Influence of subsolidus processes on the chromium number in spinel in ultramafic rocks

The chromium number of spinel Cr#^sp (atomic ratio of Cr/(Cr+Al)) is an important geochemical parameter for the estimation of the degree of partial melting, temperatures, and provenance in peridotites. In this study, a model has been developed in order to determine the effect of subsolidus reactions on the Cr#^sp in ultramafic rocks. The final model includes temperature-dependent distribution coefficients of relevant reactions as well as solubility data and has been applied to lithologies common in mid-ocean ridge settings. Significant changes in the Cr#^sp are predicted from the application of this model during cooling from 1300 to 800°C at mantle pressures. For spinel lherzolites and harzburgites, the Cr#^sp is predicted to decrease proportional to the absolute values of the Cr#^sp at (constantly) increasing spinel mass. Cpx-dunites show the same trend, although to a lower extent. Websterites show a different behavior with a slight increase in the Cr#^sp due to their lack of olivine. Modal abundance of spinel correlates with the magnitude in Cr#^sp change, too. Finally, these results were tested for possible effects on the calculated degree of partial melting as function of the Cr#^sp. Application of the Cr#^sp from a peridotite equilibrated down to 800°C would result in an underestimation of only 1.5 % in the degree of melting, justifying the use of Cr#^sp for estimations of this parameter.     

The Mesozoic–Cenozoic structural framework of the Bay of Kiel area, western Baltic Sea

A dense grid of multichannel high-resolution seismic sections from the Bay of Kiel in the western Baltic Sea has been interpreted in order to reveal the Mesozoic and Cenozoic geological evolution of the northern part of the North German Basin. The overall geological evolution of the study area can be separated into four distinct periods. During the Triassic and the Early Jurassic, E–W extension and the deposition of clastic sediments initiated the movement of the underlying Zechstein evaporites. The deposition ceased during the Middle Jurassic, when the entire area was uplifted as a result of the Mid North Sea Doming. The uplift resulted in a pronounced erosion of Upper Triassic and Lower Jurassic strata. This event is marked by a clear angular unconformity on all the seismic sections. The region remained an area of non-deposition until the end of the Early Cretaceous, when the sedimentation resumed in the area. Throughout the Late Cretaceous the sedimentation took place under tectonic quiescence. Reactivated salt movement is observed at the Cretaceous Cenozoic transition as a result of the change from an extensional to compressional regional stress field. The vertical salt movement influenced the Cenozoic sedimentation and resulted in thin-skinned faulting.     

Simulation of the development of gypsum maze caves

The development of gypsum maze caves under artesian conditions has been simulated. The numerical model simulations show that the evolution of maze caves in this type of setting requires structural preferences such as laterally extended fissure networks in a horizon of the gypsum layer. Without any structural preferences vertical shafts rather than maze caves are predicted to develop. The most important stage for the development of horizontal caves under artesian conditions is found to be the initial karstification period. During this period the structure of the mature conduit system is established. The solutional enlargement of conduits is spatially extended, total dissolution rates are higher than the later ones.     

The Purpose and Age of Underwater Walls in the Bay of Elaia of Western Turkey: A Multidisciplinary Approach

Pergamum (modern: Bergama) was operating an important harbour used by military forces and merchants at the city of Elaia during Hellenistic and Roman Imperial times. Harbour‐related facilities such as warehouses, breakwaters and wharfs document the importance of this harbour site not only for the Pergamenians. This paper focuses on the purpose and age of six submerged wall structures situated approximately 1 km south of the ancient closed harbour basin of Elaia. Geoelectric cross‐sections and semi‐aquatic coring near these walls failed to detect any solid basement under the walls which excludes their possible use as breakwaters or wharfs. Instead, the walls were most likely delineating and separating evaporation ponds of salt works, which compares well with similar structures from other periods and places around the Mediterranean. Combined OSL and ¹⁴C‐dating determined the construction age of the installation between the 4th and 6th centuries A.D. Subsequent (re‐)uses are likely and are in agreement with findings from archaeological surveys.     

