bluuebunny/crossref_metadata_2025 huggingface dataset:
Insights into the role of soot aerosols in cirrus cloud formation
Authors: Kärcher B. , Möhler O. , DeMott P. J. , Pechtl S. , Yu F.
Published: April 2010

Abstract. Cirrus cloud formation is believed to be domi\\-nated by homogeneous freezing of supercooled liquid aerosols in many instances. Heterogeneous ice nuclei such as mineral dust, metallic, and soot particles, and some crystalline solids within partially soluble aerosols are suspected to modulate cirrus properties. Among those, the role of ubiqui\\-tous soot particles is perhaps the least understood. Because aviation is a major source of upper tropospheric soot particles, we put emphasis on ice formation in dispersing aircraft plumes. The effect of aircraft soot on cirrus formation in the absence of contrails is highly complex and depends on a wide array of emission and environmental parameters. We use a microphysical-chemical model predicting the formation of internally mixed, soot-containing particles up to two days after emission, and suggest two principal scenarios, both assuming soot particles to be moderate ice nuclei relative to cirrus formation by homogeneous freezing in the presence of few efficient dust ice nuclei: high concentrations of original soot emissions could slightly increase the number of ice crystals; low concentrations of particles originating from coagulation of emitted soot with background aerosols could lead to a significant reduction in ice crystal number. A critical discussion of laboratory experiments reveals that the ice nucleation efficiency of soot particles depends strongly on their source, and, by inference, on atmospheric aging processes. Mass and chemistry of soluble surface coatings appear to be crucial factors. Immersed soot particles tend to be poor ice nuclei, some bare ones nucleate ice at low supersaturations. However, a fundamental understanding of these studies is lacking, rendering extrapolations to atmospheric conditions speculative. In particular, we cannot yet decide which indirect aircraft effect scenario is more plausible, and options suggested to mitigate the problem remain uncertain.
Urban Visible/SWIR surface reflectance ratios from satellite and sun photometer measurements in Mexico City
Authors: de Almeida Castanho A. D. , Prinn R. , Martins V. , Herold M. , Ichoku C. , Molina L. T.
Published: April 2010

Abstract. The surface reflectance ratio between the visible (VIS) and shortwave infrared (SWIR) radiation is an important quantity for the retrieval of the aerosol optical depth (τa) from the MODIS sensor data. Based on empirically determined VIS/SWIR ratios, MODIS τa retrieval uses the surface reflectance in the SWIR band (2.1 μm), where the interaction between solar radiation and the aerosol layer is small, to predict the visible reflectances in the blue (0.47 μm) and red (0.66 μm) bands. Therefore, accurate knowledge of the VIS/SWIR ratio is essential for achieving accurate retrieval of aerosol optical depth from MODIS. The heterogeneity of the surface cover in an urban environment increases the uncertainties in the estimation of the surface reflectance and, consequently, τa. We analyzed the surface reflectance over some distinct surface covers in and around the Mexico City metropolitan area (MCMA) using MODIS radiances at 0.66 μm and 2.1 μm. The analysis was performed at 1.5 km×1.5 km spatial resolution. Also, ground-based AERONET sun-photometer data acquired in Mexico City from 2002 to 2005 were analyzed for aerosol optical thickness and other aerosol optical properties. In addition, a network of hand-held sun-photometers deployed in Mexico City, as part of the MCMA-2006 Study during the MILAGRO Campaign, provided an unprecedented measurement of τa in 5 different sites well distributed in the city. We found that the average RED/SWIR ratio representative of the urbanized sites analyzed is 0.73±0.06. This average ratio was significantly different for non-urban sites, which was approximately 0.55. The aerosol optical thickness retrieved from MODIS radiances at a spatial resolution of 1.5 km×1.5 km and averaged within 10 x 10 km boxes were compared with collocated 1-h τa averaged from sun-photometer measurements. The use of the new RED/SWIR ratio of 0.73 in the MODIS retrieval led to a significant improvement in the agreement between the MODIS and sun-photometer results; with the slope, offset, and the correlation coefficient of the linear regression changing from (τaMODIS = 0.91 τa sun-photometer + 0.33 ,R2=0.66) to (τaMODIS = 0.96 τa sun-photometer −0.006, R2=0.87).
Retrieval of stratospheric and tropospheric BrO columns from multi-axis DOAS measurements at Reunion Island (21° S, 56° E)
Authors: Theys N. , Van Roozendael M. , Hendrick F. , Fayt C. , Hermans C. , Baray J.-L. , Goutail F. , Pommereau J.-P. , De Mazière M.
Published: April 2010

