Rafael Ferreiro Mählmann

The pioneer work of Bernard Kübler and Martin Frey in very low-grade metamorphic terranes: paleo-geothermal potential of variation in Kübler-Index/organic matter reflectance correlations. A review

Low-temperature metamorphic petrology occupies the P–T field between sedimentary and metamorphic petrology. Two important pillars of low-temperature metamorphism are coal petrology and clay mineralogy. When low temperature petrology was established bridging a hiatus between the two classical geological disciplines of sedimentary geology and metamorphic petrology, geologists faced a need for the usage of different terminology tenets. Martin Frey and Bernard Kübler were two pioneers in low-grade metamorphic petrology. They focused their research on clarifying the relationships of clay mineralogy and organic petrology to metamorphic pressure (P) and temperature (T) conditions. The ultimate aim of M. Frey and B. Kübler was to establish a correlation between clay indices and organic parameters for different geodynamic setting and therefore for various pressure–temperature (P–T) conditions occurring in low grade metamorphic terranes. For this purpose, a special attention was addressed to the correlation between the Kübler-Index (KI) and vitrinite reflectance (VR). All these efforts are dedicated to estimate the P–T conditions and thus to gain insight into the geodynamic evolution of low-grade metamorphic terranes. B. Kübler and M. Frey honored here concentrated their studies to the Helvetic Central Alps area. The very low-grade Helvetic domain is therefore of basic interest of this paper. Ensuing the extensive compilation of data from the Helvetic domain, a reinterpretation of Kübler and Frey’s research is presented in the light of last decade’s scientific progress. A comprehensive dataset available enables to discriminate many factors influencing the Kübler-Index and organic-matter reflectance alongside to time, temperature and pressure. The correlation is restricted to the KI and organic matter reflectance (mostly VR) because most of the studies used both methods. Organic matter reflectance (OMR) includes data from vitrinite reflectance and bituminite reflectance measurements. Geodynamics has important control on the KI/VR (OMR) correlation. Tectonic units having a similar geodynamic evolution are featured by the comparable KI/OMR trends, related to the particular paleo-geothermal conditions. Obviously the KI/OMR correlations provide a mean to characterise geothermal gradients and metamorphic very-low-grade pressure–temperature conditions. In terranes where high deformations rates are reported, exceeding the high anchizone conditions, strain promotes the kinetic effects of temperature and pressure on the KI versus OMR ratio.

Vitrinite alteration rate as a function of temperature, time, starting material, aqueous fluid pressure and oxygen fugacity—Laboratory corroboration of prior work

Abstract Kinetic investigations were performed on disaggregated samples of lignite, mainly pure huminite fragments composed of angiosperm and gymnosperm xylite. We conducted experiments at 2.0 kbar aqueous fluid ( = total) pressure, and at contrasting oxygen fugacity ranges defined by the hematite-magnetite (HM) and magnetite + quartz-fay alite (FMQ) buffers. Initial heating rates were 4–8°C/min; individual samples were held at 200, 250, 300 and 400°C for 5–204 days. After prolonged heating, mean vitrinite reflectance (VR) R r values at these temperatures are 0.54, 0.74, 1.10 and 2.25% R r , respectively. The experimentally determined alteration rate is defined by the expression % R r = K 0 t 0.076 , where K 0 is a function of temperature, and t is in days. The overall activation energy describing the kinetics of complex devolatilization reactions responsible for increased VR measured in our laboratory experiments is 21.8 ± 0.3 kJ mol -1 . Combined with earlier rate studies by Dalla Torre et al. in 1997, we conclude that the rate of vitrinite maturation apparently is unaffected by oxidation state and nature of the starting lignitic material (conifer or hardwood). Elevated total aqueous fluid pressure very slightly retards the rate of VR increase. Non-systematic trends are observed for the resinite-exudatinite-bituminite present in the run products. Our new experimental data confirm that VR is chiefly a function of temperature and time. In support of earlier field, theoretical and laboratory studies, the crucial variable that determines VR over geologic time intervals is host-rock temperature.

Metamorphic evolution of a very low- to low-grade metamorphic core complex (Danubian window) in the South Carpathians

Abstract The Danubian window, characterized by diagenetic to low greenschist facies conditions at a high thermal gradient, is evidently of great interest for methodological studies, because high metamorphic thermal gradient conditions during low grade metamorphism have received little attention so far. The general increase in metamorphic grade from SW to NE in the Danubian window is indicated by mineral Parageneses studies, as well as by illite Kübler index (KI) measurements and organic matter reflectance (OMR). For the first time, this study distinguishes between metamorphic conditions related to Jurassic ocean floor, Cretaceous nappe stacking, post-collisional accommodation and syn-kinematic Getic detachment metamorphism and cooling after Oligocene exhumation. The occurrence of the prehnite–pumpellyite facies in the Severin–Cosustea units in the southeastern area is the result of Cretaceous metamorphism. Remnants of ocean floor metamorphism prevailed. The highest pressure is constrained by the upper stability limit of prehnite to be at around 4.0 kbar. The Danubian units situated within the diagenetic zone were not below 200 °C, due to epidote formation. The KI, OMR and mineral data, indicate diagenetic conditions. Assuming temperatures between >200 and <250 °C, pressures between 1.8 and 2.6 kbar were calculated using kinetic and numerical maturity models. Orogenic collisional Cretaceous peak pressure conditions of 4.0±1.0 kbar are found in the Danubian nappes not altered by a subsequent syn-detachment metamorphic overprint. Highest temperatures in chloritoid schists and epidote–hornblende-bearing mylonites have been inferred for samples from the northern border of the Danubian window (between >300 and <400 °C). Along a syn- to post-detachment retrograde pressure path, post-dating the chloritoid formation, the occurrence of clinozoisite+chlorite+quartz suggests temperatures >300 °C in the northwest, while the association andalusite+quartz and biotite+muscovite indicates temperatures between 370 and 400 °C at <3.5 kbar in the northeast. It is demonstrated that the slope of the regression lines between KI and OMR data gives valuable qualitative information about the relative magnitudes of P and T: the slope of the regression line for the Danubian window samples indicates normal heat flow conditions during nappe stacking and hyperthermal conditions during the formation of the Getic detachment. High thermal gradient conditions can easily be explained by partly isothermal decompression during the Getic detachment event, the elevation of the geotherm being caused by crustal thinning and rapid exhumation of the Danubian units. Probably, also a higher heat-flux prevailed at the end of the Getic detachment, at a time when the retrograde chloritoid decomposition reactions took place, documenting late-stage HT greenschist facies metamorphism.

