Dolomite characteristics and diagenetic model of the Calcari Grigi Group (Asiago Plateau,Southern Alps – Italy): an example of multiphase dolomitization

A multidisciplinary study, conducted over the carbonate platform deposits of the Liassic Calcari Grigi Group (Southern Alps), highlighted how the use of outcrop analogues can contribute to better define the distribution of dolomitic bodies related to fault networks, to characterize the petrophysical properties of the dolomitic sequence and unravel a complex diagenetic history. This study was carried out in the Asiago Plateau (southernmost part of the eastern Southern Alps, northern Italy) which provides excellent outcrops of the Jurassic Calcari Grigi Group. The dolomitization of the Jurassic sequence is variable in terms of stratigraphic extension and geographic distribution. In the studied localities the dolomitization is generally limited to the Mount Zugna Formation and is characterized by an undulatory front, with ‘sub‐vertical dolomitic chimneys’ along the major faults. Within this unit, and often associated with faults, stacked high‐porosity and permeability bed‐parallel dolomitic bodies are developed that show excellent petrophysical properties. The dolomitic intervals are characterized by pervasive unimodal and patchy polymodal dolomite crystals. Thin section, cathodoluminescence, isotopic and fluid inclusion analyses were used to constrain the paragenetic evolution of the sequence which is similar in all the studied localities. The first dolomitization stage is marked by zoned dolomite crystals with a dull luminescent core. The porosity is thought to have increased after this stage, with dark blue luminescent dolomite accompanied by the corrosion of older crystals. The appearance of saddle dolomite marks the onset of the porosity reduction stage, ending with the infilling of vugs and the remaining open pores with calcite cement. The diagenetic evolution locally stopped at the saddle dolomite stage with the complete occlusion of the remaining pores. Paragenetic and fluid‐inclusion data suggest an evolutionary trend of increasing temperatures and decreasing salinity toward brackish fluids responsible for dolomite and calcite precipitation. The integration of the available data seem to indicate that the diagenetic evolution of the study area is related to: (i) the interplay between evolving fluids (from marine to brackish); (ii) the burial of the sequence (increasing temperature); and (iii) the evolution of the hydrogeological system (fault and fracture network, fluid mixing). This complex paragenetic evolution is strongly linked to the evolution of the porosity framework that evolved from a good, widespread network in the early stages of the burial history to a confined system in the later stages due to reduction of porosity by the deposition of late calcite and dolomite cements.     

Groundwater dolocretes from the Upper Triassic of the Paris Basin, France: a case study of an arid, continental diagenetic facies

Thick dolomite-cemented horizons (dolocretes) occur within a fluvial sandstone-mudstone sequence of Late Triassic age in the western part of the Paris Basin, France. Two types of dolomites can be distinguished: (a) nodular dolomitic beds less than a few metres thick, which formed within mottled overbank siltstones and mudstones; and (b) massive dolomite up to 16 m thick, which occurs in coarse grained channel sandstones and conglomerates. The majority of the dolomite consists of a finely crystalline groundmass of dolomicrospar and, less commonly, dolomicrite. Glaebules, irregular spar-filled cracks, spheroidal dolomite, silicification and vuggy porosity are locally abundant in the massive dolomite. In contrast, biologically induced micromorphological features such as rhizocretions and alveolar-septal fabrics were observed in the thin, nodular dolomite beds. The dolomite is near stoichiometric, well ordered and non-ferroan. 18O values range from ?7·7 to ?0·4%o PDB and 18O values range from ?5·1 to + 1·8%0 PDB and no obvious difference in the stable isotopic composition between both types of dolomites was observed. Sr isotope ratios range from 0·7101 to 0·7126 and are invariably higher than the contemporary Triassic sea water. A vadose—pedogenic origin for the thin dolocrete layers is indicated by the occurrence of rhizocretions and other biological structures. Several features, however, argue against a pedogenic origin for the massive carbonates, most notably the absence of biologically induced structures, the occurrence in coarse grained channel (and not overbank) deposits, and the great thickness. These units are thus interpreted as groundwater in origin. Phreatic calcretes of Quaternary age, widespread in inland Australia, are regarded as a modern analogue for the Triassic Paris Basin dolocretes. Petrographic observations argue in favour of primary (proto)dolomite precipitation, although early diagenetic replacement of calcite by (proto)dolomite cannot be ruled out. Strontium and carbon isotope data of early diagenetic dolocrete cements and oxygen isotope data of early diagenetic silica indicate an entirely non-marine, continental origin for the groundwaters. The poorly ordered and non-stoichiometric protodolomite probably underwent stabilization upon further burial resulting in a near-stoichiometric, well ordered dolomite that clearly lacks evidence for pervasive recrystallization.     

Evidence of ''Mid-Pliocene (˜3 Ma) global warmth'' in the eastern Arctic Ocean and implications for the Svalbard/Barents Sea ice sheet during the late Pliocene and early Pleistocene (˜3 – 1.7 Ma)

A multiproxy analysis of Hole 911A (Ocean Drilling Program (ODP) Leg 151) drilled on the Yermak Plateau (eastern Arctic Ocean) is used to investigate the behaviour of the Svalbard/Barents Sea ice sheet (SBIS) during late Pliocene and early Pleistocene (~3.0-1.7 Ma) climate changes. Contemporary with the 'Mid-Pliocene (~3 Ma) global warmth' (MPGW), a warmer period lasting ~300 kyr with seasonally ice-free conditions in the marginal eastern Arctic Ocean is assumed to be an important regional moisture source, and possibly one decisive trigger for intensification of the Northern Hemisphere glaciation in the Svalbard/Barents Sea area at ~2.7 Ma. An abrupt pulse of ice-rafted debris (IRD) to the Yermak Plateau at ~2.7 Ma reflects distinct melting of sediment-laden icebergs derived from the SBIS and may indicate the protruding advance of the ice sheet onto the outer shelf. Spectral analysis of the total organic carbon (TOC) record being predominantly of terrigenous/fossil-reworked origin indicates SBIS and possibly Scandinavian Ice Sheet response to incoming solar radiation at obliquity and precession periodicities. The strong variance in frequencies near the 41 kyr obliquity cycle between 2.7 and 1.7 Ma indicates, for the first time in the Arctic Ocean, a close relationship of SBIS growth and decay patterns to the Earth's orbital obliquity amplitudes, which dominated global ice volume variations during late Pliocene/early Pleistocene climate changes.     

