO2 profiles from SCIAMACHY and those from HALOE NO2 but transformed to the SCIAMACHY solar zenith angle, for collocations from July to October 2002, show good agreement (within +/-12%) between the altitude range from 22 to 33km. The results from the comparison of all collocated NO2 profiles from SCIAMACHY and those from SAGE II transformed to the SCIAMACHY solar zenith angle show a systematic negative bias of 10 to 35% between 20km to 38km with a small standard deviation between 5 to 14%. These results agree with those of Newchurch and Ayoub (2004), implying that above 20km NO2 profiles from SAGE II sunset are probably somewhat high.
A practical demonstration on AMSU retrieval precision for upper tropospheric humidity by a non-linear multi-channel regression method
Authors: Jiménez C. , Eriksson P. , John V. O. , Buehler S. A.
Published: April 2010

Abstract. A neural network algorithm inverting selected channels from the Advance Microwave Sounding Unit instruments AMSU-A and AMSU-B was applied to retrieve layer averaged relative humidity. The neural network was trained with a global synthetic dataset representing clear-sky conditions. A precision of around 6% was obtained when retrieving global simulated radiances, the precision deteriorated less than 1% when real mid-latitude AMSU radiances were inverted and compared with co-located data from a radiosonde station. The 6% precision outperforms by 1% the reported precision estimate from a linear single-channel regression between radiance and weighting function averaged relative humidity, the more traditional approach to exploit AMSU data. Added advantages are not only a better precision; the AMSU-B humidity information is more optimally exploited by including temperature information from AMSU-A channels; and the layer averaged humidity is a more physical quantity than the weighted humidity, for comparison with other datasets. The training dataset proved adequate for inverting real radiances from a mid-latitude site, but it is limited by not considering the impact of clouds or surface emissivity changes, and further work is needed in this direction for further validation of the precision estimates.
Improved mid-infrared cross-sections for peroxyacetyl nitrate (PAN) vapour
Authors: Allen G. , Remedios J. J. , Newnham D. A. , Smith K. M. , Monks P. S.
Published: April 2010

Abstract. Absorption spectra of peroxyacetyl nitrate (PAN, CH3C(O)OONO2) vapour at room temperature (295K) have been measured in the mid-infrared range, 550-2200cm-1 (18.2-4.55µm), using a Fourier Transform infrared spectrometer at instrument resolutions of 0.25 and 0.03cm-1 (unapodised). Between five and eight measurements were obtained for each spectral band of PAN in the pressure range 0.24-2.20mb showing good agreement with Beer's law. Both cross-section data and integrated absorption intensities for the five principal bands in the PAN spectra in this spectral range have been derived with peak cross-sections of the 794, 1163, 1302, 1741 and 1842cm-1 bands measured to be 0.95(±0.02), 1.21(±0.03), 0.92(±0.02), 2.39(±0.06) and 0.74(±0.03) (x10-18cm2molecule-1) respectively. Band intensities and band centre absorptivities are also reported for four weaker PAN absorption bands in the mid infrared for the first time. These observations are the highest spectral resolution measurements of PAN bands reported in the infrared to date. For three of the five strongest bands, the absolute integrated absorption intensities are in excellent agreement with previous studies. A 4.8% lower integrated intensity was found for the 1741cm-1νas(NO2) PAN absorption band, possibly as a result of the removal in this work of spectra affected by acetone contamination, while a 10.6% higher intensity was determined for the 1163cm-1ν(C-O) absorption band. No resolution of fine structure in the PAN absorption bands was observed at the resolutions studied. The confirmation of absorption cross-sections and estimated errors in this work will allow more accurate investigations of PAN using infrared spectroscopy, particularly for remote sensing of PAN in the atmosphere.
Microphysics and heterogeneous chemistry in aircraft plumes - high sensitivity on local meteorology and atmospheric composition
Authors: Meilinger S. K. , Kärcher B. , Peter Th.
Published: April 2010

