Microphysics of clouds at Kleiner Feldberg

During a field measuring campaign at Kleiner Feldberg (Taunus) in 1990, microphysical characteristics of clouds have been measured by Forward Scattering Spectrometer Probes (FSSP). The aim was to study the influence of aerosol and meteorological factors on droplet size and number. The results are: More mass in the accumulation size range of the aerosol leads to more droplets in stratocumulus clouds and to higher soluble masses in droplets of stratus clouds. However, the aerosol distribution was coarser in the stratus clouds compared to the stratocumulus clouds. Within the first 200 m from cloud base, the droplets grow while their number decreases. The growth results in a stable size of about 14 µm diameter over a large distance from cloud base in many stratocumulus clouds. Two types of mixing processes were observed: processes with reductions in the number of droplets (inhomogeneous mixing) and with reductions in the size of the droplets (homogeneous mixing).     

Oceanic events and biotic effects of the Cenomanian-Turonian anoxic event, Tarfaya Basin, Morocco

Profound biotic changes accompanied the late Cenomanian δ¹³C excursion and OAE2 in planktic foraminifera in the Tarfaya Basin of Morocco. Planktic foraminifera experienced a severe turnover, though no mass extinction, beginning with the rapid δ¹³C excursion and accelerating with the influx of oxic bottom waters during the first peak and trough of the excursion. Species extinctions equaled the number of evolving species, though only the disaster opportunists Guembelitria and Hedbergella thrived along with a low oxygen tolerant benthic assemblage. The succeeding δ¹³C plateau and organic-rich black shale deposition marks the anoxic event and maximum biotic stress accompanied by a prolonged drop in diversity to just two species, the dominant (80–90%) low oxygen tolerant Heterohelix moremani and surface dweller Hedbergella planispira. After the anoxic event other species returned, but remained rare and sporadically present well into the lower Turonian, whereas Heterohelix moremani remained the single dominant species. The OAE2 biotic turnover suggests that the stress to calcareous plankton was related to changes in the watermass stratification, intensity of upwelling, nutrient flux and oxic levels in the water column driven by changes in climate and oceanic circulation. Results presented here demonstrate a 4-stage pattern of biotic response to the onset, duration, and recovery of OAE2 that is observed widely across the Tethys and its bordering epicontinental seas.     

A closure study of sub-micrometer aerosol particle hygroscopic behaviour

The hygroscopic properties of sub-micrometer aerosol particles were studied in connection with a ground-based cloud experiment at Great Dun Fell, in northern England in 1995. Hygroscopic diameter growth factors were measured with a Tandem Differential Mobility Analyser (TDMA) for dry particle diameters between 35 and 265 nm at one of the sites upwind of the orographic cloud. An external mixture consisting of three groups of particles, each with different hygroscopic properties, was observed. These particle groups were denoted less-hygroscopic, more-hygroscopic and sea spray particles and had average diameter growth factors of 1.11–1.15, 1.38–1.69 and 2.08–2.21 respectively when taken from a dry state to a relative humidity of 90%. Average growth factors increased with dry particle size. A bimodal hygroscopic behaviour was observed for 74–87% of the cases depending on particle size. Parallel measurements of dry sub-micrometer particle number size distributions were performed with a Differential Mobility Particle Sizer (DMPS). The inorganic ion aerosol composition was determined by means of ion chromatography analysis of samples collected with Berner-type low pressure cascade impactors at ambient conditions. The number of ions collected on each impactor stage was predicted from the size distribution and hygroscopic growth data by means of a model of hygroscopic behaviour assuming that only the inorganic substances interacted with the ambient water vapour. The predicted ion number concentration was compared with the actual number of all positive and negative ions collected on the various impactor stages. For the impactor stage which collected particles with aerodynamic diameters between 0.17–0.53 μm at ambient relative humidity, and for which all pertinent data was available for the hygroscopic closure study, the predicted ion concentrations agreed with the measured values within the combined measurement and model uncertainties for all cases but one. For this impactor sampling occasion, the predicted ion concentration was significantly higher than the measured. The air mass in which this sample was taken had undergone extensive photochemical activity which had probably produced hygroscopically active material other than inorganic ions, such as organic oxygenated substances.     

Burial and Preservation of Carbonate Rocks Over Phanerozoic Time

Comparison of results for the original burial rate of carbonate sediments over Phanerozoic time, as calculated using the GEOCARBSULFvolc model, with their rate of preservation to the present (survival rate) shows a considerable loss of mass, partly by subduction of oceanic crust, during the past 250 million years. Before that time, despite the evidence that preserved Paleozoic carbonates appear to have been deposited only in shallow water, we contend that there was also inorganic deposition of carbonates in the Paleozoic deep sea with subsequent loss by subduction. Inorganic carbonate deposition may have been abetted by the vastly different seawater and atmospheric composition for most of the Paleozoic than those of post-Cretaceous and end Paleozoic–early Mesozoic times. The hypothesis helps to explain the loss of mass greater than that predicted for shallow-water carbonates prior to 250 Ma.     

