Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks: example from the Erzgebirge, Germany

Metamorphic textures in medium-grade (~500–550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.     

Implications of the serpentine phase transition on the behaviour of beryllium and lithium-boron of subducted ultramafic rocks

The Totalp-Platta-Malenco ophiolites in the Eastern Central Alps offer a unique opportunity to study the behaviour of Li, Be and B in ultramafic rocks in response to serpentinization and to progressive Alpine metamorphism. These units represent the remnants of a former ocean-continent transition that was intensely serpentinized during exposure on the Jurassic seafloor of the Ligurian Tethys. From north to the south, three isograd reactions (lizardite⇒antigorite+brucite;lizardite+talc⇒antigorite;lizardite+tremolite⇒antigorite+diopside) have been used to quantify the evolution of the light element content of metamorphic minerals. We determined the Li, Be and B concentrations in major silicate minerals from the ultramafic bodies of Totalp, Platta and Malenco by secondary ion mass spectrometry. Mantle minerals have Be concentrations (e.g. <0.001-0.009 μg/g in olivine) similar to the metamorphic minerals that replace them (e.g. <0.001-0.016 μg/g in serpentine). The mantle signature of Be is thus neither erased during seafloor alteration nor by progressive metamorphism from prehnite-pumpellyite to epidote-amphibolite facies. In contrast, the Li and B inventories of metamorphic minerals are related to the lizardite-to-antigorite transition. Both elements display higher concentrations in the low-temperature serpentine polymorph lizardite (max. 156 μg/g Li, max. 318 μg/g B) than in antigorite (max. 0.11 μg/g Li, max. 12 μg/g B). Calculated average B/Li ratios for lizardite (∼1395) and antigorite (∼115) indicate that Li fractionates from B during the lizardite-to-antigorite transition during prograde metamorphism in ultramafic rocks. In subduction zones, this signature is likely to be recorded in the B-rich nature of forearc fluids.Relative to oceanic mantle the Be content of mantle clinopyroxene is much higher, but similar to Be values from mantle xenoliths and subduction-related peridotite massifs. These data support previous hypothesis that the mantle rocks from the Eastern Central Alps have a subcontinental origin. We conclude that Be behaves conservatively during subduction metamorphism of ultramafic rocks, at least at low-temperature, and thus retains the fingerprint of ancient subduction-related igneous events in mantle peridotites.     

Dissolution of calcitic marble and dolomitic rock in high iron concentrated acid mine drainage: application to anoxic limestone drains

Oxidation of sulphide mining waste can generate acid mine drainage (AMD) that has the potential to seriously affect the ecosystems. Acid mine drainage is characterised by a high acidity, high concentrations of sulphates and metals. To reduce the environmental impacts due to AMD, neutralisation using limestone drains is an option proposed in the literature and used around the world. The present study focuses on the influence of the carbonate rock mineralogy and their particle size on the neutralising capacity. The tests were performed in two different anoxic conditions: in batch reactors, and in columns having a hydraulic retention time of 15?h. The results showed that the neutralisation capacity of calcite was more important than for dolomitic rock, and smaller particle size gave higher alkalinity production (fine calcite dissolved faster in contact with AMD). A characterization of metal precipitate in sludge and in limestone coating was performed and demonstrated that gypsum, lepidocrocite and goethite were the predominant secondary minerals to be formed. Finally, this study underlines that anoxic limestone drain cannot be used alone to treat high iron concentrated AMD.     

Empirical calibration of six geobarometers for the mineral assemblage quartz+muscovite+biotite+plagioclase+garnet

Six equilibria among quartz, plagioclase, biotite, muscovite, and garnet were empirically calibrated using mineral composition data from 43 samples having the assemblage quartz+muscovite+biotite+garnet+plagioclase+Al₂SiO₅ (sillimanite or kyanite). Pressures and temperatures in the data set used for calibration were determined through the simultaneous application of garnet-biotite geothermometry and garnet-quartz-plagioclase-Al₂SiO₅ geobarometry. Thermodynamic expressions for four of the six equilibria incorporate interaction parameters that model non-ideality in the mixing of cations in the octahedral sites of both muscovite and biotite. With pressure chosen as the dependent variable, multiple regression was used to solve for unknowns in the equilibrium thermodynamic expressions. The regressions yielded multiple correlation coefficients ranging from 0.983 to 0.999, with corresponding standard deviations of 338 and 92 bars in the residuals. The standard deviations in the residuals may be explained largely or entirely by the propagation of errors associated with electron microprobe analysis. These equilibria enable the determination of pressures from equilibrium assemblages of quartz+garnet+plagioclase+muscovite+biotite, and give results closely comparable to the experimentally calibrated garnet-quartz-plagioclase-Al₂SiO₅ geobarometer. Geobarometric applications should be restricted to rocks in which equilibrium constants and compositional variables fall within the same ranges as those used for calibration.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Stability and dynamics of the continental tectosphere