Abstract. An aircraft plume model has been developed on the basis of two coupled trajectory box models. Two boxes, one for plume and one for background conditions, are coupled by means of a mixing parameterization based on turbulence theory. The model considers comprehensive gas phase chemistry for the tropopause region including acetone, ethane and their oxidation products. Heterogeneous halogen, N2O5 and HOx chemistry on various types of background and aircraft-induced aerosols (liquid and ice) is considered, using state-of-the-art solubility dependent uptake coefficients for liquid phase reactions. The microphysical scheme allows for coagulation, gas-diffusive particle growth and evaporation, so that the particle development from 1s after emission to several days can be simulated. Model results are shown, studying emissions into the upper troposphere as well as into the lowermost stratosphere for contrail and non-contrail conditions. We show the microphysical and chemical evolution of spreading plumes and use the concept of mean plume encounter time, tl, to define effective emission and perturbation indices (EEIs and EPIs) for the North Atlantic Flight Corridor (NAFC) showing EEI(NOy) and EPI(O3) for various background conditions, such as relative humidity, local time of emission, and seasonal variations. Our results show a high sensitivity of EEI and EPIs on the exact conditions under which emissions take place. The difference of EEIs with and without considering plume processes indicates that these processes cannot be neglected.
Measurements of total odd nitrogen (NOy) aboard MOZAIC in-service aircraft: instrument design, operation and performance
Authors: Volz-Thomas A. , Berg M. , Heil T. , Houben N. , Lerner A. , Petrick W. , Raak D. , Pätz H.-W.
Published: April 2010

Abstract. A small system for the unattended measurement of total odd nitrogen (NOy, i.e., the sum of NO and its atmospheric oxidation products) aboard civil in-service aircraft in the framework of MOZAIC is described. The instrument employs the detection of NO by its chemiluminescence with O3 in combination with catalytic conversion of the other NOy compounds to NO at 300°C on a gold surface in the presence of H2. The instrument has a sensitivity of 0.4-0.7cps/ppt and is designed for unattended operation during 1-2 service cycles of the aircraft (400-800 flight hours). The total weight is 50kg, including calibration system, compressed gases, mounting, and safety measures. The layout and inlet configuration are governed by requirements due to the certification for passenger aircraft. Laboratory tests are described regarding the conversion efficiency for NO2 and HNO3 (both >98%). Interference by non-NOy species is <1% for CH3CN and NH3, <5x10-5% for N2O (corresponding to <0.2ppt fake NOy from ambient N2O) and 100% for HCN. The time response of the instrument is <1s (90% change) for NO2. The response for HNO3 is nonlinear: 20s for 67%, 60s for 80%, and 150s for 90% response, respectively.
A re-evaluation of the ClO/Cl2O2 equilibrium constant based on stratospheric in-situ observations
Authors: von Hobe M. , Grooß J.-U. , Müller R. , Hrechanyy S. , Winkler U. , Stroh F.
Published: April 2010

Abstract. In-situ measurements of ClO and its dimer carried out during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation campaigns in the Arctic winter 2003 suggest that the thermal equilibrium between the dimer formation and dissociation is shifted significantly towards the monomer compared to the current JPL 2002 recommendation. Detailed analysis of observations made in thermal equilibrium allowed to re-evaluate the magnitude and temperature dependence of the equilibrium constant. A fit of the JPL format for equilibrium constants yields KEQ=3.61x10-27exp(8167/T), but to reconcile the observations made at low temperatures with the existing laboratory studies at room temperature, a modified equation, KEQ=5.47x10-25(T/300)-2.29exp(6969/T), is required. This format can be rationalised by a strong temperature dependence of the reaction enthalpy possibly induced by Cl2O2 isomerism effects. At stratospheric temperatures, both equations are practically equivalent. Using the equilibrium constant reported here rather than the JPL 2002 recommendation in atmospheric models does not have a large impact on simulated ozone loss. Solely at large zenith angles after sunrise, a small decrease of the ozone loss rate due to the ClO dimer cycle and an increase due to the ClO-BrO cycle (attributed to the enhanced equilibrium ClO concentrations) is observed, the net effect being a slightly stronger ozone loss rate.
Ice supersaturations exceeding 100% at the cold tropical tropopause: implications for cirrus formation and dehydration
Authors: Jensen E. J. , Smith J. B. , Pfister L. , Pittman J. V. , Weinstock E. M. , Sayres D. S. , Herman R. L. , Troy R. F. , Rosenlof K. , Thompson T. L. , Fridlind A. M. , Hudson P. K. , Cziczo D. J. , Heymsfield A. J. , Schmitt C. , Wilson J. C.
Published: April 2010

