Solution-precipitation creep and fluid flow in halite: a case study of Zechstein (Z1) rocksalt from Neuhof salt mine (Germany)

Zechstein (Z1) rocksalt from the Fulda basin, from the immediate vicinity of the Hessen potash bed is folded into tight to isoclinal folds which are cut by an undeformed, 1 cm thick, coarse-grained halite vein. Microstructures were investigated in etched, gamma-irradiated thin sections from both the wall rock and the vein. The lack of synsedimentary dissolution structures and the widespread occurrence of plate-shaped and hopper grains in the wall-rock suggests that the sedimentary environment was perennial lake. Deformation microstructures are in good agreement with solution-precipitation creep process, and salt flow under very low differential stress. Strength contrast between anhydrite-rich and anhydrite-poor layers caused the small scale folding in the halite beds. The vein is completely sealed and composed mainly of euhedral to subhedral halite grains, which often overgrow the wall-rock grains. Those microstructures, together with the presence of occasional fluid inclusion bands, suggest that the crystals grew into a solution-filled open space. Based on considerations on the maximum value of in-situ differential stress, the dilatancy criteria, the amount of released fluids from the potash bed during metamorphism and the volume change, it is proposed that the crack was generated by hydrofracturing of the rocksalt due to the presence of the salt-metamorphic fluid at near-lithostatic pressure.     

Origin and deformation of intra-salt sulphate layers: an example from the Dutch Zechstein (Late Permian)

From salt mine galleries and well data it is known that thick rock salt layers can contain anhydrite and carbonate layers with thicknesses on the millimetre to tens of metre scale. The relatively thick Zechstein 3 anhydrite–carbonate layer in the northern Netherlands has been studied previously using 3-D seismic data. Observations from geophysical well logs in this study reveal the presence of thin sulphate layers on the sub-seismic scale imbedded in the Zechstein 2 (Z2) salt. Core samples, thin sections, seismic data and geochemical measurements were used to determine the mineralogy and origin of one of these Z2 sulphate layers. Bromine analyses show that they mark a freshening event in the Z2 salt, which can be correlated over large distances in the northern Netherlands. Their core-calibrated log signature indicates that the Z2 sulphate layers consist either of pure anhydrite or of anhydrite and polyhalite. The mineralogy and thickness of the sulphate layers are interpreted to vary between synsedimentary morphologic lows (thin anhydrite–polyhalite couplets) and highs (thicker anhydrite layers). Such a combination of core observations and well log analysis is a powerful tool to detect lateral trends in evaporite mineralogy and to reconstruct the environmental setting of their formation. Salt internal geometries can further be used to distinguish between different deformation mechanisms. In our study area, the distribution of sulphate layers within the Z2 salt indicates that subjacent salt dissolution was not the dominant process leading to salt-related deformation.     

Microstructural evidence of time-relationships between metamorphism and deformation in the metasedimentary sequence of the Northern Hill end trough, New South Wales, Australia

Microstructural evidence of time-relationships between regional metamorphism and deformation has been obtained in the higher-grade, biotite-bearing parts of the metasedimentary sequence of the northern Hill End Tough, New South Wales. The rocks have only one prominent foliation (slaty cleavage) and one mineral-streaking lineation, which are of consistent orientation through the area. Therefore, they should be suitable for obtaining clear evidence of time-relationships. Microstructural criteria in many of the rocks are ambiguous, but relatively clear evidence is shown by porphyroblastic biotite phyllites (locally containing garnet), in which some of the porphyroblasts show microboudinage, new biotite occurring with quartz in the interboudin areas. These rocks indicate that biotite was stable during the later stages of deformation. The study shows that careful microstructural studies can be diagnostic of time-relationships in low-grade metamorphic areas, where critical rocks are available.     