Continental cratons overlie thick, high-viscosity, thermal and chemical boundary layers, where the chemical boundary layers are less dense than they would be due to thermal effects alone, perhaps because they are depleted in basaltic constituents. If the continental tectosphere is the same age as the overlying Archaean crust, then the continental tectosphere must be able to survive for several billion years without undergoing a convective instability, despite being both cold and thick. Since platforms and shields correlate only weakly with Earth's gravity and geoid anomalies, acceptable models of the continental tectosphere must also satisfy this gravity constraint. We investigate the long-term stability of the continental tectosphere by carrying out a number of numerical convection experiments within a two-dimensional Cartesian domain. We initiate our experiments with a tectosphere (thermal and chemical boundary layers) immersed in a region of uniform composition, temperature, and viscosity, and consider the effects on the stability of the tectosphere of (1) activation energy (used to define the temperature dependence of viscosity), (2) compositional buoyancy, and (3) linear or non-linear rheology. The large lateral thermal gradients required to match oceanic and tectosphere structures initiate the dominant instability, a “drip” which develops at the side of the tectosphere and moves to beneath its center. High activation energies and high background viscosities restrict the amount and rate of entrainment. Compositional buoyancy does not significantly change the flow pattern. Rather, compositional buoyancy slows the destruction process somewhat and reduces the stress within the tectosphere. With a non-Newtonian rheology, this reduction in stress helps to stiffen the tectosphere. In these experiments, dynamical systems that adequately model the present ocean-continent structures have activation energy E*≥180 kJ mole⁻¹ — a value about one third the estimate of activation energy for olivine, E*≈520 kJ mole⁻¹. Although for E*≈520 kJ mole⁻¹, compositional buoyancy is not required for the tectosphere to survive, the joint application of longevity and gravity constraints allows us to reject all models not containing compositional buoyancy, and to predict that the ratio of compositional to thermal buoyancy within the continental tectosphere is approximately unity.     

Chromian spinel as a petrogenetic indicator in abyssal and alpine-type peridotites and spatially associated lavas

The composition of chromian spinel in alpine-type peridotites has a large reciprocal range of Cr and Al, with increasing Cr# (Cr/(Cr+Al)) reflecting increasing degrees of partial melting in the mantle. Using spinel compositions, alpine-type peridotites can be divided into three groups. Type I peridotites and associated volcanic rocks contain spinels with Cr#<0.60; Type III peridotites and associated volcanics contain spinels with Cr#>0.60, and Type II peridotites and volcanics are a transitional group and contain spinels spanning the full range of spinel compositions in Type I and Type II peridotites. Spinels in abyssal peridotites lie entirely within the Type I spinel field, making ophiolites with Type I alpine-type peridotites the most likely candidates for sections of ocean lithosphere formed at a midocean ridge. The only modern analogs for Type III peridotites and associated volcanic rocks are found in arc-related volcanic and intrusive rocks, continental intrusive assemblages, and oceanic plateau basalts. We infer a sub-volcanic arc petrogenesis for most Type III alpine-type peridotites. Type II alpine-type peridotites apparently reflect composite origins, such as the formation of an island-arc on ocean crust, resulting in large variations in the degree and provenance of melting over relatively short distances. The essential difference between Type I and Type III peridotites appears to be the presence or absence of diopside in the residue at the end of melting.Based on an examination of co-existing rock and spinel compositions in lavas, it appears that spinel is a sensitive indicator of melt composition and pressure of crystallization. The close similarity of spinel composition fields in genetically related basalts, dunites and peridotites at localities in the oceans and in ophiolite complexes indicates that its composition reflects the degree of melting in the mantle source region. Accordingly, we infer from the restricted range of spinel compositions in abyssal basalts that the degree of mantle melting beneath mid-ocean ridges is generally limited to that found in Type I alpine-type peridotites. It is apparent, therefore, that the phase boundary OL-EN-DI-SP +meltOL-EN-SP+melt has limited the degree of melting of the mantle beneath mid-ocean ridges. This was clearly not the case for many alpine-type peridotites, implying very different melting conditions in the mantle, probably involving the presence of water.