Magmatic provenance and diagenesis of Miocene tuffs from the Dinaride Lake System (the Sinj Basin, Croatia)

This study presents new insights on the provenance, genesis, and post-depositional history of the Miocene pyroclastic tuffaceous layers (~18 and ~15 Ma) preserved in argillaceous sediments and interbedded within the lacustrine sedimentary succession of the Sinj Basin in central Dalmatia (Dinaride Lake System, Croatia). Analysed tuffs are classified as smectitic tuffs composed of three main lithotypes: (a) vitriclastic tuffs, (b) altered vitriclastic tuff, and (c) tuffaceous clays. The high field strength element (HFSE) contents of the tuffs, as well as the major- element chemistry of the vitric glass, suggests that parental magmas were high-K calc-alkaline trachyandesites. This is consistent with the distinctive heavy-mineral assemblages including clinopyroxene, zircon and apatite, identified in less evolved parental magmas, and biotite in more evolved ones. The regional geological data imply the placement of the parent volcano(es) outside the Dinaric Alps region, most probably in an area corresponding to the present-day southern margin of the Pannonian Basin where volcanic rock suites of analogous age and geochemistry are reported. Minor compaction and high permeability of coarse ash-sized pyroclastic material allowed for extensive in situ diagenetic clay mineral formation dominated by smectite. Following discrete smectite formation, the illite-smectite mixed-layering took place as a result of mica/illite alteration or surface illitization processes. On the basis of the very-low grade alteration of volcanic materials, it is suggested that diagenesis operated in an open hydrologic system of a lacustrine environment.

Preface: clay mineral diagenesis and very low-grade metamorphic processes. Proceedings of the 2011 Frey–Kübler symposium

In 2002, after the death of Prof. Bernard Kubler (Univ. Neuchâtel) and Prof. Martin Frey (Univ. Basel), Schmidt and Ferreiro Mahlmann published a special issue on ‘‘Diagenesis and Low-Grade Metamorphism’’ in the Swiss Bulletin of Mineralogy and Petrology. Most contributions had been presented during the Symposium on ‘‘Diagenesis and Low-Grade Metamorphism’’ at the EUG meeting 2001 in Strasbourg, France, and had been dedicated to the two most important researchers in that field. The underlying philosophy of the ‘‘Diagenesis and Low-Grade Metamorphism’’ issue, was to provide a compilation of the state of the art in very low-grade metamorphic (VLGM) and low temperature petrologic research to: (i) Geologists who wanted to use low-grade metamorphic petrologic, geochemical, clay mineralogical, isotopic and coal petrographic methods for their specific studies (e.g. in sedimentary geology, basin analysis, hydrocarbon geology, and regional metamorphic geology), (ii) Research scientists interested in methodical and process aspects of diagenesis and low-grade metamorphism, and (iii) Structural geologists with specialization in orogenic research.

EFFECTS OF CHEMICAL STRUCTURE ON THE STABILITY OF SMECTITES IN SHORT-TERM ALTERATION EXPERIMENTS

Because of their isolating capacity, smectite-rich clays have been proposed as buffer and backfill materials in high-level radioactive waste repositories. These repositories have to guarantee long-term safety for ~1 million years. Thermodynamics and kinetics of possible alteration processes of bentonite determine its long-term performance as a barrier material. Smectites in 25 different clays and bentonites were investigated in order to identify possible differences in their rates of alteration. These samples were saturated for 30 days in 1 M NaCl solution and deionized water, and then overhead rotated at speeds of 20 rpm and 60 rpm. Depending on the octahedral and interlayer composition, each of the smectites studied had specific rate of alteration, a so-called specific dissolution potential of smectite. The bentonites were classed as ‘slow-reacting bentonite’, ‘moderate-reacting bentonite’, or ‘fast-reacting bentonite’ corresponding to a relatively low (ΔP specific dissolution potential — <-5%), moderate (-5% < ΔP < -20%), or high specific dissolution potential (ΔP > -20%), respectively. The larger the amount of octahedral Fe and Mg compared to octahedral Al, the greater the specific dissolution potential. The present study found that the interlayer composition has a discernible impact on the rate of alteration. In experiments with rotation speeds of 60 rpm and a 1 M NaCl solution, Na+ was found to be the stabilizing cation in the interlayers of all the smectites. The Na-stabilizing mechanism was identified in only some of the smectites (type A) in experiments with 20 rpm (1 M NaCl solution). A second stabilization mechanism (by interlayer cations; Ca and Mg) was identified for other smectites (type B). Each bentonite has a specific rate of alteration. ‘Slow-reacting bentonite’ and clay with smectite-illite interstratifications are recommended as potential clay barriers in HLW repositories. The experimental and analytical procedures described here could be applied to potential barrier materials to identify ‘slow-reacting bentonite’.