Aerosol Plume Research Articles

Detecting high contributions of primary organic matter to marine aerosol: A case study

[1] Using on-line High-Resolution Aerosol Mass Spectrometry, we report submicron organic marine aerosol plume concentrations peaking at 3.8 μg m−3. These concentrations are far greater than previously determined by off-line techniques and can exceed typical terrestrial concentrations of organic aerosol. The organic mass comprised 77% of the total submicron non-refractory mass and such plumes were associated with regions of high biological activity and moderately-high wind speeds over the N.E. Atlantic. High-resolution mass spectra analysis revealed a unique marine organic aerosol fingerprint, when compared to anthropogenic organic aerosol, and in particular, anthropogenic hydrocarbons. 37% hydrocarbon and 63% oxygenated hydrocarbon speciation was observed for the organic mass, indicating that at least 37% of the organic mass is produced via primary sea-spray. The hydrocarbon and oxygenated hydrocarbon species were highly correlated (r > 0.99) suggesting a significant, if not dominant, fraction of the oxygenated component is also likely to be sea-spray in origin.

Smoke injection heights from agricultural burning in Eastern Europe as seen by CALIPSO

Abstract. High frequency of agricultural fires is observed every year during the summer months over SW Russia and Eastern Europe. This study investigates the initial injection height of aerosol generated by the fires over these regions during the biomass burning season, which determines the potential for long-range transport of the smoke. This information is critical for aerosol transport modeling, as it determines the smoke plume evolution. The study focuses on the period 2006–2008, and is based on observations made by the CALIOP instrument on board the NASA CALIPSO satellite. MODIS data are synergistically used for the detection of the fires and the characterization of their intensity. CALIPSO aerosol vertical distributions generated by the active fires are analyzed to investigate the aerosol top height which is considered dependent on the heat generated by the fires and can be associated with the initial injection height. Aerosol top heights of the vertically homogenous smoke layers are found to range between 1.6 and 5.9 km. Smoke injection heights from CALIPSO are compared with mixing layer heights taken by the European Centre for Medium-range Weather Forecast (ECMWF), to investigate the direct injection of smoke particles into the free troposphere. Our results indicate that the aerosol plumes are observed within the boundary layer for the 50% of the cases examined. For the rest of the cases, the strong updrafts generated by the fires resulted to smoke injection heights greater than the ECMWF estimated mixing layer by 0.5 to 3.0 km, indicating a direct smoke injection into the free troposphere. The smoke injection height showed a dependence on the MODIS-Land Fire Radiative Power product which is indicative of the fire intensity, especially in the cases of lower static stability in the upper part of the boundary layer and the free troposphere.

Structural influence of cohesive mixtures of salbutamol sulphate and lactose on aerosolisation and de-agglomeration behaviour under dynamic conditions

PurposeThe purpose of this study was to understand the behaviour of cohesive powder mixtures of salbutamol sulphate (SS) and micronized lactose (LH300) at ratios of SS:LH300 of 1:1, 1:2, 1:4 and 1:8 under varying air flow conditions. MethodsAerosolisation of particles less than 5.4μm at air flow rates from 30 to 180lmin−1 was investigated by determining particle size distributions of the aerosolised particles using laser diffraction and fine particle fractions of SS using the twin stage impinger modified for different air flow rates using a Rotahaler®. The de-agglomeration data were best fitted by a 3-parameter sigmoidal equation using non-linear least squares regression and characterised by the estimated parameters. ResultsDe-agglomeration air flow rate profiles showed that SS:LH300 mixtures with increased lactose content (1:4 and 1:8) improved powder aerosolisation, but lactose had negligible effect on SS aerosolisation at the higher and lower limits of air flow rates studied. De-agglomeration flow rate profiles of SS–LH300 mixtures with increased lactose content (1:4 and 1:8) were greater than theoretically expected based on weighted individual SS and LH300 profiles. This indicated that interactions between the cohesive components led to enhanced de-agglomeration. The composition of the aerosol plume changed with air flow rate. ConclusionThis approach to characterising aerosolisation behaviour has significant applications in understanding powder structures and in formulation design for optimal aerosolisation properties.

