bluuebunny/crossref_metadata_2025 huggingface dataset:
Laboratory studies of ice formation pathways from ammonium sulfate particles
Authors: Wise M. E. , Baustian K. J. , Tolbert M. A.
Published: April 2010

Abstract. Cirrus clouds are composed of ice particles and their formation pathways have been studied extensively in the laboratory. The ability of ammonium sulfate particles to act as nuclei for cirrus clouds has been of particular importance because of their ubiquitous presence in the upper troposphere. The results of past laboratory experiments of homogeneous ice nucleation from ammonium sulfate particles show a wide range of freezing conditions. In the present study, a flow tube apparatus equipped with Fourier transform infrared spectroscopy was used to resolve these discrepancies. It was found that when ammonium sulfate particles were preconditioned at 100% relative humidity (RH) prior to experimentation, the particles froze at conditions predicted by the homogeneous ice nucleation model developed by Koop et al. (2000). If the particles were not preconditioned at 100% RH, they froze at warmer temperatures and lower ice saturation ratios than predicted by Koop et al. (2000). In order to determine if a population of effloresced particles affected freezing conditions for particles that were not preconditioned at 100% RH, a series of depositional ice nucleation experiments were carried out on dry ammonium sulfate particles. For freezing temperatures between 215 and 231 K, ice nucleated on the particles at ice saturation ratios (Sice) between 1 and 1.05. These conditions are much lower than predicted by Koop et al. (2000) and explain the differences in freezing conditions among preconditioning methods. In similar experiments, Abbatt et al. (2006) hypothesized that a small fraction of effloresced ammonium sulfate particles induced ice nucleation at Sice values lower than expected. The current study confirms the Abbatt et al. (2006) hypothesis and, to our knowledge, is the first study to directly observe ice nucleating onto freely flowing dry ammonium sulfate particles at Sice values approaching unity.
Attribution of projected changes in US ozone and PM2.5 concentrations to global changes
Authors: Avise J. , Chen J. , Lamb B. , Wiedinmyer C. , Guenther A. , Salathé E. , Mass C.
Published: April 2010

Abstract. The impact that changes in future climate, anthropogenic US emissions, background tropospheric composition, and land-use have on regional US ozone and PM2.5 concentrations is examined through a matrix of downscaled regional air quality simulations using the Community Multi-scale Air Quality (CMAQ) model. Projected regional scale changes in meteorology due to climate change under the Intergovernmental Panel on Climate Change (IPCC) A2 scenario are derived through the downscaling of Parallel Climate Model (PCM) output with the MM5 meteorological model. Future chemical boundary conditions are obtained through downscaling of MOZART-2 (Model for Ozone and Related Chemical Tracers, version 2.4) global chemical model simulations based on the IPCC Special Report on Emissions Scenarios (SRES) A2 emissions scenario. Projected changes in US anthropogenic emissions are estimated using the EPA Economic Growth Analysis System (EGAS), and changes in land-use are projected using data from the Community Land Model (CLM) and the Spatially Explicit Regional Growth Model (SERGOM). For July conditions, changes in chemical boundary conditions are found to have the largest impact (+5 ppbv) on average daily maximum 8-h (DM8H) ozone. Changes in US anthropogenic emissions are projected to increase average DM8H ozone by +3 ppbv. Land-use changes are projected to have a significant influence on regional air quality due to the impact these changes have on biogenic hydrocarbon emissions. When climate changes and land-use changes are considered simultaneously, the average DM8H ozone decreases due to a reduction in biogenic VOC emissions (−2.6 ppbv). Changes in average 24-h (A24-h) PM2.5 concentrations are dominated by projected changes in anthropogenic emissions (+3 μg m−3), while changes in chemical boundary conditions have a negligible effect. On average, climate change reduces A24-h PM2.5 concentrations by −0.9 μg m−3, but this reduction is more than tripled in the Southeastern US due to increased precipitation and wet deposition.
Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: comparison of measurements with the box model MECCA
Authors: Kubistin D. , Harder H. , Martinez M. , Rudolf M. , Sander R. , Bozem H. , Eerdekens G. , Fischer H. , Gurk C. , Klüpfel T. , Königstedt R. , Parchatka U. , Schiller C. L. , Stickler A. , Taraborrelli D. , Williams J. , Lelieveld J.
Published: April 2010

Abstract. As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx=OH+HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2±3.5 and 4.1±1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes >3 km), observation and simulation agree fairly well, for mixing ratios >200 pptV (<3 km over the rainforest) the model tends to underestimate the HOx observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required.
Cloud and aerosol effects on radiation in deep convective clouds: comparison with warm stratiform clouds
Authors: Lee S. S. , Donner L. J. , Phillips V. T. J.
Published: April 2010

