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Technical Note: Using a high finesse optical resonator to provide a long light path for differential optical absorption spectroscopy: CE-DOAS

Cavity enhanced methods in absorption spectroscopy have seen a considerable increase in popularity during the past decade. Especially Cavity Enhanced Absorption Spectroscopy (CEAS) established itself in atmospheric trace gas detection by providing tens of kilometers of effective light path length using a cavity as short as 1 m. In this paper we report on the construction and testing of a compact and power efficient light emitting diode based broadband Cavity Enhanced Differential Optical Absorption Spectrometer (CE-DOAS) for in situ observation of atmospheric NO3. This device combines the small size of the cavity with the advantages of the DOAS approach in terms of sensitivity, specificity and insensivity to intensity fluctuations of the light source. In particular, no selective removal of the analyte (here NO3) is necessary for calibration of the instrument if appropriate corrections are applied to the CEAS theory. Therefore the CE-DOAS technique can – in principle – measure any gas detectable by DOAS. We will discuss the advantages of using a light emitting diode (LED) as light source particularly the precautions which have to be considered for the use of LEDs with a broad wavelength range. The instrument was tested in the lab by detecting NO3 formed by mixing of NO2 and O3 in air. It was then compared to other trace gas detection techniques in an intercomparison campaign in the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich at NO3 concentrations as low as 6.3 ppt.
Volcanic ash as fertiliser for the surface ocean

Iron is a key limiting micro-nutrient for marine primary productivity. It can be supplied to the ocean by atmospheric dust deposition. Volcanic ash deposition into the ocean represents another external and so far largely neglected source of iron. This study demonstrates strong evidence for natural fertilisation in the iron-limited oceanic area of the NE Pacific, induced by volcanic ash from the eruption of Kasatochi volcano in August 2008. Atmospheric and oceanic conditions were favourable to generate a massive phytoplankton bloom in the NE Pacific Ocean which for the first time strongly suggests a connection between oceanic iron-fertilisation and volcanic ash supply.
Greenhouse gas relationships in the Indian summer monsoon plume measured by the CARIBIC passenger aircraft

During the Indian summer monsoon period 2008, regular measurement flights were performed by the CARIBIC aircraft between Germany and India. Measurements included whole air sampling and subsequent analysis for greenhouse gases (CH4, CO2, N2O, SF6) and in-situ measurements of CO, O3, and H2O. For all these tracers a distinct monsoon signature was observed in the longitude range 50–80° E south of 40° N at flight altitudes 8–12.5 km. The formation of a monsoon plume with enhanced mixing ratios was observed for CH4, N2O, SF6, CO and H2O. The plume began to develop in May and persisted through September, and maximum mixing ratios and maximum spatial extension of the plume were observed in August. For CO2 and O3 a minimum was observed. The amplitude of the CO2 seasonal cycle was larger than at comparable latitudes outside the monsoon region, and the CO2 spring maximum was observed with a delay of one month. Different tracer relationships show strong spatial variations across the plume. The comparison with NOAA ground station data shows a clear enhancement for CH4, N2O, SF6 and CO and a decrease in CO2 mixing ratios. Assuming seasonally invariant SF6 emissions based on the EDGAR 4.0 inventory, monthly emissions were estimated for the period June–September for CH4, N2O, and CO, and the CO2 uptake was estimated. While for N2O an emission decrease during the monsoon period was derived, emissions of CH4 were highest in September indicating a different seasonal cycle of emissions. Net CO2 uptake by the vegetation was largest in September.
Vertically-resolved particle size distribution within and above the mixing layer over the Milan metropolitan area

Vertical aerosol profiles were directly measured over the city of Milan during three years (2005–2008) of field campaigns. An optical particle counter, a portable meteorological station and a miniaturized cascade impactor were deployed on a tethered balloon. More than 300 vertical profiles were measured, both in winter and summer, mainly in conditions of clear, dry skies. The mixing height was determined from the observed vertical aerosol concentration gradient, and from potential temperature and relative humidity profiles. Results show that inter-consistent mixing heights can be retrieved highlighting good correlations between particle dispersion in the atmosphere and meteorological parameters. Mixing height growth speed was calculated for both winter and summer showing the low potential atmospheric dispersion in winter. Aerosol number size distribution and chemical composition profiles allowed us to investigate particle behaviour along height. Aerosol measurements showed changes in size distribution according to mixing height. Coarse particle profiles (dp>1.6 μm) were distributed differently than the fine ones (dp<1.6 μm) were, at different heights of the mixing layer. The sedimentation process influenced the coarse particle profiles, and led to a reduction in mean particle diameter for those particles observed by comparing data above the mixing height with ground data (−14.9±0.6% in winter and −10.7±1.0% in summer). Conversely, the mean particle diameter of fine particles increased above the mixing height under stable atmospheric conditions; the average increase, observed by comparing data above the mixing height with ground data, was +2.1±0.1% in winter and +3.9±0.3% in summer. A hierarchical statistical model was created to describe the changes in the size distribution of fine particles along height. The proposed model can be used to estimate the typical vertical profile characterising launches within pre-specified groups starting from: aerosol size and meteorological conditions measured at ground-level, and a mixing height estimation. The average increase of fine particle diameter, estimated on the basis of the model, was +1.9±0.5% in winter and +6.1±1.2% in summer, in keeping with experimental findings.
Influence of vortex dynamics and atmospheric turbulence on the early evolution of a contrail