A detailed aerosol particle plume analysis

Aerosol particle dynamics were observed in the summertime marine boundary layer 10 km offshore of the northeast American coast. Particle dynamics were observed using a scanning mobility particle sizer for observation of the number‐based size distribution, and a quadrupole aerosol mass spectrometer (Q‐AMS) for quantification of the mass‐based size distributions and bulk particle mass loadings of nonrefractory components. Analysis was supported by meteorological data, extensive trace gas data, and aerosol Berner impactor data. No new particle formation with clearly identifiable growth of ultrafine particles was identified. One event exhibited a clear banana‐shaped evolution of the number‐based size distribution. However, the conditions were nonstationary in various aspects. In some phases of the event, particle growth mechanisms could not be confirmed despite an increase of the geometric mean of the number‐based size distribution. Air mass changes and dilution of boundary layer air are possible causes for the observed dynamics. The observation of particle number‐based size distributions did not provide sufficient proof for the occurrence of a growth event. Continental organics were the predominant species driving particle dynamics. The contribution of industrial sulfate also was important. The mass size distributions of the Q‐AMS and the impactor agreed reasonably well for the species analyzed. Overall, we conclude that a detailed analysis of aerosol plume dynamics and temporal evolution, including both meteorology and chemistry, reveals much more detail about the aerosol evolution that could be deduced from the number size distribution alone.

Optical-chemical-microphysical relationships and closure studies for mixed carbonaceous aerosols observed at Jeju Island; 3-laser photoacoustic spectrometer, particle sizing, and filter analysis

Abstract. Transport of aerosols in pollution plumes from the mainland Asian continent was observed in situ at Jeju, South Korea during the Cheju Asian Brown Cloud Plume-Asian Monsoon Experiment (CAPMEX) field campaign throughout August and September 2008 using a 3-laser photoacoustic spectrometer (PASS-3), chemical filter analysis, and size distributions. The PASS-3 directly measures the effects of morphology (e.g. coatings) on light absorption that traditional filter-based instruments are unable to address. Transport of mixed sulfate, carbonaceous, and nitrate aerosols from various Asian pollution plumes to Jeju accounted for 74% of the deployment days, showing large variations in their measured chemical and optical properties. Analysis of eight distinct episodes, spanning wide ranges of chemical composition, optical properties, and source regions, reveals that episodes with higher organic carbon (OC)/sulfate (SO42−) and nitrate (NO3−)/SO42− composition ratios exhibit lower single scatter albedo at shorter wavelengths (ω405). We infer complex refractive indices (n–ik) as a function of wavelength for the high, intermediate, and low OC/SO42− pollution episodes by using the observed particle size distributions and the measured optical properties. The smallest mean particle diameter corresponds to the high OC/SO42− aerosol episode. The imaginary part of the refractive index (k) is greater for the high OC/SO42− episode at all wavelengths. A distinct, sharp increase in k at short wavelength implies enhanced light absorption by OC, which accounts for 50% of the light absorption at 405 nm, in the high OC/SO42− episode. Idealized analysis indicates increased absorption at 781 nm by factors greater than 3 relative to denuded black carbon in the laboratory. We hypothesize that coatings of black carbon cores are the mechanism of this enhancement. This implies that climate warming and atmospheric heating rates from black carbon particles can be significantly larger than have been estimated previously. The results of this study demonstrate ways in which atmospheric processing and mixing can amplify particle light absorption for carbonaceous aerosol, significantly at short wavelength, underscoring the need to understand and predict chemical composition effects on optical properties to accurately estimate the climate radiative forcing by mixed carbonaceous aerosols.

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

Abstract. As a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O3, NO, NO2, CO, VOC, CO2, and H2O. Aerosol loads were characterized by concentrations of total aerosol number (CN) and cloud condensation nuclei (CCN), and by light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios within the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h−1. Within the plume core, aerosol concentrations were strongly enhanced, with ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large fraction of the total particle number served as CCN (about 60–80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16±12%) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The CO-normalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species. We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NOx and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance >1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.

