bluuebunny/crossref_metadata_2025 huggingface dataset:
Observations and model calculations of trace gas scavenging in a dense Saharan dust plume during MINATROC
Authors: de Reus M. , Fischer H. , Sander R. , Gros V. , Kormann R. , Salisbury G. , Van Dingenen R. , Williams J. , Zöllner M. , Lelieveld J.
Published: April 2010

Abstract. An intensive field measurement campaign was performed in July/August 2002 at the Global Atmospheric Watch station Izaña on Tenerife to study the interaction of mineral dust aerosol and tropospheric chemistry (MINATROC). A dense Saharan dust plume, with aerosol masses exceeding 500 µg m-3, persisted for three days. During this dust event strongly reduced mixing ratios of ROx (HO2, CH3O2 and higher organic peroxy radicals), H2O2, NOx (NO and NO2) and O3 were observed. A chemistry boxmodel, constrained by the measurements, has been used to study gas phase and heterogeneous chemistry. It appeared to be difficult to reproduce the observed HCHO mixing ratios with the model, possibly related to the representation of precursor gas concentrations or the absence of dry deposition. The model calculations indicate that the reduced H2O2 mixing ratios in the dust plume can be explained by including the heterogeneous removal reaction of HO2 with an uptake coefficient of 0.2, or by assuming heterogeneous removal of H2O2 with an accommodation coefficient of 3×10-4. However, these heterogeneous reactions cannot explain the low ROx mixing ratios observed during the dust event. Whereas a mean daytime net ozone production rate (NOP) of 1.06 ppbv/hr occurred throughout the campaign, the reduced ROx and NOx mixing ratios in the Saharan dust plume contributed to a reduced NOP of 0.14–0.32 ppbv/hr, which likely explains the relatively low ozone mixing ratios observed during this event.
Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach
Authors: Aumont B. , Szopa S. , Madronich S.
Published: April 2010

Abstract. Organic compounds emitted in the atmosphere are oxidized in complex reaction sequences that produce a myriad of intermediates. Although the cumulative importance of these organic intermediates is widely acknowledged, there is still a critical lack of information concerning the detailed composition of the highly functionalized secondary organics in the gas and condensed phases. The evaluation of their impacts on pollution episodes, climate, and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various phases down to the ultimate oxidation products, CO and CO2. However, a fully detailed representation of the atmospheric transformations of organic compounds involves a very large number of intermediate species, far in excess of the number that can be reasonably written manually. This paper describes (1) the development of a data processing tool to generate the explicit gas-phase oxidation schemes of organic compounds under tropospheric conditions and (2) the protocol used to select the reaction products and the rate constants. Results are presented using the fully explicit oxidation schemes generated for two test species: n-heptane and isoprene. Comparisons with well-established mechanisms were performed to evaluate these generated schemes. Some preliminary results describing the gradual change of organic carbon during the oxidation of a given parent compound are presented.
Convective damping of buoyancy anomalies and its effect on lapse rates in the tropical lower troposphere
Authors: Folkins I.
Published: April 2010

Abstract. In actively convecting regions of the tropics, lapse rates in the lower troposphere (2.0 km to 5.2 km) vary with height in a way which is inconsistent with both reversible moist adiabatic and pseudoadiabatic assumptions. It is argued that this anomalous behavior arises from the tendency for the divergence of a convective buoyancy anomaly to be primarily offset by the collective divergence of all other updrafts and downdrafts within one Rossby radius of deformation. (Ordinarily, convective divergences are at least partially offset by an induced radiative divergence in the background atmosphere.) If convective divergences are balanced purely by other convective divergences, it would force the vertical clear sky radiative mass flux to be independent of altitude. This is consistent with what is observed at several radiosonde locations in the Western Tropical Pacific between 2.0 and 5.2 km. It is conjectured, that at tropical locations where SST's exceed 27°C over a region whose horizontal extent exceeds the local Rossby radius, this condition on the clear sky radiative mass flux serves to partially constrain the range of physically allowed mean temperature and moisture profiles in the lower troposphere.
The impact of ice uptake of nitric acid on atmospheric chemistry
Authors: von Kuhlmann R. , Lawrence M. G.
Published: April 2010

Abstract. The potential impact of the uptake of HNO3 on ice on the distribution of NOy species, ozone and OH has been assessed using the global scale chemistry-transport model MATCH-MPIC. Assuming equilibrium uptake according to dissociative Langmuir theory results in significant reductions of gas phase HNO3. Comparison to a large set of observations provides support that significant uptake of HNO3 on ice is occurring, but the degree of the uptake cannot be inferred from this comparison alone. Sensitivity simulations show that the uncertainties in the total amount of ice formation in the atmosphere and the actual expression of the settling velocity of ice particles only result in small changes in our results. The largest uncertainty is likely to be linked to the actual theory describing the uptake process. The inclusion of non-methane hydrocarbon chemistry buffers the overall effect of neglected uptake of HNO3 on ice. The calculated overall effect on upper tropospheric ozone concentrations and the tropospheric methane lifetime are moderate to low. These results support a shift in the motivation for future experimental and theoretical studies of HNO3-ice interaction towards the role of HNO3 in hydrometeor surface physics.
Assessment of the reduction methods used to develop chemical schemes: building of a new chemical scheme for VOC oxidation suited to three-dimensional multiscale HOx-NOx-VOC chemistry simulations
Authors: Szopa S. , Aumont B. , Madronich S.
Published: April 2010