Abstract. Recent in situ measurements at tropical tropopause temperatures as low as 187 K indicate supersaturations with respect to ice exceeding 100% with little or no ice present. In contrast, models used to simulate cloud formation near the tropopause assume a supersaturation threshold for ice nucleation of about 65% based on laboratory measurements of aqueous aerosol freezing. The high supersaturations reported here, along with cloud simulations assuming a plausible range of temperature histories in the sampled air mass, indicate that the vast majority of aerosols in the air sampled on this flight must have had supersaturation thresholds for ice nucleation exceeding 100% (i.e. near liquid water saturation at these temperatures). Possible explanations for this high threshold are that (1) the expressions used for calculating vapor pressure over supercooled water at low temperatures give values are at least 20% too low, (2) organic films on the aerosol surfaces reduce their accommodation coefficient for uptake of water, resulting in aerosols with more concentrated solutions when moderate-rapid cooling occurs and correspondingly inhibited homogeneous freezing, and (3) if surface freezing dominates, organic coatings may increase the surface energy of the ice embryo/vapor interface resulting in suppressed ice nucleation. Simulations of in situ cloud formation in the tropical tropopause layer (TTL) throughout the tropics indicate that if decreased accommodation coefficients and resulting high thresholds for ice nucleation prevailed throughout the tropics, then the calculated occurrence frequency and areal coverage of TTL cirrus would be significantly suppressed. However, the simulations also show that even if in situ TTL cirrus form only over a very small fraction of the tropics in the western Pacific, enough air passes through them due to rapid horizontal transport such that they can still effectively freeze-dry air entering the stratosphere. The TTL cirrus simulations show that even if very large supersaturations are required for ice nucleation, these large supersaturations should occur very rarely.
Estimating the NOx produced by lightning from GOME and NLDN data: a case study in the Gulf of Mexico
Authors: Beirle S. , Spichtinger N. , Stohl A. , Cummins K. L. , Turner T. , Boccippio D. , Cooper O. R. , Wenig M. , Grzegorski M. , Platt U. , Wagner T.
Published: April 2010

Abstract. Nitrogen oxides (NOxNO+NO2) play an important role in tropospheric chemistry, in particular in catalytic ozone production. Lightning provides a natural source of nitrogen oxides, dominating the production in the tropical upper troposphere, with strong impact on tropospheric ozone and the atmosphere's oxidizing capacity. Recent estimates of lightning produced NOx (LNOx) are of the order of 5 Tg [N] per year with still high uncertainties in the range of one order of magnitude. The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows the retrieval of tropospheric column densities of NO2 on a global scale. Here we present the GOME NO2 measurement directly over a large convective system over the Gulf of Mexico. Simultaneously, cloud-to-ground (CG) flashes are counted by the U.S. National Lightning Detection Network (NLDNTM), and extrapolated to include intra-cloud (IC)+CG flashes based on a climatological IC:CG ratio derived from NASA's space-based lightning sensors. A series of 14 GOME pixels shows largely enhanced column densities over thick and high clouds, coinciding with strong lightning activity. The enhancements can not be explained by transport of anthropogenic NOx and must be due to fresh production of LNOx. A quantitative analysis, accounting in particular for the visibility of LNOx from satellite, yields a LNOx production of 90 (32-240) moles of NOx, or 1.3 (0.4-3.4) kg [N], per flash. If simply extrapolated, this corresponds to a global LNOx production of 1.7 (0.6-4.7)Tg [N]/yr.
A study of dispersion in complex terrain under winter conditions using high-resolution mesoscale and Lagrangian particle models
Authors: Palau J. L. , Pérez-Landa G. , Meliá J. , Segarra D. , Millán M. M.
Published: April 2010

