ALBERT

Description: For the first time, three different temperature lidar methods are combined to obtain time-resolved complete temperature profiles with high altitude resolution over an altitude range from the planetary boundary layer up to the lower thermosphere (about 1–105 km). The Leibniz-Institute of Atmospheric Physics (IAP) at Kühlungsborn, Germany (54° N, 12° E) operates two lidar instruments, using three different temperature measurement methods, optimized for three altitude ranges: (1) Probing the spectral Doppler broadening of the potassium D1 resonance lines with a tunable narrow-band laser allows atmospheric temperature profiles to be determined at metal layer altitudes (80–105 km). (2) Between about 20 and 90 km, temperatures were calculated from Rayleigh backscattering by air molecules, where the upper start values for the calculation algorithm were taken from the potassium lidar results. Correction methods have been applied to account for, e.g. Rayleigh extinction or Mie scattering of aerosols below about 32 km. (3) At altitudes below about 25 km, backscattering in the Rotational Raman lines is strong enough to obtain temperatures by measuring the temperature dependent spectral shape of the Rotational Raman spectrum. This method works well down to about 1 km. The instrumental configurations of the IAP lidars were optimized for a 3–6 km overlap of the temperature profiles at the method transition altitudes. We present two night-long measurements with clear wave structures propagating from the lower stratosphere up to the lower thermosphere.

Description: In the past, many studies have been carried out to demonstrate the influence of meteoroids on the atmospheric metal layer, observed roughly in the altitude range 80–105 km. Even with the capability of present day resonance lidars to measure metal densities within single meteor trails, it has been difficult to prove any influence of meteors on the average metal layer. In contrast to approaches taken earlier, we discuss here the seasonal characteristics of potassium, calcium, calcium ion, iron and sodium above 110 km altitude where the average nocturnal densities are so low that the existence of a baseline level of metal atoms and ions is often overlooked. By comparing simultaneous and common-volume observations of different metal layers at one location, we demonstrate that despite their different seasonal characteristics at lower altitudes remarkably similar seasonal characteristics are observed at higher altitudes. In addition, a qualitative agreement is also found for potassium at different latitudes. A comparison of metal densities at 113 km altitude with known meteor showers indicates a strong influence of shower meteoroids on the topside of the metal layers. Simultaneous observations of K along with Ca, Fe and/or Na permit the calculation of abundance ratios, which at 113 km altitude are quite similar to values measured in single meteor trails by ground based lidars. Furthermore, the increase in densities throughout summer is strong evidence for the influence of sporadic meteoroids on the high metal layers. This increase correlates well with the seasonal variation of sporadic micrometeor input independent of meteor showers. Given these evidences, we contend that there is a direct influence of ablating meteoroids on the topside of the mesospheric metal layer.

Description: Nitrogen oxide (NOx=NO+NO2) emissions from various sources contribute to the ozone budget. The identification of these contributions is important, e.g. for the assessment of emissions from traffic. The non-linear character of ozone chemistry complicates the online diagnosis during multi-decadal chemistry-climate simulations. A methodology is suggested, which is efficient enough to be incorporated in multi-decadal simulations. Eight types of NOx emissions are included in the model. For each a NOy (=all N components, except N2 and N2O) tracer and an ozone tracer is included in the model, which experience the same emissions and loss processes like the online chemistry fields. To calculate the ozone changes caused by an individual NOx emission, the assumption is made that the NOx relative contributions from various sources are identical to the NOy relative contributions. To evaluate this method each NOx emission has been increased by 5% and a detailed error analysis is given. In the regions of the main impact of individual sources the potential error of the calculated contribution is significantly smaller than the contribution. Moreover, the changes caused by an increase of the emissions of 5% were detected with a higher accuracy than the potential error of the absolute contribution.

Description: The aspect sensitivity of VHF echoes from field aligned irregularities (FAI) within meteor trails and thin ionization layers is studied using numerical models. Although the maximum power is obtained when a radar is pointed perpendicular to the field line (B), substantial power can be obtained off the B direction if the ionization trail/layer is thin. When the FAI length along B is 20 m, the power observed 6° off B is about 10 db below that perpendicular to the B direction. Meteoric FAI echoes can potentially be used to determine the diffusion rate in the mesopause region. Based on the aspect sensitivity analysis, we conclude that the range spread trail echoes far off B observed by powerful VHF radars are likely due to overdense meteors. Our simulation also shows that ionospheric FAI echoes can have an altitude smearing effect of about 4 km if the vertical extension of a FAI-layer is around 100 m, which has often been observed at Arecibo. The altitude smearing effect can account for the fact that the Es-layers observed by the Arecibo incoherent scatter radar are typically much narrower than FAI-layers and the occurrence of double spectral peaks around the Es-layer altitude in FAI echoes.

Description: Atmospheric gravity waves have been the subject of intense research for several decades because of their extensive effects on the atmospheric circulation and the temperature structure. The U. Bonn lidar at the Esrange and the ALOMAR RMR lidar at the Andøya Rocket Range are located in northern Scandinavia 250 km apart on the east and west side of the Scandinavian mountain ridge. During January and February 2003 both lidar systems conducted measurements and retrieved atmospheric temperatures. On 19/20 January 2003 simultaneous measurements for more than 7 h were possible. Although during most of the campaign time the atmosphere was not transparent for the propagation of orographically induced gravity waves, they were nevertheless observed at both lidar stations with considerable amplitudes during these simultaneous measurements. And while the source of the observed waves cannot be determined unambiguously, the observations show many characteristics of orographically excited gravity waves. The wave patterns at ALOMAR show a random distribution with time whereas at the Esrange a persistency in the wave patterns is observable. This persistency can also be found in the distribution of the most powerful vertical wavelengths. The mode values are both at about 5 km vertical wavelength, however the distributions are quite different, narrow at the Esrange with values from λz=2–6 km and broad at ALOMAR, covering λz=1–12 km vertical wavelength. In particular the difference between the observations at ALOMAR and at the Esrange can be understood by different orographic conditions while the propagation conditions were quite similar. At both stations the waves deposit energy in the atmosphere with increasing altitude, which leads to a decrease of the observed gravity wave potential energy density with altitude. The meteorological situation during these measurements was different from common winter situations. The ground winds were mostly northerlies, changed in the upper troposphere and lower stratosphere to westerlies and returned to northerlies in the middle stratosphere.

Description: The radar system described here (CMOR) comprises a basic 5-element receiving system, co-located with a pulsed transmitter, specifically designed to observe meteor echoes and to determine their position in space with an angular resolution of ~1° and a radial resolution of ~3 km. Two secondary receiving sites, a few km distant and arranged to form approximately a right angle with the base station, allow the determination of the velocity (speed and direction) of the meteor that, together with the time of occurrence, lead to an estimate of the orbit of the original meteoroid. Some equipment details are presented along with a method used to determine the orbits. Representative echoes are shown and observations on the 2002 Leonid shower presented.

Description: We studied the oxidation of dimethylsulfide (DMS) in the marine boundary layer (MBL) with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA) with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV)* (=SO2,aq+HSO3-+SO32-) with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA) to non-sea salt sulfate (nss-SO42-) production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

Description: The nucleation of nanoparticles in the exhaust of a modern light-duty diesel vehicle was investigated on a chassis dynamometer. This laboratory study is focused on the influence of volatile organic compounds (VOCs) on nucleation of volatile nanoparticles. Different organic compounds were added to the dilution air of the particle sampling under different sampling conditions. Sample temperature and relative sample humidity were varied in a wide range. The number size distribution of the particles was measured with a scanning mobility particle sizer (SMPS) and showed significant differences in response to the added organic compounds. While the nucleation mode particles showed a large variation in concentration, the accumulation mode particles remained unchanged for all compounds. Depending on the functional group, organic compounds were capable of initiating and increasing (alcohols and toluene) or decreasing (acetone, aniline, and methyl tert-butyl ether (MTBE)) nucleation mode particles. Short volatile aliphatic hydrocarbons (hexane and cyclohexane) turned out to be without effect on nucleation of nanoparticles. Possible reasons for the differences are discussed.

Description: Since the very first meteor observations at EISCAT in December 1990, the experimental method has improved significantly. This is due to a better understanding of the phenomenon and a recent major upgrade of the EISCAT signal processing and data storage capabilities. Now the simultaneous spatial-time resolution is under 100 m-ms class. To illuminate the meteor target for as long as possible and simultaneously get as good altitude resolution as possible, various coding techniques have been used, such as Barker codes and random codes with extremely low side lobe effects. This paper presents some background and the current view of the meteor head echo process at EISCAT as well as the observations which support this view, such as altitude distributions, dual-frequency target sizes and vector velocities. It also presents some preliminary results from recent very high resolution tristatic observations.

Description: Precise knowledge of the angle between the meteor vector velocity and the radar beam axis is one of the largest source of errors in the Arecibo Observatory (AO) micrometeor observations. In this paper we study ~250 high signal-to-noise ratio (SNR) meteor head-echoes obtained using the dual-beam 430 MHz AO Radar in Puerto Rico, in order to reveal the distribution of this angle. All of these meteors have been detected first by the radar first side lobe, then by the main beam and finally seen in the side lobe again. Using geometrical arguments to calculate the meteor velocity in the plane perpendicular to the beam axis, we find that most of the meteors are travelling within ~15° with respect to the beam axis, in excellent agreement with previous estimates. These results suggest that meteoroids entering the atmosphere at greater angles may deposit their meteoric material at higher altitudes explaining at some level the missing mass inconsistency raised by the comparisson of meteor fluxes derived from satellite and traditional meteor radar observations. They also may be the source of the observed high altitude ions and metalic layers observed by radars and lidars respectively.

Description: Net vertical air mass export by thermally driven flows from the atmospheric boundary layer (ABL) to the free troposphere (FT) above deep Alpine valleys was investigated. The vertical export of pollutants above mountainous terrain is presently poorly represented in global chemistry transport models (GCTMs) and needs to be quantified. Air mass budgets were calculated using aircraft observations obtained in deep Alpine valleys. The results show that on average 3 times the valley air mass is exported vertically per day under fair weather conditions. During daytime the type of valleys investigated in this study can act as an efficient "air pump" that transports pollutants upward. The slope wind system within the valley plays an important role in redistributing pollutants. Nitrogen oxide emissions in mountainous regions are efficiently injected into the FT. This could enhance their ozone (O3) production efficiency and thus influences tropospheric pollution budgets. Once lifted to the FT above the Alps pollutants are transported horizontally by the synoptic flow and are subject to European pollution export. Forward trajectory studies show that under fair weather conditions two major pathways for air masses above the Alps dominate. Air masses moving north are mixed throughout the whole tropospheric column and further transported eastward towards Asia. Air masses moving south descend within the subtropical high pressure system above the Mediterranean.

Description: A sequential synthesis inversion method is described to estimate CO2 sources from continuous atmospheric data. The sequential method makes the problem computationally feasible. The method is assessed using four-hourly synthetic concentration data generated from known sources. Multi-year mean sources and seasonal cycles are estimated with comparable quality as those from a traditional inversion of monthly mean data. Interannual variations in the estimated sources are closer to those of the known sources using the four-hourly data rather than monthly data. The computational cost of the basis function simulations can be reduced by generating responses that are only six months long. This does not significantly degrade the inversion results compared to using responses that are 12 months in length.

Description: We present results of recent observations of meteor-head echoes obtained with the high-power large-aperture Jicamarca 50MHz radar (11.95°S, 76.87°W) in an interferometric mode. The large power-aperture of the system allows us to record more than 3000 meteors per hour in the small volume subtended by the 1° antenna beam, albeit when the cluttering equatorial electrojet (EEJ) echoes are not present or are very weak. The interferometry arrangement allows the determination of the radiant (trajectory) and speed of each meteor. It is found that the radiant distribution of all detected meteors is concentrated in relative small angles centered around the Earth's Apex as it transits over the Jicamarca sky, i.e. around the corresponding Earth heading for the particular observational day and time, for all seasons observed so far. The dispersion around the Apex is ~18° in a direction transverse to the Ecliptic plane and only 8.5° in heliocentric longitude in the Ecliptic plane both in the Earth inertial frame of reference. No appreciable interannual variability has been observed. Moreover, no population related to the optical (larger meteors) Leonid showers of 1998-2002 is found, in agreement with other large power-aperture radar observations. A novel cross-correlation detection technique (adaptive match-filtering) is used in combination with a 13 baud Barker phase-code. The technique allows us to get good range resolution (0.75km) without any sensitivity deterioration for the same average power, compared to the non-coded long pulse scheme used at other radars. The matching Doppler shift provides an estimation of the velocity within a pulse with the same accuracy as if a non-coded pulse of the same length had been used. The velocity distribution of the meteors is relatively narrow and centered around 60kms-1. Therefore most of the meteors have an almost circular retrograde orbit around the Sun. Less than 8% of the velocities correspond to interstellar orbits, i.e. with velocities larger than the solar escape velocity (72kms-1). Other statistical distributions of interest are also presented.