Abstract. Cloud and aerosol effects on radiation in two contrasting cloud types, a deep convective mesoscale cloud ensemble (MCE) and warm stratocumulus clouds, are simulated and compared. At the top of the atmosphere, 45–81% of shortwave cloud forcing (SCF) is offset by longwave cloud forcing (LCF) in the MCE, whereas warm stratiform clouds show the offset of less than ~20%. 28% of increased negative SCF is offset by increased LCF with increasing aerosols in the MCE at the top of the atmosphere. However, the stratiform clouds show the offset of just around 2–5%. Ice clouds as well as liquid clouds play an important role in the larger offset in the MCE. Hence, this study indicates effects of deep convective clouds on radiation and responses of deep convective clouds to aerosols are quite different from those of shallow clouds through the different modulation of longwave radiation; the presence of ice clouds in deep convective clouds contributes to the different modulation of longwave radiation significantly. Different cloud types, characterized by cloud depth and cloud-top height, play critical roles in those different modulations of LCF between the MCE and stratocumulus clouds. Lower cloud-top height and cloud depth lead to smaller offset of SCF by LCF and offset of increased negative SCF by increased LCF at high aerosol in stratocumulus clouds than in the MCE. Supplementary simulations show this dependence of modulation of LCF on cloud depth and cloud-top height is not limited to those two contrasting cloud types. The dependence is also simulated among different types of convective clouds, indicating the assessment of effects of varying cloud types on radiation due to climate changes can be critical to better prediction of climate.
A framework for comparing remotely sensed and in-situ CO2 concentrations
Authors: Macatangay R. , Warneke T. , Gerbig C. , Körner S. , Ahmadov R. , Heimann M. , Notholt J.
Published: April 2010

Abstract. A framework that allows validating CO2 column averaged volume mixing ratios (VMRs) retrieved from ground-based solar absorption measurements using Fourier transform infrared spectrometry (FTS) against measurements made in-situ (such as from aircrafts and tall towers) has been developed. Since in-situ measurements are done frequently and at high accuracy on the global calibration scale, linking this scale with FTS total column retrievals ultimately provides a calibration scale for remote sensing. FTS, tower and aircraft data were analyzed from measurements during the CarboEurope Regional Experiment Strategy (CERES) from May to June 2005 in Biscarrosse, France. Carbon dioxide VMRs from the MetAir Dimona aircraft, the TM3 global transport model and Observations of the Middle Stratosphere (OMS) balloon based experiments were combined and integrated to compare with FTS measurements. The comparison agrees fairly well with differences resulting from the spatial variability of CO2 around the FTS as measured by the aircraft. Additionally, the Stochastic Time Inverted Lagrangian Transport (STILT) model served as a "transfer standard" between the in-situ data measured at a co-located tower and the remotely sensed data from the FTS. The variability of carbon dioxide VMRs was modeled well by STILT with differences coming partly from uncertainties in the spatial variation of carbon dioxide.
Dispersion of traffic-related exhaust particles near the Berlin urban motorway: estimation of fleet emission factors
Authors: Birmili W. , Alaviippola B. , Hinneburg D. , Knoth O. , Tuch T. , Kleefeld-Borken J. , Schacht A.
Published: April 2010

Abstract. Atmospheric particle number size distributions of airborne particles (diameter range 10–500 nm) were measured over ten weeks at three sites in the vicinity of the A100 urban motorway in Berlin, Germany. The A100 carries about 180 000 vehicles on a weekday, and roadside particle size distributions showed a number maximum between 20 and 60 nm clearly related to the motorway emissions. The average total number concentration at roadside was 28 000 cm−3 with a total range between 1200 and 168 000 cm−3. At distances of 80 and 400 m from the motorway the concentrations decreased to mean levels of 11 000 and 9 000 cm−3, respectively. An obstacle-resolving dispersion model was applied to simulate the 3-D flow field and traffic tracer transport in the urban environment around the motorway. By inverse modelling, vehicle emission factors were derived, representative of a relative share of 6% lorry-like vehicles, and a driving speed of about 80 km h−1. Three different calculation approaches were compared, which differ in the choice of the experimental winds driving the flow simulation. The average emission factor per vehicle was 2.1(±0.2) · 1014 km−1 for particle number and 0.077(±0.01) · 1014 cm3 km−1 for particle volume. Regression analysis suggested that lorry-like vehicles emit 116 (± 21) times more particulate number than passenger car-like vehicles, and that lorry-like vehicles account for about 91% of particulate number emissions on weekdays. Our work highlights the increasing applicability of 3-D flow models in urban microscale environments and their usefulness in determining traffic emission factors.
Parameterizing the competition between homogeneous and heterogeneous freezing in cirrus cloud formation – monodisperse ice nuclei
Authors: Barahona D. , Nenes A.
Published: April 2010

