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- ItemMechanisms of bonding effected by nanoparticles in zirconia coatings applied by spraying of suspensions(Saarbrücke : Leibniz-Institut für Neue Materialien, 2008) Adam, Jens; Aslan, Mesut; Drumm, Robert; Veith, MichaelZirconia coatings consisting of a mixture of coarse and fine grained zirconia powders prepared by spraying of suspensions and subsequent thermal treatment at limited temperatures (up to 500°C) are poor in adherence and in intrinsic mechanical strength. We have shown elsewhere that mechanical properties of these coatings can be improved clearly by adding a small amount of nanoscaled zirconia. Here, the structural and the chemical development of this coating material and of the nanoparticles is examined to gain information about the underlying bonding mechanisms. The applied temperature is relatively low in comparison to the usual onset temperature of accelerated sintering. Nevertheless, the results show that diffusion controlled material transport mechanisms play their role in bonding. The condensation of surface OH groups may participate in bonding, too. These first results confirm the potential of nanoparticles to act as inorganic binder. Additional research effort to clarify the underlying mechanisms in detail is of interest. For the practical side, it can be concluded that the resulting effect of mechanical consolidation of ceramic structures at relatively low temperatures enables new ceramic applications, for example a new type of ceramic coatings on metallic substrates.
- ItemEvaluation of a global aerosol microphysics model against size-resolved particle statistics in the marine atmosphere(München : European Geopyhsical Union, 2007) Spracklen, D.V.; Pringle, K.J.; Carslaw, K.S.; Mann, G.W.; Manktelow, P.; Heintzenberg, J.A statistical synthesis of marine aerosol measurements from experiments in four different oceans is used to evaluate a global aerosol microphysics model (GLOMAP). We compare the model against observed size resolved particle concentrations, probability distributions, and the temporal persistence of different size particles. We attempt to explain the observed sub-micrometre size distributions in terms of sulfate and sea spray and quantify the possible contributions of anthropogenic sulfate and carbonaceous material to the number and mass distribution. The model predicts a bimodal size distribution that agrees well with observations as a grand average over all regions, but there are large regional differences. Notably, observed Aitken mode number concentrations are more than a factor 10 higher than in the model for the N Atlantic but a factor 7 lower than the model in the NW Pacific. We also find that modelled Aitken mode and accumulation mode geometric mean diameters are generally smaller in the model by 10–30%. Comparison with observed free tropospheric Aitken mode distributions suggests that the model underpredicts growth of these particles during descent to the marine boundary layer (MBL). Recent observations of a substantial organic component of free tropospheric aerosol could explain this discrepancy. We find that anthropogenic continental material makes a substantial contribution to N Atlantic MBL aerosol, with typically 60–90% of sulfate across the particle size range coming from anthropogenic sources, even if we analyse air that has spent an average of >120 h away from land. However, anthropogenic primary black carbon and organic carbon particles (at the emission size and quantity assumed here) do not explain the large discrepancies in Aitken mode number. Several explanations for the discrepancy are suggested. The lack of lower atmospheric particle formation in the model may explain low N Atlantic particle concentrations. However, the observed and modelled particle persistence at Cape Grim in the Southern Ocean, does not reveal a diurnal cycle consistent with a photochemically driven local particle source. We also show that a physically based cloud drop activation scheme better explains the observed change in accumulation mode geometric mean diameter with particle number.