Description: We have analysed the upper tropospheric humidity with respect to ice (UTHi) data product obtained from the Television Infrared Observation Satellite (TIROS) Operational Vertical Sounder (TOVS) instrument onboard the National Oceanic and Atmospheric Administration NOAA-14 polar orbiting satellite. While in the production of the official UTHi product values in excess of 100% are ignored, we do not so - in view of many recent results obtained from a variety of other in-situ and remote sensing instruments showing that ice supersaturation frequently occurs in the upper troposphere. We show that TOVS is able to detect ice supersaturation at the correct locations (however, only in less than one percent of its soundings, presumably because of TOVS's low vertical resolution), and that the supersaturation follows the well known exponential behaviour. We conclude that values of UTHi in excess of saturation should not be considered a measurement error anymore. The similar re-analysis of TOVS data back to 1979 could give important insights into trends of upper tropospheric humidity.

Description: The three-dimensional photochemical model UAM-V is used to investigate the effects of various meteorological conditions and of the coarseness of emission inventories on the ozone concentration and ROG/NOx limitation of the ozone production in the Po Basin in the northern part of Italy. As a base case, the high ozone episode with up to 200ppb on 13 May 1998 was modelled and previously thoroughly evaluated with measurements gained during a large field experiment. Systematic variations in meteorology are applied to mixing height, air temperature, specific humidity and wind speed. Three coarser emission inventories are obtained by resampling from 3x3km2 up to 54x54km2 emission grids. The model results show that changes in meteorological input files strongly influence ozone in this area. For instance, temperature changes peak ozone by 10.1ppb/°C and the ozone concentrations in Milan by 2.8ppb/°C. The net ozone formation in northern Italy is more strongly temperature than humidity dependent, while the humidity is very important for the ROG/NOx limitation of the ozone production. For all meteorological changes (e.g. doubling the mixing height), the modelled peak ozone remains ROG limited. A strong change towards NOx sensitivity in the ROG limited areas is only found if much coarser emission inventories were applied. Increasing ROG limited areas with increasing wind speed are found, because the ROG limited ozone chemistry induced by point sources is spread over a larger area. Simulations without point sources tend to increase the NOx limited areas.

Description: Halogen species (HCl* (primarily HCl), Cl* (including Cl2 and HOCl), BrO, total gaseous inorganic Br and size-resolved particulate Cl- and Br -) and related chemical and physical parameters were measured in surface air at Oahu, Hawaii during September 1999. Aerosol pH as a function of particle size was inferred from phase partitioning and thermodynamic properties of HCl. Mixing ratios of halogen compounds and aerosol pHs were simulated with a new version of the photochemical box model MOCCA that considers multiple aerosol size bins. Inferred aerosol pHs ranged from 4.5 to 5.4 (median 5.1, n=22) for super-mm (primarily sea-salt) size fractions and 2.6 to 5.3 (median 4.6) for sub-mm (primarily sulphate) fractions. Inferred daytime pHs tended to be slightly lower than those at night, although daytime median values did not differ statistically from nighttime medians. Simulated pHs for most sea-salt size bins were within the range of inferred values. However, simulated pHs for the largest size fraction in the model were somewhat higher (oscillating around 5.9) due to the rapid turnover rates and relatively larger infusions of sea-salt alkalinity associated with fresh aerosols. Measured mixing ratios of HCl* ranged from

Description: Aerosol number size distributions have been measured since 5 May 1997 in Helsinki, Finland. The presented aerosol data represents size distributions within the particle diameter size range 8-400nm during the period from May 1997 to March 2003. The daily, monthly and annual patterns of the aerosol particle number concentrations were investigated. The temporal variation of the particle number concentration showed close correlations with traffic activities. The highest total number concentrations were observed during workdays; especially on Fridays, and the lowest concentrations occurred during weekends; especially Sundays. Seasonally, the highest total number concentrations were observed during winter and spring and lower concentrations were observed during June and July. More than 80% of the number size distributions had three modes: nucleation mode (30nm), Aitken mode (20-100nm) and accumulation mode (90nm). Less than 20% of the number size distributions had either two modes or consisted of more than three modes. Two different measurement sites were used; in the first (Siltavuori, 5.5.1997-5.3.2001), the arithmetic means of the particle number concentrations were 7000cm, 6500cm, and 1000cm respectively for nucleation, Aitken, and accumulation modes. In the second site (Kumpula, 6.3.2001-28.2.2003) they were 5500cm, 4000cm, and 1000cm. The total number concentration in nucleation and Aitken modes were usually significantly higher during workdays than during weekends. The temporal variations in the accumulation mode were less pronounced. The lower concentrations at Kumpula were mainly due to building construction and also the slight overall decreasing trend during these years. During the site changing a period of simultaneous measurements over two weeks were performed showing nice correlation at both sites.

Description: Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) in the atmosphere is a novel measurement technique that represents a significant advance on the well-established zenith scattered sunlight DOAS instruments which are mainly sensitive to stratospheric absorbers. MAX-DOAS utilizes scattered sunlight received from multiple viewing directions. The spatial distribution of various trace gases close to the instrument can be derived by combining several viewing directions. Ground based MAX-DOAS is highly sensitive to absorbers in the lowest few kilometres of the atmosphere and vertical profile information can be retrieved by combining the measurements with Radiative Transfer Model (RTM) calculations. The potential of the technique for a wide variety of studies of tropospheric trace species and its (few) limitations are discussed. A Monte Carlo RTM is applied to calculate Airmass Factors (AMF) for the various viewing geometries of MAX-DOAS. Airmass Factors can be used to quantify the light path length within the absorber layers. The airmass factor dependencies on the viewing direction and the influence of several parameters (trace gas profile, ground albedo, aerosol profile and type, solar zenith and azimuth angles) are investigated. In addition we give a brief description of the instrumental MAX-DOAS systems realised and deployed so far. The results of the RTM studies are compared to several examples of recent MAX-DOAS field experiments and an outlook for future possible applications is given.

Description: The radiative scattering by clouds leads to errors in the retrieval of column densities and concentration profiles of atmospheric trace gas species from satellites. Moreover, the presence of clouds changes the UV actinic flux and the photo-dissociation rates of various species significantly. The Global Ozone Monitoring Experiment (GOME) instrument on the ERS-2 satellite, principally designed to retrieve trace gases in the atmosphere, is also capable of detecting clouds. Four cloud fraction retrieval methods for GOME data that have been developed are discussed in this paper (the Initial Cloud Fitting Algorithm, the PMD Cloud Recognition Algorithm, the Optical Cloud Recognition Algorithm (an in-house version and the official implementation) and the Fast Retrieval Scheme for Clouds from the Oxygen A-band). Their results of cloud fraction retrieval are compared to each-other and also to synoptic surface observations. It is shown that all studied retrieval methods calculate an effective cloud fraction that is related to a cloud with a high optical thickness. Generally, we found ICFA to produce the lowest cloud fractions, followed by our in-house OCRA implementation, FRESCO, PC2K and finally the official OCRA implementation along four processed tracks (+2%, +10%, +15% and +25% compared to ICFA respectively). Synoptical surface observations gave the highest absolute cloud fraction when compared with individual PMD sub-pixels of roughly the same size.

Description: During the MINOS campaign (28 July-18 August 2001) the nitrate (NO3) radical was measured at Finokalia station, on the north coast of Crete in South-East Europe using a long path (10.4 km) Differential Optical Absorption Spectroscopy instrument (DOAS). Hydroxyl (OH) radical was also measured by a Chemical Ionization Mass-Spectrometer (Berresheim et al., 2003). These datasets represent the first simultaneous measurements of OH and NO3 radicals in the area. NO3 radical concentrations ranged from less than 3x107 up to 9x108 radicals· cm-3 with an average nighttime value of 1.1x108 radicals· cm-3. The observed NO3 mixing ratios are analyzed on the basis of the corresponding meteorological data and the volatile organic compound (VOC) observations which were measured simultaneously at Finokalia station. The importance of the NO3 radical chemistry relatively to that of OH in the dimethylsulfide (DMS) and nitrate cycles is also investigated. The observed NO3 levels regulate the nighttime variation of DMS. The loss of DMS by NO3 during night is about 75% of that by OH radical during day. NO3 and nitrogen pentoxide (N2O5) reactions account for about 21% of the total nitrate (HNO3(g)+NO-3(g)) production.

Description: Downwelling longwave fluxes, DLFs, have been derived for each month over a ten year period (1984-1993), on a global scale with a spatial resolution of 2.5x2.5 degrees and a monthly temporal resolution. The fluxes were computed using a deterministic model for atmospheric radiation transfer, along with satellite and reanalysis data for the key atmospheric input parameters, i.e. cloud properties, and specific humidity and temperature profiles. The cloud climatologies were taken from the latest released and improved International Satellite Climatology Project D2 series. Specific humidity and temperature vertical profiles were taken from three different reanalysis datasets; NCEP/NCAR, GEOS, and ECMWF (acronyms explained in main text). DLFs were computed for each reanalysis dataset, with differences reaching values as high as 30 Wm-2 in specific regions, particularly over high altitude areas and deserts. However, globally, the agreement is good, with the rms of the difference between the DLFs derived from the different reanalysis datasets ranging from 5 to 7 Wm-2. The results are presented as geographical distributions and as time series of hemispheric and global averages. The DLF time series based on the different reanalysis datasets show similar seasonal and inter-annual variations, and similar anomalies related to the 86/87 El Niño and 89/90 La Niña events. The global ten-year average of the DLF was found to be between 342.2 Wm-2 and 344.3 Wm-2, depending on the dataset. We also conducted a detailed sensitivity analysis of the calculated DLFs to the key input data. Plots are given that can be used to obtain a quick assessment of the sensitivity of the DLF to each of the three key climatic quantities, for specific climatic conditions corresponding to different regions of the globe. Our model downwelling fluxes are validated against available data from ground-based stations distributed over the globe, as given by the Baseline Surface Radiation Network. There is a negative bias of the model fluxes when compared against BSRN fluxes, ranging from -7 to -9 Wm-2, mostly caused by low cloud amount differences between the station and satellite measurements, particularly in cold climates. Finally, we compare our model results with those of other deterministic models and general circulation models.

Description: Global water vapour column amounts have been derived for the first time from measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) on the European environmental satellite ENVISAT. For this purpose, two different existing retrieval algorithms have been adapted, namely the Air Mass Corrected Differential Absorption Spectroscopy (AMC-DOAS) which was originally designed for GOME and the Weighting Function Modified Differential Absorption Spectroscopy (WFM-DOAS) which was mainly designed for the retrieval of CH4, CO2 and CO from SCIAMACHY near-infrared spectra. Here, both methods have been applied to SCIAMACHY's nadir measurements in the near-visible spectral region around 700 nm. Taking into account a systematic offset of 10%, the results of these two methods agree within a scatter of about ±0.5 g/cm2 with corresponding SSM/I and ECMWF water vapour data. This deviation includes contributions from the temporal and spatial variability of water vapour. In fact, the mean deviation between the SCIAMACHY and the correlative data sets is much smaller: the SCIAMACHY total water vapour columns are typically about 0.15 g/cm2 lower than the SSM/I values and less than 0.1 g/cm2 lower than corresponding ECMWF data. The SCIAMACHY water vapour results agree well with correlative data not only over ocean but also over land, thus showing the capability of SCIAMACHY to derive water vapour concentrations on the global scale.