Abstract. We present a parameterization of cirrus cloud formation that computes the ice crystal number and size distribution under the presence of homogeneous and heterogeneous freezing. The parameterization is very simple to apply and is derived from the analytical solution of the cloud parcel equations, assuming that the ice nuclei population is monodisperse and chemically homogeneous. In addition to the ice distribution, an analytical expression is provided for the limiting ice nuclei number concentration that suppresses ice formation from homogeneous freezing. The parameterization is evaluated against a detailed numerical parcel model, and reproduces numerical simulations over a wide range of conditions with an average error of 6±33%.
Laboratory investigation of photochemical oxidation of organic aerosol from wood fires – Part 1: Measurement and simulation of organic aerosol evolution
Authors: Grieshop A. P. , Logue J. M. , Donahue N. M. , Robinson A. L.
Published: April 2010

Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in wood smoke by exposing diluted emissions from soft- and hard-wood fires to UV light in a smog chamber. Particle- and gas-phase concentrations were monitored with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder to measure aerosol volatility. The measurements highlight how in-plume processing can lead to considerable evolution of the mass and volatility of biomass burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using the measured decay of traditional secondary organic aerosol (SOA) precursors and a state-of-the-art SOA model. Aging also created less volatile OA; at 50°C between 50 and 80% of the fresh primary OA evaporated but only 20 to 40% of aged OA. Therefore, the data provide additional evidence that primary OA is semivolatile. They also raise questions about the current approach used to simulate OA in chemical transport models, which assume that primary OA are non-volatile but that SOA is semivolatile. Predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatile organics are compared to the chamber data. This model demonstrates that the OA production observed in these experiments can be explained by oxidation of low volatility organic vapors. The basis-set model can also simulate observed changes in OA volatility and composition, predicting the OA production and the increased oxygenation and decreased volatility of the OA.
Ozone production, nitrogen oxides, and radical budgets in Mexico City: observations from Pico de Tres Padres
Authors: Wood E. C. , Herndon S. C. , Onasch T. B. , Kroll J. H. , Canagaratna M. R. , Kolb C. E. , Worsnop D. R. , Neuman J. A. , Seila R. , Zavala M. , Knighton W. B.
Published: April 2010

Abstract. Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, the nitrogen oxide budget, and the radical budget during the MILAGRO campaign. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO2. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NOx oxidation products (NOz) For [NOx]/[NOy] values between 0.2 and 0.8, gas-phase HNO3 typically accounted for less than 10% of NOz and accumulation-mode particulate nitrate (NO3−(PM)) accounted for 20%–70% of NOz, consistent with high ambient NH3 concentrations. The fraction of NOz accounted for by the sum of HNO3(g) and NO3−(PM) decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO3 is accounted for, and indicates that HNO3 formation decreased relative to other NOx "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NOx on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.
The impact of diurnal variability in sea surface temperature on the atlantic air-sea CO2 flux
Authors: Kettle H. , Merchant C. J. , Jeffery C. D. , Filipiak M. J. , Gentemann C. L.
Published: April 2010

Abstract. The effect of diurnal variations in sea surface temperature (SST) on the air-sea flux of CO2 over the central Atlantic ocean and Mediterranean Sea is evaluated for 2005–2006. We use high resolution hourly satellite SST data to determine the diurnal warming (ΔSST). The CO2 flux is then computed using three different temperature fields – a foundation temperature (Tf, measured at a depth where there is no diurnal variation), Tf plus the hourly ΔSST and Tf plus monthly-averaged ΔSST. This is done in conjunction with a physically-based parameterisation for the gas transfer velocity (NOAA-COARE). The differences between the fluxes evaluated for these three different temperature fields quantifies the effects of both diurnal warming and diurnal covariations. We find that including diurnal warming increases the CO2 flux out of the Atlantic for 2005–2006 from 9.6 Tg C a−1 to 30.4 Tg C a−1 (hourly ΔSST) and 31.2 Tg C a−1 (monthly ΔSST). Diurnal warming, therefore, has a large impact on the annual net CO2 flux but diurnal covariations in variables are negligible implying that CO2 fluxes may be adequately computed using monthly averaged ΔSSTs along with a suitable foundation temperature.
Saharan dust transport and deposition towards the Tropical Northern Atlantic
Authors: Schepanski K. , Tegen I. , Macke A.
Published: April 2010

Abstract. We present a study of Saharan dust export towards the tropical North Atlantic using the regional dust emission, transport and deposition model LM-MUSCAT. Horizontal and vertical distribution of dust optical thickness, concentration, and dry and wet deposition rates are used to describe seasonality of dust export and deposition towards the eastern Atlantic for three exemplary months in different seasons. Deposition rates strongly depend on the vertical dust distribution, which differs with seasons. Furthermore the contribution of dust originating from the Bodélé Depression to Saharan dust over the Atlantic is investigated. A maximum contribution of Bodélé dust transported towards the Cape Verde Islands is evident in winter when the Bodélé source area is most active and dominant with regard activation frequency and dust emission. Limitations of using satellite retrievals to estimate dust deposition are highlighted.
Measurements of UV Aerosol Optical Depth in the French Southern Alps
Authors: Lenoble J. , Brogniez C. , de La Casinière A. , Cabot T. , Buchard V. , Guirado F.
Published: April 2010