- ItemClouds and aerosols in Puerto Rico – a new evaluation(München : European Geopyhsical Union, 2008) Allan, J.D.; Baumgardner, D.; Raga, G.B.; Mayol-Bracero, O.L.; Morales-García, F.; García-García, F.; Montero-Martínez, G.; Borrmann, S.; Schneider, J.; Mertes, S.; Walter, S.; Gysel, M.; Dusek, U.; Frank, G.P.; Krämer, M.The influence of aerosols, both natural and anthropogenic, remains a major area of uncertainty when predicting the properties and behaviour of clouds and their influence on climate. In an attempt to better understand warm cloud formation in a tropical marine environment, a period of intensive measurements took place in December 2004 in Puerto Rico, using some of the latest developments in online instrumentation such as aerosol mass spectrometers, cloud condensation nuclei counters and a hygroscopicity tandem differential mobility analyser. Simultaneous online measurements of aerosol size distributions, composition, hygroscopicity and optical properties were made near the lighthouse of Cape San Juan in the north-eastern corner of the island and at the top of East Peak mountain (1040 m a.s.l.), the two sites separated by 17 km. Additional measurements of the cloud droplet residual and interstitial aerosol properties were made at the mountain site, accompanied by measurements of cloud droplet size distributions, liquid water content and the chemical composition of cloud and rain water samples. Both aerosol composition and cloud properties were found to be sensitive to wind sector. Air from the east-northeast (ENE) was mostly free of anthropogenic influences, the submicron fraction being mainly composed of non-sea salt sulphate, while that from the east-southeast (ESE) was found to be moderately influenced by populated islands upwind, adding smaller (<100 nm), externally mixed, carbonaceous particles to the aerosol that increased the number concentrations by over a factor of 3. This change in composition was also accompanied with a reduction in the measured hygroscopicity and fractional cloud activation potential of the aerosol. At the mountain site, the average cloud droplet concentrations increased from 193 to 519 cm−3, median volume diameter decreased from 20 to 14 μm and the liquid water content increased from 0.24 to 0.31 g m−3 when the winds shifted from the ENE to ESE. Larger numbers of interstitial particles were recorded, most notably at sizes greater than 100 nm, which were absent during clean conditions. The average size of the residual particles and concentrations of cloudwater nitrate, sulphate and insoluble material increased during polluted conditions. Previous studies in Puerto Rico had reported the presence of a significant non-anthropogenic organic fraction in the aerosols measured and concluded that this was a factor controlling the in situ cloud properties. However, this was not observed in our case. In contrast to the 1.00±0.14 μg m−3 of organic carbon measured in 1992 and 1995, the organic matter measured in the current study of 0.17±0.35 μg m−3 is many times lower, most of which can be attributed to anthropogenic sources. During clean conditions, the submicron aerosol was observed to be almost entirely inorganic, an observation supported by the hygroscopicity measurements. This suggests that organic aerosols from marine sources may not be completely ubiquitous (either spatially or temporally) in this environment and requires further investigation to quantify their true extent and implications, with more extensive, longer-term sampling in conjunction with wind field analyses.
- ItemSpectral actinic flux in the lower troposphere: Measurement and 1-D simulations for cloudless, broken cloud and overcast situations(München : European Geopyhsical Union, 2005) Kylling, A.; Webb, A.R.; Kift, R.; Gobbi, G.P.; Ammannato, L.; Barnaba, F.; Bais, A.; Kazadzis, S.; Wendisch, M.; Jäkel, E.; Schmidt, S.; Kniffka, A.; Thiel, S.; Junkermann, W.; Blumthaler, M.; Silbernagl, R.; Schallhart, B.; Schmitt, R.; Kjeldstad, B.; Thorseth, T.M.; Scheirer, R.; Mayer, B.In September 2002, the first INSPECTRO campaign to study the influence of clouds on the spectral actinic flux in the lower troposphere was carried out in East Anglia, England. Measurements of the actinic flux, the irradiance and aerosol and cloud properties were made from four ground stations and by aircraft. The radiation measurements were modelled using the uvspec model and ancillary data. For cloudless conditions, the measurements of the actinic flux were reproduced by 1-D radiative transfer modelling within the measurement and model uncertainties of about ±10%. For overcast days, the ground-based and aircraft radiation measurements and the cloud microphysical property measurements are consistent within the framework of 1-D radiative transfer and within experimental uncertainties. Furthermore, the actinic flux is increased by between 60-100% above the cloud when compared to a cloudless sky, with the largest increase for the optically thickest cloud. Correspondingly, the below cloud actinic flux is decreased by about 55-65%. Just below the cloud top, the downwelling actinic flux has a maximum that is seen in both the measurements and the model results. For broken clouds the traditional cloud fraction approximation is not able to simultaneously reproduce the measured above-cloud enhancement and below-cloud reduction in the actinic flux.