Chemical modelling of the groundwater composition in aquifers affected by lignite mine dumps discharge (surface mine Inden,Germany)

The oxidation of pyrite results in sulphate concentrations from 1,300 to 2,000 mg/l in the dump water of the open cast mine Inden, which is located in Germany. Under near-neutral pH and reduced redox conditions, precipitation of siderite (FeCO₃) retains up to 85% of the pre-liberated ferrous iron, so that iron concentrations in the dump water are relatively low as compared to the concentrations of sulphate. The highly mineralised dump water will enter the aquifer system northwards of Inden during the next centuries. This area is used intensely for water extraction. Model calculations show that there will be no problem of acidification in the adjacent aquifer system and, therefore, no problem of high heavy metal concentrations during the next centuries. The most important problem will be high sulphate concentrations in the groundwater. Besides dispersion and diffusion, there are no chemical mechanisms that lower the sulphate concentrations downstream. On the basis of the simulations, sulphate plumes of about 1–2 km in width and up to 15 km in length are expected. Within the core of these plumes, sulphate concentrations will be above the drinking water limits.     

Unconventional reservoir potential of the upper Permian Zechstein Group: a slope to basin sequence stratigraphic and sedimentological evaluation of carbonates and organic-rich mudrocks, Northern Germany

The Late Permian Zechstein Group in northeastern Germany is characterized by shelf and slope carbonates that rimmed a basin extending from eastern England through the Netherlands and Germany to Poland. Conventional reservoirs are found in grainstones rimming islands created by pre-existing paleohighs and platform-rimming shoals that compose steep margins in the north and ramp deposits in the southern part. The slope and basin deposits are characterized by debris flows and organic-rich mudstones. Lagoonal and basinal evaporites formed the seal for these carbonate and underlying sandstone reservoirs. The objective of this investigation is to evaluate potential unconventional reservoirs in organic-rich, fine-grained and/or tight mudrocks in slope and basin as well as platform carbonates occurring in this stratigraphic interval. Therefore, a comprehensive study was conducted that included sedimentology, sequence stratigraphy, petrography, and geochemistry. Sequence stratigraphic correlations from shelf to basin are crucial in establishing a framework that allows correlation of potential productive facies in fine-grained, organic-rich basinal siliceous and calcareous mudstones or interfingering tight carbonates and siltstones, ranging from the lagoon, to slope to basin, which might be candidates for forming an unconventional reservoir. Most organic-rich shales worldwide are associated with eustatic transgressions. The basal Zechstein cycles, Z1 and Z2, contain organic-rich siliceous and calcareous mudstones and carbonates that form major transgressive deposits in the basin. Maturities range from over–mature (gas) in the basin to oil-generation on the slope with variable TOC contents. This sequence stratigraphic and sedimentologic evaluation of the transgressive facies in the Z1 and Z2 assesses the potential for shale-gas/oil and hybrid unconventional plays. Potential unconventional reservoirs might be explored in laminated organic-rich mudstones within the oil window along the northern and southern slopes of the basin. Although the Zechstein Z1 and Z2 cycles might have limited shale-gas potential because of low thickness and deep burial depth to be economic at this point, unconventional reservoir opportunities that include hybrid and shale-oil potential are possible in the study area.     

Microstructural evolution and geologic significance of garnet pyriclasites in the Hoher-Bogen shear zone (Bohemian Massif, Germany)

Ductile extensional movements along the steeply inclined Hoher-Bogen shear zone caused the juxtaposition of Teplá-Barrandian amphibolites, granulites, and metaperidotites against Moldanubian mica schists and paragneisses. Garnet pyriclasites are well preserved within low-strain domains of this shear zone. Their degree of metamorphism is significantly higher than that of the surrounding rocks. Microstructural and mineral chemical data suggest in situ formation of the garnet pyriclasite by dehydration of pyroxene amphibolite at T>750–840°C and P<10–13 kbar including recrystallization-accommodated grain-size reduction of plagioclase and clinopyroxene, nucleation of garnet, and breakdown of amphibole into garnet+clinopyroxene+rutile. Subsequent decompression and retrograde extensional shearing led to the formation of mylonitic epidote amphibolite. The presence of lower crustal and mantle-derived slices within the Hoher-Bogen shear zone supports the view that (a) in Upper Devonian times the Teplá-Barrandian unit was thrust over Moldanubian rocks as a complete crustal unit, and (b) that during the subsequent Lower Carboniferous orogenic collapse, the garnet pyriclasite and metaperidotite were scraped off from the basal parts of the Teplá-Barrandian unit being dragged into the Hoher-Bogen shear zone due to dramatic and large-scale elevator-style movements. Received: 23 March 1999 / Accepted: 25 August 1999     