Abstract. Routine measurements of global and diffuse UV irradiances at Briançon station (1310 m a.s.l.) are used to retrieve the direct solar irradiance and the aerosol optical depth (AOD), for cloudless days. Data of three years (2003, 2004, 2005) are analyzed; the results confirm those of a preliminary analysis for 2001, 2002. The atmosphere is very clear in winter, with AODs between 0.05 and 0.1. The turbidity increases slowly in spring, starting end of February, with AODs around 0.2–0.3 in mid summer, some values reaching 0.4. A similar behaviour is observed for all years, with somewhat higher values in late summer for the year 2003.
Validation of stratospheric water vapour measurements from the airborne microwave radiometer AMSOS
Authors: Müller S. C. , Kämpfer N. , Feist D. G. , Haefele A. , Milz M. , Sitnikov N. , Schiller C. , Kiemle C. , Urban J.
Published: April 2010

Abstract. We present the validation of a water vapour dataset obtained by the Airborne Microwave Stratospheric Observing System AMSOS, a passive microwave radiometer operating at 183 GHz. Vertical profiles are retrieved from spectra by an optimal estimation method. The useful vertical range lies in the upper troposphere up to the mesosphere with an altitude resolution of 8 to 16 km and a horizontal resolution of about 57 km. Flight campaigns were performed once a year from 1998 to 2006 measuring the latitudinal distribution of water vapour from the tropics to the polar regions. The obtained profiles show clearly the main features of stratospheric water vapour in all latitudinal regions. Data are validated against a set of instruments comprising satellite, ground-based, airborne remote sensing and in-situ instruments. It appears that AMSOS profiles have a dry bias of 3–20%, when compared to satellite experiments. A good agreement with a difference of 3.3% was found between AMSOS and in-situ hygrosondes FISH and FLASH and an excellent matching of the lidar measurements from the DIAL instrument in the short overlap region in the upper troposphere.
Large-scale planetary disturbances in stratospheric temperature at high-latitudes in the Southern Summer Hemisphere
Authors: Shepherd M. G. , Tsuda T.
Published: April 2010

Abstract. The global structure and propagation of large-scale (periods >5 days) waves in the Southern Hemisphere summer (December 2006–February 2007) at 60° S–75° S latitude are examined using temperature data from GPS radio occultation measurements by COSMIC/FORMOSAT 3 satellite constellation from 10 to 40 km altitude. Spectral analysis has revealed eastward propagating planetary scale perturbations with wavenumbers 1 and 2 and periods of 10-, 16- and 23 days, zonally symmetric waves with the same periods and stationary waves with wavenumber 1 and 2. The presence of the zonally symmetric waves is interpreted as an indication of the coupling of the stationary and traveling waves. The results obtained show a very dynamically active Antarctic summer stratosphere. The novel aspect of the work is in the use of the GPS COSMIC data providing multiple local times each day, thus allowing large-scale wave analysis at high Southern latitudes and revealing planetary wave activity not normally observed in summer, but more consistent with late winter and spring conditions in the stratosphere.
Evaluation of the global oceanic isoprene source and its impacts on marine organic carbon aerosol
Authors: Arnold S. R. , Spracklen D. V. , Williams J. , Yassaa N. , Sciare J. , Bonsang B. , Gros V. , Peeken I. , Lewis A. C. , Alvain S. , Moulin C.
Published: April 2010

Abstract. We have combined the first satellite maps of the global distribution of phytoplankton functional type and new measurements of phytoplankton-specific isoprene productivities, with available remote marine isoprene observations and a global model, to evaluate our understanding of the marine isoprene source and its impacts on organic aerosol abundances. Using satellite products to scale up data on phytoplankton-specific isoprene productivity to the global oceans, we infer a mean "bottom-up" oceanic isoprene emission of 0.31±0.08 (1 σ) Tg/yr. By minimising the mean bias between the model and isoprene observations in the marine atmosphere remote from the continents, we produce a "top-down" oceanic isoprene source estimate of 1.9 Tg/yr. We suggest our reliance on limited atmospheric isoprene data, and limited knowledge of isoprene productivity across the broad range of phytoplankton communities in the oceans as contributors to this difference between the two estimates. Inclusion of secondary organic aerosol (SOA) production from oceanic isoprene in the model with a 2% yield produces small contributions (0.01–1.6%) to observed organic carbon (OC) aerosol mass at three remote marine sites in the Northern and Southern Hemispheres. In addition, we find the seasonal cycle of the isoprene SOA source is out of phase with the observed cycle in OC in the remote Southern Ocean. Based on these findings we suggest an insignificant role for isoprene in modulating remote marine aerosol abundances, giving further support to a recently postulated primary OC source in the remote marine atmosphere.
Measurement of glyoxal using an incoherent broadband cavity enhanced absorption spectrometer
Authors: Washenfelder R. A. , Langford A. O. , Fuchs H. , Brown S. S.
Published: April 2010