Abstract. The objective of this work was to develop and assess an automatic procedure to write reduced chemical schemes for modeling gaseous photooxidant pollution at different scales. The method is based on (i) the development of a tool for writing the fully explicit schemes 5 for VOC oxidation and (ii) the assessment of reduced schemes using the fully explicit scheme as a reference. The reference scheme contained ca. seventy emitted VOCs chosen to be representative of both anthropogenic and biogenic emissions, and their atmospheric degradation chemistry involving more than two million reactions and 350 000 species was written using an expert system generator approach. 10 Three methods were applied to reduce the size of chemical schemes: (i) use of operators, based on the redundancy of the reaction sequences involved in the VOC oxidation, (ii) lumping of primary species having similar reactivities and (iii) lumping of secondary products into surrogate species. The number of species in the final reduced scheme is 150, i.e. low enough for 3-D modeling purposes using CTMs. Comparisons 15 between the fully explicit and reduced schemes, carried out with a box model for several typical tropospheric conditions, showed that the reduced chemical scheme accurately predicts ozone concentrations and some other aspects of oxidant chemistry for both polluted and clean tropospheric conditions.
A redistribution of water due to pileus cloud formation near the tropopause
Authors: Garrett T. J. , Liu C. , Dean-Day J. , Barnett B. K. , Mace G. G. , Baumgardner D. G. , Webster C. R. , Bui T. P. , Read W. G.
Published: April 2010

Abstract. Thin stratiform clouds called pileus can form in the earth's atmosphere when humid air is lifted above rising convection. In the lower troposphere pileus lifetimes are short, so they have been considered little more than an attractive curiosity. This paper describes pileus cloud forming near the tropopause at low-latitudes, and discusses how they may be associated with a redistribution of water vapor and ice at cold temperatures.
Shipborne solar absorption measurements of CO2, CH4, N2O and CO and comparison with SCIAMACHY WFM-DOAS retrievals
Authors: Warneke T. , de Beek R. , Buchwitz M. , Notholt J. , Schulz A. , Velazco V. , Schrems O.
Published: April 2010

Abstract. CO, CH4, N2O and CO2 were retrieved from high resolution solar absorption spectra obtained during a ship cruise from Capetown to Bremerhaven in January/February 2003 by Fourier Transform Infrared (FTIR) spectroscopy. Precisions of better than 0.5% for the column averaged volume mixing ratios (VMR) of CH4 and CO2 are achieved using of O2 as a reference gas. Shipborne FTIR-measurements of CO and data from SCIAMACHY/ENVISAT retrieved by the Weighting Function Modified Differential Optical Absorption Spectroscopy (WFM-DOAS) retrieval algorithm show qualitatively the same latitudinal variations. WFM-DOAS data of CH4, N2O and CO2 measured over sea exhibit a great spread. The spread is significantly reduced for satellite measurements over land and a reasonable agreement can be obtained if the shipborne data is compared with the closest SCIAMACHY measurements over land. The number of comparisons is too small to draw conclusions. However, by including only WFM-DOAS data with small errors the shipborne and WFM-DOAS data compare within 5% for CH4 and CO2 and within 30% for N2O.
Midlatitude ClO during the maximum atmospheric chlorine burden: in situ balloon measurements and model simulations
Authors: Vogel B. , Müller R. , Engel A. , Grooß J.-U. , Toohey D. , Woyke T. , Stroh F.
Published: April 2010

Abstract. Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloonborne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in León, Spain, and in May 1999 in Aire sur l'Adour, France. For both flights a ClO daylight and night time vertical profile could be derived over an altitude range of approximately 15–31 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-h backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l'Adour 1999 show a good agreement with the ClO measurements. For the flight launched in León 1996, a similar good agreement is found, except at around ≈650 K potential temperature (≈26 km altitude). However, a tendency is found that for solar zenith angles greater than 86°–87° the simulated ClO mixing ratios substantially overestimate measured ClO by approximately a factor of 2.5 or more for both flights. Therefore we conclude that no indication can be deduced from the presented ClO measurements that substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere. An exception is the situation at solar zenith angles greater than 86°–87° where model simulations substantial overestimate ClO observations.
The effect of aerosol on surface cloud radiative forcing in the Arctic
Authors: Hu R.-M. , Blanchet J.-P. , Girard E.
Published: April 2010