Abstract. A mesoscale model (MM5), a dispersive Langrangian particle model (FLEXPART), and intensive meteorological and COrrelation SPECtrometer (COSPEC) measurements from a field campaign are used to examine the advection and turbulent diffusion patterns associated with interactions and forcings between topography, synoptic atmospheric flows and thermally-driven circulations. This study describes the atmospheric dispersion of emissions from a power plant with a 343-m tall chimney, situated on very complex terrain in the North-East of Spain, under winter conditions. During the field campaign, the plume was transported with low transversal dispersion and deformed essentially due to the effect of mechanical turbulence. The main surface impacts appeared at long distances from the emission source (more than 30 km). The results show that the coupled models (MM5 and FLEXPART) are able to predict the plume integral advection from the power plant on very complex terrain. Integral advection and turbulent dispersion are derived from the dispersive Lagrangian model output for three consecutive days so that a direct quantitative comparison has been made between the temporal evolution of the predicted three-dimensional dispersive conditions and the COSPEC measurements. Comparison between experimental and simulated transversal dispersion shows an index of agreement between 80% and 90%, within distance ranges from 6 to 33 km from the stack. Linked to the orographic features, the simulated plume impacts on the ground more than 30 km away from the stack, because of the lee waves simulated by MM5.
OH and HO2 chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake
Authors: Sommariva R. , Bloss W. J. , Brough N. , Carslaw N. , Flynn M. , Haggerstone A.-L. , Heard D. E. , Hopkins J. R. , Lee J. D. , Lewis A. C. , McFiggans G. , Monks P. S. , Penkett S. A. , Pilling M. J. , Plane J. M. C. , Read K. A. , Saiz-Lopez A. , Rickard A. R. , Williams P. I.
Published: April 2010

Abstract. Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM), have been used to study the chemistry of OH and HO2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland) in summer 2002. The base models, which were constrained to measured CO, CH4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO2] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone), highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO) and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO2] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HOx was dependant on the uptake coefficients used for HOI, HOBr and HO2. Better agreement, within the combined uncertainties of the measurements and of the model, was achieved when using high uptake coefficients for HO2 and HOI (γHO2=1, γHOI=0.6). A rate of production and destruction analysis of the models allowed a detailed study of OH and HO2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br) as co-reactants for OH and HO2 and of HOX photolysis as a source for OH.
Convective formation of pileus cloud near the tropopause
Authors: Garrett T. J. , Dean-Day J. , Liu C. , Barnett B. , Mace G. , Baumgardner D. , Webster C. , Bui T. , Read W. , Minnis P.
Published: April 2010