Abstract. Spectral measurements of BrO using zenith-sky and off-axis viewing geometries are combined in a linear multiple regression retrieval algorithm to provide stratospheric and tropospheric BrO vertical columns. One year of measurement data are investigated over Reunion-Island (20.9° S, 55.5° E), from July 2004 to July 2005. No seasonal variations of the retrieved BrO columns could be observed, in line with previous studies. A comparison between the stratospheric columns retrieved at 45°, 80°, 85°, 87.5° and 92.5° solar zenith angles and photochemical simulations initialized by chemical fields from the 3-D-CTM SLIMCAT and further constrained by observed NO2 profiles shows a good agreement only by considering a contribution from the very short-lived organic bromine substances to the stratospheric inorganic bromine budget, of 6 to 8 pptv. Furthermore, stratospheric BrO profiles retrieved from late twilight zenith-sky observations are consistent with a total inorganic bromine (Bry) loading of approximately 23 pptv. This represents 6 to 7 pptv more than can be supplied by long-lived organic bromine sources, and therefore supports an added contribution from very short-lived organic bromine substances as recently suggested in several other studies. Moreover strong evidences are presented for the existence of a substantial amount of BrO in the tropical free-troposphere, around 6 km altitude, possibly supplied by the decomposition of short-lived biogenic bromine organic compounds. Tropospheric BrO vertical columns of 1.1±0.45×1013 molec/cm2 are derived for the entire observation period. Comparisons between ground-based BrO vertical columns and total BrO columns derived from SCIAMACHY (onboard the ENVISAT satellite) nadir observations in a latitudinal band centered around 21° S present a good level of consistency, which further strengthens the conclusions of our study.
Development of a secondary organic aerosol formation mechanism: comparison with smog chamber experiments and atmospheric measurements
Authors: Olcese L. E. , Penner J. E. , Sillman S.
Published: April 2010

Abstract. A new mechanism to simulate the formation of secondary organic aerosols (SOA) from reactive primary hydrocarbons is presented, together with comparisons with experimental smog chamber results and ambient measurements found in the literature. The SOA formation mechanism is based on an approach using calculated vapor pressures and a selection of species that can partition to the aerosol phase from a gas phase photochemical mechanism. The mechanism has been validated against smog chamber measurements using α-pinene, xylene and toluene as SOA precursors, and has an average error of 17%. Qualitative comparisons with smog chamber measurements using isoprene were also performed. A comparison against SOA production in the TORCH 2003 experiment (atmospheric measurements) had an average error of only 12%. This contrasts with previous efforts, in which it was necessary to increase partition coefficients by a factor of 500 in order to match the observed values. Calculations for rural and urban-influenced regions in the eastern U.S. suggest that most of the SOA is biogenic in origin, mainly originated from isoprene. A 0-dimensional calculation based on the New England Air Quality Study also showed good agreement with measured SOA, with about 40% of the total SOA from anthropogenic precursors. This mechanism can be implemented in a general circulation model (GCM) to estimate global SOA formation under ambient NOx and HOx levels.
The tropical forest and fire emissions experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning
Authors: Karl T. G. , Christian T. J. , Yokelson R. J. , Artaxo P. , Min Hao W. , Guenther A.
Published: April 2010

Abstract. Volatile Organic Compound (VOC) emissions from fires in tropical forest fuels were quantified using Proton-Transfer-Reaction Mass Spectrometry (PTRMS), Fourier Transformation Infrared Spectroscopy (FTIR) and gas chromatography (GC) coupled to PTRMS (GC-PTR-MS). We investigated VOC emissions from 19 controlled laboratory fires at the USFS Fire Sciences Laboratory and 16 fires during an intensive airborne field campaign during the peak of the burning season in Brazil in 2004. The VOC emissions were dominated by oxygenated VOCs (OVOC) (OVOC/NMHC ~4:1, NMHC: non-methane hydrocarbons) The specificity of the PTR-MS instrument, which measures the mass to charge ratio of VOCs ionized by H3O+ ions, was validated by gas chromatography and by intercomparing in-situ measurements with those obtained from an open path FTIR instrument. Emission ratios for methyl vinyl ketone, methacrolein, crotonaldehyde, acrylonitrile and pyrrole were measured in the field for the first time. Our measurements show a higher contribution of OVOCs than previously assumed for modeling purposes. Comparison of fresh (<15 min) and aged (>1hour-1day) smoke suggests altered emission ratios due to gas phase chemistry for acetone but not for acetaldehyde and methanol. Emission ratios for numerous, important, reactive VOCs with respect to acetonitrile (a biomass burning tracer) are presented.
The diurnal evolution of 222Rn and its progeny in the atmospheric boundary layer during the Wangara experiment
Authors: Vinuesa J.-F. , Basu S. , Galmarini S.
Published: April 2010

Abstract. The diurnal atmospheric boundary layer evolution of the 222Rn decaying family is studied by using a state-of-the-art large-eddy simulation model. In particular, a diurnal cycle observed during the Wangara experiment is successfully simulated together with the effect of diurnal varying turbulent characteristics on radioactive compounds in a secular equilibrium. This study allows us to clearly analyze and identify the boundary layer processes driving the 222Rn and its progeny concentration behaviors. The activity disequilibrium observed in the nocturnal boundary layer is due to the proximity of the radon source and the trapping of fresh 222Rn close to the surface induced by the weak vertical transport. During the morning transition, the secular equilibrium is fast restored by the vigorous turbulent mixing. The evolution of 222Rn and its progeny concentration in the unsteady growing convective boundary layer depends on the strength of entrainment events.
Is there a stratospheric fountain?
Authors: Pommereau J.-P. , Held G.
Published: April 2010