Ductile deformation of garnet in mylonitic gneisses from the Münchberg Massif (Germany)

Mylonitic gneisses from the Münchberg Massif contain single grains (type I) and polycrystalline aggregates (type II) of garnet displaying a distinct elongation parallel to a macroscopic lineation which is interpreted as the result of ductile deformation. Lattice-preferred orientations of quartz (textures) symmetrical to the macroscopic foliation and lineation and the lack of rotational microfabrics indicate that the bulk deformation was pure shear at least during the latest strain increments. Garnet textures measured by EBSD together with microprobe analyses demonstrate that these two structural types of garnet can be related to two different processes of ductile deformation: (1) For the single grains stretching can be attributed to diffusion creep along grain boundary zones (Coble creep). The related mass transfer is indicated by the fact that primary growth zones are cut off at the long faces of the grains while the related strain shadow domains do not show comparable chemical zoning. Pressure solution and precipitation suitable to produce similar structures can be largely ruled out because retrogressive reactions pointing to the presence of free hydrous fluids are missing. (2) For the polycrystalline garnet aggregates consisting of cores grading into fine-grained mantles, dislocation creep and associated rotation recrystallization can be assumed. Continuous lattice rotation from the core to the outer polycrystalline rim allow a determination of the related dominant slip systems which are {100}<010> and equivalent systems according to the cubic lattice symmetry. The same holds for garnets which appear to be completely recrystallized. For this type of fine-grained aggregates an alternative nucleation model is discussed. Due to penetrative dislocation glide in connection with short range diffusion and the resulting lattice rotation, primary growth zones are strongly disturbed.Since for the considered rock unit of the Münchberg Massif peak metamorphic temperatures between 630 and 670 °C can be assumed, this study clearly demonstrates that the inferred processes of ductile garnet deformation can occur not only in HT regimes as often suggested in the literature even if embedded within a matrix of “low-strength” minerals like quartz, feldspars and micas.     

High temperature fracturing and ductile deformation during cooling of a pluton: The Lake Edison granodiorite (Sierra Nevada batholith,California)

In the Bear Creek area of the Sierra Nevada batholith, California, the high temperature postmagmatic deformation structures of the Lake Edison granodiorite include steeply-dipping orthogneiss foliations, joints, and ductile shear zones that nucleated on joints and leucocratic dykes. Exploitation of segmented joints resulted in sharply bounded, thin shear zones and in large slip gradients near the shear zone tips causing the deformation of the host rock at contractional domains. The orthogneiss foliation intensifies towards the contact with the younger Mono Creek granite and locally defines the dextral Rosy Finch Shear Zone (RFSZ), a major kilometre-wide zone crosscutting the pluton contacts. Joints predominantly strike at N70–90°E over most of the Lake Edison pluton and are exploited as sinistral shear zones, both within and outside the RFSZ. In a narrow (∼250 m thick) zone at the contact with the younger Mono Creek granite, within the RFSZ, the Lake Edison granodiorite includes different sets of dextral and sinistral shear zones/joints (the latter corresponding to the set that dominates over the rest of the Lake Edison pluton). These shear zones/joints potentially fit with a composite Y–R–R′ shear fracture pattern associated with the RFSZ, or with a pattern consisting of Y–R-shear fractures and rotated T′ mode I extensional fractures. The mineral assemblage of shear zones, and the microstructure and texture of quartz mylonites indicate that ductile deformation occurred above 500 °C. Joints and ductile shearing alternated and developed coevally. The existing kinematic models do not fully capture the structural complexity of the area or the spatial distribution of the deformation and magmatic structures. Future models should account more completely for the character of ductile and brittle deformation as these plutons were emplaced and cooled.     