This study describes three-dimensional numerical simulations of the evolution of an aircraft contrail during the first 30 min following the emission of exhausts. The wake is modeled as a vortex pair descending in a stratified atmosphere where turbulent fluctuations are sustained in the late dissipation regime. The focus of the study is laid on the interactions between vortex dynamics, atmospheric turbulence and contrail microphysics, and their role in determining the growth and the distribution of ice crystals. The atmospheric turbulence is synthesized using a methodology developed to force anisotropic turbulent fluctuations. The results show the feasibility of three-dimensional simulations of the early development of a contrail in supersaturated conditions before its transition into a contrail-cirrus. %(when radiative heating and sedimentation are no more negligible). It is shown that in case of strongly supersaturated and shear-free atmosphere the optical depth is maintained as the contrail spreads by turbulent diffusion in the late dissipation regime.
An investigation of the origins of reactive gaseous mercury in the Mediterranean marine boundary layer

Atmospheric mercury species concentrations were measured during two oceanographic cruise campaigns covering the Adriatic Sea, the first during the autumn in 2004 and the second in the summer of 2005. The inclement weather during the autumn campaign meant that no clear in-situ production of oxidised gas phase mercury was seen. Events where high values of HgII(g) and/or Hg associated with particulates (HgP) were observed, could be linked to probable anthropogenic emission source areas. During the summer campaign however, the by now rather familiar diurnal variation of HgII(g) concentration, with maxima around midday, was observed. Again there were events when high HgII(g) and particulates (HgP) concentrations were seen which did not fit with the pattern of daily in-situ HgII(g) production. These events were traceable, with the help of back trajectory calculations, to areas of anthropogenic emissions. The back trajectories for all the events during which high Hg species concentrations were encountered showed that the airmass being sampled had passed near port areas in the previous 24 h. Not all these ports are associated with major industrial installations, it is possible therefore (bearing in mind the uncertainty associated with the back trajectory calculations) that either shipping or port activities are a Hg source. Box modelling studies of the summer 2005 campaign show that although the in-situ production of HgII(g) occurs in the MBL, the exact chemical mechanism responsible is difficult to determine. However given the high O3 concentrations encountered during this campaign it seems clear that if Hg0 does react with O3, it does not produce gas phase HgII. Equally, the reaction between Hg0 and OH if it occurs, does not contribute appreciably to HgII(g) production.
Subseasonal variability of low cloud radiative properties over the southeast Pacific Ocean

Subseasonal variability of cloud radiative properties in the persistent southeast Pacific stratocumulus deck is investigated using MODIS satellite observations and NCEP reanalysis data. A once-daily albedo proxy is derived based on the fractional coverage of low cloud (a macrophysical field) and the cloud albedo, with the latter broken down into contributions from microphysics (cloud droplet concentration) and macrophysics (liquid water path). Subseasonal albedo variability is dominated by the contribution of low cloud fraction variability, except within 10–15° of the South American coast, where cloud albedo variability contributes significantly. Covariance between cloud fraction and cloud albedo also contributes significantly and positively to the variance in albedo, which highlights how complex and inseparable the factors controlling albedo are. Droplet concentration variability contributes only weakly to the subseasonal variability of albedo, which emphasizes that attributing albedo variability to the indirect effects of aerosols against the backdrop of natural meteorological variability is extremely challenging. The dominant large scale meteorological variability is associated with the subtropical high pressure system. Two indices representing changes in the subtropical high strength and extent explain 80–90% of this variability, and significantly modulate the cloud microphysical, macrophysical, and radiative cloud properties. Variations in droplet concentration of up to 50% of the mean are associated with the meteorological driving. We hypothesize that these fluctuations in droplet concentration are a result of the large scale meteorology and their correlation with cloud macrophysical properties should not be used as evidence of aerosol effects. Mechanisms by which large scale meteorology affects cloud properties are explored. Our results support existing hypotheses linking cloud cover variability to changes in cold advection, subsidence, and lower tropospheric stability. Within 10° of the coast interactions between variability in the surface high pressure system and the orography appear to modulate both cloud macrophysical properties and aerosol transport through suppression of the marine boundary layer depth near the coast. This suggests one possible way in which cloud macrophysical properties and droplet concentration may be correlated independently of the second aerosol indirect effect. The results provide variability constraints for models that strive to represent both meteorological and aerosol impacts on stratocumulus clouds.
Corrigendum to "A novel downscaling technique for the linkage of global and regional air quality modeling" published in Atmos. Chem. Phys., 9, 9169–9185, 2009