Abstract. Cloud radiative forcing is a very important concept to understand what kind of role the clouds play in climate change with thermal effect or albedo effect. In spite of that much progress has been achieved, the clouds are still poorly described in the climate models. Due to the complex aerosol-cloud-radiation interactions, high surface albedo of snow and ice cover, and without solar radiation in long period of the year, the Arctic strong warming caused by increasing greenhouse gases (as most GCMs suggested) has not been verified by the observations. In this study, we were dedicated to quantify the aerosol effect on the Arctic cloud radiative forcing by Northern Aerosol Regional Climate Model (NARCM). Major aerosol species such as Arctic haze sulphate, black carbon, sea salt, organics and dust have been included during our simulations. By inter-comparisons with the Atmospheric Radiation Measurement (ARM) data, we find surface cloud radiative forcing (SCRF) is −22 W/m2 for shortwave and 36 W/m2 for longwave. Total cloud forcing is 14 W/m2 with minimum of −35 W/m2 in early July. If aerosols are taken into account, the SCRF has been increased during winter while negative SCRF has been enhanced during summer. Our estimate of aerosol forcing is about −6 W/m2 in the Arctic.
A computationally efficient inorganic atmospheric aerosol phase equilibrium model (UHAERO)
Authors: Amundson N. R. , Caboussat A. , He J. W. , Martynenko A. V. , Savarin V. B. , Seinfeld J. H. , Yoo K. Y.
Published: April 2010

Abstract. A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model also computes deliquescence and crystallization behavior without any a priori specification of the relative humidities of deliquescence or crystallization. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition.
Atmospheric trends of the halon gases from polar firn air
Authors: Reeves C. E. , Sturges W. T. , Sturrock G. A. , Preston K. , Oram D. E. , Schwander J. , Mulvaney R. , Barnola J.-M. , Chappellez J.
Published: April 2010

Abstract. Four halons (H-1301, H-1211, H-2402 and H-1202) have been measured in air samples collected from polar firn from Dome Concordia (Dome C), Antarctica, from Devon Island, Canada and the North Greenland Ice Core Project (NGRIP) site, Greenland. H-2402 and H-1202 are reported for the first time in firn air. The depth profiles show the concentrations of all four halons to be zero at the base of the firn thus demonstrating their entirely anthropogenic origin. This is the first evidence of this for H-2402 and H-1202. A 2-D atmospheric model was run to produce historical trends in the atmospheric concentrations at the firn sites, which were then input into a firn diffusion model to produce concentration depth profiles for comparison with the measurements. The firn measurements provide constraints on the atmospheric concentrations in both hemispheres which allow the global emission rates and their latitudinal distribution in the atmospheric model to be evaluated. Global emission trends previously determined from measurements at Cape Grim are found to be consistent with the firn data. Further emissions of H-1202 in recent years (late 1980s onwards) are likely to have come from latitudes mostly south of 40° N, but emissions prior to that may have come from further north. Emissions of H-1211 may also have shifted to latitudes south of 40° N during the late 1980s. The firn data is used to derive atmospheric trends in total organic bromine in the form of halons for both polar regions.
Constraining the total aerosol indirect effect in the LMDZ and ECHAM4 GCMs using MODIS satellite data
Authors: Quaas J. , Boucher O. , Lohmann U.
Published: April 2010

Abstract. Aerosol indirect effects are considered to be the most uncertain yet important anthropogenic forcing of climate change. The goal of the present study is to reduce this uncertainty by constraining two different general circulation models (LMDZ and ECHAM4) with satellite data. We build a statistical relationship between cloud droplet number concentration and the optical depth of the fine aerosol mode as a measure of the aerosol indirect effect using MODerate Resolution Imaging Spectroradiometer (MODIS) satellite data, and constrain the model parameterizations to match this relationship. We include here ''empirical'' formulations for the cloud albedo effect as well as parameterizations of the cloud lifetime effect. When fitting the model parameterizations to the satellite data, consistently in both models, the radiative forcing by the combined aerosol indirect effect is reduced considerably, down to −0.5 and −0.3 Wm-2, for LMDZ and ECHAM4, respectively.
Detection of organic compound signatures in infra-red, limb emission spectra observed by the MIPAS-B2 instrument
Authors: Remedios J. J. , Allen G. , Waterfall A. M. , Oelhaf H. , Kleinert A.
Published: April 2010