Description: Mass spectrometric analysis of volatile and semi-volatile (=non-refractory) aerosol particles have been performed during a field study in the summer Eastern Mediterranean. A size-resolved, quantitative mass spectrometric technique (the Aerodyne Aerosol Mass Spectrometer, AMS) has been used, and the results are compared to filter sampling methods and particle sizing techniques. The different techniques agree with the finding that the fine particle mode (D

Description: Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is the organic compounds that are surface active i.e. tend to concentrate on droplet surface and decrease the surface tension. Gibbsian surface thermodynamics was used to find out how partitioning between droplet surface and the bulk of the droplet affects the surface tension and the surfactant bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate (SDS) was used together with sodium chloride to investigate the effect of surfactant partitioning on the Raoult effect (solute effect). While accounting for the surface to bulk partitioning is known to lead to lowered bulk surfactant concentration and thereby to increased surface tension compared to a case in which the partitioning is neglected, the present results show that the partitioning also alters the Raoult effect, and that the change is large enough to further increase the critical supersaturation and hence decrease cloud droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solutions were studied in order to study the partitioning with compounds found in the atmosphere and to find out the combined effects of dissolution and partitioning behavior. The results show that the partitioning consideration presented in this paper alters the shape of the Köhler curve when compared to calculations in which the partitioning is neglected either completely or in the Raoult effect. In addition, critical supersaturation was measured for SDS particles with dry radii of 25-60nm using a static parallel plate Cloud Condensation Nucleus Counter. The experimentally determined critical supersaturations agree very well with theoretical calculations taking the surface to bulk partitioning fully into account and are much higher than those calculated neglecting the partitioning.

Description: The first Rayleigh lidar observation of a stratopause warming over a tropical site, Gadanki (13.5° N; 79.2° E), is presented in this paper. The warming event was observed on 22-23 February 2001, and found to occur in the stratopause region (~45km). The magnitude of the warming was found to be ~18K with respect to the winter-mean temperature profile derived from the lidar data collected over March 1998 to July 2001. The event observed by the lidar has also been seen in data from the Halogen Occultation Experiment (HALOE) on board the UARS satellite. The zonal-mean temperature at 80° N and the zonal-mean zonal wind at 60° N from the National Centre for Environmental Prediction (NCEP) reanalysis and the European Centre for Medium-Range Weather Forecasts (ECMWF) analysis indicate that a major warming episode took place in the northern polar hemisphere a week before the day of the observation over Gadanki. Eliassen-Palm (E-P) flux calculations from ECMWF analysis show evidence of propagation of planetary-wave activity from high and mid- to low latitudes subsequent to the major warming episode over the pole. Our results support the view that the most likely source mechanism for the observed stratopause warming is the increase in planetary-wave activity.

Description: A Lagrangian trajectory model used to simulate photochemistry has been extended to include a simple parameterisation of primary and secondary aerosol particles. The model uses emission inventories of primary particles for the UK from the NAEI (National Atmospheric Emissions Inventory for the UK), and for Europe from the TNO (Institute of Environmental Sciences, Energy Research and Process Innovation, the Netherlands) respectively, to transport tracers representing PM10. One biogenic and two anthropogenic organic compounds were chosen as surrogates to model the formation of condensable material suitable for the production of secondary organic aerosol (SOA). The SOA is added to the primary PM10 and compared to measured PM10 at one urban and two rural UK receptor sites. The results show an average under-prediction by factors of 4.5 and 8.9 in the urban and rural cases respectively. The model is also used to simulate production of two secondary inorganic species, H2SO4 and HNO3, which are assumed, as a limiting case, to be present in the particle phase. The relationships between modelled and measured total PM10 improved with the addition of secondary inorganic compounds, and the overall model under-prediction factors are reduced to 3.5 and 3.9 in the urban and rural cases respectively. Nevertheless, our conclusion is that current emissions and chemistry do not appear to provide sufficient information to model PM10 well (i.e. to within a factor of two). There is a need for further process studies to inform global climate modelling that includes climate forcing by aerosol.

Description: A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.

Description: The heterogeneous freezing temperatures of single binary sulfuric acid solution droplets were measured in dependency of acid concentration down to temperatures as low as -50°C. In order to avoid influence of supporting substrates on the freezing characteristics, a new technique has been developed to suspend the droplet by means of an acoustic levitator. The droplets contained immersed particles of graphite, kaolin or montmorillonite in order to study the influence of the presence of such contamination on the freezing temperature. The radii of the suspended droplets spanned the range between 0.4 and 1.1mm and the concentration of the sulfuric acid solution varied between 5 and 14 weight percent. The presence of the particles in the solution raises the freezing temperature with respect to homogeneous freezing of these solution droplets. The pure solution droplets can be supercooled up to 40 degrees below the ice-acid solution thermodynamic equilibrium curve. Depending on the concentration of sulfuric acid and the nature of the impurity the polluted droplets froze between -11°C and -35°C. The new experimental set-up, combining a deep freezer with a movable ultrasonic levitator and suitable optics, proved to be a useful approach for such investigations on individual droplets.

Description: In this study the ion production rates in a boreal forest were studied based on two different methods: 1) cluster ion and particle concentration measurements, 2) external radiation and radon concentration measurements. Both methods produced reasonable estimates for ion production rates. The average ion production rate calculated from aerosol particle size distribution and air ion mobility distribution measurements was 2.6 ion pairs cm-3s-1, and based on external radiation and radon measurements, 4.5 ion pairs cm-3s-1. The first method based on ion and particle measurements gave lower values for the ion production rates especially during the day. A possible reason for this is that particle measurements started only from 3nm, so the sink of small ions during the nucleation events was underestimated. It may also be possible that the hygroscopic growth factors of aerosol particles were underestimated. Another reason for the discrepancy is the nucleation mechanism itself. If the ions are somehow present in the nucleation process, there could have been an additional ion sink during the nucleation days.

Description: The Global Ozone Monitoring Experiment (GOME) allows the retrieval of tropospheric vertical column densities (VCDs) of NO2 on a global scale. Regions with enhanced industrial activity can clearly be detected, but the standard spatial resolution of the GOME ground pixels (320x40km2) is insufficient to resolve regional trace gas distributions or individual cities. Every 10 days within the nominal GOME operation, measurements are executed in the so called narrow swath mode with a much better spatial resolution (80x40km2). We use this data (1997-2001) to construct a detailed picture of the mean global tropospheric NO2 distribution. Since - due to the narrow swath - the global coverage of the high resolution observations is rather poor, it has proved to be essential to deseasonalize the single narrow swath mode observations to retrieve adequate mean maps. This is done by using the GOME backscan information. The retrieved high resolution map illustrates the shortcomings of the standard size GOME pixels and reveals an unprecedented wealth of details in the global distribution of tropospheric NO2. Localised spots of enhanced NO2 VCD can be directly associated to cities, heavy industry centers and even large power plants. Thus our result helps to check emission inventories. The small spatial extent of NO2 "hot spots" allows us to estimate an upper limit of the mean lifetime of boundary layer NOx of 17h on a global scale. The long time series of GOME data allows a quantitative comparison of the narrow swath mode data to the nominal resolution. Thus we can analyse the dependency of NO2 VCDs on pixel size. This is important for comparing GOME data to results of new satellite instruments like SCIAMACHY (launched March 2002 on ENVISAT), OMI (launched July 2004 on AURA) or GOME II (to be launched 2005) with an improved spatial resolution.

Description: This paper compares column measurements of NO2 made by the GOME instrument on ERS-2 to model results from the TOMCAT global CTM. The overall correlation between the model and observations is good (0.79 for the whole world, and 0.89 for North America) but the modelled columns are larger than GOME over polluted areas (gradient of 1.4 for North America and 1.9 for Europe). NO2 columns in the region of outflow from North America into the Atlantic are higher in winter in the model compared to the GOME results, whereas the modelled columns are smaller off the coast of Africa where there appear to be biomass burning plumes in the satellite data. Several hypotheses are presented to explain these discrepancies. Weaknesses in the model treatment of vertical mixing and chemistry appear to be the most likely explanations.

Description: The use of PV equivalent latitude for assimilating stratospheric tracer observations is discussed - with particular regard to the errors in the equivalent latitude coordinate, and to the assimilation of sparse data. Some example measurements are assimilated: they sample the stratosphere sporadically and inhomogeneously. The aim was to obtain precise information about the isentropic tracer distribution and evolution as a function of equivalent latitude. Precision is important, if transport across barriers like the vortex edge are to be detected directly. The main challenges addressed are the errors in modelled equivalent latitude, and the non-ideal observational sampling. The methods presented allow first some assessment of equivalent latitude errors and a picture of how good or poor the observational coverage is. This information determines choices in the approach for estimating as precisely as possible the true equivalent latitude distribution of the tracer, in periods of good and poor observational coverage. This is in practice an optimisation process, since better understanding of the equivalent latitude distribution of the tracer feeds back into a clearer picture of the errors in the modelled equivalent latitude coordinate. Error estimates constrain the reliability of using equivalent latitude to make statements like "this observation samples air poleward of the vortex edge" or that of more general model-measurement comparisons. The approach is demonstrated for ground-based lidar soundings of the Mount Pinatubo aerosol cloud, focusing on the 1991-92 arctic vortex edge between 475-520K. Equivalent latitude is estimated at the observation times and locations from Eulerian model tracers initialised with PV and forced by UK Meteorological Office analyses. With the model formulation chosen, it is shown that tracer transport of a few days resulted in an error distribution that was much closer to Gaussian form, although the mean error was not significantly affected. The analysis of the observations revealed a small amount of irreversible transport of aerosol across the vortex edge during late January 1992, coincident with a strongly disturbed vortex.

Description: Polar stratospheric clouds (PSC) have been observed in early winter (December 2002) during the SOLVE II/Vintersol campaign, both from balloons carrying comprehensive instrumentation for measurements of chemical composition, size distributions, and optical properties of the particles, as well as from individual backscatter soundings from Esrange and Sodankylä. The observations are unique in the sense that the PSC particles seem to have formed in the early winter under synoptic temperature conditions and not being influenced by mountain lee waves. A sequence of measurements during a 5-days period shows a gradual change between liquid and solid type PSCs with the development of a well-known sandwich structure. It appears that all PSC observations show the presence of a background population of solid particles, occasionally mixed in with more optically dominating liquid particles. The measurements have been compared with results from a detailed microphysical and optical simulation of the formation processes. Calculated extinctions are in good agreement with SAGE-III measurements from the same period. Apparently the solid particles are controlled by the synoptic temperature history while the presence of liquid particles is controlled by the local temperatures at the time of observation. The temperature histories indicate that the solid particles are nucleated above the ice frost point, and a surface freezing mechanism for this is included in the model. Reducing the calculated freezing rates by a factor 10-20, the model is able to simulate the observed particle size distributions and reproduce observed HNO3 gas phase concentrations.

Description: A retrieval algorithm based on the Optimal Estimation Method (OEM) has been developed in order to provide vertical distributions of NO2 in the stratosphere from ground-based (GB) zenith-sky UV-visible observations. It has been applied to observational data sets from the NDSC (Network for Detection of Stratospheric Change) stations of Harestua (60° N, 10° E) and Andøya (69° N, 16° E) in Norway. The information content and retrieval errors have been analyzed following a formalism used for characterizing ozone profiles retrieved from solar infrared absorption spectra. In order to validate the technique, the retrieved NO2 vertical profiles and columns have been compared to correlative balloon and satellite observations. Such extensive validation of the profile and column retrievals was not reported in previously published work on the profiling from GB UV-visible measurements. A good agreement - generally better than 25% - has been found with the SAOZ (Système d'Analyse par Observations Zénithales) and DOAS (Differential Optical Absorption Spectroscopy) balloons. A similar agreement has been reached with correlative satellite data from the HALogen Occultation Experiment (HALOE) and Polar Ozone and Aerosol Measurement (POAM) III instruments above 25km of altitude. Below 25km, a systematic underestimation - by up to 40% in some cases - of both HALOE and POAM III profiles by our GB profile retrievals has been observed, pointing out more likely a limitation of both satellite instruments at these altitudes. We have concluded that our study strengthens our confidence in the reliability of the retrieval of vertical distribution information from GB UV-visible observations and offers new perspectives in the use of GB UV-visible network data for validation purposes.

Description: First results concerning the retrieval of tropospheric carbon monoxide (CO) from satellite solar backscatter radiance measurements in the near-infrared spectral region (~2.3µm) are presented. The Weighting Function Modified (WFM) DOAS retrieval algorithm has been used to retrieve vertical columns of CO from SCIAMACHY/ENVISAT nadir spectra. We present detailed results for three days from the time periode January to October 2003 selected to have good overlap with the daytime CO measurements of MOPITT onboard EOS Terra. Because the WFM-DOAS Version 0.4 CO columns presented in this paper are scaled by a constant factor of 0.5 to compensate for an obvious overestimation we focus on the variability of the retrieved columns rather than on their absolute values. It is shown that plumes of CO resulting from, e.g. biomass burning in Africa, are detectable with single overpass SCIAMACHY data. Globally, the SCIAMACHY CO columns are in reasonable agreement with the Version 3 CO column data product of MOPITT. For example, for measurements over land, where the quality of the data is typically better than over ocean due to higher surface reflectivity, the standard deviation of the difference with respect to MOPITT is in the range 0.4-0.6x1018 molecules/cm2 and the linear correlation coefficient is between 0.4 and 0.7. The level of agreement between the data of both sensors depends on time and location but is typically within 30% for most latitudes. In the southern hemisphere outside Antarctica SCIAMACHY tends to give systematically higher values than MOPITT. More studies are needed to find out what the reasons for the observed differences with respect to MOPITT are and how the algorithm can be modified to improve the quality of the CO columns as retrieved from SCIAMACHY.