GEM-Selektor geochemical modeling package: revised algorithm and GEMS3K numerical kernel for coupled simulation codes

Reactive mass transport (RMT) simulation is a powerful numerical tool to advance our understanding of complex geochemical processes and their feedbacks in relevant subsurface systems. Thermodynamic equilibrium defines the baseline for solubility, chemical kinetics, and RMT in general. Efficient RMT simulations can be based on the operator-splitting approach, where the solver of chemical equilibria is called by the mass transport part for each control volume whose composition, temperature, or pressure has changed. Modeling of complex natural systems requires consideration of multiphase–multicomponent geochemical models that include nonideal solutions (aqueous electrolytes, fluids, gases, solid solutions, and melts). Direct Gibbs energy minimization (GEM) methods have numerous advantages for the realistic geochemical modeling of such fluid–rock systems. Substantial improvements and extensions to the revised GEM interior point method algorithm based on Karpov’s convex programming approach are described, as implemented in the GEMS3K C/C+?+ code, which is also the numerical kernel of GEM-Selektor v.3 package (http://gems.web.psi.ch). GEMS3K is presented in the context of the essential criteria of chemical plausibility, robustness of results, mass balance accuracy, numerical stability, speed, and portability to high-performance computing systems. The stand-alone GEMS3K code can treat very complex chemical systems with many nonideal solution phases accurately. It is fast, delivering chemically plausible and accurate results with the same or better mass balance precision as that of conventional speciation codes. GEMS3K is already used in several coupled RMT codes (e.g., OpenGeoSys-GEMS) capable of high-performance computing.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

Miocene diagenetic and epigenetic strontium mineralization in calcareous series from Cyprus and the Arabian Gulf: Metallogenic perspective on sub- and suprasalt redox-controlled base metal deposits

During the Neogene, celestite deposits evolved in the Neo-Tethys basins, in what is today called the Mediterranean Sea and the Arabian Gulf. Two evaporite deposits, in Cyprus and in Qatar have been investigated from the sedimentological and mineralogical point of view with emphasis placed on Sr, S and Ca isotopes of carbonate, gypsum and celestite.During the early Miocene shallow marine environments occurred in the Gulf region and in Cyprus both of which are abundant in syndiagenetic sulphate minerals. The calcareous environments had a strong impact on the fluid migration leading to the Sr mineralization. In the Gulf region algal biostromes favored the lateral migration of fluids but had a sealing effect so that any epigenetic mineralization based on vertical fluid flow was hampered. In contrast, the Cypriot depocentre overlying the Troodos ophiolite is dominated by patch and knoll reefs (bioherms) which provide enough porosity and permeability to be favorable for the circulation of fluids with a strong vertical component. Owing to these changes in the calcareous host series, epigenetic sulphate mineralization evolved in Cyprus during the late Miocene. This occurred as the Mediterranean Sea gradually became isolated from the open ocean and, as a precursor to the “Messinian salinity crisis” evaporitic brines circulated deep into the Meso-Cenozoic platform sediments and the underlying Troodos ophiolite where these fluids leached some base metals and sulphur for the celestite mineralization. The Red Sea Rifting was at full swing during the Late Miocene and its northern propagation into the Mediterranean Sea is assumed to have had a structural control on the positioning of the Sr deposits in Cyprus. In the Gulf area, the final closure of the Neo-Tethys and Zagros folding terminated deposition of marine calcareous rocks and alluvial-fluvial siliciclastic rocks were deposited across an unconformity. Missing circulation of highly saline brines was responsible for the absence of an epigenetic Sr mineralization of Cyprus-type in the Gulf area. Assemblages of light (e.g. zeolites) and heavy minerals (e.g. rutile, zoisite, clinopyroxene) and Ca isotope analyses support basic igneous rocks as the source for the detrital and dissolved matter in the depositional environments in Cyprus and the Arabian Gulf. The Ca isotope data imply formation of the sulphate and carbonate minerals in a marine environment without significant contributions of more radiogenic ⁴⁰Ca coming from old continental crust, e.g., the Kyrenia Range or Mamonia Complex, both of which containing rocks as old as Permian.Cyprus-type (bioherm-type) and Gulf-type (biostrome-type) evaporites are potential progenitors of sediment-hosted mineral deposits (SHSCD) or base metal vein-type deposits. Syndiagenetic celestite-bearing evaporites of the Gulf-type are a model source and progenitor of base metal deposits of stratigraphically-controlled fixed or mobile reductants such as Kupferschiefer-type deposits. Is the Arabian Gulf a Kupferschiefer basin in the making? The epigenetic celestite-bearing mineralization of the Cyprus-type reflects an advanced stage of fluid migration relative to the celestite deposits along the Trucial coast but this brine mobilization failed to create a base metal deposit of its own mainly due to the absence of fixed or mobile reductants. These reductants were present in the western Mediterranean regions in Tunisia and Algeria, where evaporite-associated base metal deposits are going to be mined and in the Mesozoic through Cenozoic platform sediments in central Europe, where numerous suprasalt unconformity-related metal deposits were mined in the past.     

Sulfate reduction and the rate of deposition of marine sediments

The initial gradient of dissolved sulfate in the pore waters of anoxic marine sediments, representing a wide variety of environments from the deep-sea to estuaries, has been found to be directly proportional, within a factor of two, to the rate of sedimentation. Data from all areas considered, except the Mississippi Delta, fall along the same straight line. The linear proportionality can be explained on the basis of a theoretical model which assumes that organic matter decomposition by sulfate-reducing bacteria, plus associated fermentative micro-organisms, is first order with respect to the concentration of metabolizable organic matter. The model also assumes that the reactivity of metabolizable organic matter varies considerably from sediment to sediment while its concentration remains essentially constant. It is likely that the proportionality observed here also applies to other sediments and, thus, the initial sulfate gradient may be a useful parameter for estimating the rate of deposition of anoxic sediments.