Abstract. Organic compounds play a central role in troposphere chemistry and increasingly are a viable target for remote sensing observations. In this paper, infra-red spectral features of three organic compounds are investigated in thermal emission spectra recorded by a balloon-borne instrument, MIPAS-B2, operating at high spectral resolution. It is demonstrated, for the first time, that PAN and acetone can be detected in infra-red remote sensing spectra of the upper troposphere; detection results are presented at tangent altitudes of 10.4 km and 7.5 km (not acetone). In addition, the results provide the first observation of spectral features of formic acid in thermal emission, as opposed to solar occultation, and confirm that concentrations of this gas are likely to be measurable in the free troposphere, given accurate spectroscopic data. For PAN, two bands are observed centred at 794 cm−1 and 1163 cm−1. For acetone and formic acid, one band has been detected for each so far with band centres at 1218 cm−1 and 1105 cm−1 respectively. Mixing ratios inferred at 10.4 km tangent altitude are 180 pptv and 530 pptv for PAN and acetone respectively, and 200 pptv for formic acid with HITRAN 2000 spectroscopy. Accuracies are on the order of 30 to 50%. The detection technique applied here is verified by examining weak but known signatures of CFC-12 and HCFC-22 in the same spectral regions as those of the organic compounds, with results confirming the quality of both the instrument and the radiative transfer model. The results suggest the possibility of global sensing of the organic compounds studied here which would be a major step forward in verifying and interpreting global tropospheric model calculations.
Evaluation of ozonesondes, HALOE, SAGE II and III, Odin-OSIRIS and SMR, and ENVISAT-GOMOS, -SCIAMACHY and -MIPAS ozone profiles in the tropics from SAOZ long duration balloon measurements in 2003 and 2004
Authors: Borchi F. , Pommereau J.-P.
Published: April 2010

Abstract. The performances of satellite and sondes ozone measuring instruments available in the tropics between 10 and 26 km during the southern hemisphere summer in 2003 and 2004, have been investigated by comparison with series of profiles obtained by solar occultation in the visible Chappuis bands using a SAOZ UV-Vis spectrometer carried by circumnavigating long duration balloons. When compared to SAOZ, systematic positive or negative altitude shifts could be observed in satellite profiles, varying from <50 m for the GOMOS stellar occultation instrument, followed by +100/200 m for solar occultation systems (SAGE II, HALOE above 22 km), but as large as −900 m or +2000 m for limb viewing systems (OSIRIS, SCIAMACHY). The ozone relative biases are generally limited, between −4% and +4%, for measurements in the visible Chappuis bands (SAGE II and III, GOMOS above 22 km and OSIRIS), the near IR (HALOE above 22 km) and the ozonesondes, but increase to −7% in the UV (SCIAMACHY), and +7% in the mid-IR (MIPAS) and the submillimetric range (SMR). Regarding precision, evaluated statistically from the zonal variability of ozone concentration, the best measurements are found to be those of SAGE II (2%), followed by HALOE above 22 km (3–4%), then the ozonesondes, SAGE III moon and OSIRIS (4–5%), GOMOS above 22 km and SCIAMACHY (~6%), MIPAS (8.5%) and finally SMR (16%). Overall, all satellite ozone measurements appear little reliable in the tropical troposphere except those of SAGE II (and eventually SAGE III), though low biased by 50% and of limited (50%) precision.
Evaluation of a new convective cloud field model: precipitation over the maritime continent
Authors: Graf H.-F. , Yang J.
Published: April 2010

Abstract. A convective cloud field model (CCFM) is substituted for a standard mass flux parameterisation of convective clouds in a limited area atmospheric model (REMO) and is tested for a whole annual cycle (July 1997 to June 1998) over the Maritime Continent. REMO with CCFM is run in 0.5-degree resolution and the model at the boundaries is forced 6-hourly by ECMWF reanalysis data. Simulated precipitation from runs with the standard convection parameterisation and with CCFM is compared against two sets of observations. The use of CCFM clearly improves the simulated precipitation patterns and total rainfall over the whole model domain. The distribution between large-scale and convective precipitation becomes more realistic. CCFM shows to be a useful concept to describe convective cloud spectra in atmospheric models, although there are still similar problems with occasionally extreme precipitation as in the original set-up of REMO.
Do organic surface films on sea salt aerosols influence atmospheric chemistry? – A model study
Authors: Smoydzin L. , von Glasow R.
Published: April 2010

Abstract. Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL) we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we saw a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film can be increased by either assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. Differences for gas phase NO2 or NO are very small (less than 5%) whereas liquid phase NO2 concentrations increased in some cases by nearly 100%.
Aerosol formation over the Boreal forest in Hyytiälä, Finland: monthly frequency and annual cycles – the roles of air mass characteristics and synoptic scale meteorology
Authors: Nilsson E. D. , Kulmala M.
Published: April 2010