Description: This paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0) has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA), a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations.

Description: A variety of C1-C12 carbonyl compounds were measured in the air of a boreal coniferous forest located in Hyytiälä, Southern Finland. 24-hour samples were collected during March and April in 2003 using DNPH (2,4-dinitrophenyl hydrazine) coated C18-cartridges and analyzed by liquid chromatography-mass spectrometry (LC-MS). Altogether 22 carbonyl compounds were quantified. The most abundant carbonyls were acetone (24-hour average 1340ng/m3), formaldehyde (480ng/m3) and acetaldehyde (360ng/m3). Concentrations of monoterpene reaction products nopinone (9ng/m3) and limona ketone (5ng/m3) were low compared to the most abundant low molecular weight carbonyls. Trajectory analysis showed that highest concentrations of carbonyls were measured in the air masses coming from the East and the lowest in the air masses cycled long time over Scandinavia. The total concentration of carbonyl compounds in Hyytiälä in March/April 2003 was much higher than the concentration of aromatic hydrocarbons and monoterpenes in April 2002. Scaling the concentrations against reactivity with the OH-radical showed, that in spite of relatively low ambient concentrations higher molecular weight aldehydes contribute significantly to the total OH-reactive mass of carbonyls. The impact of carbonyl compounds on OH-radical chemistry is important. Contribution of carbonyls as an OH sink is comparable to that of NO2 and higher than monoterpenes and aromatic hydrocarbons. Lifetimes of the measured carbonyls with respect to reactions with OH radicals, ozone (O3), and nitrate (NO3) radicals as well as photolysis were estimated. The main sink reactions for most of the carbonyl compounds in Hyytiälä in springtime are expected to be reactions with the OH radical and photolysis. For 6-methyl-5-hepten-2-one and limona ketone also reactions with ozone are important. The sources of carbonyl compounds are presently highly uncertain. Based on the comparisons with urban concentrations the direct anthropogenic emissions are not as important as secondary biogenic and anthropogenic sources or primary biogenic sources in Hyytiälä.

Description: The vertical transport of tracers by a cumulus ensemble at the TOGA-COARE site is modelled during a 7 day episode using 2-D and 3-D cloud-resolving setups of the Weather Research and Forecast (WRF) model. Lateral boundary conditions (LBC) for tracers, water vapour, and wind are specified and the horizontal advection of trace gases across the lateral domain boundaries is considered. Furthermore, the vertical advection of trace gases by the large-scale motion (short: vertical large-scale advection of tracers, VLSAT) is considered. It is shown that including VLSAT partially compensates the calculated net downward transport from the middle and upper troposphere (UT) due to the mass balancing mesoscale subsidence induced by deep convection. Depending on whether the VLSAT term is added or not, modelled domain averaged vertical tracer profiles can differ significantly. Differences between a 2-D and a 3-D model run were mainly attributed to an increase in horizontal advection across the lateral domain boundaries due to the meridional wind component not considered in the 2-D setup.

Description: The formation and detailed composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of α- and β-pinene has been simulated using the Master Chemical Mechanism version 3 (MCM v3), coupled with a representation of gas-to-aerosol transfer of semivolatile and involatile oxygenated products. A kinetics representation, based on equilibrium absorptive partitioning of ca. 200 semivolatile products, was found to provide an acceptable description of the final mass concentrations observed in a number of reported laboratory and chamber experiments, provided partitioning coefficients were increased by about two orders of magnitude over those defined on the basis of estimated vapour pressures. This adjustment is believed to be due, at least partially, to the effect of condensed phase association reactions of the partitioning products. Even with this adjustment, the simulated initial formation of SOA was delayed relative to that observed, implying the requirement for the formation of species of much lower volatility to initiate SOA formation. The inclusion of a simplified representation of the formation and gas-to-aerosol transfer of involatile dimers of 22 bi- and multifunctional carboxylic acids (in addition to the absorptive partitioning mechanism) allowed a much improved description of SOA formation for a wide range of conditions. The simulated SOA composition recreates certain features of the product distributions observed in a number of experimental studies, but implies an important role for multifunctional products containing hydroperoxy groups (i.e. hydroperoxides). This is particularly the case for experiments in which 2-butanol is used to scavenge OH radicals, because [HO2]/[RO2] ratios are elevated in such systems. The optimized mechanism is used to calculate SOA yields from α- and β-pinene ozonolysis in the presence and absence of OH scavengers, and as a function of temperature.

Description: A forecast system has been developed in preparation for an upcoming aircraft measurement campaign, where the same air parcels polluted by emissions over North America shall be sampled repeatedly as they leave the continent, during transport over the Atlantic, and upon their arrival over Europe. This paper describes the model system in advance of the campaign, in order to make the flight planners familiar with the novel model output. The aim of a Lagrangian strategy is to infer changes in the chemical composition and aerosol distribution occurring en route by measured upwind/downwind differences. However, guiding aircraft repeatedly into the same polluted air parcels requires careful forecasting, for which no suitable model system exists to date. This paper describes a procedure using both Eulerian-type (i.e. concentration fields) and Lagrangian-type (i.e. trajectories) model output from the Lagrangian particle dispersion model FLEXPART to predict the best opportunities for a Lagrangian experiment. The best opportunities are defined as being highly polluted air parcels which receive little or no emission input after the first measurement, which experience relatively little mixing, and which are reachable by as many aircraft as possible. For validation the system was applied to the period of the NARE 97 campaign where approximately the same air masses were sampled on different flights. Measured upwind/downwind differences in carbon monoxide (CO) and ozone (O3) decreased significantly as the threshold values used for accepting cases as Lagrangian were tightened. This proves that the model system can successfully identify Lagrangian opportunities.

Description: We measured the mixing ratios of ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), hydrochloric acid (HCl), sulfur dioxide (SO2 and the corresponding water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), nitrite (NO2-), chloride (Cl- and sulfate (SO42-), and their diel and seasonal variations at a pasture site in the Amazon Basin (Rondônia, Brazil). This study was conducted within the framework of LBA-SMOCC (Large Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall and Climate: Aerosols from Biomass Burning Perturb Global and Regional Climate). Sampling was performed from 12 September to 14 November 2002, extending from the dry season (extensive biomass burning activity), through the transition period to the wet season (background conditions). Measurements were made continuously using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC) followed by suitable on-line analysis. A detailed description and verification of the inlet system for simultaneous sampling of soluble gases and aerosol compounds is presented. Overall measurement uncertainties of the ambient mixing ratios usually remained below 15%. The limit of detection (LOD) was determined for each single data point measured during the field experiment. Median LOD values (3σ-definition) were ≤0.015ppb for acidic trace gases and aerosol anions and ≤0.118ppb for NH3 and aerosol NH4+. Mixing ratios of acidic trace gases remained below 1ppb throughout the measurement period, while NH3 levels were an order of magnitude higher. Accordingly, mixing ratios of NH4+ exceeded those of other inorganic aerosol contributors by a factor of 4 to 10. During the wet season, mixing ratios decreased by nearly a factor of 3 for all compounds compared to those observed when intensive biomass burning took place. Additionally, N-containing gas and aerosol species featured pronounced diel variations. This is attributed to strong relative humidity and temperature variations between day and night as well as to changing photochemistry and stability conditions of the planetary boundary layer. HONO exhibited a characteristic diel cycle with high mixing ratios at nighttime and was not completely depleted by photolysis during daylight hours.

Description: A new approach to derive tropospheric concentrations of some atmospheric trace gases from ground-based UV/vis measurements is described. The instrument, referred to as the MAX-DOAS, is based on the well-known UV/vis instruments, which use the sunlight scattered in the zenith sky as the light source and the method of Differential Optical Absorption Spectroscopy (DOAS) to derive column amounts of absorbers like ozone and nitrogen dioxide. Substantial enhancements have been applied to this standard setup to use different lines of sight near to the horizon as additional light sources (MAX - multi axis). Results from measurements at Ny-Ålesund (79° N, 12° E) are presented and interpreted with the full-spherical radiative transfer model SCIATRAN. In particular, measurements of the oxygen dimer O4 which has a known column and vertical distribution in the atmosphere are used to evaluate the sensitivity of the retrieval to parameters such as multiple scattering, solar azimuth, surface albedo and refraction in the atmosphere and also to validate the radiative transfer model. As a first application, measurements of NO2 emissions from a ship lying in Ny-Ålesund harbour are presented. The results of this study demonstrate the feasibility of long term UV/vis multi axis measurement that can be used to derive not only column amounts of different trace gases but also some information on the vertical location of these absorbers.

Description: We present joint optical-radar observations of meteors collected near the peak of the Leonid activity in 2002. We show four examples of joint detections with a large, phased array L-band radar and with intensified video cameras. The general characteristic of the radar-detected optical meteors is that they show the radar detection below the termination of the optical meteor. Therefore, at least some radar events associated with meteor activity are neither head echoes nor trail echoes, but probably indicate the formation of "charged clouds" after the visual meteor is extinguished.

Description: The isotopically substituted nitrous oxide species 14N14NO, 15N14NO, 14N15NO and 15N15NO were investigated by ultra-violet (UV) absorption spectroscopy. High precision cross sections were obtained for the wavelength range 181 to 218nm at temperatures of 233 and 283K. These data are used to calculate photolytic isotopic fractionation constants as a function of wavelength. The fractionation constants were used in a three-dimensional chemical transport model in order to simulate the actual fractionation of N2O in the stratosphere, and the results were found to be in good agreement with field studies.

Description: A box model has been used to study the annual cycle in hydrogen peroxide concentrations with the objective of determining whether the observed difference in summer and winter values reflects instability in the underlying photochemistry. The model is run in both steady-state and time-dependent modes. The steady-state calculations show that, for some range of NOx background levels, two stable solutions to the continuity equations exist for a period of days in spring and fall. The corresponding time-dependent model indicates that, for sufficiently high background NOx concentrations, the spring and fall changes in H2O2 concentration may be interpreted as a forced transition between the two underlying stable regimes. The spring transition is more rapid than that in fall, an asymmetry that becomes more marked as background NOx increases. This asymmetry is related to the different time scales involved in chemical production and loss of H2O2. Observations of the spring increase in H2O2 concentration may therefore provide a better measure of the change in the underlying chemical regime than does the fall decrease. The model results developed in this paper will be compared with two sets of observations that cover annual variations of peroxide concentrations under different background pollution conditions.

Description: We report the observation and analysis of ionization flashes associated with the decay of meteoroids (so-called head echos) detected by the Arecibo 430 MHz radar during regular ionospheric observations in the spring and autumn equinoxes. These two periods allow pointing well-above and nearly-into the ecliptic plane at dawn when the event rate maximizes. The observation of many thousands of events allows a statistical interpretation of the results, which show that there is a strong tendency for the observed meteoroids to come from the apex as has been previously reported (Chau and Woodman, 2004). The velocity distributions agree with Janches et al. (2003a) when they are directly comparable, but the azimuth scan used in these observations allows a new perspective. We have constructed a simple statistical model which takes meteor velocities as input and gives radar line of sight velocities as output. The intent is to explain the fastest part of the velocity distribution. Since the speeds interpreted from the measurements are distributed fairly narrowly about nearly 60 km s-1, double the speed of the earth in its orbit, is consistent with the interpretation that many of the meteoroids seen by the Arecibo radar are moving in orbits about the sun with similar parameters as the earth, but in the retrograde direction. However, it is the directional information obtained from the beam-swinging radar experiment and the speed that together provide the evidence for this interpretation. Some aspects of the measured velocity distributions suggest that this is not a complete description even for the fast part of the distribution, and it certainly says nothing about the slow part first described in Janches et al. (2003a). Furthermore, we cannot conclude anything about the entire dust population since there are probably selection effects that restrict the observations to a subset of the population.

