Doppler radar observation, CG lightning activity and aerial survey of a multiple downburst in southern Germany on 23 March 2001

Two downburst events from one thunderstorm are investigated, which occurred on 23 March 2001, in Germany's climatologic annual minimum of downburst activity. Observations by two Doppler radars are combined with hail reports, ground lightning detection and an aerial survey conducted after the event. The downburst-producing storm had formed at a synoptic convergence line within the warm sector of a cyclone. It had a remarkably high propagation speed of up to 31 m s^− 1 corresponding to the mid-tropospheric flow. Thus, by superposition with the storm motion, even two weak downbursts were sufficient to cause the observed damage of F1 and F2 intensity, respectively. While in its late stages, the storm was dynamically characterized by lower- and mid-tropospheric divergence; at about the time of the first downburst, a mesocyclonic vortex signature was verified. Aside from mid-tropospheric dry air entrainment, a thermodynamic explanation for the triggering of the two downbursts by melting of small hail according to recent findings by Atlas et al. [Atlas, D., Ulbrich, C.W., Williams, C.R., 2004. Physical origin of a wet microburst: observations and theory. J. Atmos. Sci. 61, 1186–1196] appears probable. Despite the lack of warnings to the public, the storm's potential for hail and strong straight-line winds was detected by the German weather service radar software CONRAD more than a half hour before the downbursts occurred.     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions

We report results of hydrothermal experiments on four alluvial zircons from Sri Lanka, which cover a wide range of radiation damage, at 450 °C and 1.3 kbar for 744 h with 2 M CaCl₂ solution as reactive fluid. After the hydrothermal treatment, the most metamict samples show micrometer-thick reaction rims, which surround apparently unreacted zircon, as revealed by cathodoluminescence (CL) and Nomarski differential interference contrast (NDIC) images. These rims have sharp, curved, and transgressive boundaries with unreacted zircon and are, in some cases, spread out along cracks. The thickness of reaction rims increases with increasing cumulated !-dosage of the starting materials. The reaction rims are strongly enriched in Ca (up to 7000 ppm) and a water species and depleted in radiogenic Pb, Zr, and Si, as revealed by electron microprobe analyses. A significant Th loss from the reaction rims was detected in the case of the most metamict sample, whereas U remained in the structure. FT-infrared spectrometry and X-ray diffraction measurements revealed that the bulk run products were recrystallized. Using micro-Raman spectrometry, we were able to demonstrate that differential recrystallization took place. The reaction rims are strongly recrystallized, whereas the unreacted grain interiors underwent only minor recrystallization. Recrystallization of the rims is accompanied by an enhancement of the integral CL intensity. It is suggested that recrystallization in the reaction rims was catalyzed by water infiltration and ion exchange and prevented significant congruent zircon dissolution under the given experimental conditions. Previous zircon studies have shown that (1) a transgressive morphology, (2) a reduced Th-U ratio, and (3) an enhanced CL emission are also characteristics of rims in zircons from high-grade metamorphic rocks. Based on these similarities between natural and experimentally produced rims, it is suggested that leaching-catalyzed recrystallization is an important alteration process in zircon under wet geological conditions and can account for many complex core-rim structures found in natural zircons. Furthermore, the strong enrichment of Ca in the reaction rims supports previous assumptions that high Ca concentrations in natural zircons are of secondary origin. It is suggested that lower U-Pb concordia intercept ages obtained from single-phase zircons with high Ca contents date a leaching event.     

Wave Flow Simulations Over Arctic Leads

We investigate the flow over Arctic leads using a mesoscale numerical model, typical of both summer and winter, under idealised conditions. We find that Arctic leads may be the source of standing atmospheric internal gravity waves during both seasons. The summertime wave may be compared with the wave generated by a small ridge, though with the phase reversed. The mechanism for exciting the wave is found to be the internal boundary layer developing due to horizontal variations in surface temperature and roughness length. During the more exploratory wintertime simulations, with substantial temperature difference between the lead and the ice surface, we find that secondary circulations and intermittent wave-breaking may occur. The effects of the lead appear far downstream.     

Single-Column Model Intercomparison for a Stably Stratified Atmospheric Boundary Layer

The parameterization of the stably stratified atmospheric boundary layer is a difficult issue, having a significant impact on medium-range weather forecasts and climate integrations. To pursue this further, a moderately stratified Arctic case is simulated by nineteen single-column turbulence schemes. Statistics from a large-eddy simulation intercomparison made for the same case by eleven different models are used as a guiding reference. The single-column parameterizations include research and operational schemes from major forecast and climate research centres. Results from first-order schemes, a large number of turbulence kinetic energy closures, and other models were used. There is a large spread in the results; in general, the operational schemes mix over a deeper layer than the research schemes, and the turbulence kinetic energy and other higher-order closures give results closer to the statistics obtained from the large-eddy simulations. The sensitivities of the schemes to the parameters of their turbulence closures are partially explored.