ALBERT

Description: Deeply rooted thrust zones are key features of tectonic processes and the evolution of mountain belts. Exhumed and deeply eroded orogens like the Scandinavian Caledonides allow us to study such systems from the surface. Previous seismic investigations of the Seve Nappe Complex have shown indications of a strong but discontinuous reflectivity of this thrust zone, which is only poorly understood. The correlation of seismic properties measured on borehole cores with surface seismic data can constrain the origin of this reflectivity. To this end, we compare seismic velocities measured on cores to in situ velocities measured in the borehole. For some intervals of the COSC-1 borehole, the core and downhole velocities deviate by up to 2 km s−1. These differences in the core and downhole velocities are most likely the result of microcracks mainly due to depressurization. However, the core and downhole velocities of the intervals with mafic rocks are generally in close agreement. Seismic anisotropy measured in laboratory samples increases from about 5 % to 26 % at depth, correlating with a transition from gneissic to schistose foliation. Thus, metamorphic foliation has a clear expression in seismic anisotropy. These results will aid in the evaluation of core-derived seismic properties of high-grade metamorphic rocks at the COSC-1 borehole and elsewhere.

Description: We present here results from a new mechanism, CRI-HOM, which we have developed to simulate the formation of highly oxygenated organic molecules (HOMs) from the gas-phase oxidation of α-pinene, one of the most widely emitted biogenic volatile organic compounds (BVOCs) by mass. This concise scheme adds 12 species and 66 reactions to the Common Representative Intermediates (CRI) mechanism v2.2 Reduction 5 and enables the representation of semi-explicit HOM treatment suitable for long-term global chemistry–aerosol–climate modelling, within a comprehensive tropospheric chemical mechanism. The key features of the new mechanism are (i) representation of the autoxidation of peroxy radicals from the hydroxyl radical and ozone initiated reactions of α-pinene, (ii) formation of multiple generations of peroxy radicals, (iii) formation of accretion products (dimers), and (iv) isoprene-driven suppression of accretion product formation, as observed in experiments. The mechanism has been constructed through optimisation against a series of flow tube laboratory experiments. The mechanism predicts a HOM yield of 2 %–4.5 % under conditions of low to moderate NOx, in line with experimental observations, and reproduces qualitatively the decline in HOM yield and concentration at higher NOx levels. The mechanism gives a HOM yield that also increases with temperature, in line with observations, and our mechanism compares favourably to some of the limited observations of [HOM] observed in the boreal forest in Finland and in the southeast USA. The reproduction of isoprene-driven suppression of HOMs is a key step forward as it enables global climate models to capture the interaction between the major BVOC species, along with the potential climatic feedbacks. This suppression is demonstrated when the mechanism is used to simulate atmospheric profiles over the boreal forest and rainforest; different isoprene concentrations result in different [HOM] distributions, illustrating the importance of BVOC interactions in atmospheric composition and climate. Finally particle nucleation rates calculated from [HOM] in present-day and pre-industrial atmospheres suggest that “sulfuric-acid-free” nucleation can compete effectively with other nucleation pathways in the boreal forest, particularly in the pre-industrial period, with important implications for the aerosol budget and radiative forcing.

Description: Limb sounding instruments play an important role in the monitoring of climate trends, as they provide a good vertical resolution. Traceability to the International System of Units (SI) via onboard reference or transfer standards is needed to compare trend estimates from multiple instruments. This study investigates the required uncertainty of these radiation standards to properly resolve decadal trends of climate-relevant trace species like ozone, water vapor, and temperature distribution for the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA). Temperature nonuniformities of the onboard reference blackbodies, used for radiometric calibration, have an impact on the calibration uncertainty. The propagation of these nonuniformities through the retrieval is analyzed. A threshold for the maximum tolerable uncertainty of the blackbody temperature is derived, so that climate trends can be significantly identified with GLORIA.