Abstract. We describe an instrument for simultaneous measurements of glyoxal (CHOCHO) and nitrogen dioxide (NO2) using cavity enhanced absorption spectroscopy with a broadband light source. The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N2+O2). Least-squares fitting, using published reference spectra, allow the simultaneous retrieval of CHOCHO, NO2, O4, and H2O in the 441 to 469 nm spectral range. For a 1-min sampling time, the minimum detectable absorption is 4×10−10 cm−1, and the precision (±1σ) on signal for measurements of CHOCHO and NO2 is 29 pptv and 20 pptv, respectively. We directly compare the incoherent broadband cavity enhanced absorption spectrometer to 404 and 532 nm cavity ringdown instruments for CHOCHO and NO2 detection, and find linear agreement over a wide range of concentrations. The instrument has been tested in the laboratory with both synthetic and real air samples, and the demonstrated sensitivity and specificity suggest a strong potential for field measurements of both CHOCHO and NO2.
The effects of experimental uncertainty in parameterizing air-sea gas exchange using tracer experiment data
Authors: Asher W. E.
Published: April 2010

Abstract. It is not practical to measure air-sea gas fluxes in the open ocean for all conditions and areas of interest. Therefore, in many cases fluxes are estimated from measurements of air-phase and water-phase gas concentrations, a measured environmental forcing function such as wind speed, and a parameterization of the air-sea transfer velocity in terms of the environmental forcing function. One problem with this approach is that when direct measurements of the transfer velocity are plotted versus the most commonly used forcing function, wind speed, there is considerable scatter, leading to a relatively large uncertainty in the flux. Because it is known that multiple processes can affect gas transfer, it is commonly assumed that this scatter is caused by single-forcing function parameterizations being incomplete in a physical sense. However, scatter in the experimental data can also result from experimental uncertainty (i.e., measurement error). Here, results from field and laboratory results are used to estimate how experimental uncertainty contributes to the observed scatter in the measured fluxes and transfer velocities as a function of environmental forcing. The results show that experimental uncertainty could explain a major portion of the observed scatter in field and laboratory measurements of the air-sea gas transfer velocity.
The influence of natural and anthropogenic secondary sources on the glyoxal global distribution
Authors: Myriokefalitakis S. , Vrekoussis M. , Tsigaridis K. , Wittrock F. , Richter A. , Brühl C. , Volkamer R. , Burrows J. P. , Kanakidou M.
Published: April 2010

Abstract. Glyoxal, the smallest dicarbonyl, which has recently been observed from space, is expected to provide indications on VOC oxidation and secondary aerosol formation in the troposphere. Glyoxal is known to be mostly of natural origin and is produced during biogenic VOC oxidation. However, a number of anthropogenically emitted hydrocarbons, like acetylene and aromatics, have been positively identified as glyoxal precursors. The present study investigates the contribution of pollution emissions to the glyoxal levels by taking into account only the secondary chemical formation of glyoxal from precursors emitted from biogenic, anthropogenic and biomass burning sources. For this purpose, a global 3-dimensional chemistry transport model of the troposphere (TM4) able to simulate the gas phase chemistry coupled with all major aerosol components is used. The model results are compared with satellite observations of glyoxal columns over hot spot areas. According to TM4 model results, the anthropogenic contribution to the glyoxal columns is found to reach 70% in the industrialized areas of the northern hemisphere and up to 20% in the tropics. It is on average three times larger than the secondary production of glyoxal from biomass burning sources. The chemical production of glyoxal is calculated to equal about 56 Tg y−1 with 70% produced from biogenic hydrocarbons oxidation, 17% from acetylene, 11% from aromatic chemistry, and 2% from ethene and propene. Glyoxal is destroyed by reactions mainly with OH radicals (22%) and by photolysis (65%), but it is also removed from the atmosphere through wet (11%) and dry deposition (6%). Secondary organic aerosol potential formation through glyoxal losses on/in aerosols and clouds was neglected here due to the significant uncertainties associated with the underlying chemistry. The global annual mean glyoxal burden and lifetime in the model domain are estimated at 0.02 Tg and 3 h, respectively.
Parameterization of cloud droplet formation for global and regional models: including adsorption activation from insoluble CCN
Authors: Kumar P. , Sokolik I. N. , Nenes A.
Published: April 2010