The Numba ductile deformation zone (northwest Cameroon): A geometric analysis of folds based on the Fold Profiler method

The Numba ductile deformation zone (NDDZ) is characterised by folds recorded during the three deformation phases that affected the banded amphibole gneiss. Fold-shape analyses using the program Fold Profiler with the aim to show the importance of folding events in the structural analysis of the NDDZ and its contribution to the Pan-African orogeny in central Africa have been made. Classical field method, conic sections method and Ramsay’s fold classification method were applied to (i) have the general orientation of folds, (ii) analyze the fold shapes and (iii) classify the geometry of the folded bands. Fold axes in banded amphibole gneiss plunge moderately (\(<\)15\(^{\circ }\)) towards the NNE or SSW. The morphology of F\(_{1}\), F\(_{2}\) and F\(_{3}\) folds in the study area clearly points to (i) Z-shape folds with SE vergence and (ii) a dextral sense of shear motion. Conic section method reveals two dominant families: F\(_{1}\) and F\(_{3}\) folds belong to parabolic shape folds, while F\(_{2}\) folds belong to parabolic shape and hyperbolic shape folds. Ramsay’s scheme emphasizes class 1C (for F\(_{1}\), F\(_{2}\) and F\(_{3}\) folds) and class 3 (for F\(_{2}\) folds) as main fold classes. The co-existence of the various fold shapes can be explained by (i) the structuration of the banded gneiss, (ii) the folding mechanisms that associate shear with a non-least compressive or flattening component in a ductile shear zone and (iii) the change in rheological properties of the band during the period of fold formation. These data allow us to conclude that the Numba region underwent ductile dextral shear and can be integrated (i) in a correlation model with the Central Cameroon Shear Zone (CCSZ) and associated syn-kinematic intrusions and (ii) into the tectonic model of Pan-African belt of central Africa in Cameroon.     

Infrared spectroscopic characterisation of arsenate (V) ion adsorption from mine waters,Macraes mine,New Zealand

Processing waters contain up to 10 mg l⁻¹ dissolved As at the Macraes mine, New Zealand, and this is all removed by adsorption as the water percolates through a large earth dam. Laboratory experiments were set up to identify which mineral is the most effective substrate for this adsorption of As. The experiments were conducted using infrared (IR) spectroscopy of thin mineral films adhering to a ZnSe prism. Silicates, including kaolinite, adsorbed only small amounts of As which was readily washed off. Hydrated Fe oxides (HFO) were extremely effective at adsorbing As, particularly the natural amorphous HFO currently being deposited from dam discharge waters at the Macraes mine. An adsorption isotherm determined for this natural material has the adsorption constant, K_ads=(1.9±0.4)×10⁴ M⁻¹, and the substrate becomes saturated with adsorbed As when solution concentrations exceed about 50 mg l⁻¹. Saturation is not being reached at the Macraes mine. Arsenic adsorbed on to natural HFO has a distinctive IR spectrum with the absorption peak varying from 800 cm⁻¹ (alkaline solutions) to 820 cm⁻¹ (neutral to acid solutions). Much of this adsorbed As is strongly bound and difficult to wash off. Arsenate ions adsorb in a bidentate structure which may be a precursor for scorodite crystallisation.     