Origin and palaeoenvironmental significance of lamination in stalagmites from Katerloch Cave,Austria

The origin and environmental dependencies of lamination in stalagmites from Katerloch, common in speleothems from other cave sites, are examined in detail. Petrographic observations and chemical analyses (including isotopes) of stalagmites and modern calcite were combined with multi‐annual cave monitoring. All investigated stalagmites are composed of low‐Mg calcite and show white, porous laminae and typically thinner, translucent dense laminae. The binary lamination pattern results from changes in the calcite fabric: white, porous laminae are characterized by a high porosity and abundant fluid inclusions and also by enhanced vertical growth and thinning towards the flanks. Translucent, dense laminae exhibit a compact fabric and constant thickness of individual growth layers. U‐Th dating supports an annual origin of the lamination and the seasonally changing intensity of cave ventilation provides a robust explanation for the observed relationships between lamination, stable C isotopic compositions and trace elements (Mg, Sr and Ba). The seasonally variable air exchange, driven by temperature contrasts between the cave interior and outside atmosphere, modulates the rate and amount of CO₂ degassing from the drip water and affects the hydrochemistry and consequently the fabric of the precipitating calcite. Although cave air composition and drip rate are both major variables in controlling CO₂ degassing from the drip water, the seasonally changing ventilation in Katerloch exerts the primary control and the results suggest a secondary (amplifying/attenuating) influence of the drip rate. Drip rate, however, might be the controlling parameter for lamina development at cave sites experiencing only small seasonal cave air exchange. Importantly, the seasonally variable composition of drip water does not reflect the seasonal cycle of processes in the soil zone, but results from exchange with the cave atmosphere. The alternating porous and dense calcite fabric is the expression of a variable degree of lateral coalescence of smaller crystallites forming large columnar crystals. The white, porous laminae represent partial coalescence and form during the warm season: low calcite δ¹³C values are linked to low δ¹³C values of cave air and drip water during that time. This observation corresponds to times of reduced cave ventilation, high pCO₂ of cave air, low drip water pH, lower calcite supersaturation and typically high drip rates. In contrast, the translucent, dense laminae represent more or less complete lateral coalescence (inclusion‐free) during the cold season (high calcite, drip water and cave air δ¹³C values), i.e. times of enhanced cave ventilation, low cave air pCO₂, increased drip water pH, relatively high calcite supersaturation and typically low drip rates. In essence, the relative development of the two lamina types reflects changes in the seasonality of external air temperature and precipitation, with a strong control of the winter air temperature on the intensity of cave‐air exchange. Thick translucent, dense laminae are favoured by long, cold and wet winters and such conditions may be related closely to the North Atlantic Oscillation mode (weak westerlies) and enhanced Mediterranean cyclone activity during the cold season. Studies of speleothem lamination can thus help to better understand (and quantify) the role of seasonality changes, for example, during rapid climate events.     

Chlorine partitioning in the stratosphere based on in situ measurements

Balloon‐borne cryogenic air sampler experiments have been conducted from a tropical (Hyderabad, 17.5°N) and a midlatitude (GAP, southern France, 44°N) station since 1987 in the altitude range of about 8‐35 km. Air samples are analysed at the Max Planck Institute for Aeronomy (MPAE) and Physical Research Laboratory (PRL) using various gas chromatographic techniques to obtain the vertical distributions of several halogenated source gases and long‐lived dynamical tracers. These observations are used to determine the stratospheric partitioning of the chlorine species into their organic and inorganic forms for the altitude range of 20 to 35 km. Distributions of inorganic chlorine indicate increase in their abundances with altitude, latitude and time. Mixing ratio correlations of organic and inorganic chlorine with N₂O have been obtained which also suggest that the rate of increase in inorganic halogens component in the stratosphere is larger than the increase rate of total organic halogen. This supports previous assessments that halogen‐induced ozone depletion will continue to be observed for a few more years, despite the decrease of halocarbon loading into the stratosphere since 1994.     

Abiogenic silica layers within a fluvio-lacustrine succession,Bolzano Volcanic Complex,northern Italy: a Permian analogue for Magadi-type cherts?

Thin layers of chert occur within a fluvio-lacustrine succession sandwiched between acidic volcanic rocks of the Lower Permian Bolzano Volcanic Complex in northern Italy. These cherts are interpreted as analogues to Magadi-type abiogenic chert known from modern volcanic lake settings. Soft-sediment deformation features, shrinkage cracks, and well-preserved palynomorphs document very early diagenetic silica precipitation, volume loss by dehydration, and consolidation prior to mechanical compaction of the sediment. Transformation to quartz and concomitant (re)crystallization resulted in a variety of silica textures, dominated by microflamboyant quartz. The oxygen isotopic composition of chert samples ranges from +25·4 to +29·0‰ and is negatively correlated with crystal size and ordering.