Eckfeld Maar: Window into an Eocene Terrestrial Habitat in Central Europe

<正>To mark the occasion of the 175th anniversary of the Rheinische Naturforschende Gesellschaft in 2009 and of the centennial of the Mainz Natural History Museum in 2010,we present a short account of our present knowledge of the Eckfeld Maar after 20 years of continuous research.This paper does not attempt to include all of the detailed results on the geology of the Eckfeld site or its biota.To date,nearly 250 papers and books have been published since the start of our project.An up-to-date list of these publications can be found at www.eckfeldermaar. de.     

In situ Sr/Sr investigation of igneous apatites and carbonates using laser-ablation MC-ICP-MS

In situ Sr isotopic compositions of coexisting apatite and carbonate for carbonatites from the Sarfartoq alkaline complex, Greenland, have been determined by laser-ablation multicollector inductively coupled plasma mass spectrometry. This study is the first to examine the extent of Sr isotopic homogeneity among coexisting igneous minerals containing high Sr (>3000 ppm) and low Rb (?1 ppm) contents within a single ∼50-μm-thick thin-section mount. This technique is capable of producing measured ⁸⁷Sr/⁸⁶Sr values with analytical precision (∼0.005%, 2σ) approaching those obtained by thermal ionization mass spectrometry but in a much shorter interval of time (100 s vs. >1 h, respectively). The combined total analyses (n = 107) of apatite and carbonate yield ⁸⁷Sr/⁸⁶Sr compositions ranging from ∼0.7025 to ∼0.7031. This relatively large variation in Sr isotopic compositions (∼0.0006) is ∼1 order of magnitude larger than the estimated external reproducibility (∼0.00005, 2σ) of the method. The large range in ⁸⁷Sr/⁸⁶Sr values suggests that apatite and carbonate precipitated predominantly under nonequilibrium conditions. The isotopic variations observed within individual hand specimens may therefore reflect larger (regional) scale open-system processes, possibly involving mixing of carbonatitic melts derived from distinct mantle sources or from a common isotopically heterogeneous mantle.     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).     

Inheritance of early Archaean Pb-isotope variability from long-lived Hadean protocrust

Comparison of initial Pb-isotope signatures of several early Archaean (3.65-3.82 Ga) lithologies (orthogneisses and metasediments) and minerals (feldspar and galena) documents the existence of substantial isotopic heterogeneity in the early Archaean, particularly in the ²⁰⁷Pb/²⁰⁴Pb ratio. The magnitude of isotopic variability at 3.82-3.65 Ga requires source separation between 4.3 and 4.1 Ga, depending on the extent of U/Pb fractionation possible in the early Earth. The isotopic heterogeneity could reflect the coexistence of enriched and depleted mantle domains or the separation of a terrestrial protocrust with a ²³⁸U/²⁰⁴Pb (µ) that was ca. 20-30% higher than coeval mantle. We prefer this latter explanation because the high-µ signature is most evident in metasediments (that formed at the Earth's surface). This interpretation is strengthened by the fact that no straightforward mantle model can be constructed for these high-µ lithologies without violating bulk silicate Earth constraints. The Pb-isotope evidence for a long-lived protocrust complements similar Hf-isotope data from the Earth's oldest zircons, which also require an origin from an enriched (low Lu/Hf) environment. A model is developed in which ́.8-Ga tonalite and monzodiorite gneiss precursors (for one of which we provide zircon U-Pb data) are not mantle-derived but formed by remelting or differentiation of ancient (ca. 4.3 Ga) basaltic crust which had evolved with a higher U/Pb ratio than coeval mantle in the absence of the subduction process. With the initiation of terrestrial subduction at, we propose, ca. 3.75 Ga, most of the ́.8-Ga basaltic shell (and its differentiation products) was recycled into the mantle, because of the lack of a stabilising mantle lithosphere. We argue that the key event for preservation of all ́.8-Ga terrestrial crust was the intrusion of voluminous granitoids immediately after establishment of global subduction because of complementary creation of a lithospheric keel. Furthermore, we argue that preservation of ́.8-Ga material (in situ rocks and zircons) globally is restricted to cratons with a high U/Pb source character (North Atlantic, Slave, Zimbabwe, Yilgarn, and Wyoming), and that the Pb-isotope systematics of these provinces are ultimately explained by reworking of material that was derived from ca. 4.3 Ga (i.e. Hadean) basaltic crust.     