Release of toxic elements from rocks and mine wastes at the Furtei gold mine (Sardinia, Italy)

The Furtei gold mine in Sardinia (Italy) exploits a volcanic-hosted high-sulphidation epithermal deposit. Large amounts of materials derived from exploitation are present in open pits, waste rock dumps and cyanidation tailings impoundment. Mineralized rocks in outcrops and waste dumps contain significant amounts of sulphides (mainly pyrite and enargite). These materials have a high potential for acid drainage generation and release of toxic elements (notably Cu and As, but also Al, Ni, Co and Cd) as pointed out by laboratory leaching tests and in agreement with chemical composition of waters draining the mining area, that show pH as low as 2, up to 180 mg/L Cu, up to 5 mg/L As, and up to 788 mg/L Al. On the other hand, leaching solutions and waters interacting with mineral assemblages of the propylitic alteration zone (mainly composed of chlorite, quartz, and calcite, with relic magmatic plagioclase) show higher pH, and lower metal loads. Leachates from cyanidation tailings show variable pH (between 6.2 and 9.7, depending on sulphide content in tailings); cyanide concentration varies between 110 µg/L and about 3 mg/L, whereas contents of toxic elements in leachates are, with the exception of Hg, within the limits of Italian regulations for non-dangerous industrial wastes. Reclamation plans provide for confinement of tailings within specific repositories. This measure should effectively reduce the environmental impact of these materials. Reclamation plans should also include an adequate management of other high-sulphide wastes.     

Quartz and feldspar zoning in the eastern Erzgebirge volcano-plutonic complex (Germany, Czech Republic): evidence of multiple magma mixing

Zoned quartz and feldspar phenocrysts of the Upper Carboniferous eastern Erzgebirge volcano-plutonic complex were studied by cathodoluminescence and minor and trace element profiling. The results verify the suitability of quartz and feldspar phenocrysts as recorders of differentiation trends, magma mixing and recharge events, and suggest that much heterogeneity in plutonic systems may be overlooked on a whole-rock scale. Multiple resorption surfaces and zones, element concentration steps in zoned quartz (Ti) and feldspar phenocrysts (anorthite content, Ba, Sr), and plagioclase-mantled K-feldspars etc. indicate mixing of silicic magma with a more mafic magma for several magmatic phases of the eastern Erzgebirge volcano-plutonic complex. Generally, feldspar appears to be sensitive to the physicochemical changes of the melt, whereas quartz phenocrysts are more stable and can survive a longer period of evolution and final effusion of silicic magmas. The regional distribution of mixing-compatible textures suggests that magma mingling and mixing was a major process in the evolution of these late-Variscan granites and associated volcanic rocks.

Quartz phenocrysts from 14 magmatic phases of the eastern Erzgebirge volcano-plutonic complex provide information on the relative timing of different mixing processes, storage and recharge, allowing a model for the distribution of magma reservoirs in space and time. At least two levels of magma storage are envisioned: deep reservoirs between 24 and 17 km (the crystallisation level of quartz phenocrysts) and subvolcanic reservoirs between 13 and 6 km. Deflation of the shallow reservoirs during the extrusion of the Teplice rhyolites triggered the formation of the Altenberg-Teplice caldera above the eastern Erzgebirge volcano-plutonic complex. The deep magma reservoir of the Teplice rhyolite also has a genetic relationship to the younger mineralised A-type granites, as indicated by quartz phenocryst populations. The pre-caldera biotite granites and the rhyodacitic Schönfeld volcanic rocks represent temporally and spatially separate magma sources. However, the deep magma reservoir of both is assumed to have been at a depth of 24–17 km. The drastic chemical contrast between the pre-caldera Schönfeld (Westfalian B–C) and the syn-caldera Teplice (Westfalian C–D) volcanic rocks is related to the change from late-orogenic geotectonic environment to post-orogenic faulting, and is considered an important chronostratigraphic marker.     