Abstract. The impact of convection on the thermal structure of the Tropical Tropopause Layer (TTL) was investigated from a series of four daily radiosonde ascents and weather S-band radar observations carried out during the HIBISCUS campaign in the South Atlantic Convergence Zone in Southeast Brazil in February 2004. The temperature profiles display a large impact of convective activity on the thermal structure of the TTL. Compared to non-active periods, convection is observed to result in a cooling of 4.5°C to 7.5°C at the Lapse Rate Tropopause at 16 km, propagating up to 19 km or 440 K potential temperature levels in the stratosphere in most intense convective cases. Consistent with the diurnal cycle of echo top heights seen by a S-band weather radar, a systematic temperature diurnal cycle is observed in the layer, displaying a rapid cooling of 3.5°C on average (–9°, –2°C extremes) during the development phase of convection in the early afternoon during the most active period. Since the cooling occurs during daytime within a timescale of 6-h, its maximum amplitude is at the altitude of the Cold Point Tropopause at 390 K and temperature fluctuations associated to gravity waves do not display significant diurnal change, the afternoon cooling of the TTL cannot be attributed to radiation, advection, gravity waves or adiabatic lofting. It implies a fast insertion of adiabatically cooled air parcels by overshooting turrets followed by mixing with the warmer environment. During most intense convective days, the overshoot is shown to penetrate the stratosphere up to 450 K potential temperature level. Such fast updraft offers an explanation for the presence of ice crystals, and enhanced water vapour layers observed up to 18–19 km (410–430 K) in the same area by the HIBISCUS balloons and the TROCCINOX Geophysica aircraft, as well as high tropospheric chemical species concentrations in the TTL over land observed from space. Overall, injection of cold air by irreversible mixing of convective overshoots as proposed by Danielsen (1982) do not appear as episodic isolated features, but common and systematic events over a land convective area, that is a Stratospheric Fountain. Though the two-stages process proposed by Sherwood (2000) may also be operative, it offers a mechanism for producing the chemical, moisture and thermal properties observed in the stratosphere. The consistency between convective cooling of the TTL and weather radar echoes heights observed during the summer over South-East Brazil and the TRMM radar OPFs and LIS lightning events maximum frequencies, the latter showing also maximum events over Africa, South-East Asia, the Indonesian Islands and Northern Australia depending on the season (Liu and Zipser, 2005), suggests the existence of several "Stratospheric Fountains" over continents instead of the oceanic area of Micronesia as proposed by Newell and Gould-Stewart (1982), which appears a region of little overshoot.
Modeling secondary organic aerosol formation through cloud processing of organic compounds
Authors: Chen J. , Griffin R. J. , Grini A. , Tulet P.
Published: April 2010

Abstract. Interest in the potential formation of secondary organic aerosol (SOA) through reactions of organic compounds in condensed aqueous phases is growing. In this study, the potential formation of SOA from irreversible aqueous-phase reactions of organic species in clouds was investigated. A new proposed aqueous-phase chemistry mechanism (AqChem) is coupled with the existing gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) and the Model to Predict the Multiphase Partitioning of Organics (MPMPO) that simulate SOA formation. AqChem treats irreversible organic reactions that lead mainly to the formation of carboxylic acids, which are usually less volatile than the corresponding aldehydic compounds. Zero-dimensional model simulations were performed for tropospheric conditions with clouds present for three consecutive hours per day. Zero-dimensional model simulations show that 48-h averaged SOA formation are increased by 27% for a rural scenario with strong monoterpene emissions and 7% for an urban scenario with strong emissions of aromatic compounds, respectively, when irreversible organic reactions in clouds are considered. AqChem was also incorporated into the Community Multiscale Air Quality Model (CMAQ) version 4.4 with CACM/MPMPO and applied to a previously studied photochemical episode (3–4 August 2004) focusing on the eastern United States. The CMAQ study indicates that the maximum contribution of SOA formation from irreversible reactions of organics in clouds is 0.28 μg m−3 for 24-h average concentrations and 0.60 μg m−3 for one-hour average concentrations at certain locations. On average, domain-wide surface SOA predictions for the episode are increased by 8.6% when irreversible, in-cloud processing of organics is considered.
Alkene ozonolysis SOA: inferences of composition and droplet growth kinetics from Köhler theory analysis
Authors: Asa-Awuku A. , Nenes A. , Gao S. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. The CCN properties, surfactant characteristics, and droplet growth kinetics of secondary organic aerosol (SOA) formed from the ozonolysis of three parent alkene hydrocarbons (terpinolene, 1-methlycycloheptene and cycloheptene) are explored. Based on measurements of CCN activity, total carbon and inorganic ion concentrations, we estimate the average molar volume of the water-soluble organic component using Köhler Theory Analysis (KTA). The results suggest that the water-soluble organics in the SOA are composed of relatively low molecular weight species, with an effective molar mass less than 200 g mol−1. This finding is consistent with the speciated fraction for some of the SOA, and suggests that KTA can be applied to complex organic aerosol, such as that found in the atmosphere. From measurements of CCN activity and Köhler Theory, we apply a novel method to infer the surface tension at the point of activation; this is used to infer the presence of surface-active organics. It is found that the water-soluble carbon can be surface-active, depressing surface tension 10–15% from that of pure water at concentrations relevant for CCN activation. Although important, this level of surface tension depression is lower than expected for HULIS, which suggest that they are not likely in the SOA examined. In all cases, the CCN exhibit droplet growth kinetics similar to (NH4)2SO4.
Intercontinental transport of pollution and dust aerosols: implications for regional air quality
Authors:   Mian Chin, Diehl T. , Ginoux P. , Malm W.
Published: April 2010