Abstract. New atmospheric particles with diameters of 3–10 nm and their subsequent growth to cloud condensation nucleus have been observed at various places in the European boundary layer. These events have been observed simultaneously within wide geographical areas (over 1000 km) in connection to specific weather systems, the cold air behind cyclones. Here we show that atmospheric aerosol formation (i.e. nucleation and initial growth) is favoured by the outbreak of cold Arctic air over northern Europe. Aerosol formation was about twice as common in Arctic air as in sub-Polar air, and even more so compared to other air masses. The most important general factor favouring aerosol formation in Arctic air and marine air was weaker competing condensational sink (CS) for the precursor gases (less pre-existing aerosols), while high CS prevented aerosol formation in heated sub-Polar air and mid-latitude air. High SO2 levels favoured nucleation in continental air and high UV-B radiation in sub-tropical air. The critical factor that determined if aerosol formation would start on a day with Arctic air was the UV-B radiation. The same applied to sub-Polar air and continental air, while increased SO2 concentration could trigger formation in heated sub-Polar and mid-latitude air, and reduced CS could cause formation in mid-latitude, marine or mixed/transient air. We speculate that strong emissions of volatile organic compounds from the Boreal forest and strong boundary layer dynamics may have caused aerosol formation in sub-Polar air masses and air in transition from a marine to a continental character. The monthly frequency of Arctic air masses and the probability for photo-chemically driven aerosol formation explains the observed annual cycle in monthly particle formation frequency as well as much of the inter annual variability. The same cyclones that transport cold, clean air from the Arctic to Europe will also transport warm polluted air in the other direction, which help cause the Arctic Haze phenomena. The cyclones have a key role for the atmospheric aerosol life cycle in mid to high latitudes. Due to the observed growth to the size of CCN in one to two days, there is a potential feed back from the effects on the CCN population and cloud albedo even within the same weather system, but also on the climatic time scale.
Free radical modelling studies during the UK TORCH Campaign in summer 2003
Authors: Emmerson K. M. , Carslaw N. , Carslaw D. C. , Lee J. D. , McFiggans G. , Bloss W. , Gravestock T. , Heard D. E. , Hopkins J. , Ingham T. , Pilling M. J. , Smith S. C. , Jacob M. J. , Monks P. S.
Published: April 2010

Abstract. The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. The concentrations of the hydroxyl radical, the hydroperoxy radical and the sum of peroxy radicals, were measured between 25 July and 31 August using laser-induced fluorescence at low pressure and the peroxy radical chemical amplifier techniques. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. OH initiation was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main initiation route for HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.
A criterion to discriminate between solar and cosmic ray forcing of the terrestrial climate
Authors: Fichtner H. , Scherer K. , Heber B.
Published: April 2010

Abstract. There is increasing evidence that there exist interstellar-terrestrial relations and that the heliosphere's effectivity to serve as a protecting shield for the Earth, specifically against cosmic rays, is varying in time. Nonetheless, a debate is going on whether, amongst other drivers, the Sun or the cosmic rays are influencing the terrestrial climate, particularly on periods of hundred years and shorter. As the modelling of the transport of cosmic rays in the heliosphere has evolved from pure test particle simulations to far more consistent treatments, one can explain various correlations within the framework of physical models and one can make quantitative predictions regarding terrestrial indicators of interstellar-terrestrial relations. This level of understanding and modelling allows to identify a criterion with which one can discriminate between solar and cosmic ray forcing on a period of several decades. We define such a criterion and discuss related existing observations.
Simultaneous ground-based observations of O3, HCl, N2O, and CH4 over Toronto, Canada by three Fourier transform spectrometers with different resolutions
Authors: Wunch D. , Taylor J. R. , Fu D. , Bernath P. , Drummond J. R. , Midwinter C. , Strong K. , Walker K. A.
Published: April 2010

Abstract. An intercomparison of three Fourier transform spectrometers (FTSs) with significantly different resolutions is presented. The highest-resolution instrument has a maximum optical path difference of 250 cm, and the two lower-resolution instruments have maximum optical path differences of 50 cm and 25 cm. The results indicate that the two lower-resolution instruments can retrieve total column amounts of O3, HCl, N2O and CH4 using the SFIT2 retrieval code with percent differences from the high-resolution instrument generally better than 3%, with respect to the high-resolution FTS. Total column amounts of the stratospheric species (O3 and HCl) have larger differences than those of the tropospheric species (N2O and CH4). Instrument line shape (ILS) information is found to be of critical importance when retrieving total columns of stratospheric gases from the lower-resolution instruments. Including the ILS information in the retrievals significantly reduces the difference in total column amounts between the three instruments. The remaining errors for stratospheric species total column amounts can be attributed to the lower sensitivity of the lower-resolution FTSs to the stratosphere.
Investigation of how observed methane concentrations in Ny-Ålesund are influenced by atmospheric flow patterns
Authors: Pedersen I. T. , Holmén K. J.
Published: April 2010