Description: The deployment of the imaging Fourier Transform Spectrometer GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) on board a long-duration balloon for stratospheric research requires a blackbody for in-flight calibration in order to provide traceability to the International Temperature Scale (ITS-90) to ensure comparability with the results of other experiments and over time. GLORIA, which has been deployed onboard various research aircraft such as the Russian M55 Geophysica or the German HALO in the past, shall also be used for detailed atmospheric measurements in the stratosphere up to 40 km altitude. The instrument uses a two-dimensional detector array and an imaging optics with a large aperture diameter of 36 mm and an opening angle of 4.07∘ × 4.07∘ for infrared limb observations. To overfill the field of view (FOV) of the instrument, a large-area blackbody radiation sources (125 mm × 125 mm) is required for in-flight calibration. In order to meet the requirements regarding the scientific goals of the GLORIA missions, the radiance temperature of the blackbody calibration source has to be determined to better than 100 mK and the spatial temperature uniformity shall be better than 150 mK. As electrical resources on board a stratospheric balloon are very limited, the latent heat of the phase change of a eutectic material is utilized for temperature stabilization of the calibration source, such that the blackbody has a constant temperature of about −32 ∘C corresponding to a typical temperature observed in the stratosphere. The Institute for Atmospheric and Environmental Research at the University of Wuppertal designed and manufactured a prototype of the large-area blackbody for in-flight calibration of an infrared interferometer deployed on board a long-duration balloon for stratospheric research. This newly developed calibration source was tested under lab conditions as well as in a climatic and environmental test chamber in order to verify its performance especially under flight conditions. At the PTB (Physikalisch-Technische Bundesanstalt), the German national metrology institute, the spatial radiance distribution of the blackbody was determined and traceability to the International Temperature Scale (ITS-90) has been assured. In this paper the design and performance of the balloon-borne blackbody (BBB) is presented.

Description: This paper describes the implementation of a kinetic gas-particle partitioning approach used for the simulation of secondary organic aerosol (SOA) formation within the SPectral Aerosol Cloud Chemistry Interaction Model (SPACCIM). The kinetic partitioning considers the diffusion of organic compounds into aerosol particles and the subsequent chemical reactions in the particle phase. The basic kinetic partitioning approach is modified by the implementation of chemical backward reaction of the solute within the particle phase as well as a composition-dependent particle-phase bulk diffusion coefficient. The adapted gas-phase chemistry mechanism for α-pinene oxidation has been updated due to the recent findings related to the formation of highly oxidized multifunctional organic compounds (HOMs). Experimental results from a LEAK (Leipziger Aerosolkammer) chamber study for α-pinene ozonolysis were compared with the model results describing this reaction system.The performed model studies reveal that the particle-phase bulk diffusion coefficient and the particle-phase reactivity are key parameters for SOA formation. Using the same particle-phase reactivity for both cases, we find that liquid particles with higher particle-phase bulk diffusion coefficients have 310 times more organic material formed in the particle phase compared to higher viscous semi-solid particles with lower particle-phase bulk diffusion coefficients. The model results demonstrate that, even with a moderate particle-phase reactivity, about 61 % of the modeled organic mass consists of reaction products that are formed in the liquid particles. This finding emphasizes the potential role of SOA processing. Moreover, the initial organic aerosol mass concentration and the particle radius are of minor importance for the process of SOA formation in liquid particles. A sensitivity study shows that a 22-fold increase in particle size merely leads to a SOA increase of less than 10 %.Due to two additional implementations, allowing backward reactions in the particle phase and considering a composition-dependent particle-phase bulk diffusion coefficient, the potential overprediction of the SOA mass with the basic kinetic approach is reduced by about 40 %. HOMs are an important compound group in the early stage of SOA formation because they contribute up to 65 % of the total SOA mass at this stage. HOMs also induce further SOA formation by providing an absorptive medium for SVOCs (semi-volatile organic compounds). This process contributes about 27 % of the total organic mass. The model results are very similar to the LEAK chamber results. Overall, the sensitivity studies demonstrate that the particle reactivity and the particle-phase bulk diffusion require a better characterization in order to improve the current model implementations and to validate the assumptions made from the chamber simulations. The successful implementation and testing of the current kinetic gas-particle partitioning approach in a box model framework will allow further applications in a 3-D model for regional-scale process investigations.