Abstract. We use the global model GOCART to examine the impact of pollution and dust aerosols emitted from their major sources on surface fine particulate matter concentrations at regional and hemispheric scales. Focusing on the North America region in 2001, we use measurements from the IMPROVE network in the United States to evaluate the model-simulated surface concentrations of the "reconstructed fine mass" (RCFM) and its components of ammonium sulfate, black carbon (BC), organic matter (OM), and fine mode dust. We then quantify the RCFM budget in terms of the RCFM composition, type, and origin to find that in the eastern U.S., ammonium sulfate is the dominant RCFM component (~60%) whereas in the western U.S., dust and OM are just as important as sulfate but have considerable seasonal variations, especially in the NW. On an annual average, North America regional pollution accounts for nearly 30–40% of the surface RCFM in the western U.S., and for a much higher proportion of 65–70% in the eastern U.S. By contrast, pollution from outside of North America contributes to just 2–6% (~0.2 μg m−3) of the total RCFM over the U.S. on an annual average. In comparison, long-range transport of dust is more efficient than that of pollution, which brings 3 to 4 times more fine particles to the U.S. (0.5–0.8 μg m−3 on an annual average) with a maximum influence in spring and over the NW. Of the major pollution regions, Europe has the largest potential to affect the surface aerosol concentrations in other continents due to its shorter distance from receptor continents and its larger fraction of sulfate-producing precursor gas in the outflow. With the IPCC emission scenario for the year 2000, we find that European emissions increase levels of ammonium sulfate by 1–5 μg m−3 over the surface of northern Africa and western Asia, and its contribution to eastern Asia (≥0.2 μg m−3) is twice as much as the Asian contribution to North America. Asia and North America pollution emissions exert strong impacts on their neighboring oceans, but their influences on other continents are relatively small (≤10%) due to the long traveling distance across the oceans and efficient removal during transport. Among the major dust source regions, Asia displays a significant influence over large areas in the Northern Hemisphere except over the North Atlantic and the tropics, where African dust dominates. The trans-Pacific transport of Asian dust is much more efficient than that of Asian pollution because of the higher elevation and lower removal rate of dust. We notice that the African dust can travel eastward through a pathway spanning across Asia and North Pacific to settle down over the surface of western North America. African dust transported through such a pathway is difficult to detect because it usually merges and travels together with the Asian dust.
The influence of biogenic emissions on upper-tropospheric methanol as revealed from space
Authors: Dufour G. , Szopa S. , Hauglustaine D. A. , Boone C. D. , Rinsland C. P. , Bernath P. F.
Published: April 2010

Abstract. The distribution and budget of oxygenated organic compounds in the atmosphere and their impact on tropospheric chemistry are still poorly constrained. Near-global space-borne measurements of seasonally resolved upper tropospheric profiles of methanol by the ACE Fourier transform spectrometer provide a unique opportunity to evaluate our understanding of this important oxygenated organic species. The comparison with distributions simulated by a state-of-the-art chemistry transport model shows fair agreement during the March 2004 to August 2005 period with about 50% of the measurements reproduced by the model within 50%. However, in the northern hemisphere and during summertime, the satellite measurements reveal that the emissions from the continental biosphere lead to upper-tropospheric methanol concentrations significantly higher than expected.
Sand/dust storms over Northeast Asia and associated large-scale circulations in spring 2006
Authors: Yang Y. Q. , Hou Q. , Zhou C. H. , Liu H. L. , Wang Y. Q. , Niu T.
Published: April 2010

Abstract. This paper presents a study on the meteorological conditions that accompany the sand/dust storms (SDS) of East Asia in spring 2006, based on the SDS data collected both by WMO during 2000–2006 and by 2456 Chinese surface stations, and on the meteorological reanalysis data from NCEP-NCAR . The evolution of 3-D structures of the general circulations prevailed in both winter and spring as well as their annual anomalies were investigated by comparing the years having most and least occurrences of SDS between 2000 and 2006. It is found that spring 2006 featured a noticeably increased occurrence of SDS, compared with previous years. The general circulations prevailed through both winter and spring, especially the 3-D structure of the polar circulation, show the significant anomalies compared to a normal year. This produced a range of corresponding weather phenomena, including circumpolar vortices at the upper troposphere, mid-level westerly jets, and lower zonal winds, which all favored the SDS production and transport in 2006. The study also reveals a fact that comparing with a normal year, the transitional period from the winter of 2005 to the spring of 2006 has witnessed a fast-developed high center at the upper troposphere of the northern hemisphere and the circumpolar vortex area, which pushes the area dominated by the circumpolar vortices further to mid-latitudes. The circumpolar vortices shifted southwards, and prevailed over an extensive area across the northeast hemisphere for a sustained period. The mid-high latitude areas that sit in the south of the circumpolar vortices in Asia have experienced significantly abnormal westerly jets at the mid-level of troposphere. Zonal winds prevailed at the mid and lower levels of troposphere. Sea level pressure registered an abnormal high at 4–10 hPa, compared with a normal year. The above-mentioned 3-D structures of general circulation have created thermal and dynamic conditions that favor the repeated genesis and momentous development of the Mongolian cyclones, which in turn contributes to the frequent occurrences and long distance transport of SDS.
A twenty-year study on natural and manmade global interannual fluctuations of cirrus cloud cover
Authors: Eleftheratos K. , Zerefos C. S. , Zanis P. , Balis D. S. , Tselioudis G. , Gierens K. , Sausen R.
Published: April 2010

