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Measurements of organic gases during aerosol formation events in the boreal forest atmosphere during QUEST

Biogenic VOCs are important in the growth and possibly also in the early stages of formation of atmospheric aerosol particles. In this work, we present 10 min-time resolution measurements of organic trace gases at Hyytiälä, Finland during March 2002. The measurements were part of the project QUEST (Quantification of Aerosol Nucleation in the European Boundary Layer) and took place during a two-week period when nucleation events occurred with various intensities nearly every day. Using a ground-based Chemical Ionization Mass Spectrometer (CIMS) instrument, the following trace gases were detected: acetone, TMA, DMA, mass 68amu (candidate=isoprene), monoterpenes, methyl vinyl ketone (MVK) and methacrolein (MaCR) and monoterpene oxidation products (MTOP). For all of them except for the amines, we present daily variations during different classes of nucleation events, and non-event days. BVOC oxidation products (MVK, MaCR and MTOP) show a higher ratio to the CS on event days compared to non-event days, indicating that their abundance relative to the surface of aerosol available is higher on nucleation days. Moreover, BVOC oxidation products are found to show significant correlations with the condensational sink (CS) on nucleation event days, which indicates that they are representative of less volatile organic compounds that contribute to the growth of the nucleated particles and generally secondary organic aerosol formation. Behaviors of BVOC on event and non event days are compared to the behavior of CO.
Deployment of a ground-based CIMS apparatus for the detection of organic gases in the boreal forest during the QUEST campaign

Measurements of atmospheric volatile organic compounds were performed in the Finnish Boreal forest atmosphere during spring 2003, as part of the project QUEST (Quantification of Aerosol Nucleation in the European Boundary Layer), using a ground-based Chemical Ionization Mass Spectrometer (CIMS) instrument. Based on the study of their hydrate distribution, methanol, acetonitrile, acetaldehyde, dimethyl amine (DMA), ethanol/formic acid, acetone, trimethyl amine (TMA), propanol/acetic acid, isoprene, methyl vinyl ketone (MVK) and metacrolein (MaCR), monoterpenes and monoterpene oxidation product (MTOP) are proposed as candidates for masses 32, 41, 44, 45, 46, 58, 59, 60, 68, 70, 136, and 168amu, respectively. It would be, to our knowledge, the first time DMA, TMA and MTOP are measured with this method. Most compounds show a clear diurnal variation with a maximum in the early night, corresponding to the onset of the noctural inversion and in agreement with independant measurements of CO. Biogenic compounds are highly correlated with each other and the ratio monoterpene/oxidation product shows a typical daily pattern of nightime maxima. However, because isoprene mixing ratios are also maximum during the early night, it is likely that it suffers of the interference from another unidentified biogenic compound. Hence mass 68amu is identified as isoprene+compound X.
Fluorescence from atmospheric aerosol detected by a lidar indicates biogenic particles in the lowermost stratosphere

With a lidar system that was installed in Lindenberg/Germany, we observed in June 2003 an extended aerosol layer at 13km altitude in the lowermost stratosphere. This layer created an inelastic backscatter signal that we detected with a water vapour Raman channel, but that was not produced by Raman scattering. Also, we find evidence for inelastic scattering from a smoke plume from a forest fire that we observed in the troposphere. We interpret the unexpected properties of these aerosols as fluorescence induced by the laser beam at organic components of the aerosol particles. Fluorescence from ambient aerosol had not yet been considered detectable by lidar systems. However, organic compounds such as polycyclic aromatic hydrocarbons sticking to the aerosol particles, or bioaerosol such as bacteria, spores or pollen fluoresce when excited with UV-radiation in a way that is detectable by our lidar system. Therefore, we conclude that fluorescence from organic material released by biomass burning creates, inelastic backscatter signals that we measured with our instrument and thus demonstrate a new and powerful way to characterize aerosols by a remote sensing technique. The stratospheric aerosol layer that we have observed in Lindenberg for three consecutive days is likely to be a remnant from Siberian forest fire plumes lifted across the tropopause and transported around the globe.
On the growth of nucleation mode particles: source rates of condensable vapor in polluted and clean environments