- ItemHigh-field ESR studies of the quantum spin magnet CaCu2O 3(Milton Park : Taylor & Francis, 2006) Goiran, M.; Costes, M.; Broto, J.M.; Chou, F.C.; Klingeler, R.; Arushanov, E.; Drechsler, S.-L.; Büchner, B.; Kataev, V.We report an electron spin resonance (ESR) study of the s = 1/2 Heisenberg pseudo-ladder magnet CaCu2O3 in pulsed magnetic fields up to 40 T. At sub-terahertz frequencies we observe an ESR signal originating from a small amount of uncompensated spins residing presumably at the imperfections of the strongly antiferromagnetically correlated host spin lattice. The data give evidence that these few per cent of 'extra' spin states are coupled strongly to the bulk spins and are involved in the antiferromagnetic (AF) ordering at TN = 25 K. By mapping the frequency/resonance field diagram we have determined a small gap for magnetic excitations below TN of the order of ~0.3–0.8 meV. Such a small value of the gap explains the occurrence of the spin-flop transition in CaCu2O3 at weak magnetic fields μ0Hsf ~ 3 T. Qualitative changes of the ESR response with the increasing field strength give indications that strong magnetic fields reduce the AF correlations and may even suppress the long-range magnetic order in CaCu2O3. ESR data support scenarios with a significant role of the 'extra' spin states for the properties of low-dimensional quantum magnets.
- ItemInfluence of clouds on the spectral actinic flux density in the lower troposphere (INSPECTRO): Overview of the field campaigns(München : European Geopyhsical Union, 2008) Thiel, S.; Ammannato, L.; Bais, A.; Bandy, B.; Blumthaler, M.; Bohn, B.; Engelsen, O.; Gobbi, G.P.; Gröbner, J.; Jäkel, E.; Junkermann, W.; Kazadzis, S.; Kift, R.; Kjeldstad, B.; Kouremeti, N.; Kylling, A.; Mayer, B.; Monks, P.S.; Reeves, C.E.; Schallhart, B.; Scheirer, R.; Schmidt, S.; Schmitt, R; Schreder, J.; Silbernagl, R.; Topaloglou, C.; Thorseth, T.M.; Webb, A.R.; Wendisch, M.; Werle, P.Ultraviolet radiation is the key factor driving tropospheric photochemistry. It is strongly modulated by clouds and aerosols. A quantitative understanding of the radiation field and its effect on photochemistry is thus only possible with a detailed knowledge of the interaction between clouds and radiation. The overall objective of the project INSPECTRO was the characterization of the three-dimensional actinic radiation field under cloudy conditions. This was achieved during two measurement campaigns in Norfolk (East Anglia, UK) and Lower Bavaria (Germany) combining space-based, aircraft and ground-based measurements as well as simulations with the one-dimensional radiation transfer model UVSPEC and the three-dimensional radiation transfer model MYSTIC. During both campaigns the spectral actinic flux density was measured at several locations at ground level and in the air by up to four different aircraft. This allows the comparison of measured and simulated actinic radiation profiles. In addition satellite data were used to complete the information of the three dimensional input data set for the simulation. A three-dimensional simulation of actinic flux density data under cloudy sky conditions requires a realistic simulation of the cloud field to be used as an input for the 3-D radiation transfer model calculations. Two different approaches were applied, to derive high- and low-resolution data sets, with a grid resolution of about 100 m and 1 km, respectively. The results of the measured and simulated radiation profiles as well as the results of the ground based measurements are presented in terms of photolysis rate profiles for ozone and nitrogen dioxide. During both campaigns all spectroradiometer systems agreed within ±10% if mandatory corrections e.g. stray light correction were applied. Stability changes of the systems were below 5% over the 4 week campaign periods and negligible over a few days. The J(O1D) data of the single monochromator systems can be evaluated for zenith angles less than 70°, which was satisfied by nearly all airborne measurements during both campaigns. The comparison of the airborne measurements with corresponding simulations is presented for the total, downward and upward flux during selected clear sky periods of both campaigns. The compliance between the measured (from three aircraft) and simulated downward and total flux profiles lies in the range of ±15%.
- ItemHydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study(München : European Geopyhsical Union, 2009) Kurtén, T.; Berndt, T.; Stratmann, F.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.