Abstract. The seasonal variability and the interannual variance explained by ENSO and NAO to cirrus cloud cover (CCC) are examined during the twenty-year period 1984–2004. CCC was found to be significantly correlated with vertical velocities and relative humidity from ECMWF/ERA40 in the tropics (correlations up to –0.7 and +0.7 at some locations, respectively) suggesting that variations in large-scale vertical winds and relative humidity fields can be the origin of up to half of the local variability in CCC over these regions. These correlations reflect mostly the seasonal cycle. Although the annual cycle is dominant in all latitudes and longitudes, peaking over the tropics and subtropics, its amplitude can be exceeded during strong El Nino/La Nina events. Over the eastern tropical Pacific Ocean the interannual variance of CCC which can be explained by ENSO is about 6.8% and it is ~2.3 times larger than the amplitude of the annual cycle. Natural long-term trends in the tropics are generally small (about –0.3% cloud cover per decade) and possible manmade trends in those regions are also small. The contributions of NAO and QBO to the variance of CCC in the tropics are also small. In the northern mid–latitudes, on the other hand, the effect of NAO is more significant and can be very important regionally. Over northern Europe and the eastern part of the North Atlantic Flight Corridor (NAFC) there is a small positive correlation between CCC and NAO index during the wintertime of about 0.3. In this region, the interannual variance of CCC explained by NAO is 2.6% and the amplitude of the annual cycle is 3.1%. Long-term trends over this region are about +1.6% cloud cover per decade and compare well with the observed manmade trends over congested air traffic regions in Europe and the North Atlantic as have been evidenced from earlier findings.
Characterization of positive air ions in boreal forest air at the Hyytiälä SMEAR station
Authors: Hõrrak U. , Aalto P. P. , Salm J. , Komsaare K. , Tammet H. , Mäkelä J. M. , Laakso L. , Kulmala M.
Published: April 2010

Abstract. The behavior of the concentration of positive small (or cluster) air ions and naturally charged nanometer aerosol particles (aerosol ions) has been studied on the basis of measurements carried out in a boreal forest at the Hyytiälä SMEAR station, Finland, during the BIOFOR III campaign in spring 1999. Statistical characteristics of the concentrations of cluster ions, two classes of aerosol ions of the sizes of 2.5–8 nm and 8–ca. 20 nm and the quantities that determine the balance of small ions in the atmosphere have been given for the nucleation event days and non-event days. The dependence of small ion concentration on the ion loss (sink) due to aerosol particles was investigated applying a model of bipolar diffusion charging of particles by small ions. The small ion concentration and the ion sink were closely correlated (correlation coefficient –87%) when the fog events and the hours of high relative humidity (above 95%), as well as nocturnal calms and weak wind (wind speed <0.6 m s−1) had been excluded. However, an extra ion loss term presumably due to small ion deposition on coniferous forest with a magnitude equal to the average ion loss to pre-existing particles is needed to explain the observations. Also the hygroscopic growth correction of measured aerosol particle size distributions was found to be necessary for proper estimation of the ion sink. In the case of nucleation burst events, variations in the concentration of small positive ions were in accordance with the changes caused by the ion sink due to aerosols; no clear indication of positive ion depletion by ion-induced nucleation was found. The estimated average ionization rate of the air at the Hyytiälä station in early spring, when the ground was partly covered with snow, was about 6 ion pairs cm−3 s−1. The study of the charging state of nanometer aerosol particles (2.5–8 nm) revealed a strong correlation (correlation coefficient 88%) between the concentrations of particles and positively charged particles (positive air ions) during nucleation bursts. The estimated charged fraction of particles, which varied from 3% to 6% considering various nucleation event days, confirms that these particles are almost quasi-steady state charged. Also the particles and air ions in the size range of 8–ca. 20 nm showed a good qualitative consistency; the correlation coefficient was 92%.
Source apportionment of fine organic aerosol in Mexico City during the MILAGRO Experiment 2006
Authors: Stone E. A. , Snyder D. C. , Sheesley R. J. , Sullivan A. P. , Weber R. J. , Schauer J. J.
Published: April 2010