A novel approach for the characterisation of transport and optical properties of aerosol particles near sources – Part II: Microphysics–chemistry-transport model development and application

Abstract A new high-resolution microphysics–chemistry-transport model (LES-AOP) was developed and applied for the investigation of aerosol transformation and transport in the vicinity of a livestock facility in northern Germany (PLUS1 field campaign). The model is an extension of a Large-Eddy Simulation (LES) model. The PLUS1 field campaign included the first deployment of the new eye-safe scanning aerosol lidar system of the University of Hohenheim. In a combined approach, model and lidar results were used to characterise a faint aerosol source. The farm plume structure was investigated and the absolute value of its particle backscatter coefficient was determined. Aerosol optical properties were predicted on spatial and temporal resolutions below 100 m and 1 min, upon initialisation by measured meteorological and size-resolved particulate matter mass concentration and composition data. Faint aerosol plumes corresponding to a particle backscatter coefficient down to 10−6 sr−1 m−1 were measured and realistically simulated. Budget-related quantities such as the emission flux and change of the particulate matter mass, were estimated from model results and ground measurements.

Micro pulse lidar observations of mineral dust layer in the lower troposphere over the southwest coast of Peninsular India during the Asian summer monsoon season

A large aerosol plume with optical depth exceeding 0.7 engulfs most parts of the Arabian Sea during the Asian summer monsoon season. Based on Micro Pulse Lidar observations during the June–September period of 2008 and 2009, the present study depicts, for the first time, the existence of an elevated dust layer occurring very frequently in the altitude band of 1–3.5 km over the west coast of peninsular India with relatively large values of linear depolarization ratio ( δ L ). Large values of δ L indicate the dominance of significantly non-spherical aerosols. The aerosol optical depth of this layer (0.2) is comparable to that of the entire atmospheric column during dust-free days. Back-trajectory analysis clearly shows the advection of airmass from the arid regions of Arabia and the west Arabian Sea, through the altitude region centered around 3 km. This is in contrast to the airmass below 1 km originating from the pristine Indian Ocean region which contains relatively spherical aerosols of marine origin with δ L generally <0.05.

Aerosol concentrations observed at Mt. Haruna, Japan, in relation to long-range transport of Asian mineral dust aerosols

As a part of the effort to understand the structure of long-range transported aerosol plumes and local pollution, aerosol observations monitored the mass concentrations and number-size distributions during the period August 2006 to July 2009 near the top of Mt. Haruna (1365 m), an isolated mountain in the Kanto Plain in Japan. The mass concentrations observed at Mt. Haruna and plain sites showed a seasonal variation with a maximum in spring and summer, respectively. The spring peaks in aerosols at Mt. Haruna were probably caused by long-range transport of mineral dust and anthropogenic particles from the Asian continent. The summer peaks at the plain sites was attributed to local pollution from the Tokyo metropolitan area. Three examples of 2007 Asian dust events were investigated to show that aerosols may be dispersed in a complicated three-dimensional structure and that delayed arrivals of the dust plumes at plain sites compared to Mt. Haruna were not a rare case. Because of the boundary layer being stable at night, the dust layer was advected eastward without the vertical mixing before sunrise. This study suggests that after thermal convection activated by sunlight during daytime Asian dust transported in the free troposphere may be brought down into the atmospheric boundary layer, increasing the dust concentration there.

Warming influenced by the ratio of black carbon to sulphate and the black-carbon source

Black-carbon aerosols absorb solar radiation and are thought to be a significant source of global warming. Surface and aircraft measurements of aerosol plumes in China suggest that solar absorption increases with the ratio of black carbon to sulphate.