Description: Micrometeorological measurements of size-segregated particle number fluxes above Dutch heathlands and forests have repeatedly shown simultaneous apparent emission of particles with a diameter (Dp)

Description: Satellite based GOME (Global Ozone Measuring experiment) data are used to characterize the amount of tropospheric ozone over the tropical Pacific. Tropospheric ozone was determined from GOME data using the Tropospheric Excess Method (TEM). In the tropical Pacific a significant seasonal variation is detected. Tropospheric excess ozone is enhanced during the biomass burning season from September to November due to outflow from the continents. In September 1999 GOME data reveal an episode of increased excess ozone columns over Tahiti (18.0° S; 149.0° W) (Eastern Pacific) compared to Am. Samoa (14.23° S; 170.56° W) and Fiji (18.13° S; 178.40° E), both situated in the Western Pacific. Backtrajectory calculations show that none of the airmasses arriving over the three locations experienced anthropogenic pollution (e. g. biomass burning). Consequently other sources of ozone have to be considered. One possible process leading to an increase of tropospheric ozone is stratosphere-troposphere-exchange. An analysis of the potential vorticity along trajectories arriving above each of the locations reveals that airmasses at Tahiti are subject to enhanced stratospheric influence, compared to Am. Samoa and Fiji. As a result this study shows clear incidents of transport of airmasses from the stratosphere into the troposphere.

Description: Model-measurement comparisons of HOx in extremely clean air ([NO]

Description: In order to estimate the anthropogenic influence of gas and aerosol emissions from the Petroleum Industry in maritime zones with clouds of small vertical extent, a numerical 1-D Eulerian cloud-chemical model with detailed microphysics (Alfonso and Raga, 2002) is used to simulate the influence of water soluble organic compounds (WSOC) and organic+inorganic gas emissions on cloud development. Following Mircea et al. (2002), we tested the sensitivity of the cloud and precipitation development in the classical inorganic case (CIC) and the inorganic+organic case (IOC) with respect to CCN compositions. The results indicate an increase in the droplet concentration for the IOC, and a delay in the development of precipitation. The pH spectral evolution was studied during both the development and precipitation stages. The influence of the diffusion of formic acid and its generation by oxidation of hydrated formaldehyde in the aqueous phase result in a reduction in the pH of precipitation in the range between 0.05 and 0.15 pH units (from 1 to 3%) for the high ambient SO2 concentration (20 ppb) and between 0.2-0.5 pH units (from 4 to 10%) for the low ambient SO2 concentration (1 ppb) case.

Description: Nitrate is an important component of (secondary inorganic) fine aerosols in Europe. We present a model simulation for the year 1995 in which we account for the formation of secondary inorganic aerosols including ammonium sulphate and ammonium nitrate, a semi volatile component. For this purpose, the chemistry-transport model LOTOS was extended with a thermodynamic equilibrium module and additional relevant processes to account for secondary aerosol formation and deposition. During winter, fall and especially spring high nitrate levels are projected over north western, central and eastern Europe. During winter nitrate concentrations are highest in Italy, in accordance with observed data. In winter nitric acid, the precursor for aerosol nitrate is formed through heterogeneous reactions on the surface of aerosols. Modelled and observed sulphate concentrations show little seasonal variation. Compared to sulphate levels, appreciable ammonium nitrate concentrations in summer are limited to those areas with high ammonia emissions, e.g. the Netherlands, since high ammonia concentrations are necessary to stabilise this aerosol component at high temperatures. As a consequence of the strong seasonal variation in nitrate levels the AOD depth of nitrate over Europe is especially significant compared to that of sulphate in winter and spring when equal AOD values are calculated over large parts of Europe. Averaged over all stations the model reproduces the measured concentrations for NO3, SO4, NH4, TNO3 (HNO3+NO3), TNH4 (NH3+NH4) and SO2 within 20%. The daily variation is captured well, albeit that the model does not always represent the amplitude of single events. The model underestimates wet deposition which was attributed to the crude representation of cloud processes. Comparison of retrieved and computed aerosol optical depth (AOD) showed that the model underestimates AOD significantly, which was expected due to the lack of carbonaceous aerosols, sea salt and dust in the model. The treatment of ammonia was found to be a major source for uncertainties in the model representation of secondary aerosols. Also, inclusion of sea salt is necessary to properly assess the nitrate and nitric acid levels in marine areas.

Description: Size-dependent particle number fluxes measured by eddy-covariance (EC) and continuous fluxes of ammonium (NH4+) measured with the aerodynamic gradient method (AGM) are reported for a Dutch heathland. Daytime deposition velocities (Vd) by EC with peak values of 5 to 10 mm s-1 increased with particle diameter (dp) over the range 0.1–0.5 µm, and are faster than predicted by current models. With a mean Vd of 2.0 mm s-1 (daytime: 2.7; night-time 0.8 mm s-1) NH4+ fluxes by AGM are overall in agreement with former measurements and NH4+-N dry deposition amounts to 20% of the dry input of NH3-N over the measurement period. These surface exchange fluxes are analyzed together with simultaneous gas-phase flux measurements for indications of gas-particle interactions. On warm afternoons the apparent fluxes of acids and aerosol above the heathland showed several coinciding anomalies, all of which are consistent with NH4+ evaporation during deposition: (i) canopy resistances for HNO3 and HCl of up to 100 s m-1, (ii) simultaneous particle emission of small particles (Dp0.18 µm), (iii) NH4+ deposition faster than derived from size-distributions and size-segregated EC particle fluxes. These observations coincide with the observations of (i) surface concentration products of NH3 and HNO3 well below the thermodynamic equilibrium value and (ii) Damköhler numbers that indicate chemical conversion to be sufficiently fast to modify exchange fluxes. The measurements imply a removal rate of volatile NH4+ of 3−30×10-6 s-1 averaged over the 1 km boundary-layer, while NH3 deposition is underestimated by typically 20 ng m-2 s-1 (28%) and flux reversal may occur.

Description: During the ESCOMPTE precampaign (summer 2000, over Southern France), a 3-day period of intensive observation (IOP0), associated with ozone peaks, has been simulated. The comprehensive RAMS model, version 4.3, coupled on-line with a chemical module including 29 species, is used to follow the chemistry of the polluted zone. This efficient but time consuming method can be used because the code is installed on a parallel computer, the SGI 3800. Two runs are performed: run 1 with a single grid and run 2 with two nested grids. The simulated fields of ozone, carbon monoxide, nitrogen oxides and sulfur dioxide are compared with aircraft and surface station measurements. The 2-grid run looks substantially better than the run with one grid because the former takes the outer pollutants into account. This on-line method helps to satisfactorily retrieve the chemical species redistribution and to explain the impact of dynamics on this redistribution.

Description: .

Description: Mixing ratios of water (H2O) in the stratosphere appear to increase due to increased input of H2O and methane from the troposphere and due to intensified oxidation of CH4 in the stratosphere, but many of the underlying mechanisms are not yet understood. Here we identify and quantify three chemical mechanisms which must have led to more efficient oxidation of CH4 in the stratosphere over the past several decades: 1) The increase in stratospheric chlorine levels due to anthropogenic CFC emissions, 2) the thinning of the stratospheric ozone column and 3) enhanced OH levels in the stratosphere due to increasing H2O levels themselves. In combination with the increase in tropospheric CH4 mixing ratios and with solar cycle related variations of upper stratospheric ozone, these effects can explain about 50% of the additional conversion of CH4 to H2O as observed throughout the stratosphere. The relative contributions from the individual processes have varied over the past decades.

Description: Physical and chemical characterizations of the atmospheric aerosol were carried out at Mt. Cimone (Italy) during the 4 June-4 July 2000 period. Particle size distributions in the size range 6nm-10µm were measured with a differential mobility analyzer (DMA) and an optical particle counter (OPC). Size-segregated aerosol was sampled using a 6-stage low pressure impactor. Aerosol samples were submitted to gravimetric and chemical analyses. Ionic, carbonaceous and refractory components of the aerosol were quantified. We compared the sub- and superµm aerosol mass concentrations determined by gravimetric measurements (mGM), chemical analyses (mmCA), and by converting particle size distribution to aerosol mass concentrations (mmSD). Mean random uncertainties associated with the determination of mmGM, mmCA, and mmSD were assessed. The three estimates of the sub-µm aerosol mass concentration agreed, which shows that within experimental uncertainty, the sub-µm aerosol was composed of the quantified components. The three estimates of the super-µm aerosol mass concentration did not agree, which indicates that random uncertainties and/or possible systematic errors in aerosol sampling, sizing or analyses were not adequately accounted for. Aerosol chemical composition in air masses from different origins showed differences, which were significant in regard to experimental uncertainties. During the Saharan dust advection period, coarse dust and fine anthropogenic particles were externally mixed. No anthropogenic sulfate could be found in the super-µm dust particles. In contrast, nitrate was shifted towards the aerosol super-µm fraction in presence of desert dust.

Description: The chemical composition of cloud water was investigated during the winter-spring months of 2001 and 2002 at the Puy de Dôme station (1465 m above sea level, 45°46′22′′ N, 2°57′43′′ E) in an effort to characterize clouds in the continental free troposphere. Cloud droplets were sampled with single-stage cloud collectors (cut-off diameter approximately 7 µm) and analyzed for inorganic and organic ions, as well as total dissolved organic carbon. Results show a very large variability in chemical composition and total solute concentration of cloud droplets, ranging from a few mg l-1 to more than 150 mg l-1. Samplings can be classified in three different categories with respect to their total ionic content and relative chemical composition: background continental (BG, total solute content lower than 18 mg l-1), anthropogenic continental (ANT, total solute content from 18 to 50 mg l-1), and special events (SpE, total solute content higher than 50 mg l-1). The relative chemical composition shows an increase in anthropogenic-derived species (NO3-, SO42- and NH4+) from BG to SpE, and a decrease in dissolved organic compounds (ionic and non-ionic) that are associated with the anthropogenic character of air masses. We observed a high contribution of solute in cloud water derived from the dissolution of gas phase species in all cloud events. This was evident from large solute fractions of nitrate, ammonium and mono-carboxylic acids in cloud water, relative to their abundance in the aerosol phase. The comparison between droplet and aerosol composition clearly shows the limited ability of organic aerosols to act as cloud condensation nuclei. The strong contribution of gas-phase species limits the establishment of direct relationships between cloud water solute concentration and LWC that are expected from nucleation scavenging.

Description: A size-segregated aerosol dynamics model UHMA (University of Helsinki Multicomponent Aerosol model) was developed for studies of multicomponent tropospheric aerosol particles. The model includes major aerosol microphysical processes in the atmosphere with a focus on new particle formation and growth; thus it incorporates particle coagulation and multicomponent condensation, applying a revised treatment of condensation flux onto free molecular regime particles and the activation of nanosized clusters by organic vapours (Nano-Köhler theory), as well as recent parameterizations for binary H2SO4-H2O and ternary H2SO4-NH3-H2O homogeneous nucleation and dry deposition. The representation of particle size distribution can be chosen from three sectional methods: the hybrid method, the moving center method, and the retracking method in which moving sections are retracked to a fixed grid after a certain time interval. All these methods can treat particle emissions and atmospheric transport consistently, and are therefore suitable for use in large scale atmospheric models. In a test simulation against an accurate high resolution solution, all the methods showed reasonable treatment of new particle formation with 20 size sections although the hybrid and the retracking methods suffered from artificial widening of the distribution. The moving center approach, on the other hand, showed extra dents in the particle size distribution and failed to predict the onset of detectable particle formation. In a separate test simulation of an observed nucleation event, the model captured the key qualitative behaviour of the system well. Furthermore, its prediction of the organic volume fraction in newly formed particles, suggesting values as high as 0.5 for 3–4 nm particles and approximately 0.8 for 10 nm particles, agrees with recent indirect composition measurements.

Description: Renewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O'Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical. When small, those formed in the molecular iodine system swell only moderately when exposed to increased humidity environments, and swell progressively less with increasing size; this behaviour occurs whether they are formed in dry or humid environments, in contrast to those in the CH2I2 system. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed.

Description: We have analysed relative humidity statistics from measurements in cirrus clouds taken unintentionally during the Measurement of OZone by Airbus In-service airCraft project (MOZAIC). The shapes of the in-cloud humidity distributions change from nearly symmetric in relatively warm cirrus (warmer than −40°C) to considerably positively skew (i.e. towards high humidities) in colder clouds. These results are in agreement to findings obtained recently from the INterhemispheric differences in Cirrus properties from Anthropogenic emissions (INCA) campaign (Ovarlez et al., 2002). We interprete the temperature dependence of the shapes of the humidity distributions as an effect of the length of time a cirrus cloud needs from formation to a mature equilibrium stage, where the humidity is close to saturation. The duration of this transitional period increases with decreasing temperature. Hence cold cirrus clouds are more often met in the transitional stage than warm clouds.