Abstract. Dust and black carbon aerosol have long been known to have potentially important and diverse impacts on cloud droplet formation. Most studies to date focus on the soluble fraction of such particles, and ignore interactions of the insoluble fraction with water vapor (even if known to be hydrophilic). To address this gap, we develop a new parameterization framework that considers cloud droplet formation within an ascending air parcel containing insoluble (but wettable) particles mixed with aerosol containing an appreciable soluble fraction. Activation of particles with a soluble fraction is described through well-established Köhler Theory, while the activation of hydrophilic insoluble particles is treated by "adsorption-activation" theory. In the latter, water vapor is adsorbed onto insoluble particles, the activity of which is described by a multilayer Frankel-Halsey-Hill (FHH) adsorption isotherm modified to account for particle curvature. We further develop FHH activation theory, and i) find combinations of the adsorption parameters AFHH, BFHH for which activation into cloud droplets is not possible, and, ii) express activation properties (critical supersaturation) that follow a simple power law with respect to dry particle diameter. Parameterization formulations are developed for sectional and lognormal aerosol size distribution functions. The new parameterization is tested by comparing the parameterized cloud droplet number concentration against predictions with a detailed numerical cloud model, considering a wide range of particle populations, cloud updraft conditions, water vapor condensation coefficient and FHH adsorption isotherm characteristics. The agreement between parameterization and parcel model is excellent, with an average error of 10% and R2 ~0.98.
Dust aerosol optical properties over North China
Authors:   Shengjie Niu,   Xiaofeng Xu
Published: April 2010

Abstract. Aerosol optical properties were obtained from ground-based sunphotometer data at nine observatories over North China during two periods of 1996–1998 and 2002–2003. The seasonal changes of aerosol optical depth (AOD) at five wavelengths were observed, with the highest value of AOD in spring, while the lowest in winter. Four patterns of AOD diurnal variation were obtained, of which the high value occurred in the morning, noon, evening and no remarkable change, respectively. Together with meteorological records, the characteristics of AOD during dust weather were analyzed, and the results show that it was more detailed and accurate to use AOD to depict the strength change of dust weather than to use surface visibility. Based on measurements by aerodynamic instrument for particle size distribution, a positive correlation between dust particle number concentration and Ångström turbidity coefficient β, and a negative correlation between aerosol geometric mean diameter (GMD) and wavelength exponent αwere revealed.
CO emission and export from Asia: an analysis combining complementary satellite measurements (MOPITT, SCIAMACHY and ACE-FTS) with global modeling
Authors: Turquety S. , Clerbaux C. , Law K. , Coheur P.-F. , Cozic A. , Szopa S. , Hauglustaine D. A. , Hadji-Lazaro J. , Gloudemans A. M. S. , Schrijver H. , Boone C. D. , Bernath P. F. , Edwards D. P.
Published: April 2010

Abstract. This study evaluates our current knowledge of pollution outflow from Asia using simulations from the LMDz-INCA global model combined with the available satellite observations of CO during the spring of 2005. CO is measured by several space-borne instruments using different techniques, allowing complementary perspectives. The CO observations from the MOPITT and SCIAMACHY nadir sounders, which provide vertically integrated information with excellent horizontal sampling, and from the ACE-FTS solar occultation instrument, which has limited spatial coverage but allows the retrieval of vertical profiles, are used. Combining observations from MOPITT (mainly sensitive to the free troposphere) and SCIAMACHY (sensitive to the full column) allow the evaluation of the boundary layer CO. Underestimated emissions in eastern Asia, and possibly too low lofting in the model, lead to an underestimate of the export to the free troposphere, as highlighted by comparisons with MOPITT and ACE-FTS. Both instruments observe large trans-Pacific transport extending from ~20° N to ~60° N, with high upper tropospheric CO observed by ACE-FTS above the eastern Pacific (with values of up to 300 ppbv around 50° N at 500 hPa and up to ~200 ppbv around 30° N at 300 hPa). The low vertical and horizontal resolutions of the global model do not allow the simulation of the strong enhancements in the observed plumes. However, the transport patterns are well captured, and are mainly attributed to export from eastern Asia, with increasing contributions from South Asia and Indonesia towards the tropics. Additional measurements of C2H2, C2H6 and HCN by ACE-FTS provide further information on the plume history. C2H2 and C2H6 enhancements are well correlated with the CO plumes, indicating common sources and rapid trans-Pacific transport. HCN observations show that the biomass burning contributes mainly at latitudes lower than ~40° N.
On the validity of representing hurricanes as Carnot heat engine
Authors: Makarieva A. M. , Gorshkov V. G. , Li B.-L.
Published: April 2010

Abstract. It is argued, on the basis of detailed critique of published literature, that the existing thermodynamic theory of hurricanes, where it is assumed that the hurricane power is formed due to heat input from the ocean, is not physically consistent, as it comes in conflict with the first and second laws of thermodynamics. A quantitative perspective of describing hurricane energetics as that of an adiabatic atmospheric process occurring at the expense of condensation of water vapor that creates drop of local air pressure, is outlined.
Physical interpretation of the spectral radiative signature in the transition zone between cloud-free and cloudy regions
Authors: Chiu J. C. , Marshak A. , Knyazikhin Y. , Pilewskie P. , Wiscombe W. J.
Published: April 2010

