Carbon isotope stratigraphy of Lochkovian to Eifelian limestones from the Devonian of central and southern Europe

Lower to Middle Devonian carbonates of the Prague Syncline, the Carnic Alps, the Montagne Noire, and the Cantabrian Mountains were investigated for δ¹³C_carb and δ¹³C_org. These values were measured on bulk rocks, selected components and cements. Many carbonates exhibit primary marine values, but some are altered by diagenesis. A δ¹³C curve can be presented for the latest Pridolian to Emsian time interval. Several sharp or broad positive excursions are obvious in the woschmidti-postwoschmidti, sulcatus, kitabicus, Late serotinus, and kockelianus conodont zones. The excursion at the Silurian–Devonian boundary is known worldwide and therefore considered global in nature. Some of the others are described for the first time from central and southern Europe, and their global nature has to be verified by further investigations in other regions. Most excursions relate to and/or started during major regressions whereas sea-level highstands correspond to minimal δ¹³C values. Similar relationships between sea-level changes and δ¹³C have been observed from other early Palaeozoic intervals. The transgressive Chote? (?) and Ka?ák events are marked by positive isotope excursions, this type of combination is usually observed in late Palaeozoic to Cenozoic black shale events.     

The 1974 eruption of mount etna

The 1974 Etna eruption that occurred on the lower, west part of the volcano is rather exceptional as it appeared independent of the central main vent activity. The products of this eruption also differ from those commonly emitted throughout historic times. They are almost aphyric and display an unusual order of crystallization, clinopyroxene being a near liquidus phase instead of plagioclase that is typical in all other recent lavas. The chemical composition is also slightly more basic than that of pyroclastics contemporaneously erupted by the summit Central Crater. These volcanological and petrological features are symptomatic of a separation at depth of the 1974 magma from the central conduit. The eruption itself, however, appears to have been governed by the general structural environment of the volcano. From this stand-point, there is evident interdependence between the various paroxysms of the past five years and it is suggested that the volcanic activity itself has direct relations with the regional tectonics. A model of the superficial structure of Mount Etna is given that best accounts for the observations.     

Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

The sinkhole enigma in the Alpine Foreland, Southeast Germany: Evidence of impact-induced rock liquefaction processes

Sudden collapse of the Quaternary soil to form sinkholes on the order of meters and tens of meters has been a geologic phenomenon within living memory in a localized area north of Lake Chiemsee in Southeast Germany. Failing a satisfying explanation, a relation with an undefined glaciation process has always been proposed. Excavations and geophysical measurements at three newly affected sites show underground features such as prominent sandy-gravelly intrusions and extrusions typical of rock liquefaction processes well known to occur during strong earthquakes. Since strong earthquakes can reasonably be excluded to have affected the area under discussion, it has been suggested that the observed widespread liquefaction is related with the recently proposed Holocene Chiemgau meteorite impact event. Except for one earlier proposed but unassertive relation between impact and liquefaction, the obviously direct association of both processes in the Chiemgau area emphasizes that observed paleoliquefaction features need not necessarily have originated solely from paleoseismicity but can provide a recognizable regional impact signature.     

Continual long-term monitoring of methane in wells above the Utica Shale using total dissolved gas pressure probes

Hydrogeology Journal - Monitoring of dissolved methane concentrations in groundwater is required to identify impacts from oil and gas development and to understand temporal variability under...     

Evidence for compressionally induced high subsidence rates in the Kurile Basin (Okhotsk Sea)

A combined volcanological, geochemical, paleo-oceanological, geochronological and geophysical study was undertaken on the Kurile Basin, in order to constrain the origin and evolution of this basin. Very high rates of subsidence were determined for the northeastern floor and margin of the Kurile Basin. Dredged volcanic samples from the Geophysicist Seamount, which were formed under subaerial or shallow water conditions but are presently located at depths in excess of 2300 m, were dated at 0.84±0.06 and 1.07±0.04 Ma with the laser ⁴⁰Ar/³⁹Ar single crystal method, yielding a minimum average subsidence rate of 1.6 mm/year for the northeast basin floor in the Quaternary. Trace element and Sr–Nd–Pb isotope data from the volcanic rocks show evidence for contamination within lower continental crust and/or the subcontinental lithospheric mantle, indicating that the basement presently at 6-km depth is likely to represent thinned continental crust. Average subsidence rates of 0.5–2.0 mm/year were estimated for the northeastern slope of the Kurile Basin during the Pliocene and Quaternary through the determination of the age and paleo-environment (depth) of formation of sediments from a canyon wall. Taken together, the data from the northeastern part of the Kurile Basin indicate that subsidence began in or prior to the Early Pliocene and that subsidence rates have increased in the Quaternary. Similar rates of subsidence have been obtained from published studies on the Sakhalin Shelf and Slope and from volcanoes in the rear of the Kurile Arc. The recent stress field of the Kurile Basin is inferred from the analysis of seismic activity, focal mechanism solutions and from the structure of the sedimentary cover and of the Alaid back-arc volcano. Integration of these results suggests that compression is responsible for the rapid subsidence of the Kurile Basin and that subsidence may be an important step in the transition from basin formation to its destruction. The compression of the Kurile Basin results from squeezing of the Okhotsk Plate between four major plates: the Pacific, North American, Eurasian and Amur. We predict that continued compression could lead to subduction of the Kurile Basin floor beneath Hokkaido and the Kurile Arc in the future and thus to basin closure.     