Characterization of aerosol plumes in nanosecond laser ablation of molecular solids at atmospheric pressure

Ablation of molecular solids with pulsed ultraviolet lasers at atmospheric pressure is an important process in (bio-)organic mass spectrometry. Of practical importance for analytical sampling and analysis are the plume formation and expansion. Plumes formed by atmospheric-pressure laser ablation of anthracene and 2,5-dihydroxybenzoic acid (2,5-DHB) were studied by light scattering imaging, which showed significant material release in the form of aerosols. The monitored plume expansion dynamics could be fitted to the drag-force model, yielding initial plume velocities of 150 m/s for anthracene and 43 m/s for DHB. While the angle of incidence does not affect the plume direction and propagation, a large dependence of the plume-expansion velocity on the laser pulse energy could be found, which is limited at atmospheric pressure by the onset of plasma shielding. With respect to analytical applications, the efficiency of sampling of the laser ablation products by a capillary could be experimentally visualized.

How can aerosols affect the Asian summer monsoon? Assessment during three consecutive pre-monsoon seasons from CALIPSO satellite data

Abstract. The impact of aerosols above and around the Tibetan Plateau on the Asian Summer Monsoon during pre-monsoon seasons March-April-May 2007, 2008, and 2009 is investigated by means of remote sensing and radiative transfer modelling. Four source regions are found to be responsible for the high aerosol loading around the Tibetan Plateau: the Taklamakan Desert, the Ganges Plains, the Indus Plains, and the Arabian Sea. CALIPSO lidar satellite data, providing vertically resolved images of aerosols, shows aerosol concentrations to be highest in the lower 5 km of the atmosphere with only little amounts reaching the Tibetan Plateau altitude. Using a radiative transfer model we find that aerosol plumes reduce shortwave radiation throughout the Monsoon region in the seasonal average by between 20 and 30 W/m2. Peak shortwave heating in the lower troposphere reaches 0.2 K/day. In higher layers this shortwave heating is partly balanced by longwave cooling. Although high-albedo surfaces, such as deserts or the Tibetan Plateau, increase the shortwave heating by around 10%, the overall effect is strongest close to the aerosol sources. A strong elevated heating which could influence large-scale monsoonal circulations as suggested by previous studies is not found.

An Aerosol-Dipole Event Over the Tropical Indian Ocean During 2006

Using aerosol optical depth (AOD at 550 nm) from the moderate-resolution imaging spectroradiometer, surface winds, outgoing long-wave radiation from National Centers for Environmental Prediction/National Center for Atmospheric Research reanalysis, and rainfall from Tropical Rainfall Measuring Mission data sets, we report a dipolelike variability in the aerosol concentration over the region (40°E-130° E; 10° S-10°;N) during September, October, and November 2006. Positive AOD anomalies (+ 0.4 to + 0.6) (relative to the 2000-2008 climatological average) along the equatorial East Indian Ocean and Indonesia and negative AOD anomalies (-0.2 to -0.4) over the western, northwestern, and central Indian Ocean characterize an aerosol-dipolelike variability. This east-west variability of the aerosol loading along the Indian Ocean is linked to the anomalously weak easterlies associated with the 2006 Indian Ocean Dipole event. The weaker easterlies lead to the hovering of the aerosol plume over Indonesia/Sumatra coast (98° E), enhancing the positive anomalies of AODs, while excessive rainfall over the central Arabian Sea caused the negative AOD anomalies.

Aerosol distribution around Svalbard during intense easterly winds

Abstract. This paper reports on backscatter and depolarization measurements by an airborne lidar in the Arctic during the ASTAR 2004 campaign. A unique weather situation facilitated the observation of the aerosol concentration under strongly forced atmospheric conditions. The vigorous easterly winds distorted the flow past Svalbard in such a way that mesoscale features were visible in the remote-sensing observations: The formation of a well-mixed aerosol layer inside the Adventdalen and the subsequent thinning of the aerosol plume were observed over the Isfjorden. Additionally, mobilization of sea salt aerosols due to a coastal low-level jet at the northern tip of Svalbard resulted in a sloped boundary layer toward north. Mesoscale numerical modelling was applied to identify the sources of the aerosol particles and to explain the observed patterns.

