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.     

Tracer studies on the updrift margin of a complex inlet system

Three sediment transport studies using tracers were performed at Ancão Inlet (southern Portugal). The objectives of the experiments were to understand the sediment transport pathways and to determine their magnitudes on the updrift margin of an inlet. In order to apply the traditionally used Space Integration Methodology to the tracer experiments, adaptations were required. The study area was divided into four morphologically defined sectors and this was found to be a key factor for the applicability of tracers in a complex area. The four sectors are as follows: sector A is the straight part of the updrift beach; sector B is the upper area of the swash platform; sector C is the lower area of the swash platform; and sector D represents the inner parts of the inlet margin. The integrated analysis of all collected data (forcing mechanisms, tracer distribution and topographic evolution) led to the determination of the sediment pathways. A semi-quantitative conceptual model was developed in order to explain the sediment transport pathways and magnitudes that a known mass of sediment would follow after arriving at the swash platform. It was found that the areas with the largest sediment accumulation were sectors B and C, while almost no sediment was retained in sector D, which experienced significant erosion. According to the model, 53% of the initial mass of sediments remain in the system after two tidal cycles. It is hypothesised that sediment losses are caused by sediment transport towards the ebb delta and by sediment bypassing occurring from the ebb delta to the downdrift beach through swash bar processes. The herein defined conceptual model represents a useful tool that could be applied to other tidal inlets under similar conditions, facilitating sediment budget studies around tidal inlets.     

Mineralogy of HED Meteorites Using the Modified Gaussian Model

The correlation between specific meteorites and asteroids is a long-standing problem. The best-known correlation seems to be the HED–Vesta, although several problems still remain to be solved. We report the spectral reflectance analysis (0.4–2.5 μm) of a set of HED meteorites, taken from the RELAB database and three V-type asteroids, taken from MIT-UH-IRTF Joint Campaign for NEO Reconnaissance. We used the Modified Gaussian Model to fit the spectra to a series of overlapping, modified Gaussian absorptions. The fitted individual bands are validated against established laboratory calibrations. With spectral resolution extending to the near-infrared, we are able to resolve the presence of both high-calcium pyroxene (HCP) and low-calcium pyroxene (LCP) and, thus, use the HCP/(HCP + LCP) ratios to remotely trace igneous processing on the parent asteroids. A search of this mineral provides a useful probe of differentiation. The high HCP/(HCP + LCP) ratios found require extensive differentiation of these asteroids and/or their primordial parent body. The degree of melting obtained for the eucrites, using the former ratio, is comparable with that obtained for all V-type asteroids here analyzed, suggesting a comparable geologic history.     

Carbon and oxygen isotopes of Maastrichtian–Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ¹³C, +2‰ δ¹⁸O). The top of the member reveals an isotopic shift of δ¹³C (−5‰) and δ¹⁸O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ¹³C, −1‰ δ¹⁸O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.     

Localized algal blooms induced by river inflows in a canyon type reservoir

The local response of the phytoplankton community to river inflow processes was investigated with modeling and field analyses in a long and narrow, stratified reservoir in mid-summer. The river water had high concentrations of phosphorus and nitrogen (ammonium and nitrate) and temperature had large variations at diurnal scales. As a consequence of the large variation in river temperature, the level of neutral buoyancy (the depth where the river water spreads laterally in the reservoir) oscillated between the surface (overflows) during the day, and the depth of the metalimnion (interflows) during the night. The reservoir remained strongly stratified, which favoured the presence of cyanobacteria. It is shown that under these conditions, nutrient-rich river water injected during overflows into the surface layers promoted the occurrence of localized algal blooms in the zones where the overflow mixed with the quiescent water of the reservoir. A series of hydrodynamic simulations of the reservoir were conducted both with synthetic and realistic forcing to assess the importance of river temperatures and wind-driven hydrodynamics for algal blooms. The simulations confirmed that the river inflow was the main forcing mechanism generating the localized bloom.     