Description: A time-resolved model of the Na layer in the mesosphere/lower thermosphere region is described, where the continuity equations for the major sodium species Na, Na+ and NaHCO3 are solved explicity, and the other short-lived species are treated in steady-state. It is shown that the diurnal variation of the Na layer can only be modelled satisfactorily if sodium species are permanently removed below about 85 km, both through the dimerization of NaHCO3 and the uptake of sodium species on meteoric smoke particles that are assumed to have formed from the recondensation of vaporized meteoroids. When the sensitivity of the Na layer to the meteoroid input function is considered, an inconsistent picture emerges. The ratio of the column abundance of Na+ to Na is shown to increase strongly with the average meteoroid velocity, because the Na is injected at higher altitudes. Comparison with a limited set of Na+ measurements indicates that the average meteoroid velocity is probably less than about 25 km s-1, in agreement with velocity estimates from conventional meteor radars, and considerably slower than recent observations made by wide aperture incoherent scatter radars. The Na column abundance is shown to be very sensitive to the meteoroid mass input rate, and to the rate of vertical transport by eddy diffusion. Although the magnitude of the eddy diffusion coefficient in the 80–90 km region is uncertain, there is a consensus between recent models using parameterisations of gravity wave momentum deposition that the average value is less than 3×105 cm2 s-1. This requires that the global meteoric mass input rate is less than about 20 td-1, which is closest to estimates from incoherent scatter radar observations. Finally, the diurnal variation in the meteoroid input rate only slight perturbs the Na layer, because the residence time of Na in the layer is several days, and diurnal effects are effectively averaged out.

Description: Recent measurements conducted at the Arecibo Observatory report high-speed sporadic meteors having velocities near 50 km/s. The results seem to indicate a bimodal velocity distribution in the sporadic meteors (maxima at ~20 km/s and ~50 km/s). The particles have a maximum mass of ~1µg. This paper will present an analysis of the ablation of 1µg meteoroids having velocities of 20, 30, 50, and 70 km/s. The calculations show that there is fractionation even for the fast meteoroids, the effect being particularly noticeable for the 1µg sporadic particles, and less so for the heavier particles. The relevance of the calculations to the radar observations of the sporadic meteors will be discussed.

Description: The possible connections between the carbon balance of ecosystems and aerosol-cloud-climate interactions play a significant role in climate change studies. Carbon dioxide is a greenhouse gas, whereas the net effect of atmospheric aerosols is to cool the climate. Here, we investigated the connection between forest-atmosphere carbon exchange and aerosol dynamics in the continental boundary layer by means of multiannual data sets of particle formation and growth rates, of CO2 fluxes, and of monoterpene concentrations in a Scots pine forest in southern Finland. We suggest a new, interesting link and a potentially important feedback among forest ecosystem functioning, aerosols, and climate: Considering that globally increasing temperatures and CO2 fertilization are likely to lead to increased photosynthesis and forest growth, an increase in forest biomass would increase emissions of non-methane biogenic volatile organic compounds and thereby enhance organic aerosol production. This feedback mechanism couples the climate effect of CO2 with that of aerosols in a novel way.

Description: The effect of nitric acid on the equilibrium size distributions of upper tropospheric aerosols is calculated as a function of relative humidity. It is shown that HNO3 concentrations above a few tenths of a ppb can cause substantial increases in haze mode particle concentrations at relative humidities at about 60% and above. The effect can be strongly magnified when letovicite particles are present in addition to sulfuric acid aerosols. Letovicite particles are less acidic than the sulfuric acid particles and so more nitric acid can be absorbed. This effect can be seen even at RH below 50% due to the lowering of the deliquescence RH of letovicite in the presence of gaseous nitric acid at low temperatures. We have also compared equilibrium calculations of the HNO3 effect with observations of increased haze mode concentrations at relative humidities above 50% (Petzold et al., 2000). Nitric acid mixing ratios on the order of 0.5-2ppb may explain the observed increase of haze mode particles at least partially.

Description: A new method for measuring gas-phase naphthalene in the atmosphere is based on laser-induced fluorescence at low pressure. The fluorescence spectrum of naphthalene near 308 nm was identified. Naphthalene fluorescence quenching by N, O and HO was investigated in the laboratory. No significant quenching was found for HO with mixing ratio up to 2.5%. The quenching rate of naphthalene fluorescence is (1.980.18) 10cmmolecules for N, and (2.480.08)10cmmolecules for O at 297 K. Instrument calibrations were performed with a range of naphthalene mixing ratios between 5 and 80 parts per billion by volume (ppbv, 10. In the current instrument configuration, the detection limit is estimated to be about 20 parts per trillion by volume (pptv, 10 with 2 confidence and a 1-min integration time. Measurements of atmospheric naphthalene in three cities, Nashville, TN, Houston, TX, and New York City, NY, are presented. Good correlation between naphthalene and major anthropogenic pollutants is found.

Description: During the Northern hemisphere winter season, biomass burning is widespread in West Africa, yet the total tropospheric column ozone values (

Description: Particle size distribution (size-range 3-900nm) and PM10 was measured simultaneously at an urban background station in Copenhagen, a near-city background and a rural location during a period in September-November 2002. The study investigates the contribution from urban versus regional sources of particle number and mass concentration. The total particle number (ToN) and NOx are well correlated at the urban and near-city level and show a distinct diurnal variation, indicating the common traffic source. The average ToN at the three stations differs by a factor of 3. The observed concentrations are 2500#cm, 4500#cm and 7700#cm at rural, near-city and urban level, respectively. PM10 and total particle volume (ToV) are well correlated between the three different stations and show similar concentration levels, in average within 30% relative difference, indicating a common source from long-range transport that dominates the concentrations at all locations. Measures to reduce the local urban emissions of NOx and ToN are likely to affect both the street level and urban background concentrations, while for PM10 and ToV only measurable effects at the street level are probable. Taking into account the supposed stronger health effects of ultrafine particles reduction measures should address particle number emissions. The traffic source contributes strongest in the 10-200nm particle size range. The maximum of the size distribution shifts from about 20-30nm at kerbside to 50-60nm at rural level. Particle formation events were observed in the 3-20nm size range at rural location in the afternoon hours, mainly under conditions with low concentrations of pre-existing aerosol particles. The maximum in the size distribution of the "traffic contribution" seems to be shifted to about 28nm in the urban location compared to 22nm at kerbside. Assuming NOx as an inert tracer on urban scale allows to estimate that ToN at urban level is reduced by 15-30% compared to kerbside. Particle removal processes, e.g. deposition and coagulation, which are most efficient for smallest particle sizes (20nm) and condensational growth are likely mechanisms for the loss of particle number and the shift in particle size.

Description: Routine lidar measurements of the vertical distribution of the aerosol extinction coefficient and the extinction-to-backscatter ratio have been performed at Thessaloniki, Greece using a Raman lidar system in the frame of the EARLINET project since 2000. Co-located spectral and broadband solar UV-B irradiance measurements, as well as total ozone observations, were available whenever lidar measurements were obtained. From the available measurements several cases could be identified that allowed the study of the effect of different types of aerosol on the levels of the UV-B solar irradiance at the Earth's surface. The TUV radiative transfer model has been used to simulate the irradiance measurements, using total ozone and the lidar aerosol data as input. From the comparison of the model results with the measured spectra the effective single scattering albedo was determined using an iterative procedure, which has been verified against results from the 1998 Lindenberg Aerosol Characterization Experiment. It is shown that for the same aerosol optical depth and for the same total ozone values the UV-B irradiances at the Earth's surface can show differences up to 10%, which can be attributed to differences in the aerosol type. It is shown that the combined use of the estimated single scattering albedo and of the measured extinction-to-backscatter ratio leads to a better characterization of the aerosol type probed.

Description: Using the proton transfer reaction mass spectrometry (PTR-MS) technique, acetonitrile was measured during the wet season in a Venezuelan woodland savanna. The site was located downwind of the Caribbean Sea and no biomass burning events were observed in the region. High boundary layer concentrations of 211±36pmol/mol (median, ±standard deviation) were observed during daytime in the well mixed boundary layer, which is about 60pmol/mol above background concentrations recently measured over the Mediterranean Sea and the Pacific Ocean. Most likely acetonitrile is released from the warm waters of the Caribbean Sea thereby enhancing mixing ratios over Venezuela. Acetonitrile concentrations will probably still be much higher in biomass burning plumes, however, the general suitability of acetonitrile as a biomass burning marker should be treated with care. During nights, acetonitrile dropped to levels typically around 120pmol/mol, which is consistent with a dry deposition velocity of 0.14cm/s when a nocturnal boundary layer height of 100m is assumed.

Description: Measurements of biogenic volatile organic compounds (VOCs) were performed at Hyytiälä, a Boreal forest site in Southern Finland as part of the OSOA (origin and formation of secondary organic aerosol) project in August 2001. At this site, frequent formation of new particles has been observed and the role of biogenic VOCs in this process is still unclear. Tethered balloons served as platforms to collect VOC samples within the planetary boundary layer at heights up to 1.2 km above ground during daytime. Mean mixed layer concentrations of total monoterpenes varied between 10 and 170 pptv, with a-pinene, limonene and D3-carene as major compounds, isoprene was detected at levels of 2-35 pptv. A mixed layer gradient technique and a budget approach are applied to derive surface fluxes representative for areas of tens to hundreds of square kilometres. Effects of spatial heterogeneity in surface emissions are examined with a footprint analysis. Depending on the source area considered, mean afternoon emissions of the sum of terpenes range between 180 and 300 mg m-2 h-1 for the period of 2-12 August 2001. Surface fluxes close to Hyytiälä were higher than the regional average, and agree well with mean emissions predicted by a biogenic VOC emission model. Total rates of monoterpene oxidation were calculated with a photochemical model. The rates did not correlate with the occurrence of new particle formation, but the ozone pathway was of more importance on days with particle formation. Condensable vapour production from the oxidation of monoterpenes throughout the mixed layer can only account for a fraction of the increase in aerosol mass observed at the surface.

Description: A quartz crystal microbalance apparatus has been used to measure the room temperature uptake of water vapour by thin films of oleic acid as a function of relative humidity, both before and following exposure of the films to various partial pressures of gas phase ozone. A rapid increase in the water-sorbing ability of the film is observed as its exposure to ozone is increased, followed by a plateau region in which additional water is taken up more gradually. In this fully-processed region the mass of water taken up by the film is about 4 times that of the unprocessed film. Infrared spectra of the films, measured after variable exposures to ozone, show dramatic increases in both the "free" and hydrogen-bonded O-H stretching regions, and a decrease in the intensity of olefinic features. These results are consistent with the formation of an oxygenated polymeric product or products, as well as the gas phase products previously identified.

Description: Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation coefficient between simulated and training values of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4  (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download.

Description: Laboratory experimental results of iodine oxide nucleation are presented. Nucleation was induced following UV photolysis of CF3I or CH2I2 in the presence of excess ozone. Measurements were performed in a 70 L Teflon reactor with new particles detected using an Ultrafine Condensation Particle Counter, UCPC. The experimental results are interpreted using a coupled chemical - aerosol model to derive model parameters assuming single component homogeneous nucleation of OIO. The aerosol model results have been applied in an atmospheric box-model to interpret the possible implications of iodine oxide nucleation in the marine boundary layer. The model calculations demonstrate that IO and OIO concentrations reported in recent field measurements using long path absorption (Allan et al., 2000, 2001) are not sufficient to account for significant aerosol production either in the coastal or open ocean marine boundary layer using the mechanism presented. We demonstrate that inhomogeneous sources of iodine oxides, i.e. "hot" spots with elevated iodine species emissions, could account for the aerosol production bursts observed in the coastal region near Mace Head, Ireland.