Microscopic characterization of carbonaceous aerosol particle aging in the outflow from Mexico City

Abstract. This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City metropolitan area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (~29 km and ~65 km, respectively), the fraction of homogenously mixed organic particles increased in both size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment.

Lidar measurements of the Kasatochi aerosol plume in August and September 2008 in Ny‐Ålesund, Spitsbergen

The eruptions of the Kasatochi volcano on 7 and 8 August 2008 led to an enhanced stratospheric aerosol load which was studied with the Koldewey Aerosol Raman Lidar (KARL) and the Micro Pulse Lidar (MPL) at the French‐German Arctic Research Base AWIPEV in Ny‐Ålesund, Spitsbergen at 78.55°N, 11.56°E. During all KARL measurements from 15 August to 24 September 2008 (approximately 30 h of data), we detected distinct layers of enhanced aerosol backscatter in the lower stratosphere and the tropopause region, whose origination at the Kasatochi site can be shown by trajectory calculations. We found a 125% increase in aerosol optical depth compared to the mean values from 2004 to 2007 at 3 weeks after the eruption, validated by sunphotometer measurements. Differences in volume depolarization and color ratio signatures of the layers indicate a sinking movement of the bigger particles to the layer bottom. Furthermore, within higher stratospheric aerosol layers monitored after 25 August 2008, we observed the volume depolarization maximum to be up to 0.8 km below the backscatter maximum. Backscatter and depolarization measurements from 1 September 2008, on which data were collected over 13 h during daylight and darkness, are analyzed in detail. Calculations of the lidar ratio in the lowest aerosol layer as well as the estimation of microphysical parameters of the aerosol particles were performed.

The Added Value of a Proposed Satellite Imager for Ground Level Particulate Matter Analyses and Forecasts

Monitoring aerosols over wide areas is important for the assessment of the population's exposure to health relevant particulate matter (PM). Satellite observations of aerosol optical depth (AOD) can contribute to the improvement of highly needed analyzed and forecasted distributions of PM when combined with a model and ground-based observations. In this paper, we evaluate the contribution of column AOD observations from a future imager on a geostationary satellite by performing an Observing System Simulation Experiment (OSSE). In the OSSE simulated imager, AOD observations and ground-based PM observations are assimilated in the chemistry transport model LOTOS-EUROS to assess the added value of the satellite observations relative to the value of ground-based observations. Results show that in highly polluted situations, the imager AOD observations improve analyzed and forecasted PM2.5 concentrations even in the vicinity of simultaneously incorporated ground-based PM observations. The added value of the proposed imager is small when considering monthly averaged PM distributions. This is attributed to relatively large errors in the imager AODs in case of background aerosol loads coupled to the fact that the imager AODs are column values and an indirect estimate of PM. In the future, model improvements and optimization of the assimilation system should be achieved for better handling of situations with aerosol plumes above the boundary layer and satellite observations containing aerosol profile information. With the suggested improvements, the developed OSSE will form a powerful tool for determining the added value of future missions and defining requirements for planned satellite observations.

An aerosol boomerang: Rapid around‐the‐world transport of smoke from the December 2006 Australian forest fires observed from space

We investigate rapid around‐the‐world transport of a smoke aerosol plume released by intense forest fires in southeastern Australia in December 2006. During the first half of December 2006, southeastern Australia suffered from severe drought and exceptionally high temperatures. On 14 December 2006, a passing cold front in combination with the intense heat from the fires causing pyro‐convective lofting, injected a large mass of aerosol particles into the jet stream. We track the resulting aerosol plume using Aerosol Absorbing Index (AAI) observations from the Ozone Monitoring Instrument (OMI) and find that it circumnavigated the world in 12 days. Using observations from OMI and the CALIOP (Cloud‐Aerosol Lidar and Infrared Pathfinder Satellite Observation) spaceborne lidar, we show that the plume resided in the high troposphere at different stages of its evolution. In absence of CALIOP data, we explored OMI O2‐O2 pressures to obtain information on the aerosol plume height. Detailed radiative transfer calculations suggest that the current OMI O2‐O2 retrievals contain useful information on the altitude of the aerosol plume under specific conditions (high AAI, no clouds below). The observed two‐dimensional evolution of the smoke aerosol plume and the vertical distribution of the plume detected by CALIOP is matched by simulations with the TM4 chemistry transport model for an injection height of 248 hPa (∼10 km). Injection heights at the surface and at 540 hPa (∼5 km) resulted in simulated vertical distributions that were 2–3 km too low relative to CALIOP observations and showed less agreement with the AAI patterns. The high injection altitude of 10 km mimics the effect of pyro‐convective lofting as the additional buoyancy from the intense fires is not accounted for in the model. TM4 simulations with an inert and a water‐soluble tracer reproduce the observed dilution of the plume and show that the latter gives the best agreement with the observations, suggesting that the ultimate removal of the aerosol particles is by scavenging. To our knowledge, this is the first detailed study of around‐the‐world long‐range transport of forest fire emissions in the extratropical Southern Hemisphere.