Abstract. Long-range atmospheric transport to Svalbard has been studied with a compilation of 4 years of daily trajectories to determine how the atmospheric flow patterns influence the observed methane (CH4) at Mt. Zeppelin station (475 m.a.s.l.) in Ny-Ålesund (78°54' N, 11°53' E). The flow patterns were determined through cluster analysis of 5-day back-trajectories arriving at Ny-Ålesund twice a day (00:00 and 12:00 UTC) for the period 2000–2003. Eight cluster patterns were obtained and used in the analysis of the continuous methane measurements at Mt. Zeppelin station. The analysis shows a shift in frequencies eastward into the Arctic compared to identical studies of transport for 1992–2001. Higher concentrations of methane are mainly seen in clusters with transport from Europe and Russia in contrast to air following transport pathways within the Arctic Basin. The vertical motion of the trajectories has been investigated and shows that it has an effect on the methane concentration at the Mt. Zeppelin station. This is consistent with previous similar studies of CO2 and of other anthropogenic species. Seasonal variation in trajectory frequency can be seen, like for instance more trajectories from Europe and Siberia during winter, and short trajectories from the Arctic region in summer. The identified seasonal and indications of decadal shifts in transport pathways translate into shifts in source areas sampled by a single station. To determine shifts in regional source (and sink) strengths it is necessary to correct for transport pathway shifts when interpreting time series data.
Systematic analysis of interannual and seasonal variations of model-simulated tropospheric NO2 in Asia and comparison with GOME-satellite data
Authors: Uno I. , He Y. , Ohara T. , Yamaji K. , Kurokawa J.-I. , Katayama M. , Wang Z. , Noguchi K. , Hayashida S. , Richter A. , Burrows J. P.
Published: April 2010

Abstract. Systematic analyses of interannual and seasonal variations of tropospheric NO2 vertical column densities (VCDs) based on GOME satellite data and the regional scale chemical transport model (CTM), Community Multi-scale Air Quality (CMAQ), are presented over eastern Asia between 1996 and June 2003. A newly developed year-by-year emission inventory (REAS) was used in CMAQ. The horizontal distribution of annual averaged GOME NO2 VCDs generally agrees well with the CMAQ results. However, CMAQ/REAS results underestimate the GOME retrievals with factors of 2–4 over polluted industrial regions such as Central East China (CEC), a major part of Korea, Hong Kong, and central and western Japan. For the Japan region, GOME and CMAQ NO2 data show good agreement with respect to interannual variation and show no clear increasing trend. For CEC, GOME and CMAQ NO2 data show good agreement and indicate a very rapid increasing trend from 2000. Analyses of the seasonal cycle of NO2 VCDs show that GOME data have systematically larger dips than CMAQ NO2 during February–April and September–November. Sensitivity experiments with fixed emission intensity reveal that the detection of emission trends from satellite in fall or winter have a larger error caused by the variability of meteorology. Examination during summer time and annual averaged NO2 VCDs are robust with respect to variability of meteorology and are therefore more suitable for analyses of emission trends. Analysis of recent trends of annual emissions in China shows that the increasing trends of 1996–1998 and 2000–2002 for GOME and CMAQ/REAS show good agreement, but the rate of increase by GOME is approximately 10–11% yr−1 after 2000; it is slightly steeper than CMAQ/REAS (8–9% yr−1). The greatest difference was apparent between the years 1998 and 2000: CMAQ/REAS only shows a few percentage points of increase, whereas GOME gives a greater than 8% yr−1 increase. The exact reason remains unclear, but the most likely explanation is that the emission trend based on the Chinese emission related statistics underestimates the rapid growth of emissions.
Estimating a relationship between aerosol optical thickness and surface wind speed over the ocean
Authors: Glantz P. , Nilsson D. E. , von Hoyningen-Huene W.
Published: April 2010

Abstract. Retrieved aerosol optical thickness (AOT) based on data obtained by the Sea viewing Wide Field Sensor (SeaWiFS) is combined with surface wind speed, obtained at the European Centre for Medium-Range Weather Forecasts (ECMWFs), over the North Pacific for September 2001. In this study a cloud screening approach is introduced in an attempt to exclude pixels partly or fully covered by clouds. The relatively broad swath width for which the nadir looking SeaWiFS instrument scanned over the North Pacific means that the AOT can be estimated according to relatively large range of wind speeds for each of the scenes analyzed. The sensitivity in AOT due to sea salt and hygroscopic growth of the marine aerosols has also been investigated. The validation of the results is based on previous parameterization in combination with the environmental quantities wind speed, RH and boundary layer height (BLH), estimated at the ECMWF. In this study a factor of 2 higher mean AOT is obtained for a wind speed up to about 13 m s−1 for September 2001 over remote ocean areas. Furthermore, a factor of 2 higher AOT is more or less supported by the validation of the results. Approximately, 50% of the enhancement seems to be due to hygroscopic growth of the marine aerosols and the remaining part due to increase in the sea salt particle mass concentrations, caused by a wind driven water vapor and sea salt flux, respectively. Reasonable agreement occurs also between satellites retrieved aerosol optical thickness and AOT observed at several AERONET (Aerosol Robotic NETwork) ground-based remote sensing stations. Finally, possible reasons why relatively large standard deviations occur around the mean values of AOT estimated for a single scene are discussed.
Assimilation of TES CO into a global CTM: first results
Authors: Richards N. A. D. , Li Q. , Bowman K. W. , Worden J. R. , Kulawik S. S. , Osterman G. B. , Worden H. M. , Lamarque J.-F. , Khattatov B. V.
Published: April 2010