Description: A sensitivity study of the treatment of isoprene and related parameters in 3D atmospheric models was conducted using the global model of tropospheric chemistry MATCH-MPIC. A total of twelve sensitivity scenarios which can be grouped into four thematic categories were performed. These four categories consist of simulations with different chemical mechanisms, different assumptions concerning the deposition characteristics of intermediate products, assumptions concerning the nitrates from the oxidation of isoprene and variations of the source strengths. The largest differences in ozone compared to the reference simulation occured when a different isoprene oxidation scheme was used (up to 30-60% or about 10 nmol/mol). The largest differences in the abundance of peroxyacetylnitrate (PAN) were found when the isoprene emission strength was reduced by 50% and in tests with increased or decreased efficiency of the deposition of intermediates. The deposition assumptions were also found to have a significant effect on the upper tropospheric HOx production. Different implicit assumptions about the loss of intermediate products were identified as a major reason for the deviations among the tested isoprene oxidation schemes. The total tropospheric burden of O3 calculated in the sensitivity runs is increased compared to the background methane chemistry by 26±9  Tg( O3) from 273 to an average from the sensitivity runs of 299 Tg(O3). % revised Thus, there is a spread of ± 35% of the overall effect of isoprene in the model among the tested scenarios. This range of uncertainty and the much larger local deviations found in the test runs suggest that the treatment of isoprene in global models can only be seen as a first order estimate at present, and points towards specific processes in need of focused future work.

Description: A description of the carbonate system has been incorporated in the MIRO biogeochemical model to investigate the contribution of diatom and Phaeocystis blooms to the seasonal dynamics of air-sea CO2 exchanges in the Eastern Channel and Southern Bight of the North Sea, with focus on the eutrophied Belgian coastal waters. For this application, the model was implemented in a simplified three-box representation of the hydrodynamics with the open ocean boundary box ‘Western English Channel’ (WCH) and the ‘French Coastal Zone’ (FCZ) and ‘Belgian Coastal Zone’ (BCZ) boxes receiving carbon and nutrients from the rivers Seine and Scheldt, respectively. Results were obtained by running the model for the 1996–1999 period. The simulated partial pressures of CO2 (pCO2) were successfully compared with data recorded over the same period in the central BCZ at station 330 (51°26.05′ N; 002°48.50′ E). Budget calculations based on model simulations of carbon flow rates indicated for BCZ a low annual sink of atmospheric CO2 (−0.17 mol C m-2 y-1). On the opposite, surface water pCO2 in WCH was estimated to be at annual equilibrium with respect to atmospheric CO2. The relative contribution of biological, chemical and physical processes to the modelled seasonal variability of pCO2 in BCZ was further explored by running model scenarios with separate closures of biological activities and/or river inputs of carbon. The suppression of biological processes reversed direction of the CO2 flux in BCZ that became, on an annual scale, a significant source for atmospheric CO2 (+0.53 mol C m-2 y-1). Overall biological activity had a stronger influence on the modelled seasonal cycle of pCO2 than temperature. Especially Phaeocystis colonies which growth in spring were associated with an important sink of atmospheric CO2 that counteracted the temperature-driven increase of pCO2 at this period of the year. However, river inputs of organic and inorganic carbon were shown to increase the surface water pCO2 and hence the emission of CO2 to the atmosphere. Same calculations conducted in WCH, showed that temperature was the main factor controlling the seasonal pCO2 cycle in these open ocean waters. The effect of interannual variations of fresh water discharge (and related nutrient and carbon inputs), temperature and wind speed was further explored by running scenarios with forcing typical of two contrasted years (1996 and 1999). Based on these simulations, the model predicts significant variations in the intensity and direction of the annual air-sea CO2 flux.

Description: A 1-D model system, consisting of the 1-D version of the Princeton Ocean Model (POM) coupled with the European Regional Seas Ecosystem Model (ERSEM) has been applied to a sub-basin of the Baltic Proper, the Bornholm basin. The model has been forced with 3h meteorological data for the period 1979-1990, producing a 12-year hindcast validated with datasets from the Baltic Environmental Database for the same period. The model results demonstrate the model to hindcast the time-evolution of the physical structure very well, confirming the view of the open Baltic water column as a three layer system of surface, intermediate and bottom waters. Comparative analyses of modelled hydrochemical components with respect to the independent data have shown that the long-term system behaviour of the model is within the observed ranges. Also primary production processes, deduced from oxygen (over)saturation are hindcast correctly over the entire period and the annual net primary production is within the observed range. The largest mismatch with observations is found in simulating the biogeochemistry of the Baltic intermediate waters. Modifications in the structure of the model (addition of fast-sinking detritus and polysaccharide dynamics) have shown that the nutrient dynamics are linked to the quality and dimensions of the organic matter produced in the euphotic zone, highlighting the importance of the residence time of the organic matter within the microbial foodweb in the intermediate waters. Experiments with different scenarios of riverine nutrient loads, assessed in the limits of a 1-D setup, have shown that the external input of organic matter makes the open Baltic model more heterotrophic. The characteristics of the inputs also drive the dynamics of nitrogen in the bottom layers leading either to nitrate accumulation (when the external sources are inorganic), or to coupled nitrification-denitrification (under strong organic inputs). The model indicates the permanent stratification to be the main feature of the system as regulator of carbon and nutrient budgets. The model predicts that most of the carbon produced in the euphotic zone is also consumed in the water column and this enhances the importance of heterotrophic benthic processes as final closure of carbon and nutrient cycles in the open Baltic.

Description: By controlled experiments that simulate marine depositional environments, it is shown that accelerated weathering and clay mineral authigenesis occur during the combined process of ingestion, digestion and excretion of fine-grained sediment by two species of annelid worms. Previously characterized synthetic mud was created using finely ground, low-grade metamorphic slate (temperature approximately 300°C) containing highly crystalline chlorite and muscovite. This was added to experiment and control tanks along with clean, wind-blown sand. Faecal casts were collected at regular intervals from the experimental tanks and, less frequently, from the control tanks. Over a period of many months the synthetic mud (slate) proved to be unchanged in the control tanks, but was significantly different in faecal casts from the experimental tanks that contained the worms Arenicola marina and Lumbricus terrestris. Chlorite was preferentially destroyed during digestion in the gut of A. marina. Both chlorite and muscovite underwent XRD peak broadening with a skew developing towards higher lattice spacing, characteristic of smectite formation. A neoformed Fe-Mg-rich clay mineral (possibly berthierine) and as-yet undefined clay minerals with very high d-spacing were detected in both A. marina and L. terrestris cast samples. We postulate that a combination of the low pH and bacteria-rich microenvironment in the guts of annelid worms may radically accelerate mineral dissolution and clay mineral precipitation processes during digestion. These results show that macrobiotic activity significantly accelerates weathering and mineral degradation as well as mineral authigenesis. The combined processes of sediment ingestion and digestion thus lead to early diagenetic growth of clay minerals in clastic sediments.

Description: Observations of the net ecosystem exchange of water and CO2 were made during two seasons in 2000 and 2001 above a Larch forest in Far East Siberia (Yakutsk). The measurements were obtained by eddy correlation. There is a very sharply pronounced growing season of 100 days when the forest is leaved. Maximum half hourly uptake rates are 18 µmol m-2 s-1; maximum respiration rates are 5 µmol m-2 s-1. Net annual sequestration of carbon was estimated at 160 gCm-2 in 2001. Applying no correction for low friction velocities added 60 g C m-2. The net carbon exchange of the forest was extremely sensitive to small changes in weather that may switch the forest easily from a sink to a source, even in summer. June was the month with highest uptake in 2001. The average evaporation rate of the forest approached 1.46 mm day-1 during the growing season, with peak values of 3 mm day-1 with an estimated annual evaporation of 213 mm, closely approaching the average annual rainfall amount. 2001 was a drier year than 2000 and this is reflected in lower evaporation rates in 2001 than in 2000. The surface conductance of the forest shows a marked response to increasing atmospheric humidity deficits. This affects the CO2 uptake and evaporation in a different manner, with the CO2 uptake being more affected. There appears to be no change in the relation between surface conductance and net ecosystem uptake normalized by the atmospheric humidity deficit at the monthly time scale. The response to atmospheric humidity deficit is an efficient mechanism to prevent severe water loss during the short intense growing season. The associated cost to the sequestration of carbon may be another explanation for the slow growth of these forests in this environment.

Description: We present the first measurement of nitrogen isotopic composition (δ15N) in suspended particulate matter (SPM) of the surface Bay of Bengal (BOB) at 24 different locations during pre- (April–May 2003) and post- (September–October 2002) monsoon seasons. The δ15N of particulate organic nitrogen (PON) in surface suspended matter of coastal as well as northern open BOB shows signatures of a two end-member mixing between continental inputs and marine sources. Dilution by the organic and detrital continental material brought in by rivers leads to consistently lower δ15N, evident from the relationship between surface salinity and δ15N. δ15N of surface PON of open ocean locations during both seasons, and also at coastal locations during pre-monsoon suggest the nitrate from deeper waters as a predominant source of nutrient for planktons. The depth profiles of δ15N of SPM during pre-monsoon season at nine different locations are also presented. These indicate an increase in δ15N by a maximum of 2.8‰ between euphotic depth and 300 m, which is lower than that observed in the eastern Indian Ocean, indicating the role of higher sinking rates of particles ballasted by aggregates of organic and mineral matter in BOB.

Description: Three approaches for determining the stable isotopic composition (δ13C and δ18O) of soil CO efflux were compared. A new technique employed mini-towers, constructed of open-topped piping, that were placed on the soil surface to collect soil-emitted CO2. Samples were collected along a vertical gradient and analyzed for CO2 concentration and isotopic composition. These data were then used to produce Keeling plots to determine the δ18O and δ13C of CO2 emitted from the soil. These results were then compared to the δ18O and δ13C of soil-respired CO2 measured with two other techniques: (1) flux chambers and (2) estimation from the application of the diffusional fractionation factor to measured values of below ground soil CO2 and to CO2 in equilibrium with soil water δ18O. Mini-tower δ18O Keeling plots were linear and highly significant (0.81〈 r 2 〉 0.96), in contrast to chamber δ18O Keeling plots, which showed significant curvature, necessitating the use of a mass balance to calculate the δ18O of respired CO2. In the chambers, the values determined for the δ18O of soil respired CO2 approached the value of CO2 in equilibrium with surficial soil water, and the results were significantly δ18O enriched relative to the mini-tower results and the δ18O of soil CO2 efflux determined from soil CO2. There were close agreements between the three methods for the determination of the δ13C of soil efflux CO2. Results suggest that the mini-towers can be effectively used in the field for determining the δ18O and the δ13C of soil-respired CO2.

Description: Microzooplankton grazing rate estimates by the dilution approach have recently been criticized as systematically biased in the direction of being overestimates of actual rates in nature, and particularly in the open oceans. This argument is based on observed mortality responses of ciliated protozoa to reduced food in several coastal experiments and a global extrapolation which assumes that all grazing in all ocean systems scales to the abundance of ciliates. We suggest that these conclusions are unrealistic on several counts: they do not account for community differences in open ocean and coastal systems; they ignore experimental direct evidence supporting dilution rate estimates in the open oceans, and they discount dilution effects on mortality as well as growth in multi-layered, open-ocean food webs. High microzooplankton grazing rates in open-ocean systems are consistent with current views on export fluxes and trophic transfers. More importantly, significantly lower rates would fail to account for the efficient nutrient recycling requirements of these resource-limited and rapid-turnover communities.

Description: A very fast thermistor string has been built to accommodate the scientific need to accurately monitor fast and vigorous internal wave and overturning processes above sloping bottoms in the ocean. The thermistors and their custom designed electronics can register temperature at an estimated precision of about 1mK with a response time faster than 0.25 s down to depths of 6000 m. The present string holds 128 synoptically measuring sensors at 0.5 m intervals, which are all read-out within 0.5 s. When sampling at 1Hz, the batteries and the memory capacity of the recorder allow for deployments of up to 2 weeks. Detailed examples of the first field observations are presented, which show overturning and very high-frequency (Doppler-shifted) internal waves besides occasionally large turbulent bores moving up the sloping side of Great Meteor Seamount, Canary Basin, North-Atlantic Ocean.