Abstract. Organic carbon (OC) comprises a large fraction of fine particulate matter (PM2.5) in Mexico City. Daily and select 12-h PM2.5 samples were collected in urban and peripheral sites in Mexico City from 17–30 March 2006. Samples were analyzed for OC and elemental carbon (EC) using thermal-optical filter-based methods. Real-time water-soluble organic carbon (WSOC) was collected at the peripheral site. Organic compounds, particularly molecular markers, were quantified by soxhlet extraction with methanol and dichloromethane, derivitization, and gas chromatography with mass spectrometric detection (GCMS). A chemical mass balance model (CMB) based on molecular marker species was used to determine the relative contribution of major sources to ambient OC. Motor vehicles, including diesel and gasoline, consistently accounted for 47% of OC in the urban area and 31% on the periphery. The daily contribution of biomass burning to OC was highly variable, and ranged from 5–30% at the urban site and 11–50% at the peripheral site. The remaining OC unapportioned to primary sources showed a strong correlation with WSOC and was considered to be secondary in nature. Comparison of temporally resolved OC showed that contributions from primary aerosol sources during daylight hours were not significantly different from nighttime. This study provides quantitative understanding of the important sources of OC during the MILAGRO 2006 field campaign.
Tropospheric ozone climatology over Beijing: analysis of aircraft data from the MOZAIC program
Authors: Ding A. J. , Wang T. , Thouret V. , Cammas J.-P. , Nédélec P.
Published: April 2010

Abstract. Ozone (O3) profiles recorded over Beijing from 1995 to 2005 by the Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) program were analyzed to provide a first climatology of tropospheric O3 over Beijing and the North China Plains (NCPs), one of the most populated and polluted regions in China. A pooled method was adopted in the data analysis to reduce the influence of irregular sampling frequency. The tropospheric O3 over Beijing shows a seasonal and vertical distribution typical of mid-latitude locations in the Northern Hemisphere, but has higher daytime concentrations in the lower troposphere, when compared to New York City, Tokyo, and Paris at similar latitude. The tropospheric O3 over Beijing exhibits a common summer maximum and a winter minimum, with a broad summer maximum in the middle troposphere and a narrower early summer (June) peak in the lower troposphere. Examination of meteorological and satellite data suggests that the lower tropospheric O3 maximum in June is a result of strong photochemical production, transport of regional pollution, and possibly also more intense burnings of biomass in Central-Eastern China. Trajectory analysis indicates that in summer the regional pollution sources from the NCPs, maybe mixed with urban plumes from Beijing, played important roles on the high O3 concentrations in the boundary layer, but had limited impact on the O3 concentrations in the middle troposphere. A comparison of the data recorded before and after 2000 reveals that O3 in the lower troposphere over Beijing had a strong positive trend (approximately 2% per year from 1995 to 2005) in contrast to a flat or a decreasing trend over Tokyo, New York City, and Paris, indicating worsening photochemical pollution in Beijing and the NCPs.
Simple measures of ozone depletion in the polar stratosphere
Authors: Müller R. , Grooß J.-U. , Lemmen C. , Heinze D. , Dameris M. , Bodeker G.
Published: April 2010

Abstract. We investigate the extent to which commonly considered quantities, based on total column ozone observations and simulations, are applicable as measures of ozone loss in the polar vortices. Such quantities have been used frequently in ozone assessments by the World Meteorological Organization (WMO) and to assess the performance of chemistry-climate models. The most commonly considered quantity is monthly mean column ozone poleward of a latitude of 63° in spring. For the Arctic, these monthly means were found to be insensitive to the exact choice of the latitude threshold, unlike the Antarctic where greater sensitivity was found. Choosing a threshold based on the location of the transport barrier at the vortex boundary instead of geometric latitude led to a roughly similar year-to-year variability of the monthly means, but in particular years deviations of several tens of Dobson units occurred. Moreover, the minimum of daily total ozone minima poleward of a particular latitude, another popular measure, is debatable, insofar as it relies on one single measurement or model grid point. For Arctic conditions, this minimum value occurred often in air outside polar vortex, both in the observations and in a chemistry-climate model. As a result, we recommend that the minimum of daily minima no longer be used when comparing polar ozone loss in observations and models. As a possible alternative, we suggest considering the minimum of daily average total ozone poleward of a particular equivalent latitude (or in the vortex) in spring. This definition both obviates relying on one single data point and reduces the impact of year-to-year variability in the Arctic vortex breakup on ozone loss measures. However, compact relations of such simple measures with meteorological quantities that describe the potential for polar heterogeneous chlorine activation and thus ozone loss were not found. Therefore, we argue that where possible, more sophisticated measures of chemical polar ozone loss that include additional information to disentangle the impact of transport and chemistry on ozone, should be employed.
Nitrogen compounds and ozone in the stratosphere: comparison of MIPAS satellite data with the Chemistry Climate Model ECHAM5/MESSy1
Authors: Brühl C. , Steil B. , Stiller G. , Funke B. , Jöckel P.
Published: April 2010