A pilot-scale field experiment for the microbial neutralization of a holomictic acidic pit lake

A strategy to neutralize acidic pit lakes was tested in an upscaling process using field mesocosms of 26 to ca. 4500 m³ volume in the acidic pit Mining Lake 111 in Germany. After addition of the substrates Carbokalk and straw a neutral sediment layer formed, in which microbial sulfate and iron reduction as well as sulfide precipitation occurred. The net rate of neutralization was limited by the precipitation of iron sulfides rather than by microbial reactions. Oxidation of H₂S by ferric iron in the anoxic sediment lowered the net sulfate reduction rate. Seasonal fluctuations of iron sulfides in the sediment showed that the reaction products were not necessarily stable. The long-term success of the approach depends on the net partition of the precipitated iron-(mono-/di-) sulfide that is permanently buried in the anoxic sediment. It could be shown by field experiments that the long-term success of the neutralization depends on the spatial scale and duration of the experiments. Volumes from 26 to 4500 m³, exposition times from 4 months to 5 years, and increasingly thick coverings of the sediments with straw, from zero to 40 cm, were used. Net neutralization rates decreased from 41 meq m^− 2 d^− 1 in laboratory microcosms to a mean rate of 2.3 meq m^− 2 d^− 1 in the 4500 m³ field experiment. The results show that the success of the microbial treatment of acid pit lakes lastly depends on the limnological conditions in the lake that cannot be simulated by upscaling of simple laboratory experiments.     

Euphotic zone bacterioplankton sources major sedimentary bacteriohopanepolyols in the Holocene Black Sea

Bacteriohopanepolyols (BHPs) are lipid constituents of many bacterial groups. Geohopanoids, the diagenetic products, are therefore ubiquitous in organic matter of the geosphere. To examine the potential of BHPs as environmental markers in marine sediments, we investigated a Holocene sediment core from the Black Sea. The concentrations of BHPs mirror the environmental shift from a well-mixed lake to a stratified marine environment by a strong and gradual increase from low values (∼30 μg g⁻¹ TOC) in the oldest sediments to ∼170 μg g⁻¹ TOC in sediments representing the onset of a permanently anoxic water body at about 7500 years before present (BP). This increase in BHP concentrations was most likely caused by a strong increase in bacterioplanktonic paleoproductivity brought about by several ingressions of Mediterranean Sea waters at the end of the lacustrine stage (∼9500 years BP). δ¹⁵N values coevally decreasing with increasing BHP concentrations may indicate a shift from a phosphorus- to a nitrogen-limited setting supporting growth of N₂-fixing, BHP-producing bacteria. In sediments of the last ∼3000 years BHP concentrations have remained relatively stable at about 50 μg g⁻¹ TOC.The distributions of major BHPs did not change significantly during the shift from lacustrine (or oligohaline) to marine conditions. Tetrafunctionalized BHPs prevailed throughout the entire sediment core, with the common bacteriohopanetetrol and 35-aminobacteriohopanetriol and the rare 35-aminobacteriohopenetriol, so far only known from a purple non-sulfur α-proteobacterium, being the main components. Other BHPs specific to cyanobacteria and pelagic methanotrophic bacteria were also found but only in much smaller amounts.Our results demonstrate that BHPs from microorganisms living in deeper biogeochemical zones of marine water columns are underrepresented or even absent in the sediment compared to the BHPs of bacteria present in the euphotic zone. Obviously, the assemblage of molecular fossils in the sediments does not represent an integrated image of the entire community living in the water column. Remnants of organisms living in zones where effective transport mechanisms - such as the fecal pellet express - exist are accumulated while those of others are underrepresented. Our work shows a high stability of BHPs over geological time scales. Largely uniform distributions and only minor changes in structures like an increasing prevalence of saturated over unsaturated BHPs with time were observed. Consequently, sedimentary BHP distributions are less suitable as markers for in situ living bacteria but are useful for paleoreconstructions of bacterioplanktonic communities and productivity changes.