Diagenesis of plattenkalk: examples from the Solnhofen area (Upper Jurassic,southern Germany)

The Upper Jurassic (Tithonian) plattenkalk successions in the Solnhofen/Eichstätt area consist of alternations of thin‐bedded, laminated, fine‐grained, very pure limestones (so‐called ‘flinz beds’) and softer interlayers with slightly lower carbonate contents that are also laminated and show a foliaceous weathering appearance (‘fäule beds’). These successions are world famous for their exceptionally well‐preserved fossils. In contrast to the well‐studied wealth of fossils, little is known about the origin and diagenesis of the host rock. The reason for this discrepancy might lay in the monotonous appearance of these fine‐grained mudstones that require electron microscopical examination. Study of samples from the Solnhofen–Eichstädt area implies that flinz and fäule beds have undergone differential diagenesis. The ultrastructure of the flinz beds is characterized by interlocking microspar crystals, whereas the fäule beds show smaller and less interlocking crystals. The ratios of diagenetically inert trace elements lack clear differences between the two interlayered lithologies. While most authors agree that the flinz–fäule rhythm reflects rhythmically changing environmental conditions, primary rhythms can be taken as proven only where statistically significant differences in diagenetically resistant proxies are found. The absence of clear primary differences between flinz and fäule beds, however, leaves the question of primary differences unsolved. It is concluded that diagenesis has had a strong influence on the genesis of the lithological rhythm, and that any primary rhythm underlying the diagenetically mature rhythm is less clear than generally assumed.     

Thoracican cirripedes (Crustacea) from the Hauterivian (Lower Cretaceous) of Hannover,northern Germany

Diverse thoracican cirripedes from the Hauterivian of the Hannover district of northern Germany are described, including seven species, belonging to five genera. Of these, a new genus belonging to the Scalpellidae, Jaegerscalpellum, includes one Hauterivian species, J. elegans sp. nov., an Aptian species, J. comptum (Withers, 1910) and an Albian species, J. politum (Darwin, 1851) are also referred to it. A new Cretiscalpellum, C. mutterlosei sp. nov. is described from the Hauterivian, and C. matrioni sp. nov. is described from the Middle Albian of France. The oldest record of the Unilatera Gale, 2018, Pedupycnolepas pulcher sp. nov. is described from the Hauterivian; this displays typical shell structure of the group, retained by living Verrucidae. Finally, four species of Zeugmatolepadidae, subfamily Martillepadinae, are recorded from the Hauterivian, including Martillepas hausmanni (Koch and Dunker, 1836), M. decoratus sp. nov., M. auriculum sp. nov. and Etcheslaepas borealis (Collins, 1990). The Hauterivian fauna from Hannover shows affinities both with Late Jurassic and later Cretaceous (Aptian-Cenomanian) forms, and includes the earliest scalpellids, unilateran (Pedupycnolepas) and Cretiscalpellum species known. It constrains the age of the Cretaceous cirripede evolutionary radiation to the earliest Cretaceous.     

Long-distance correlations by sequence stratigraphy and cyclostratigraphy: examples and implications (Oxfordian from the Swiss Jura, Spain, and Normandy)

The Oxfordian sedimentary successions studied in the Swiss Jura, in Normandy, and in the Soria and Cazorla regions of Spain display complex facies evolution and stacking patterns. Based on biostratigraphy and absolute age dating, it is suggested that the shallow-water depositional settings in the Jura, Normandy, and the Soria region as well as the deeper-water environments in the Cazorla region, recorded climatic and sea-level fluctuations in the Milankovitch frequency band. Beds and bedsets corresponding to 20-, 100-, and 400-ka cyclicities can be identified. Facies evolution inside such small-scale sequences and also in the larger sequences of million-year scale is interpreted in terms of sequence stratigraphy. Superposition of high-frequency cyclicity on a longer-term sea-level trend led to multiplication of diagnostic surfaces: sequence-boundary and maximum-flooding zones in the large-scale sequences can thus be defined. These zones are correlated between closely spaced sections, but also from the Swiss Jura to Normandy and to Spain. The narrow time lines given by Milankovitch cyclicity then allow comparison of facies evolution in the different regions on a scale of 100 ka or less. By filtering out local effects of differential subsidence and sediment supply, a long-term sea-level curve valid for the northwestern margin of the Tethys ocean can be reconstructed for the Middle to Late Oxfordian. Differential subsidence is implied from varying thicknesses of the sequences as well as from the distribution of siliciclastics which have been channelized through depressions. Tilted blocks, reduced sedimentation, or increased input of siliciclastics appearing at the same time in all study areas point to a widespread regional tectonic event. Distribution through the sequences of climate-dependent facies components such as corals, ooids, palynomorphs, and siliciclastics indicates that climate changes were dependent on atmospheric circulation patterns and thus on paleolatitude. Rainy periods and related increase of siliciclastics in the Swiss Jura were more abundant during low sea-level stands, whereas in the Soria region they coincided with sea-level highs. Through the combination of high-resolution sequence stratigraphy and cyclostratigraphy, and supported by biostratigraphy and absolute dating, it becomes possible to analyze paleoenvironmental changes in a very narrow time framework.     

Chlorine transfer out of a very low permeability clay sequence (Paris Basin, France): Cl and Cl evidence

The marine Callovo-Oxfordian clay formation is found at a depth around 410m in the eastern part of the Paris Basin (France). It is a very low permeability formation investigated by the French agency for nuclear waste management (ANDRA) to study the feasibility of a radioactive waste disposal. Examining hydrogeological and geochemical characteristics of the clay sequence may test confinement properties of this formation. This study uses chlorine isotopes to investigate long-term transport processes which may carry chemical elements out of the clay layer to the surrounding rocks. Detailed chlorine concentration and δ³⁷Cl depth profiles are examined using pore waters and aquifer waters sampled in the clay formation and its surrounding aquifers (the Dogger at the bottom and the Oxfordian/Kimmeridgian/Tithonian unit at the top). They are discussed in terms of chlorine budget and hydrogeological processes.Clay pore waters and aquifer waters show strong chlorine concentration depletion (<3000 mg/L) relative to the original marine interstitial water (∼19000 mg/L). This probably results from an early dilution by meteoric water in limestones (as also indicated by oxygen and hydrogen isotopes).A steep Cl-concentration gradient from the Dogger at ∼500m in depth (∼2500 mg/L) to the Oxfordian/Kimmeridgian/Tithonian aquifer near the surface (≈ 10 mg/L) is associated to a ‘v-shaped’ profile of the δ³⁷Cl values. Modelling Cl transport shows that a hydrodynamic dispersion process explains Cl concentration and δ³⁷Cl profiles in Oxfordian Limestone. This process implies a mean upward flux of chloride in the 2.6 10⁻⁸-8.2 10⁻⁸ mole/m²/yr range from the clay formation towards upper limestones where a westward advective flow disperses the chloride. The modelling and knowledge of underground water transfer suggest a maximum effective Cl-hydrodynamic vertical dispersion coefficient (= vertical Cl-transport coefficient) of ∼7.6 10⁻¹⁰ m²/s.Chlorine transfer through the Callovo-Oxfordian clay, since deposition 160My ago, can be mainly described by the interplay of an early dilution and a later hydrodynamic dispersion event which has apparently erased most of the isotopic effects of diagenetic events (such as early diffusion, ion filtration etc.).     

Garavellite, FeSbBiS4, from the Caspari mine, North Rhine-Westphalia, Germany: composition, physical properties and determination of the crystal structure

Summary Garavellite, FeSbBiS₄, was found in a sample of the mineralogical collection of the Natural History Museum of the University of Florence. The sample is from the Cu–Fe deposit of Caspari, Saverland, North Rhine-Westphalia, Germany. Garavellite occurs as very rare, elongated prismatic crystals up to 100 μm in length, spatially associated with large berthierite crystals, bismuthinite, chalcopyrite, and siderite. It does not contain inclusions of or intergrowths with other minerals. Macroscopically garavellite is grey in colour and shows a grey-black streak. The Vickers hardness (VHN₅₀) is 206 kg/mm². In plane-polarized incident light garavellite is grey in colour, with distinct bireflectance. Reflectance percentages for R_min and R_max are 33.8, 41.8 (471.1 nm), 33.3, 40.9 (548.3 nm), 32.7, 39.5 (586.6 nm), and 32.4, 38.8 (652.3 nm), respectively. Garavellite is orthorhombic, space group Pnam, with the following unit-cell parameters: a = 11.413(1) ?, b = 14.164(1) ?, c = 3.759(1) ?, V = 607.7(2) ?³, and Z = 4. Electron microprobe analyses give the chemical formula Fe_0.94Cu_0.01As_0.01Sb_1.02Bi_0.99S_4.03. The crystal structure has been solved and refined to R = 2.38%. It consists of FeS₆ octahedra forming edge-sharing chains parallel to [001] with the Sb³⁺ and Bi³⁺ cations inserted between the chains. The crystal-chemical relationships with berthierite as well as the different lone-pair stereochemical activities of antimony and bismuth in the two structures are discussed.     

Shock deformation of quartz influenced by grain size and shock direction: Observations on quartz-plagioclase rocks from the basement of the Ries Crater,Germany

Planar elements in quartz, produced by shock induced plastic deformation, have been investigated in four quartz-plagioclase veins contained in an amphibolite from the crystalline basement of the Ries Crater from the drill hole Nördlingen 1973.The crystallographic orientation of planar elements in quartz grains is similar in all four rocks ({10¯13} predominant, {0001} less frequent, {10¯12} and others still rarer), indicating an average shock pressure in the range between 150 and 200 kbar.The spatial density of planar elements as measured by the number of systems per shocked grain, the number of individual elements per shocked grain, or as ratio shocked: unshocked grains increases with increasing grain size. This grain size effect is supposed to be primarily a consequence of the heterogeneity of the stress field which produced a random distribution of local stress maxima and locally restricted areas of plastic quartz deformation in the rock. The probability that planar elements develop within one individual grain increases, therefore, with increasing grain size.In one leucosome in which the quartz grains were randomly oriented planar elements parallel to {10¯13} cluster in a stereographic projection within one belt. It is supposed that the pole of this belt indicates the direction in which the shock front passed through the rock.     

Mineralogy, composition and PGM of chromitites from Pefki, Pindos ophiolite complex (NW Greece): evidence for progressively elevated fAs conditions in the upper mantle sequence

The Pindos ophiolite complex, located in the northwestern part of continental Greece, hosts various chromite deposits of both metallurgical (high-Cr) and refractory (high-Al) type. The Pefki chromitites are banded and sub-concordant to the surrounding serpentinized dunites. The Cr# [Cr/(Cr?+?Al)] of magnesiochromite varies between 0.75 and 0.79. The total PGE grade ranges from 105.9 up to 300.0?ppb. IPGE are higher than PPGE, typical of mantle hosted ophiolitic chromitites. The PGM assemblage in chromitites comprises anduoite, ruarsite, laurite, irarsite, sperrylite, hollingworthite, Os-Ru-Ir alloys including osmium and rutheniridosmine, Ru-bearing oxides, braggite, paolovite, platarsite, cooperite, vysotskite, and palladodymite. Iridarsenite and omeiite were also observed as exsolutions in other PGM. Rare electrum and native Ag are recovered in concentrates. This PGM assemblage is of great petrogenetic importance because it is significantly different from that commonly observed in podiform mantle-hosted and banded crustal-hosted ophiolitic chromitites. PGE chalcogenides of As and S are primary, and possibly crystallized directly from a progressively enriched in As boninitic melt before or during magnesiochromite precipitation. The presence of Ru-bearing oxides implies simultaneous desulfurization and dearsenication processes. Chemically zoned laurite and composite paolovite-electrum intergrowths are indicative of the relatively high mobility of certain PGE at low temperatures under locally oxidizing conditions. The PGM assemblage and chemistry, in conjunction with geological and petrologic data of the studied chromitites, indicate that it is characteristic of chromitites found within or close to the petrologic Moho. Furthermore, the strikingly different PGM assemblages between the high-Cr chromitites within the Pindos massif is suggestive of non-homogeneous group of ores.