Abstract. We present results from the first assimilation of carbon monoxide (CO) observations from the Tropospheric Emission Spectrometer (TES) into a global three-dimensional (3-D) chemistry and transport model (CTM). A sequential sub-optimal Kalman filter assimilation scheme (Khattatov et al., 2000) was applied to assimilate TES CO profiles during November 2004 into the GEOS-Chem global 3-D CTM. The assimilation results were compared with MOPITT and MOZAIC observations. The assimilation significantly improves model simulation of CO in the middle to upper troposphere, where the MOPITT versus model bias was reduced by up to two-thirds. Assimilation results show higher levels of CO in the southern tropics, consistent with MOPITT observations. We find good agreement between the TES assimilated model estimates of CO and in situ measurements from the MOZAIC program, which shows a negative bias of up to 10 ppbv in middle and upper tropospheric TES CO. The results demonstrate how assimilation can be used for non-coincident validation of TES CO profile retrievals.
Aerosol distribution over the western Mediterranean basin during a Tramontane/Mistral event
Authors: Salameh T. , Drobinski P. , Menut L. , Bessagnet B. , Flamant C. , Hodzic A. , Vautard R.
Published: April 2010

Abstract. This paper investigates experimentally and numerically the time evolution of the spatial distribution of aerosols over the Western Mediterranean basin during 24 March 1998 Mistral event documented during the FETCH experiment. Mistral and Tramontane are very frequent northerly winds (5–15 days per month) accelerated along the Rhône and Aude valley (France) that can transport natural and anthropogenic aerosols offshore as far as a few hundreds of kilometers which can in turn have an impact on the radiation budget over the Mediterranean Sea and on precipitation. The spatial distribution of aerosols was documented by means of the airborne lidar LEANDRE-2 and spaceborne radiometer SeaWIFS, and a validated mesoscale chemical simulation using the chemistry-transport model CHIMERE with an aerosol module, forced by the non-hydrostatic model MM5. This study shows that: (1) the Mistral contributes to the offshore exportation of a large amount of aerosols originally emitted over continental Europe (in particular ammonium nitrate in the particulate phase and sulfates) and along the shore from the industrialized and urban areas of Fos-Berre/Marseille. The Genoa surface low contributes to advect the aerosols along a cyclonic trajectory that skirts the North African coast and reaches Italy; (2) the aerosol concentration pattern is very unsteady as a result of the time evolution of the two winds (or Genoa cyclone position): The Tramontane wind prevails in the morning hours of 24 March, leaving room for the Mistral wind and an unusually strong Ligurian outflow in the afternoon. The wakes trailing downstream the Massif Central and the Alps prevent any horizontal diffusion of the aerosols and can, at times, contribute to aerosol stagnation.
The weekend effect within and downwind of Sacramento: Part 2. Observational evidence for chemical and dynamical contributions
Authors: Murphy J. G. , Day D. A. , Cleary P. A. , Wooldridge P. J. , Millet D. B. , Goldstein A. H. , Cohen R. C.
Published: April 2010

Abstract. Observations of day-of-week patterns and diurnal profiles of ozone, volatile organic compounds and nitrogen oxides are examined to assess the chemical and dynamical factors governing the daytime ozone accumulation and the distribution of chemically related species in Central California. Isoprene observations show that urban OH concentrations are higher on the weekend whereas rural OH concentrations are lower on the weekend, confirming that NOx concentrations have a direct effect on the rate of photochemical ozone production and that the transition from NOx-saturated (VOC-limited) to NOx-limited chemistry occurs between the city and the downwind rural counties. We quantify the extent to which mixing of ozone and its precursors from aloft contributes to the daytime accumulation of ozone at the surface in Sacramento. Ozone production in the rural Mountain Counties is currently NOx-limited and will decrease in response to NOx emission reductions in the Sacramento Valley. However, NOx emissions reductions of at least 50% (from weekday levels) are necessary to bring about a significant decrease in accumulation of ozone at the surface in the Sacramento Valley. The impact of NOx emission reductions on the frequency of exceeding the federal 8-hour ozone standard at an individual site will depend on the balance between reduced titration and the sign and magnitude of production changes. We further show that HNO3 production, which depends on the product of OH and NO2 mixing ratios, is a constant at high NOx, suggesting that NOx must be reduced below a threshold before nitrate aerosol can be expected to decrease.
Solar cycle variations of stratospheric ozone and temperature in simulations of a coupled chemistry-climate model
Authors: Austin J. , Hood L. L. , Soukharev B. E.
Published: April 2010