The growth properties of nucleation mode particles were investigated. The variation of source rates of condensable vapors in different locations and environmental conditions was analyzed. The measurements were performed in background stations in Antarctica, in Finnish Lapland and Boreal Forest stations (SMEAR I and SMEAR II) as well as in polluted urban sites in Athens, Marseille and New Delhi. Taking advantage of only the measured spectral evolution of aerosol particles as a function of time the formation and growth properties of nucleation mode aerosols were evaluated. The diameter growth-rate and condensation sink were obtained from the measured size distribution dynamics. Using this growth rate and condensation sink, the concentration of condensable vapors and their source rate were estimated. The growth rates and condensation sinks ranged between 0.3-20nmh-1 and 10-4-0.07s-1, respectively. The corresponding source rate of condensable vapors varied more than 4 orders of magnitude from 103 to over 107cm-1s-1. The highest condensation sink and source rate values were observed in New Delhi and the smallest values in Antarctica.
Technical Note: The Modular Earth Submodel System (MESSy) - a new approach towards Earth System Modeling

The development of a comprehensive Earth System Model (ESM) to study the interactions between chemical, physical, and biological processes, requires coupling of the different domains (land, ocean, atmosphere, ...). One strategy is to link existing domain-specific models with a universal coupler, i.e. an independent standalone program organizing the communication between other programs. In many cases, however, a much simpler approach is more feasible. We have developed the Modular Earth Submodel System (MESSy). It comprises (1) a modular interface structure to connect to a , (2) an extendable set of such for miscellaneous processes, and (3) a coding standard. MESSy is therefore not a coupler in the classical sense, but exchanges data between a and several within one comprehensive executable. The internal complexity of the is controllable in a transparent and user friendly way. This provides remarkable new possibilities to study feedback mechanisms (by two-way coupling). Note that the MESSy and the coupler approach can be combined. For instance, an atmospheric model implemented according to the MESSy standard could easily be coupled to an ocean model by means of an external coupler. The vision is to ultimately form a comprehensive ESM which includes a large set of submodels, and a base model which contains only a central clock and runtime control. This can be reached stepwise, since each process can be included independently. Starting from an existing model, process submodels can be reimplemented according to the MESSy standard. This procedure guarantees the availability of a state-of-the-art model for scientific applications at any time of the development. In principle, MESSy can be implemented into any kind of model, either global or regional. So far, the MESSy concept has been applied to the general circulation model ECHAM5 and a number of process boxmodels.
Near-IR photodissociation of peroxy acetyl nitrate

Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear-IR≈3x10-8s-1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear-IR≈10-5s-1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of freedom in PAN, which make 4νCH the lowest overtone excitation with a high photodissociation yield (as opposed to 2νOH in PNA).
Using a photochemical model for the validation of NO2 satellite measurements at different solar zenith angles

SCIAMACHY (Scanning Imaging Spectrometer for Atmospheric Chartography) aboard the recently launched Environmental Satellite (ENVISAT) of ESA is measuring solar radiance upwelling from the atmosphere and the extraterrestrial irradiance. Appropriate inversion of the ultraviolet and visible radiance measurements, observed from the atmospheric limb, yields profiles of nitrogen dioxide, NO2, in the stratosphere (SCIAMACHY-IUP NO2 profiles V1). In order to assess their accuracy, the resulting NO2 profiles have been compared with those retrieved from the space borne occultation instruments Halogen Occultation Experiment (HALOE, data version v19) and Stratospheric Aerosol and Gas Experiment II (SAGE II, data version 6.2). As the HALOE and SAGE II measurements are performed during local sunrise or sunset and because NO2 has a significant diurnal variability, the NO2 profiles derived from HALOE and SAGE II have been transformed to those predicted for the solar zenith angles of the SCIAMACHY measurement by using a 1-dimensional photochemical model. The model used to facilitate the comparison of the NO2 profiles from the different satellite sensors is described and a sensitivity ananlysis provided. Comparisons between NO2 profiles from SCIAMACHY and those from HALOE NO2 but transformed to the SCIAMACHY solar zenith angle, for collocations from July to October 2002, show good agreement (within +/-12%) between the altitude range from 22 to 33km. The results from the comparison of all collocated NO2 profiles from SCIAMACHY and those from SAGE II transformed to the SCIAMACHY solar zenith angle show a systematic negative bias of 10 to 35% between 20km to 38km with a small standard deviation between 5 to 14%. These results agree with those of Newchurch and Ayoub (2004), implying that above 20km NO2 profiles from SAGE II sunset are probably somewhat high.
The two-way nested global chemistry-transport zoom model TM5: algorithm and applications