Abstract. The chemistry climate model ECHAM5/MESSy1 (E5/M1) in a setup extending from the surface to 80 km with a vertical resolution of about 600 m near the tropopause with nudged tropospheric meteorology allows a direct comparison with satellite data of chemical species at the same time and location. Here we present results out of a transient 10 years simulation for the period of the Antarctic vortex split in September 2002, where data of MIPAS on the ENVISAT-satellite are available. For the first time this satellite instrument opens the opportunity, to evaluate all stratospheric nitrogen containing species simultaneously with a good global coverage, including the source gas N2O which allows an estimate for NOx-production in the stratosphere. We show correlations between simulated and observed species in the altitude region between 10 and 50 hpa for different latitude belts, together with the Probability Density Functions (PDFs) of model results and observations. This is supplemented by global charts on pressure levels showing the satellite data and the simulated data sampled at the same time and location. We demonstrate that the model in most cases captures the partitioning in the nitrogen family, the diurnal cycles and the spatial distribution within experimental uncertainty. There appears to be, however, a problem to reproduce the observed nighttime partitioning between N2O5 and NO2 in the middle stratosphere.
Iodine and Bromine speciation in snow and the effect of elevation
Authors: Gilfedder B. S. , Petri M. , Biester H.
Published: April 2010

Abstract. Iodine is an essential trace element for all mammals and may also influence climate through new aerosol formation. Atmospheric bromine cycling is also important due to its well-known ozone depletion capabilities. Despite precipitation being the ultimate source of iodine in the terrestrial environment, the processes effecting the distribution, speciation and transport of these elements are relatively unknown. The aim of this study was to determine the effect of orographic lifting on iodine concentrations and also quantify inorganic and organic iodine and bromine species. Snow samples were collected over an altitude profile (~800 m) from the northern Black Forest and were analysed (IC-ICP-MS) for iodine and bromine species and trace metals (ICP-MS). All elements and species showed a significant (r2>0.65) inverse relationship with altitude despite the short (5 km) horizontal distance of the transect. In fact, total iodine more than halved (38 to 13 nmol/l) over the 800 m height change. The results suggest that orographic lifting of cloud masses has a major influence on iodine levels in precipitation and is perhaps more important than lateral distances in determining iodine concentrations in terrestrial precipitation. The microphysical removal process was common to all elements. We also show that organically bound iodine is the dominant iodine species in snow (61–75%), followed by iodide. Iodate was only found in two samples despite a detection limit of 0.3 nmol/l. Two unknown but most likely anionic organo-I species were also identified in IC-ICP-MS chromatograms and comprised 2–10% of the total iodine. The majority of the bromine was inorganic bromide with a max.~of 32% organo-Br.
How many carboxyl groups does an average molecule of humic-like substances contain?
Authors: Salma I. , Láng G. G.
Published: April 2010

Abstract. The carboxyl groups of atmospheric humic-like substances (HULIS) are of special interest because they influence the solubility in water, affect the water activity and surface tension of droplets in the air, and allow formation of chelates with biologically active elements. Experimentally determined abundances of the carboxyl group within HULIS by functional group analysis are consistent with our knowledge on the average molecular mass of HULIS if the number of dissociable carboxyl groups is assumed to be rather small. The best agreement between the average molecular mass derived from the existing abundance data and the average molecular mass published earlier occurs for assuming approximately one dissociable carboxyl group only. This implies that HULIS can not be regarded as polycarboxilic acid. The average molecular mass of HULIS derived from our electrochemical measurements with the assumption of one dissociable carboxyl group per molecule ranges from 248 to 305 Da. It was concluded that HULIS are a moderately strong/weak acid with a dissociation constant of about pK=3.4, which fits well into the interval represented by fulvic and humic acids. The mean number of dissociable carboxyl groups in HULIS molecules was refined to be between 1.1 and 1.4.
Observations of the mesospheric semi-annual oscillation (MSAO) in water vapour by Odin/SMR
Authors: Lossow S. , Urban J. , Gumbel J. , Eriksson P. , Murtagh D.
Published: April 2010

Abstract. Mesospheric water vapour measurements taken by the SMR instrument onboard the Odin satellite between 2002 and 2006 have been analysed with focus on the mesospheric semi-annual circulation in the tropical and subtropical region. This analysis provides the first complete picture of mesospheric SAO in water vapour, covering altitudes above 80 km where the only previous study based on UARS/HALOE data was limited. Our analysis shows a clear semi-annual variation in the water vapour distribution in the entire altitude range between 65 km and 100 km in the equatorial area. Maxima occur near the equinoxes below 75 km and around the solstices above 80 km. The phase reversal occurs in the small layer in-between, consistent with the downward propagation of the mesospheric SAO in the zonal wind in this altitude range. The SAO amplitude exhibits a double peak structure, with maxima at about 75 km and 81 km. The observed amplitudes show higher values than the UARS/HALOE amplitudes. The upper peak amplitude remains relatively constant with latitude. The lower peak amplitude decreases towards higher latitudes, but recovers in the Southern Hemisphere subtropics. On the other hand, the annual variation is much more prominent in the northern hemispheric subtropics. Furthermore, higher volume mixing ratios during summer and lower values during winter are observed in the Northern Hemisphere subtropics, as compared to the corresponding latitude range in the Southern Hemisphere.
Trans-Pacific dust events observed at Whistler, British Columbia during INTEX-B
Authors: McKendry I. G. , Macdonald A M. , Leaitch W. R. , van Donkelaar A. , Zhang Q. , Duck T. , Martin R. V.
Published: April 2010