Sr-isotope stratigraphy of the Upper Jurassic of central Portugal (Lusitanian Basin) based on oyster shells

Strontium isotope stratigraphy was performed on oyster shells from the Late Jurassic of the Lusitanian Basin (central Portugal). This represents the first approach to obtain numerical ages for these strata. The new chronostratigraphic data provide a more precise age determination of several units. After a basin-wide hiatus sedimentation in the Late Jurassic is proven in the Cabo Mondego and Cabaços formations to resume as early as the Middle Oxfordian. The Alcobaça formation can be placed in the latest Late Oxfordian to Late Kimmeridgian, while data from the upper part of the Abadia Formation indicate an Early to Late Kimmeridgian age. The Farta Pao formation ranges from the latest Kimmeridgian to the latest Tithonian. The largely synchronous Sobral, Arranhó I, and Arranhó II members are overlain by the late Early to Late Tithonian Freixial Member. The brief, local carbonate incursion of the Arranhó I member marks the Kimmeridgian–Tithonian boundary. Oysters are shown once more to be suitable for strontium isotope studies. Their calcitic shells are often unaffected by diagenesis. In particular for marginal marine Jurassic and Cretaceous strata, where belemnites are usually absent, oysters may serve as a valuable tool for isotope stratigraphy.     

Monitoring above-zone temperature variations associated with CO2 and brine leakage from a storage aquifer

CO₂ injection in saline aquifers induces temperature changes owing to processes such as Joule–Thomson cooling, endothermic water vaporization, exothermic CO₂ dissolution besides the temperature discrepancy between injected and native fluids. CO₂ leaking from the injection zone, in addition to initial temperature contrast due to the geothermal gradient, undergoes similar processes, causing temperature changes in the above zone. Numerical simulation tools were used to evaluate temperature changes associated with CO₂ leakage from the storage aquifer to an above-zone monitoring interval and to assess the monitorability of CO₂ leakage on the basis of temperature data. The impact of both CO₂ and brine leakage on temperature response is considered for three cases (1) a leaky well co-located with the injection well, (2) a leaky well distant from the injector, and (3) a leaky fault. A sensitivity analysis was performed to determine key operational and reservoir parameters that control the temperature signal in the above zone. Throughout the analysis injection-zone parameters remain unchanged. Significant pressure drop upon leakage causes expansion of CO₂ associated with Joule–Thomson cooling. However, brine may begin leaking before CO₂ breakthrough at the leakage pathway, causing heating in the above zone. Thus, unlike the pressure which increases in response to both CO₂ and brine leakage, the temperature signal may differentiate between the leaking fluids. In addition, the strength of the temperature signal correlates with leakage velocity unlike pressure signal whose strength depends on leakage rate. Increasing leakage conduit cross-sectional area increases leakage rate and thus increases pressure change in the above zone. However, it decreases leakage velocity, and therefore, reduces temperature cooling and signal. It is also shown that the leakage-induced temperature change covers a small area around the leakage pathway. Thus, temperature data will be most useful if collected along potential leaky wells and/or wells intersecting potential leaky faults.     

Chemical fluid transport (CFT): A window into Earth and its development

Gas phase transport according to chemical fluid transport (CFT) in Earth's crust as well as in the solar nebula is characterized by very high transport efficiency. Systematic investigations of mobilization, transport and deposition of gaseous MeX (Me = metal, X = F or Cl) compounds by solid gas equilibrium reactions are suitable to explain numerous extensive accumulations of minerals and ores. More than 40 of the considered chemical elements form volatile MeX compounds. Some elements tend to form MeF compounds, whereas others are more likely to form MeCl compounds. Silicon reacts with HF to form SiF₄ and replaces other elements to form MeF compounds at low temperature ranges. Accumulations caused by SiF₄ transport explain the formation of numerous quartz varieties and silicate minerals in Earth's crust. Iron most likely reacts with HCl to form FeCl₂ as well as FeCl₃ and explain the formation of iron or iron compounds. Thermodynamically directed transport from cool to hot areas in connection with cyclic processes increases the transport efficiency of MeX-species. Such species are SiF₄, Al₂F₆, POF₃, Cu₃Cl₃, SnCl₄, BF₃, GeF₄, GeCl₄, Ga₂Cl₆, ZrF₄, NbF₅ and TiF₄. The transport gases SiF₄ and POF₃ often react with environmental compounds forming pneumatolytic and metasomatical mineral accumulations. CFT is the “motor” of pneumatolytic and metasomatical processes.