- ItemSpatio-temporal variability and principal components of the particle number size distribution in an urban atmosphere(München : European Geopyhsical Union, 2009) Costabile, F.; Birmili, W.; Klose, S.; Tuch, T.; Wehner, B.; Wiedensohler, A.; Franck, U.; König, K.; Sonntag, A.A correct description of fine (diameter <1 μm) and ultrafine (<0.1 μm) aerosol particles in urban areas is of interest for particle exposure assessment but also basic atmospheric research. We examined the spatio-temporal variability of atmospheric aerosol particles (size range 3–800 nm) using concurrent number size distribution measurements at a maximum of eight observation sites in and around Leipzig, a city in Central Europe. Two main experiments were conducted with different time span and number of observation sites (2 years at 3 sites; 1 month at 8 sites). A general observation was that the particle number size distribution varied in time and space in a complex fashion as a result of interaction between local and far-range sources, and the meteorological conditions. To identify statistically independent factors in the urban aerosol, different runs of principal component (PC) analysis were conducted encompassing aerosol, gas phase, and meteorological parameters from the multiple sites. Several of the resulting PCs, outstanding with respect to their temporal persistence and spatial coverage, could be associated with aerosol particle modes: a first accumulation mode ("droplet mode", 300–800 nm), considered to be the result of liquid phase processes and far-range transport; a second accumulation mode (centered around diameters 90–250 nm), considered to result from primary emissions as well as aging through condensation and coagulation; an Aitken mode (30–200 nm) linked to urban traffic emissions in addition to an urban and a rural Aitken mode; a nucleation mode (5–20 nm) linked to urban traffic emissions; nucleation modes (3–20 nm) linked to photochemically induced particle formation; an aged nucleation mode (10–50 nm). Additional PCs represented only local sources at a single site, or infrequent phenomena. In summary, the analysis of size distributions of high time and size resolution yielded a surprising wealth of statistical aerosol components occurring in the urban atmosphere over one single city. A paradigm on the behaviour of sub-μm urban aerosol particles is proposed, with recommendations how to efficiently monitor individual sub-fractions across an entire city.
- ItemEmission fluxes and atmospheric degradation of monoterpenes above a boreal forest: Field measurements and modelling(Milton Park : Taylor & Francis, 2001) Spanke, Jörg; Rannik, Üllar; Forkel, Renate; Nigge, Walter; Hoffman, ThorstenThe contribution of monoterpenes to aerosol formation processes within and above forests is not well understood. This is also true for the particle formation events observed during the BIOFOR campaigns in Hyytiälä, Finland. Therefore, the diurnal variation of the concentrations of several biogenic volatile organic compounds (BVOCs) and selected oxidation products in the gas and particle phase were measured on selected days during the campaigns in Hyytiälä, Finland. α-pinene and Δ3-carene were found to represent the most important monoterpenes above the boreal forest. A clear vertical gradient of their concentrations was observed together with a change of the relative monoterpene composition with height. Based on concentration profile measurements of monoterpenes, their fluxes above the forest canopy were calculated using the gradient approach. Most of the time, the BVOC fluxes show a clear diurnal variation with a maximum around noon. The highest fluxes were observed for α-pinene with values up to 20 ng m−2 s−1 in summer time and almost 100 ng m−2 s−1 during the spring campaign. Furthermore, the main oxidation products from α-pinene, pinonaldehyde, and from β-pinene, nopinone, were detected in the atmosphere above the forest. In addition to these more volatile oxidation products, pinic and pinonic acid were identified in the particle phase in a concentration range between 1 and 4 ng m−3. Beside these direct measurement of known oxidation products, the chemical sink term in the flux calculations was used to estimate the amount of product formation of the major terpenes (α-pinene, β-pinene, Δ3-carene). A production rate of very low volatile oxidation products (e.g., multifunctional carboxylic) from ·OH- and O3-reaction of monoterpenes of about 1.3·104 molecules cm−3 s−1 was estimated for daylight conditions during summer time. Additionally, model calculations with the one-dimensional multilayer model CACHE were carried out to investigate the diurnal course of BVOC fluxes and chemical degradation of terpenes.
- ItemThe polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic(London : BioMed Central, 2009) Plachá, Daniela; Raclavská, Helena; Rümmeli, Mark H.The polycyclic aromatic hydrocarbon (PAH) contamination of urban, agricultural and forest soil samples was investigated from samples obtained in the surroundings of Valasske Mezirici. Valasske Mezirici is a town located in the north-east mountainous part of the Czech Republic, where a coal tar refinery is situated. 16 PAHs listed in the US EPA were investigated. Organic oxidizable carbon was also observed in the forest soils. The PAH concentrations ranged from 0.86-10.84 (with one anomalous value of 35.14) and 7.66-79.39 mg/kg dm in the urban/agricultural and forest soils, respectively. While the PAH levels in the urban/agricultural soils are within the range typically found in industrialized areas, the forest soils showed elevated PAH concentrations compared to other forest soils in Western and Northern Europe. The PAH concentrations and their molecular distribution ratios were studied as functions of the sample location and the meteorological history. The soils from localities at higher altitudes above sea level have the highest PAH concentrations, and the PAH concentrations decrease with increasing distance from the town.