Abstract. The meteorology and physico-chemical characteristics of aerosol associated with two new cases of long range dust transport affecting western Canada during spring 2006 are described. Each event showed enhancements of both sulfate aerosol and crustal material of Asian origin. However, the events were of quite different character and demonstrate the highly variable nature of such events. The April event was a significant dust event with moderate sulfate enhancement while the May event was a weak dust event with very significant sulfate enhancement. The latter event was interesting in the sense that it was of short duration and was quickly followed by significant enhancement of organic material likely of regional origin. Comparison of these two events with other documented cases extending back to 1993, suggests that all dust events show coincident enhancements of sulfate and crustal aerosol. However, events vary across a wide continuum based on the magnitude of aerosol enhancements and their sulfate to calcium ratios. At one extreme, events are dominated by highly significant crustal enhancements (e.g. the well-documented 1998 and 2001 "dust" events) while at the other are events with some dust transport, but where sulfate enhancements are of very high magnitude (e.g. the 1993 event at Crater Lake and the 15 May 2006 event at Whistler). Other events represent a "mix". It is likely that this variability is a function of the comparative strengths of the dust and anthropogenic SO2 sources, the transport pathway and in particular the extent to which dust is transported across industrial SO2 sources, and finally, meteorological and chemical processes.
Variability of subtropical upper tropospheric humidity
Authors: Ryoo J.-M. , Waugh D. W. , Gettelman A.
Published: April 2010

Abstract. Analysis of Atmospheric Infrared Sounder (AIRS) measurements for five northern winters shows significant longitudinal variations in subtropical upper tropospheric relative humidity (RH), not only in the climatological mean values but also in the local distributions and temporal variability. The largest climatological mean values in the northern subtropics occur over the eastern Pacific and Atlantic oceans, where there is also large day-to-day variability. In contrast, there are smaller mean values, and smaller variability that occurs at lower frequency, over the Indian and western Pacific oceans. These differences in the distribution and variability of subtropical RH are related to differences in the key transport processes in the different sectors. The large variability and intermittent high and low RH over the Eastern Pacific and Atlantic oceans, and to a smaller extent over the Indian ocean, are due to intrusions of high potential vorticity air into the subtropics. Intrusions seldom occur over the eastern Indian and western Pacific oceans, and here the subtropical RH is more closely linked to the location and strength of subtropical anticyclones. In this region there are eastward propagating features in the subtropical RH that are out of phase with the tropical RH, and are caused by modulation of the subtropical anticyclones by the Madden-Julian Oscillation.
Investigation of the hygroscopic properties of Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles by micro-Raman spectrometry
Authors: Liu Y. J. , Zhu T. , Zhao D. F. , Zhang Z. F.
Published: April 2010

Abstract. To understand and predict the role of mineral aerosol particles processed by reactive nitrogen species in the atmosphere, the hygroscopic properties of both Ca(NO3)2 and Ca(NO3)2-containing mineral particles must be well understood. Using a micro-Raman system, the dehydration and hydration processes of micro-sized individual Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles were investigated systematically. In addition to accurate quantification of the dependence of water content on relative humidity (RH), significant new spectroscopic evidence related to chemical structure was also obtained to confirm the occurrence of amorphous solid state and to better understand the phase transition process. The Ca(NO3)2 particles exhibit reversible behavior in the dehydration and hydration processes; they are in the state of solution droplets above 10% RH and amorphous hydrates below 7% RH, and phase transition occurs at 7–10% RH. The hygroscopic behavior of Ca(NO3)2/CaCO3 particles is identical to that of pure Ca(NO3)2 particles, suggesting a negligible effect of the inclusion of slightly soluble CaCO3.
Continuous monitoring of the boundary-layer top with lidar
Authors: Baars H. , Ansmann A. , Engelmann R. , Althausen D.
Published: April 2010

Abstract. Continuous lidar observations of the top height of the boundary layer (BL top) have been performed at Leipzig (51.3° N, 12.4° E), Germany, since August 2005. The results of measurements taken with a compact, automated Raman lidar over a one-year period (February 2006 to January 2007) are presented. Four different methods for the determination of the BL top are discussed. The most promising technique, the wavelet covariance algorithm, is improved by implementing some modifications so that an automated, robust retrieval of BL depths from lidar data is possible. Three case studies of simultaneous observations with the Raman lidar, a vertical-wind Doppler lidar, and accompanying radiosonde profiling of temperature and humidity are discussed to demonstrate the potential and the limits of the four lidar techniques at different aerosol and meteorological conditions. The lidar-derived BL top heights are compared with respective values derived from predictions of the regional weather forecast model COSMO of the German Meteorological Service. The comparison shows a general underestimation of the BL top by about 20% by the model. The statistical analysis of the one-year data set reveals that the seasonal mean of the daytime maximum BL top is 1400 m in spring, 1800 m in summer, 1200 m in autumn, and 800 m in winter at the continental, central European site. BL top typically increases by 100–300 m per hour in the morning of convective days.