Description: Mirror mode turbulence is the lowest frequency perpendicular magnetic excitation in magnetized plasma proposed already about half a century ago by Rudakov and Sagdeev (1958) and Chandrasekhar et al. (1958) from fluid theory. Its experimental verification required a relatively long time. It was early recognized that mirror modes for being excited require a transverse pressure (or temperature) anisotropy. In principle mirror modes are some version of slow mode waves. Fluid theory, however, does not give a correct physical picture of the mirror mode. The linear infinitesimally small amplitude physics is described correctly only by including the full kinetic theory and is modified by existing spatial gradients of the plasma parameters which attribute a small finite frequency to the mode. In addition, the mode is propagating only very slowly in plasma such that convective transport is the main cause of flow in it. As the lowest frequency mode it can be expected that mirror modes serve as one of the dominant energy inputs into plasma. This is however true only when the mode grows to large amplitude leaving the linear stage. At such low frequencies, on the other hand, quasilinear theory does not apply as a valid saturation mechanism. Probably the dominant processes are related to the generation of gradients in the plasma which serve as the cause of drift modes thus transferring energy to shorter wavelength propagating waves of higher nonzero frequency. This kind of theory has not yet been developed as it has not yet been understood why mirror modes in spite of their slow growth rate usually are of very large amplitudes indeed of the order of |B/B0|2~O(1). It is thus highly reasonable to assume that mirror modes are instrumental for the development of stationary turbulence in high temperature plasma. Moreover, since the magnetic field in mirror turbulence forms extended though slightly oblique magnetic bottles, low parallel energy particles can be trapped in mirror modes and redistribute energy (cf. for instance, Chisham et al. 1998). Such trapped electrons excite banded whistler wave emission known under the name of lion roars and indicating that the mirror modes contain a trapped particle component while leading to the splitting of particle distributions (see Baumjohann et al., 1999) into trapped and passing particles. The most amazing fact about mirror modes is, however, that they evolve in the practically fully collisionless regime of high temperature plasma where it is on thermodynamic reasons entirely impossible to expel any magnetic field from the plasma. The fact that magnetic fields are indeed locally extracted makes mirror modes similar to "superconducting" structures in matter as known only at extremely low temperatures. Of course, microscopic quantum effects do not play a role in mirror modes. However, it seems that all mirror structures have typical scales of the order of the ion inertial length which implies that mirrors evolve in a regime where the transverse ion and electron motions decouple. In this case the Hall kinetics comes into play. We estimate that in the marginally stationary nonlinear state of the evolution of mirror modes the modes become stretched along the magnetic field with k||=0 and that a small number the order of a few percent of the particle density is responsible only for the screening of the field from the interior of the mirror bubbles.

Description: There is abundant observational evidence that the energization of plasma particles in space is correlated with an enhanced activity of large-scale MHD waves. Since these waves cannot interact with particles, we need to find ways for these MHD waves to transport energy in the dissipation range formed by small-scale or high-frequency waves, which are able to interact with particles. In this paper we consider the dissipation range formed by the kinetic Alfvén waves (KAWs) which are very short- wavelengths across the magnetic field irrespectively of their frequency. We study a nonlocal nonlinear mechanism for the excitation of KAWs by MHD waves via resonant decay AW(FW)→KAW1+KAW2, where the MHD wave can be either an Alfvén wave (AW), or a fast magneto-acoustic wave (FW). The resonant decay thus provides a non-local energy transport from large scales directly in the dissipation range. The decay is efficient at low amplitudes of the magnetic field in the MHD waves, B/B0~10-2. In turn, KAWs are very efficient in the energy exchange with plasma particles, providing plasma heating and acceleration in a variety of space plasmas. An anisotropic energy deposition in the field-aligned degree of freedom for the electrons, and in the cross-field degrees of freedom for the ions, is typical for KAWs. A few relevant examples are discussed concerning nonlinear excitation of KAWs by the MHD wave flux and consequent plasma energization in the solar corona and terrestrial magnetosphere.

Description: The principal objective of hydrodynamical-biological models is to provide estimates of the main carbon fluxes such as total and export oceanic production. These models are nitrogen based, that is to say that the variables are expressed in terms of their nitrogen content. Moreover models are calibrated using chlorophyll data sets. Therefore carbon to chlorophyll (C:Chl) and carbon to nitrogen (C:N) ratios have to be assumed. This paper addresses the problem of the representation of these ratios. In a 1D framework at the DYFAMED station (NW Mediterranean Sea) we propose a model which enables the estimation of the basic biogeochemical fluxes and in which the spatio-temporal variability of the C:Chl and C:N ratios is fully represented in a mechanical way. This is achieved through the introduction of new state variables coming from the embedding of a phytoplankton growth model in a more classical Redfieldian NNPZD-DOM model (in which the C:N ratio is assumed to be a constant). Following this modelling step, the parameters of the model are estimated using the adjoint data assimilation method which enables the assimilation of chlorophyll and nitrate data sets collected at DYFAMED in 1997.Comparing the predictions of the new Mechanistic model with those of the classical Redfieldian NNPZD-DOM model which was calibrated with the same data sets, we find that both models reproduce the reference data in a comparable manner. Both fluxes and stocks can be equally well predicted by either model. However if the models are coinciding on an average basis, they are diverging from a variability prediction point of view. In the Mechanistic model biology adapts much faster to its environment giving rise to higher short term variations. Moreover the seasonal variability in total production differs from the Redfieldian NNPZD-DOM model to the Mechanistic model. In summer the Mechanistic model predicts higher production values in carbon unit than the Redfieldian NNPZD-DOM model. In winter the contrary holds.

Description: In this paper, we present a detailed evaluation of cross wavelet analysis of bivariate time series. We develop a statistical test for zero wavelet coherency based on Monte Carlo simulations. If at least one of the two processes considered is Gaussian white noise, an approximative formula for the critical value can be utilized. In a second part, typical pitfalls of wavelet cross spectra and wavelet coherency are discussed. The wavelet cross spectrum appears to be not suitable for significance testing the interrelation between two processes. Instead, one should rather apply wavelet coherency. Furthermore we investigate problems due to multiple testing. Based on these results, we show that coherency between ENSO and NAO is an artefact for most of the time from 1900 to 1995. However, during a distinct period from around 1920 to 1940, significant coherency between the two phenomena occurs.

Description: We review some recent results that have been obtained in the investigation of collisionless reconnection in two dimensional magnetic configurations with a strong guide field in regimes of interest for laboratory plasmas. First we adopt a two-fluid dissipationless plasma model where the plasma evolution is described by the advection of two Lagrangian invariant fields. Then, we show that an analogous formulation in terms of Lagrangian invariants applies to the case where the electron response is obtained from a drift-kinetic model.

Description: We study the inference of long-range correlations by means of Detrended Fluctuation Analysis (DFA) and argue that power-law scaling of the fluctuation function and thus long-memory may not be assumed a priori but have to be established. This requires the investigation of the local slopes. We account for the variability characteristic for stochastic processes by calculating empirical confidence regions. Comparing a long-memory with a short-memory model shows that the inference of long-range correlations from a finite amount of data by means of DFA is not specific. We remark that scaling cannot be concluded from a straight line fit to the fluctuation function in a log-log representation. Furthermore, we show that a local slope larger than α=0.5 for large scales does not necessarily imply long-memory. We also demonstrate, that it is not valid to conclude from a finite scaling region of the fluctuation function to an equivalent scaling region of the autocorrelation function. Finally, we review DFA results for the Prague temperature data set and show that long-range correlations cannot not be concluded unambiguously.

Description: In this paper we investigate the stability of zonal flow in a baroclinic atmosphere with respect to finite-amplitude planetary-scale disturbances by applying Arnold's method. Specifically, we examine the sign of the second variation of a conserved functional for the case of a polytropic atmosphere (i.e. one with a linear lapse rate) and with a linear profile of zonal wind. Sufficient stability conditions for an infinite atmosphere (i.e. with a temperature lapse rate equal to zero) are satisfied only for an atmosphere in solid body rotation. For a polytropic atmosphere of finite extent (a lapse rate is not equal zero) the sufficient conditions of stability can be satisfied if a lid is placed below min (Zmax, polytropic atmospheric height). The dependence of height Zmax on values of the vertical gradient of the zonal wind and the zonal temperature distribution is calculated.

Description: This study presents a simple and efficient scheme for Bayesian estimation of uncertainty in soil moisture simulation by a Land Surface Model (LSM). The scheme is assessed within a Monte Carlo (MC) simulation framework based on the Generalized Likelihood Uncertainty Estimation (GLUE) methodology. A primary limitation of using the GLUE method is the prohibitive computational burden imposed by uniform random sampling of the model's parameter distributions. Sampling is improved in the proposed scheme by stochastic modeling of the parameters' response surface that recognizes the non-linear deterministic behavior between soil moisture and land surface parameters. Uncertainty in soil moisture simulation (model output) is approximated through a Hermite polynomial chaos expansion of normal random variables that represent the model's parameter (model input) uncertainty. The unknown coefficients of the polynomial are calculated using limited number of model simulation runs. The calibrated polynomial is then used as a fast-running proxy to the slower-running LSM to predict the degree of representativeness of a randomly sampled model parameter set. An evaluation of the scheme's efficiency in sampling is made through comparison with the fully random MC sampling (the norm for GLUE) and the nearest-neighborhood sampling technique. The scheme was able to reduce computational burden of random MC sampling for GLUE in the ranges of 10%-70%. The scheme was also found to be about 10% more efficient than the nearest-neighborhood sampling method in predicting a sampled parameter set's degree of representativeness. The GLUE based on the proposed sampling scheme did not alter the essential features of the uncertainty structure in soil moisture simulation. The scheme can potentially make GLUE uncertainty estimation for any LSM more efficient as it does not impose any additional structural or distributional assumptions.

Description: A novel mechanism for the short-scale Rossby waves interacting with long-scale zonal flows in the Earth's atmosphere is studied. The model is based on the parametric excitation of convective cells by finite amplitude Rossby waves. We use a set of coupled equations describing the nonlinear interaction of Rossby waves and zonal flows which admits the excitation of zonal flows. The generation of such flows is due to the Reynolds stresses of the finite amplitude Rossby waves. It is found that the wave vector of the fastest growing mode is perpendicular to that of the pump Rossby wave. We calculate the maximum instability growth rate and deduce the optimal spatial dimensions of the zonal flows as well as their azimuthal propagation speed. A comparison with previous results is made. The present theory can be used for the interpretation of existing observations of Rossby type waves in the Earth's atmosphere.

Description: We report on recent measurements of solitary waves made by the Wideband Plasma Wave Receiver located on each of the four Cluster spacecraft at 4.5-6.5RE (well above the auroral acceleration region) as they cross field lines that map to the auroral zones. These solitary waves are observed in the Wideband data as isolated bipolar and tripolar waveforms. Examples of the two types of pulses are provided. The time durations of the majority of both types of solitary waves observed in this region range from about 0.3 up to 5ms. Their peak-to-peak amplitudes range from about 0.05 up to 20mV/m, with a few reaching up to almost 70mV/m. There is essentially no potential change across the bipolar pulses. There appears to be a small, measurable potential change, up to 0.5V, across the tripolar pulses, which is consistent with weak or hybrid double layers. A limited cross-spacecraft correlation study was carried out in order to identify the same solitary wave on more than one spacecraft. We found no convincing correlations of the bipolar solitary waves. In the two cases of possible correlation of the tripolar pulses, we found that the solitary waves are propagating at several hundred to a few thousand km/s and that they are possibly evolving (growing, decaying) as they propagate from one spacecraft to the next. Further, they have a perpendicular (to the magnetic field) width of 50km or greater and a parallel width of about 2-5km. We conclude, in general, however, that the Cluster spacecraft at separations along and perpendicular to the local magnetic field direction of tens of km and greater are too large to obtain positive correlations in this region. Looking at the macroscale of the auroral zone at 4.5-6.5RE, we find that the onsets of the broadband electrostatic noise associated with the solitary waves observed in the spectrograms of the WBD data are generally consistent with propagation of the solitary waves up the field lines (away from Earth), or with particles or waves propagating up the field line, which leads to local generation of the solitary waves all along the field lines. A discussion of the importance of these solitary waves in magnetospheric processes and their possible generation mechanisms, through electron beam instabilities and turbulence, is provided.

Description: The question of which length scale equation to use in models of turbulence has long been controversial and several approaches have been suggested and used in the past. In this paper, we demonstrate that all these approaches are equivalent and the inconsistencies in the use of some of these approaches arise from improper modeling of the diffusion term in the length scale equation. We formulate a general length scale equation, which encompasses all current approaches. This equation is devoid of inconsistencies and should prove useful in its general form, or one of its subsets, in turbulence closure modeling.

Description: Particle motion is considered in incompressible two-dimensional flows consisting of a steady background gyre on which an unsteady wave-like perturbation is superimposed. A dynamical systems point of view that exploits the action-angle formalism is adopted. It is argued and demonstrated numerically that for a large class of problems one expects to observe a mixed phase space, i.e. the occurrence of "regular islands" in an otherwise "chaotic sea". This leads to patchiness in the evolution of passive tracer distributions. Also, it is argued and demonstrated numerically that particle trajectory stability is largely controlled by the background flow: trajectory instability, quantified by various measures of the "degree of chaos", increases on average with increasing , where is the angular frequency of the trajectory in the background flow and I is the action.