Abstract. Pileus clouds form where humid, vertically stratified air is mechanically displaced ahead of rising convection. This paper describes convective formation of pileus cloud in the tropopause transition layer (TTL), and explores a possible link to the formation of long-lasting cirrus at cold temperatures. The study examines in detail in-situ measurements from off the coast of Honduras during the July 2002 CRYSTAL-FACE experiment that showed an example of TTL cirrus associated with, and penetrated by, deep convection. The TTL cirrus was enriched with total water compared to its surroundings, but was composed of extremely small ice crystals with effective radii between 2 and 4 μm. Through gravity wave analysis, and intercomparison of measured and simulated cloud microphysics, it is argued that the TTL cirrus originated neither from convectively-forced gravity wave motions nor environmental mixing alone. Rather, it is hypothesized that a combination of these two processes was involved in which, first, a pulse of convection forced pileus cloud to form from TTL air; second, the pileus layer was punctured by the convective pulse and received larger ice crystals through interfacial mixing; third, the addition of this condensate inhibited evaporation of the original pileus ice crystals where a convectively forced gravity wave entered its warm phase; fourth, through successive pulses of convection, a sheet of TTL cirrus formed. While the general incidence and longevity of pileus cloud remains unknown, in-situ measurements, and satellite-based Microwave Limb Sounder retrievals, suggest that much of the tropical TTL is sufficiently humid to be susceptible to its formation. Where these clouds form and persist, there is potential for an irreversible repartition from water vapor to ice at cold temperatures.
Distinct wind convergence patterns in the Mexico City basin due to the interaction of the gap winds with the synoptic flow
Authors: de Foy B. , Clappier A. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. Mexico City lies in a high altitude basin where air quality and pollutant fate is strongly influenced by local winds. The combination of high terrain with weak synoptic forcing leads to weak and variable winds with complex circulation patterns. A gap wind entering the basin in the afternoon leads to very different wind convergence lines over the city depending on the meteorological conditions. Surface and upper-air meteorological observations are analysed during the MCMA-2003 field campaign to establish the meteorological conditions and obtain an index of the strength and timing of the gap wind. A mesoscale meteorological model (MM5) is used in combination with high-resolution satellite data for the land surface parameters and soil moisture maps derived from diurnal ground temperature range. A simple method to map the lines of wind convergence both in the basin and on the regional scale is used to show the different convergence patterns according to episode types. The gap wind is found to occur on most days of the campaign and is the result of a temperature gradient across the southern basin rim which is very similar from day to day. Momentum mixing from winds aloft into the surface layer is much more variable and can determine both the strength of the flow and the pattern of the convergence zones. Northerly flows aloft lead to a weak jet with an east-west convergence line that progresses northwards in the late afternoon and early evening. Westerlies aloft lead to both stronger gap flows due to channelling and winds over the southern and western basin rim. This results in a north-south convergence line through the middle of the basin starting in the early afternoon. Improved understanding of basin meteorology will lead to better air quality forecasts for the city and better understanding of the chemical regimes in the urban atmosphere.
Seasonal variability of monoterpene emission factors for a ponderosa pine plantation in California
Authors: Holzinger R. , Lee A. , McKay M. , Goldstein A. H.
Published: April 2010

Abstract. Monoterpene fluxes have been measured over an 11 month period from June 2003 to April 2004. During all seasons ambient air temperature was the environmental factor most closely related to the measured emission rates. The monoterpene flux was modeled using a basal emission rate multiplied by an exponential function of a temperature, following the typical practice for modelling temperature dependent biogenic emissions. A basal emission of 1.0 μmol h−1 m−2 (at 30°C, based on leaf area) and a temperature dependence (β) of 0.12°C−1 reproduced measured summer emissions well but underestimated spring and winter measured emissions by 60–130%. The total annual monoterpene emission may be underestimated by ~50% when using a model optimized to reproduce monoterpene emissions in summer. The long term dataset also reveals an indirect connection between non-stomatal ozone and monoterpene flux beyond the dependence on temperature that has been shown for both fluxes.
Inter-comparison of stratospheric O3 and NO2 abundances retrieved from balloon borne direct sun observations and Envisat/SCIAMACHY limb measurements
Authors: Butz A. , Bösch H. , Camy-Peyret C. , Chipperfield M. , Dorf M. , Dufour G. , Grunow K. , Jeseck P. , Kühl S. , Payan S. , Pepin I. , Pukite J. , Rozanov A. , von Savigny C. , Sioris C. , Wagner T. , Weidner F. , Pfeilsticker K.
Published: April 2010

Abstract. Stratospheric O3 and NO2 abundances measured by different remote sensing instruments are inter-compared: (1) Line-of-sight absorptions and vertical profiles inferred from solar spectra in the ultra-violet (UV), visible and infrared (IR) wavelength ranges measured by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) balloon payload during balloon ascent/descent and solar occultation are examined with respect to internal consistency. (2) The balloon borne stratospheric profiles of O3 and NO2 are compared to collocated space-borne skylight limb observations of the Envisat/SCIAMACHY satellite instrument. The trace gas profiles are retrieved from SCIAMACHY spectra using different algorithms developed at the Universities of Bremen and Heidelberg and at the Harvard-Smithsonian Center for Astrophysics. A comparison scheme is used that accounts for the spatial and temporal mismatch as well as differing photochemical conditions between the balloon and satellite borne measurements. It is found that the balloon borne measurements internally agree to within ±10% and ±20% for O3 and NO2, respectively, whereas the agreement with the satellite is ±20% for both gases in the 20 km to 30 km altitude range and in general worse below 20 km.