Chemical evolution of mid-ocean ridge hot springs

Chemical analyses yielding elemental concentrations of major and minor elements of four hot springs on the East Pacific Rise at 21°N and 10 hot springs from the southern trough of the Guaymas Basin, Gulf of California provide a basis for thermodynamic modeling of conductive cooling of the hydrothermal endmembers, mixing of the hydrothermal endmember with seawater, and reaction of an EPR-type fluid with sediment of bulk chemical composition corresponding to unaltered sediment from DSDP hole 477 in the Guaymas Basin. Results of the calculations indicate that conductive cooling of endmember fluids within closed chimneys and conduits accounts for the solution composition of one vent on the East Pacific Rise and several vents in Guaymas Basin. Mixing of the hydrothermal fluids with seawater yields a prediction of mineral assemblages closely approximating those observed in samples of chimneys from the East Pacific Rise and drill cores in Guaymas Basin. The hypothesis that Guaymas Basin hydrothermal fluids result from interaction of an EPR-type fluid with sediment cover in Guaymas Basin is supported by calculations which predict an increase in pH to a value similar to Guaymas Basin fluids, an order-of-magnitude decrease in metal concentrations, and an excellent agreement between predicted mineral assemblages as a function of extent of interaction with sediment, and observed mineral assemblage distribution with depth.     

Geochemical comparison of waters and stream sediments close to abandoned Sb-Au and As-Au mining areas,northern Portugal

Waters from abandoned Sb-Au mining areas have higher Sb (up to 2138 μg L⁻¹), As (up to 1252 μg L⁻¹) and lower Al, Zn, Li, Ni and Co concentrations than those of waters from the As-Au mining area of Banjas, which only contain up to 64 μg L⁻¹ As. In general, Sb occurs mainly as SbO₃⁻ and As H₂AsO₄⁻. In general, waters from old Sb-Au mining areas are contaminated in Sb, As, Al, Fe, Cd, Mn, Ni and NO₂⁻, whereas those from the abandoned As-Au mining area are contaminated in Al, Fe, Mn, Ni, Cd and rarely in NO₂⁻. Waters from the latter area, immediately downstream of mine dumps are also contaminated in As. In stream sediments from Sb-Au and As-Au mining areas, Sb (up to 5488 mg kg⁻¹) and As (up to 235 mg kg⁻¹) show a similar behaviour and are mainly associated with the residual fraction. In most stream sediments, the As and Sb are not associated with the oxidizable fraction, while Fe is associated with organic matter, indicating that sulphides (mainly arsenopyrite and pyrite) and sulphosalts containing those metalloids and metal are weathered. Arsenic and Sb are mainly associated with clay minerals (chlorite and mica; vermiculite in stream sediments from old Sb-Au mining areas) and probably also with insoluble Sb phases of stream sediments. In the most contaminated stream sediments, metalloids are also associated with Fe phases (hematite and goethite, and also lepidocrocite in stream sediments from Banjas). Moreover, the most contaminated stream sediments correspond to the most contaminated waters, reflecting the limited capacity of stream sediments to retain metals and metalloids.     

Magnetic properties of surface sediments as proxies of recent anthropogenic pollution in the Anllóns riverbed (NW Spain)

A study of surface sediments from the Anllóns riverbed (northwestern Spain) was conducted to assess the use of their magnetic properties as proxies of recent trace element contamination (i.e., As, Zn, Pb, Cr, Ni and Cu). Thermomagnetic curves, hysteresis parameters, specific magnetic susceptibility χ, frequency-dependent magnetic susceptibility κ _FD%, magnetic remanence and saturation isothermal remanent magnetization ratios (i.e., S and SIRM/χ) reveal the presence of mostly fine-grained magnetite and maghemite in these samples. The Tomlinson Pollution Load Index (PLI), as well as the magnetic parameters χ, κ _FD%, SIRM/χ and S-ratios, vary more or less in agreement to each other when they are sequentially arranged throughout a 30-km-long transect that goes from the town of Carballo to the river mouth in Ponteceso. From that profile, it is possible to identify an anomaly of χ that lies between two small peaks of the PLI and seems to define a contaminated area probably linked to a diffuse low-impact source of pollution. There is also a conspicuous peak of the PLI that is likely associated to a nearby gold mine. The variations of the κ _FD%’s along the transect are the ones that best reflect the changes in the PLI values, regardless of the level of contamination. This result suggests that adsorption is the main mechanism of trace elements removal by Fe oxides in these samples. Direct signal analyses, used to decompose the isothermal remanent magnetization curves, reveal the presence of four magnetic fractions, with varying relative concentrations all over the profile, namely single-domain magnetite, close to the superparamagnetic threshold (SD/SP) and/or maghemite (\(\log B_{1/2}\) ca 1.2), single-domain magnetite (\(\log B_{1/2}\) ca 2), hematite (\(\log B_{1/2}\) ca 2.5) and goethite (\(\log B_{1/2}\) ca 3.5). Integrating all the available information, it was sketched out a likely sequence of events that included magnetic minerals neoformation in parent soils, their subsequent chemical transformations and the contamination episodes that affected the region.