Recently, downscaling global atmospheric model outputs (GCTM) for the USEPA Community Multiscale Air Quality (CMAQ) Initial (IC) and Boundary Conditions (BC) have become practical because of the rapid growth of computational technologies that allow global simulations to be completed within a reasonable time. The traditional method of generating IC/BC by profile data has lost its advocates due to the weakness of the limited horizontal and vertical variations found on the gridded boundary layers. Theoretically, high quality GCTM IC/BC should yield a better result in CMAQ. Unfortunately, several researchers have found that the outputs from GCTM IC/BC are not necessarily better than profile IC/BC due to the excessive transport of O3 aloft in GCTM IC/BC. In this paper, we intend to investigate the effects of using profile IC/BC and global atmospheric model data. In addition, we are suggesting a novel approach to resolve the existing issue in downscaling. In the study, we utilized the GEOS-Chem model outputs to generate time-varied and layer-varied IC/BC for year 2002 with the implementation of tropopause determining algorithm in the downscaling process (i.e., based on chemical (O3) tropopause definition). The comparison between the implemented tropopause approach and the profile IC/BC approach is performed to demonstrate improvement of considering tropopause. It is observed that without using tropopause information in the downscaling process, unrealistic O3 concentrations are created at the upper layers of IC/BC. This phenomenon has caused over-prediction of surface O3 in CMAQ. In addition, the amount of over-prediction is greatly affected by temperature and latitudinal location of the study domain. With the implementation of the algorithm, we have successfully resolved the incompatibility issues in the vertical layer structure between global and regional chemistry models to yield better surface O3 predictions than profile IC/BC for both summer and winter conditions. At the same time, it improved the vertical O3 distribution of CMAQ outputs. It is strongly recommended that the tropopause information should be incorporated into any two-way coupled global and regional models, where the tropospheric regional model is used, to solve the vertical incompatibility that exists between global and regional models. We have discovered that the previously published paper was not the latest version of the manuscript we intended to use. Some corrections made during the second ACPD reviewing process were not incorporated in the text. As a result, the figure numbers (i.e., figure number below the graph) were not referenced correctly in the manuscript. Therefore, we have decided to re-publish this paper as a corrigendum.
A detailed aerosol mixing state model for investigating interactions between mixing state, semivolatile partitioning, and coagulation

A new method for describing externally mixed particles, the Detailed Aerosol Mixing State (DAMS) representation, is presented in this study. This novel method classifies aerosols by both composition and size, using a user-specified mixing criterion to define boundaries between compositional populations. Interactions between aerosol mixing state, semivolatile partitioning, and coagulation are investigated with a Lagrangian box model that incorporates the DAMS approach. Model results predict that mixing state affects the amount and types of semivolatile organics that partition to available aerosol phases, causing external mixtures to produce a more size-varying composition than internal mixtures. Both coagulation and condensation contribute to the mixing of emitted particles, producing a collection of multiple compositionally distinct aerosol populations that exists somewhere between the extremes of a strictly external or internal mixture. The selection of mixing criteria has a significant impact on the size and type of individual populations that compose the modeled aerosol mixture. Computational demands for external mixture modeling are significant and can be controlled by limiting the number of aerosol populations used in the model.
Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction

The spatial distribution of aerosol chemical composition and the evolution of the Organic Aerosol (OA) fraction is investigated based upon airborne measurements of aerosol chemical composition in the planetary boundary layer across Europe. Sub-micron aerosol chemical composition was measured using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). A range of sampling conditions were evaluated, including relatively clean background conditions, polluted conditions in North-Western Europe and the near-field to far-field outflow from such conditions. Ammonium nitrate and OA were found to be the dominant chemical components of the sub-micron aerosol burden, with mass fractions ranging from 20–50% each. Ammonium nitrate was found to dominate in North-Western Europe during episodes of high pollution, reflecting the enhanced NOx and ammonia sources in this region. OA was ubiquitous across Europe and concentrations generally exceeded sulphate by 30–160%. A factor analysis of the OA burden was performed in order to probe the evolution across this large range of spatial and temporal scales. Two separate Oxygenated Organic Aerosol (OOA) components were identified; one representing an aged-OOA, termed Low Volatility-OOA and another representing fresher-OOA, termed Semi Volatile-OOA on the basis of their mass spectral similarity to previous studies. The factors derived from different flights were not chemically the same but rather reflect the range of OA composition sampled during a particular flight. Significant chemical processing of the OA was observed downwind of major sources in North-Western Europe, with the LV-OOA component becoming increasingly dominant as the distance from source and photochemical processing increased. The measurements suggest that the aging of OA can be viewed as a continuum, with a progression from a less oxidised, semi-volatile component to a highly oxidised, less-volatile component. Substantial amounts of pollution were observed far downwind of continental Europe, with OA and ammonium nitrate being the major constituents of the sub-micron aerosol burden. Such anthropogenically perturbed air masses can significantly perturb regional climate far downwind of major source regions.