Airborne measurements of the nitric acid partitioning in persistent contrails

Abstract. This study reports the first systematic measurements of nitric acid (HNO3) uptake in contrail ice particles at typical aircraft cruise altitudes. During the CIRRUS-III campaign cirrus clouds and almost 40 persistent contrails were probed with in situ instruments over Germany and Northern Europe in November 2006. Besides reactive nitrogen, water vapor, cloud ice water content, ice particle size distributions, and condensation nuclei were measured during 6 flights. Contrails with ages up to 12 h were detected at altitudes 10–11.5 km and temperatures 211–220 K. These contrails had a larger ice phase fraction of total nitric acid (HNO3ice/HNO3tot = 6%) than the ambient cirrus layers (3%). On average, the contrails contained twice as much HNO3ice as the cirrus clouds, 14 pmol/mol and 6 pmol/mol, respectively. Young contrails with ages below 1 h had a mean HNO3ice of 21 pmol/mol. The contrails had higher nitric acid to water molar ratios in ice and slightly higher ice water contents than the cirrus clouds under similar meteorological conditions. The differences in ice phase fractions and molar ratios between developing contrails and cirrus are likely caused by high plume concentrations of HNO3 prior to contrail formation. The location of the measurements in the upper region of frontal cirrus layers might account for slight differences in the ice water content between contrails and adjacent cirrus clouds. The observed dependence of molar ratios as a function of the mean ice particle diameter suggests that ice-bound HNO3 concentrations are controlled by uptake of exhaust HNO3 in the freezing plume aerosols in young contrails and subsequent trapping of ambient HNO3 in growing ice particles in older (age &gt; 1 h) contrails.

Radiative transfer corrections for accurate spectroscopic measurements of volcanic gas emissions

There is widespread use of passive remote sensing techniques to quantify trace gas column densities in volcanic plumes utilizing scattered sunlight as a light source. Examples include passive DOAS, COSPEC, and the SO2 camera. In order to calculate trace gas concentrations or volcanic emission fluxes, knowledge about the optical path through the plume is necessary. In the past, a straight photon path through the plume has always been assumed although it was known that this is not always true. Here we present the results of model studies conducted specifically to quantify the effects of realistic radiative transfer in and around volcanic plumes on ground-based remote sensing measurements of SO2. The results show that measurements conducted without additional information on average photon paths can be inaccurate under certain conditions, with possible errors spanning more than an order of magnitude. Both over and underestimation of the true column density can occur. Actual errors depend on parameters such as distance between instrument and plume, plume SO2 concentration, plume aerosol load, as well as aerosol conditions in the ambient atmosphere. As an example, a measurement conducted with an SO2 camera is discussed, the results of which can only be correctly interpreted if realistic radiative transfer is considered. Finally, a method is presented which for the first time allows the retrieval of actual average photon paths in spectroscopic (i.e. DOAS) measurements of adequate resolution. By allowing for a wavelength dependent column density during the evaluation of DOAS measurements, we show how radiative transfer effects can be corrected using information inherently available in the measured spectra, thus greatly enhancing the accuracy of DOAS measurements of volcanic emissions.