Abstract. One-second-resolution zenith radiance measurements from the Atmospheric Radiation Measurement program's new shortwave spectrometer (SWS) provide a unique opportunity to analyze the transition zone between cloudy and cloud-free air, which has considerable bearing on the aerosol indirect effect. In the transition zone, we find a remarkable linear relationship between the sum and difference of radiances at 870 and 1640 nm wavelengths. The intercept of the relationship is determined primarily by aerosol properties, and the slope by cloud properties. We then show that this linearity can be predicted from simple theoretical considerations and furthermore that it supports the hypothesis of inhomogeneous mixing, whereby optical depth increases as a cloud is approached but the effective drop size remains unchanged. In addition, the width of transition zones from SWS data is in the range of 50–150 m, which differs from the width in satellite observations (a few kilometers) and in airborne lidar data (1–2 km).
Impacts of climate change on air pollution levels in the Northern Hemisphere with special focus on Europe and the Arctic
Authors: Hedegaard G. B. , Brandt J. , Christensen J. H. , Frohn L. M. , Geels C. , Hansen K. M. , Stendel M.
Published: April 2010

Abstract. The response of a selected number of chemical species is inspected with respect to climate change. The coupled Atmosphere-Ocean General Circulation Model ECHAM4-OPYC3 is providing meteorological fields for the Chemical long-range Transport Model DEHM. Three selected decades (1990s, 2040s and 2090s) are inspected. The 1990s are used as a reference and validation period. In this decade an evaluation of the output from the DEHM model with ECHAM4-OPYC3 meteorology input data is carried out. The model results are tested against similar model simulations with MM5 meteorology and against observations from the EMEP monitoring sites in Europe. The test results from the validation period show that the overall statistics (e.g. mean values and standard deviations) are similar for the two simulations. However, as one would expect the model setup with climate input data fails to predict correctly the timing of the variability in the observations. The overall performance of the ECHAM4-OPYC3 setup as meteorological input to the DEHM model is shown to be acceptable according to the applied ranking method. It is concluded that running a chemical long-range transport model on data from a "free run" climate model is scientifically sound. From the model runs of the three decades, it is found that the overall trend detected in the evolution of the chemical species, is the same between the 1990 decade and the 2040 decade and between the 2040 decade and the 2090 decade, respectively. The dominating impacts from climate change on a large number of the chemical species are related to the predicted temperature increase. Throughout the 21th century the ECHAM4-OPYC3 projects a global mean temperature increase of 3 K with local maxima up to 11 K in the Arctic winter based on the IPCC A2 emission scenario. As a consequence of this temperature increase, the temperature dependent biogenic emission of isoprene is predicted to increase significantly over land by the DEHM model. This leads to an increase in the O3 production and together with an increase in water vapor to an increase in the number of free OH radicals. Furthermore this increase in the number of OH radicals contributes to a significant change in the typical life time of many species, since OH are participating in a large number of chemical reactions. It is e.g. found that more SO42− will be present in the future over the already polluted areas and this increase can be explained by an enhanced conversion of SO2 to SO42− .
Gaseous elemental and reactive mercury in southern New Hampshire
Authors: Sigler J. M. , Mao H. , Talbot R.
Published: April 2010

Abstract. We conducted measurements of Hg° and RGM at two inland sites, Thompson Farm (TF) and Pac Monadnock (PM), and a marine site (Appledore Island – AI) from the UNH AIRMAP observing network in New Hampshire in 2007. Measurements of other important trace gases and meteorological variables were used to help understand influences on the atmospheric Hg budget in New England. Seasonal variation in both species observed at TF and PM is attributable to such factors as seasonal variation in deposition strength, meteorological conditions and biogenic emissions. Hg° and RGM varied diurnally at TF, particularly in spring, following the trend in air temperature and jNO2 and suggesting photochemical production of RGM. The diurnal patterns of Hg° and RGM at AI during summer were nearly opposite in phase, with Hg° decreasing through late afternoon, suggesting more significant photochemical oxidation of Hg° to RGM in the marine environment, likely due to the presence of marine halogen compounds. A strong relationship of RGM with SO2 at TF suggests a strong contribution of RGM from anthropogenic sources. Significant levels of halogen compounds measured at TF in previous studies, as well as similar Hg° levels and Hg°-CO ratios at TF and AI may suggest that similar air masses are prevalent at these sites.
Peroxy radicals in the summer free troposphere: seasonality and heterogeneous loss
Authors: Parker A. E. , Monks P. S. , Wyche K. P. , Balzani-Lööv J. M. , Staehelin J. , Reimann S. , Legreid G. , Vollmer M. K. , Steinbacher M.
Published: April 2010