Description: Magmatic sill intrusions into organic-rich sediments cause the release of thermogenic CH4 and CO2. Pore fluids from the Guaymas Basin (Gulf of California), a sedimentary basin with recent magmatic activity, were investigated to constrain the link between sill intrusions and fluid seepage as well as the timing of sill-induced hydrothermal activity. Sampling sites were close to a hydrothermal vent field at the northern rift axis and at cold seeps located up to 30 km away from the rift. Pore fluids close to the active hydrothermal vent field showed a slight imprint by hydrothermal fluids and indicated a shallow circulation system transporting seawater to the hydrothermal catchment area. Geochemical data of pore fluids at cold seeps showed a mainly ambient diagenetic fluid composition without any imprint related to high temperature processes at greater depth. Seep communities at the seafloor were mainly sustained by microbial methane, which rose along pathways formed earlier by hydrothermal activity, driving the anaerobic oxidation of methane (AOM) and the formation of authigenic carbonates. Overall, our data from the cold seep sites suggest that at present, sill-induced hydrothermalism is not active away from the ridge axis, and the vigorous venting of hydrothermal fluids is restricted to the ridge axis. Using the sediment thickness above extinct conduits and carbonate dating, we calculated that deep fluid and thermogenic gas flow ceased 28 to 7 kyr ago. These findings imply a short lifetime of hydrothermal systems, limiting the time of unhindered carbon release as suggested in previous modeling studies. Consequently, activation and deactivation mechanisms of these systems need to be better constrained for the use in climate modeling approaches.

Description: Mechanistic investigations of atmospheric H2SO4 particle formation have been performed in a laboratory study taking either H2SO4 from a liquid reservoir or using the gas-phase reaction of OH radicals with SO2. Applying both approaches for H2SO4 generation simultaneously we found that H2SO4 evaporated from the liquid reservoir acts considerably less effective for the process of particle formation and growth than the products originating from the reaction of OH radicals with SO2. Furthermore, for NOx concentrations 〉5×1011 molecule cm−3 the formation of new particles from the reaction of OH radicals with SO2 is inhibited. This suggests that substances other than H2SO4 (likely products from sulphur-containing peroxy radicals) trigger lower tropospheric new particle formation and growth. The currently accepted mechanism for SO2 gas-phase oxidation does not consider the formation of such substances making a revision necessary.

Description: Atmospheric new particle formation is generally thought to occur due to homogeneous or ion-induced nucleation of sulphuric acid. We compare ambient nucleation rates with laboratory data from nucleation experiments involving either sulphuric acid or oxidized SO2. Atmospheric nucleation occurs at H2SO4 concentrations 2–4 orders of magnitude lower than binary or ternary H2SO4 nucleation. In contrast, the atmospheric nucleation rates and H2SO4 concentrations are very well replicated in the SO2 oxidation experiments. We explain these features by the formation of free HSO5 radicals in pace with H2SO4 during the SO2 oxidation. We suggest that at temperatures above ~250 K these radicals produce nuclei of new aerosols much more efficiently than H2SO4. These nuclei are activated to further growth by H2SO4 and possibly other trace species. However, at lower temperatures the atmospheric relative acidity is high enough for the H2SO4–H2O nucleation to dominate.

Description: Within the project EUCAARI (European Integrated project on Aerosol Cloud Climate and Air Quality interactions), atmospheric nucleation was studied by (i) developing and testing new air ion and cluster spectrometers, (ii) conducting homogeneous nucleation experiments for sulphate and organic systems in the laboratory, (iii) investigating atmospheric nucleation mechanism under field conditions, and (iv) applying new theoretical and modelling tools for data interpretation and development of parameterisations. The current paper provides a synthesis of the obtained results and identifies the remaining major knowledge gaps related to atmospheric nucleation. The most important technical achievement of the project was the development of new instruments for measuring sub-3 nm particle populations, along with the extensive application of these instruments in both the laboratory and the field. All the results obtained during EUCAARI indicate that sulphuric acid plays a central role in atmospheric nucleation, in addition to which other vapours, especially organic ones, are needed to explain the nucleation and the subsequent growth processes. Both our field and laboratory data demonstrate that the nucleation rate scales to the first or second power of the nucleating vapour concentration(s). This agrees with the few earlier field observations, but is in stark contrast with classical thermodynamic nucleation theories. The average formation rates of 2-nm particles were found to vary by almost two orders of magnitude between the different EUCAARI sites, whereas the formation rates of charged 2-nm particles varied very little between the sites. Overall, our observations are indicative of frequent, yet moderate, ion-induced nucleation usually outweighed by much stronger neutral nucleation events in the lower troposphere. The most concrete outcome of the EUCAARI nucleation studies are the new semi-empirical nucleation rate parameterizations based on field observations, along with updated aerosol formation parameterizations.

Description: Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir.