Multi-stage Ag–Bi–Co–Ni–U and Cu–Bi vein mineralization at Wittichen,Schwarzwald, SW Germany: geological setting,ore mineralogy,and fluid evolution

The Wittichen Co–Ag–Bi–U mining area (Schwarzwald ore district, SW Germany) hosts several unconformity-related vein-type mineralizations within Variscan leucogranite and Permian to Triassic redbeds. The multistage mineralization formed at the intersection of two fault systems in the last 250 Ma. A Permo-Triassic ore stage I with minor U–Bi–quartz–fluorite mineralization is followed by a Jurassic to Cretaceous ore stage II with the main Ag and Co mineralization consisting of several generations of gangue minerals that host the sub-stages of U–Bi, Bi–Ag, Ni–As–Bi and Co–As–Bi. Important ore minerals are native elements, Co and Ni arsenides, and pitchblende; sulphides are absent. The Miocene ore stage III comprises barite with the Cu–Bi sulfosalts emplectite, wittichenite and aikinite, and the sulphides anilite and djurleite besides native Bi, chalcopyrite, sphalerite, galena and tennantite. The mineral-forming fluid system changed from low salinity (<5 wt.% NaCl) at high temperature (around 300°C) in Permian to highly saline (around 25 wt.% NaCl + CaCl₂) at lower temperatures (50–150°C) in Triassic to Cretaceous times. Thermodynamic calculations and comparison with similar mineralizations worldwide show that the Mesozoic ore-forming fluid was alkaline with redox conditions above the hematite–magnetite buffer. We suggest that the precipitation mechanism for native elements, pitchblende and arsenides is a decrease in pH during fluid mixing processes. REE patterns in fluorite and the occurrence of Bi in all stages suggest a granitic source of some ore-forming elements, whereas, e.g. Ag, Co and Ni probably have been leached from the redbeds. The greater importance of Cu and isotope data indicates that the Miocene ore stage III is more influenced by fluids from the overlying redbeds and limestones than the earlier mineralization stages.     

Geochronology of a composite granitoid pluton: a high-precision ID-TIMS U–Pb zircon study of the Variscan Karkonosze Granite (SW Poland)

Resolving time differences between successive magmatic pulses in composite granitoid plutons is often a difficult task. High-precision CA-ID-TIMS zircon ages obtained from such a pluton, the Variscan Karkonosze Granite (NE part of the Bohemian Massif), provide evidence that the crystallization of the two main granite facies, porphyritic and equigranular, happened between 312.5 ± 0.3 and 312.2 ± 0.3 Ma, thus unresolvable at the 0.08–0.1 % precision level of a single ²⁰⁶Pb/²³⁸U age. This finding is at odds with most other previous dating attempts and asks for a re-evaluation of the previous scattered geochronological data. The main reasons for the scatter of the earlier dates obtained by various techniques can include analytical causes, the presence of older inheritance and disturbance of the U–Pb isotopic system, due to zircon metamictization (enhanced by high-U content in zircon) or late- and post-magmatic alteration.     

Asbestos and other fibrous minerals contained in the serpentinites of the Gimigliano-Mount Reventino Unit (Calabria,S-Italy)

Serpentinites are metamorphic rocks with good technological properties and valuable ornamental characteristics, which have been exploited since ancient times. Actually, their use is limited and monitored in several countries worldwide because they can contain fibrous asbestos minerals that may be carcinogenic. Furthermore, certain types of fibrous minerals can be confused with asbestos, and must therefore be carefully investigated. We have investigated the possible presence of the asbestos and non-asbestos fibrous phases contained in serpentinitic rocks in a meta-ophiolitic sequence from the Gimigliano-Mount Reventino Unit (Southern Italy), which had not been previously assessed. The detection and quantification of asbestos and the correct distinction of the fibrous non-asbestos minerals are very important not only from a scientific point of view, but also from a legislative one. This is especially the case for the administrative agencies that have to take decisions with regards to the implementation of public and occupational health protection measures (e.g., in road yards and quarry excavations). As a consequence of this, serpentinitic rock samples have been characterized in detail through X-ray powder diffraction, scanning and transmission electron microscopy combined with energy-dispersive spectrometry, analytical electron microscopy (SEM–EDS and TEM–AEM), differential scanning calorimetry, thermogravimetry and micro-Raman spectroscopy. Two kinds of asbestos and four kinds of non-asbestos fibrous silicates have been detected in the examined samples. In order of decreasing abundance these are polygonal serpentine, chrysotile, fibrous antigorite, tremolite, gedrite and magnesiohornblende. The size, morphology, crystallinity and chemical composition of the fibres were also discussed, in the light of the possible role these properties could play in the carcinogenic effect on human health.     

Alteration kinetics of natural stones due to sodium sulfate crystallization: can reality match experimental simulations?

Salt decay is a very destructive mechanism that affects frequently the porous building materials of our architectural heritage. Sodium sulfate is one of the salts found in this context. It usually demonstrates high destructive power in salt crystallization tests because it can crystallize not only during evaporative processes but also when the temperature drops or when the salt solution comes into contact with pre-existing crystals. However, the use of extreme temperatures or successive wet/dry cycles also makes these tests unrepresentative of reality. To verify whether sodium sulfate can also be so destructive in field conditions, we have performed crystallization tests consisting of a single isothermal drying event. Three natural stones, relevant for the architectural heritage, were used for the purpose: Bentheimer sandstone, Ançã limestone, and a current Portuguese limestone of low porosity. The stones gave rise to distinct salt decay patterns: efflorescence, multilayer delamination and unilayer delamination, respectively. These morphological alterations were characterized at the micrometer scale by a new method based on what we have called the alteration kinetics curve. Such curve is calculated from topographic profiles obtained by a non-contact optical technique. The multilayer and unilayer delamination decay were also monitored by time-lapse photography. The work led us to conclude that sodium sulfate can indeed be also very destructive in field-representative conditions. Moreover, it showed that the optical method can be a valuable aid in the development of more realistic salt crystallization tests.     

New Reference Materials,Analytical Procedures and Data Reduction Strategies for Sr Isotope Measurements in Geological Materials by LA-MC-ICP-MS

Laser ablation multi-collector mass spectrometry (LA-MC-ICP-MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA-MC-ICP-MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr-baseline subtraction, Rb-peak-stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE²⁺ correction for rock glasses, yields the most accurate and precise ⁸⁷Sr/⁸⁶Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve < 100 ppm 2SE repeatability ("internal") precision for ⁸⁷Sr/⁸⁶Sr measurements for materials with < 1000 μg g^-1 Sr.