Abstract. The sum of peroxy radicals (HO2+ΣiRiO2) and supporting trace gases were measured on the Jungfraujoch (3580 m a.s.l.) during the late summer of 2005. The period was marked by extended times of heavy snow which led to reduction in the observed peroxy radicals during the snowy periods that was greater than the concomitant reduction in j(O1D). In the limit a first order loss rate of 0.0063 s−1 can be derived for the peroxy radical loss in the snowy conditions that could be ascribed to a heterogenous loss process. On snow free days photolysis of HCHO is shown to be a significant peroxy radical source. The seasonal trends of the peroxy radical concentrations have been mapped from the winter to summer transition in line with previous experiments. Net ozone production in late summer at the Jungfraujoch was net neutral to marginally ozone destructive. A value of 28±4 pptv is calculated for the ozone compensation point for the snow free days.
A self-adapting and altitude-dependent regularization method for atmospheric profile retrievals
Authors: Ridolfi M. , Sgheri L.
Published: April 2010

Abstract. MIPAS is a Fourier transform spectrometer, operating onboard of the ENVISAT satellite since July 2002.The online retrieval algorithm produces geolocated profiles of temperature and of volume mixing ratios of six key atmospheric constituents: H2O, O3, HNO3, CH4, N2O and NO2. In the validation phase, oscillations beyond the error bars were observed in several profiles, particularly in CH4 and N2O. To tackle this problem, a Tikhonov regularization scheme has been implemented in the retrieval algorithm. The applied regularization is however rather weak in order to preserve the vertical resolution of the profiles. In this paper we present a self-adapting and altitude-dependent regularization approach that detects whether the analysed observations contain information about small-scale profile features, and determines the strength of the regularization accordingly. The objective of the method is to smooth out artificial oscillations as much as possible, while preserving the fine detail features of the profile when related information is detected in the observations. The proposed method is checked for self consistency, its performance is tested on MIPAS observations and compared with that of a few scalar and altitude-dependent regularization schemes available in the literature. In all the considered cases the proposed scheme achieves a good performance, thanks to its altitude dependence and to the constrains employed, which are specific of the inversion problem under consideration. The proposed method is generally applicable to iterative Gauss-Newton algorithms for the retrieval of vertical distribution profiles from atmospheric remote sounding measurements.
Organic nitrate and secondary organic aerosol yield from NO3 oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model
Authors: Fry J. L. , Kiendler-Scharr A. , Rollins A. W. , Wooldridge P. J. , Brown S. S. , Fuchs H. , Dube W. , Mensah A. , dal Maso M. , Tillmann R. , Dorn H.-P. , Brauers T. , Cohen R. C.
Published: April 2010

Abstract. The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5<10 ppb) and β-pinene (peak~15 ppb), with no seed aerosol. SOA formation was observed to be prompt and substantial (~50% mass yield under both dry conditions and at 60% RH), and highly correlated with organic nitrate formation. The observed gas/aerosol partitioning of organic nitrates can be simulated using an absorptive partitioning model to derive an estimated vapor pressure of the condensing nitrate species of pvap~5×10−6 Torr (6.67×10−4 Pa), which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NOx-dependent oxidation of monoterpenes provide an example of a significant anthropogenic source of SOA from biogenic hydrocarbon precursors. Estimates of the NO3+β-pinene SOA source strength for California and the globe indicate that NO3 reactions with monoterpenes are likely an important source (0.5–8% of the global total) of organic aerosol on regional and global scales.
Sensitivity of satellite observations for freshly produced lightning NOx
Authors: Beirle S. , Salzmann M. , Lawrence M. G. , Wagner T.
Published: April 2010

Abstract. In this study, we analyse the sensitivity of nadir viewing satellite observations in the visible range to freshly produced lightning NOx, i.e. for meteorological and (photo-) chemical conditions found in and around cumulonimbus clouds. For the first time, such a study is performed accounting for photo-chemistry, dynamics, and radiative transfer in a consistent way: A one week episode in the TOGA COARE/CEPEX region (Pacific) in December 1992 is simulated with a 3-D cloud resolving chemistry model. The simulated hydrometeor mixing ratios are fed into a Monte Carlo radiative transfer model to calculate box-Air Mass Factors (box-AMFs) for NO2. From these box-AMFs, together with model NOx profiles, slant columns of NO2 (SNO2), i.e. synthetic satellite measurements, are calculated and set in relation to the actual model NOx vertical column (VNOx), yielding the "sensitivity" SNO2/VNOx. From this study, we find a mean sensitivity of 0.46. NOx below the cloud bottom is mostly present as NO2, but shielded from the satellites' view, whereas NOx at the cloud top or above is shifted to NO due to high photolysis and low temperature, and hence not detectable from space. But a significant fraction of the lightning produced NOx in the middle part of the cloud is present as NO2 and has a good visibility from space. Due to the resulting total sensitivity being quite high, nadir viewing satellites provide a valuable additional platform to quantify NOx production by lightning; strong lightning events over "clean" regions should be clearly detectable in satellite observations. Since the observed enhancement of NO2 column densities over mesoscale convective systems are lower than expected for current estimates of NOx production per flash, satellite measurements can in particular constrain the upper bound of lightning NOx production estimates.