Abstract. The results from three 45-year simulations of a coupled chemistry climate model are analysed for solar cycle influences on ozone and temperature. The simulations include UV forcing at the top of the atmosphere, which includes a generic 27-day solar rotation effect as well as the observed monthly values of the solar fluxes. The results are analysed for the 27-day and 11-year cycles in temperature and ozone. In accordance with previous results, the 27-day cycle results are in good qualitative agreement with observations, particularly for ozone. However, the results show significant variations, typically a factor of two or more in sensitivity to solar flux, depending on the solar cycle. We show for the first time good agreement also between the observed 11-year cycle and model results for the ozone vertical profile, which both indicate a minimum in solar response near 20 hPa. In comparison, simulations of the model with fixed solar phase (solar maximum/solar mean) and climatological sea surface temperatures lead to a poor simulation of the solar response in the ozone vertical profile. The results indicate the need for variable phase simulations in solar sensitivity experiments and the role of sea surface temperatures is discussed.
Dangerous human-made interference with climate: a GISS modelE study
Authors: Hansen J. , Sato M. , Ruedy R. , Kharecha P. , Lacis A. , Miller R. , Nazarenko L. , Lo K. , Schmidt G. A. , Russell G. , Aleinov I. , Bauer S. , Baum E. , Cairns B. , Canuto V. , Chandler M. , Cheng Y. , Cohen A. , Del Genio A. , Faluvegi G. , Fleming E. , Friend A. , Hall T. , Jackman C. , Jonas J. , Kelley M. , Kiang N. Y. , Koch D. , Labow G. , Lerner J. , Menon S. , Novakov T. , Oinas V. , Perlwitz Ja. , Perlwitz Ju. , Rind D. , Romanou A. , Schmunk R. , Shindell D. , Stone P. , Sun S. , Streets D. , Tausnev N. , Thresher D. , Unger N. , Yao M. , Zhang S.
Published: April 2010

Abstract. We investigate the issue of "dangerous human-made interference with climate" using simulations with GISS modelE driven by measured or estimated forcings for 1880–2003 and extended to 2100 for IPCC greenhouse gas scenarios as well as the "alternative" scenario of Hansen and Sato (2004). Identification of "dangerous" effects is partly subjective, but we find evidence that added global warming of more than 1°C above the level in 2000 has effects that may be highly disruptive. The alternative scenario, with peak added forcing ~1.5 W/m2 in 2100, keeps further global warming under 1°C if climate sensitivity is ~3°C or less for doubled CO2. The alternative scenario keeps mean regional seasonal warming within 2σ (standard deviations) of 20th century variability, but other scenarios yield regional changes of 5–10σ, i.e., mean conditions outside the range of local experience. We discuss three specific sub-global topics: Arctic climate change, tropical storm intensification, and ice sheet stability. We suggest that Arctic climate change has been driven as much by pollutants (O3, its precursor CH4, and soot) as by CO2, offering hope that dual efforts to reduce pollutants and slow CO2 growth could minimize Arctic change. Simulated recent ocean warming in the region of Atlantic hurricane formation is comparable to observations, suggesting that greenhouse gases (GHGs) may have contributed to a trend toward greater hurricane intensities. Increasing GHGs cause significant warming in our model in submarine regions of ice shelves and shallow methane hydrates, raising concern about the potential for accelerating sea level rise and future positive feedback from methane release. Growth of non-CO2 forcings has slowed in recent years, but CO2 emissions are now surging well above the alternative scenario. Prompt actions to slow CO2 emissions and decrease non-CO2 forcings are needed to achieve the low forcing of the alternative scenario.
Spatially resolved measurements of nitrogen dioxide in an urban environment using concurrent multi-axis differential optical absorption spectroscopy
Authors: Leigh R. J. , Corlett G. K. , Frieß U. , Monks P. S.
Published: April 2010

Abstract. A novel system using the technique of concurrent multi-axis differential optical absorption spectroscopy system has been developed and applied to the measurement of nitrogen dioxide in an urban environment. Using five fixed telescopes, slant columns of nitrogen dioxide, ozone, water vapour, and the oxygen dimer, O4, are simultaneously retrieved in five vertically separated viewing directions. The application of this remote sensing technique in the urban environment is explored. Through, the application of several simplifying assumptions a tropospheric concentration of NO2 is derived and compared with an urban background in-situ chemiluminescence detector. The remote sensing and in-situ techniques show good agreement. Owing to the high time resolution of the measurements, the ability to image and quantify plumes within the urban environment is demonstrated. The CMAX-DOAS measurements provide a useful measure of overall NO2 concentrations on a city-wide scale.