This paper describes the global chemistry Transport Model, version 5 (TM5) which allows two-way nested zooming. The model is used for global studies which require high resolution regionally but can work on a coarser resolution globally. The zoom algorithm introduces refinement in both space and time in some predefined regions. Boundary conditions of the zoom region are provided by a coarser parent grid and the results of the zoom area are communicated back to the parent. A case study using 222Rn measurements that were taken during the MINOS campaign reveals the advantages of local zooming. As a next step, it is investigated to what extent simulated concentrations over Europe are influenced by using an additional zoom domain over North America. An artificial ozone-like tracer is introduced with a lifetime of twenty days and simplified non-linear chemistry. The concentration differences at Mace Head (Ireland) are generally smaller than 10%, much smaller than the effects of the resolution enhancement over Europe. Thus, coarsening of resolution at some distance of a sampling station seems allowed. However, it is also noted that the budgets of the tracers change considerably due to resolution dependencies of, for instance, vertical transport. Due to the two-way nested algorithm, TM5 offers a consistent tool to study the effects of grid refinement on global atmospheric chemistry issues like intercontinental transport of air pollution.
The surface properties of SOA generated from limonene and toluene using specific molecular probes: exploration of a new experimental technique

A new experimental technique of characterizing the aerosol-atmosphere surface has been explored using three examples: the secondary organic aerosols (SOA) resulting from the reaction of limonene with O3 and from the photooxidation of toluene in comparison with the combustion aerosol (soot) from a toluene diffusion flame. Rather than investigating the bulk composition of the aerosol by complete chemical analysis and identification of the many dozens if not more of constituent compounds we have interrogated the type and number of functional groups located at the aerosol surface by interacting them with specific molecular probes such as O3, NO2, N(CH3)3, and NH2OH to probe for the presence of oxidizable sites, acidic sites and carbonyl functionalities, respectively, that are present on the surface of the aerosol particle. In practice, typical amounts of one to a few mg of laboratory-generated SOA of limonene, toluene and soot have been deposited on a PTFE membrane filter that subsequently has been transferred to a molecular flow reactor used for the titration reaction of the surface functional groups by the molecular probes. Absolute amounts Ni with i=O3, NO2, N(CH3)3, NH2OH of probe molecules taken up by the filter sample measured using molecular beam sampling mass spectrometry have been converted into the number of surface group functionalities per unit surface area S using the aerosol particle distribution function (PDF) of limonene and toluene SOA and the BET total surface area of toluene flame soot to result in Ni/S. Arguments are presented that support the transfer of the PDF of the suspended to the aerosol collected on the Teflon filter.
A practical demonstration on AMSU retrieval precision for upper tropospheric humidity by a non-linear multi-channel regression method

A neural network algorithm inverting selected channels from the Advance Microwave Sounding Unit instruments AMSU-A and AMSU-B was applied to retrieve layer averaged relative humidity. The neural network was trained with a global synthetic dataset representing clear-sky conditions. A precision of around 6% was obtained when retrieving global simulated radiances, the precision deteriorated less than 1% when real mid-latitude AMSU radiances were inverted and compared with co-located data from a radiosonde station. The 6% precision outperforms by 1% the reported precision estimate from a linear single-channel regression between radiance and weighting function averaged relative humidity, the more traditional approach to exploit AMSU data. Added advantages are not only a better precision; the AMSU-B humidity information is more optimally exploited by including temperature information from AMSU-A channels; and the layer averaged humidity is a more physical quantity than the weighted humidity, for comparison with other datasets. The training dataset proved adequate for inverting real radiances from a mid-latitude site, but it is limited by not considering the impact of clouds or surface emissivity changes, and further work is needed in this direction for further validation of the precision estimates.