Experimental and numerical investigations on CO2 injection and enhanced gas recovery effects in Altmark gas field (Central Germany)

The feasibility of CO₂ storage and enhanced gas recovery (EGR) effects in the mature Altmark natural gas field in Central Germany has been studied in this paper. The investigations were comprehensive and comprise the characterization of the litho- and diagenetic facies, mineral content, geochemical composition, the petrophysical properties of the reservoir rocks with respect to their potential reactivity to CO₂ as well as reservoir simulation studies to evaluate the CO₂ wellbore injectivity and displacement efficiency of the residual gas by the injected CO₂. The Rotliegend sediments of the Altmark pilot injection area exhibit distinct mineralogical, geochemical, and petrophysical features related to litho- and diagenetic facies types. The reservoir rock reactivity to CO₂ has been studied in autoclave experiments and associated effects on two-phase transport properties have been examined by means of routine and special core analysis before and after the laboratory runs. Dissolution of calcite and anhydrite during the short-term treatments leading to the enhancements of permeability and porosity as well as stabilization of the water saturation relevant for CO₂ injection have been observed. Numerical simulation of the injection process and EGR effects in a sector of the Altmark field coupled with a wellbore model revealed the possibility of injecting the CO₂ gas at temperatures as low as 10 °C and pressures around 40 bar achieving effective inflow in the reservoir without phase transition in the wellbore. The small ratio of injected CO₂ volume versus reservoir volume indicated no significant EGR effects. However, the retention and storage capacity of CO₂ will be maximized. The migration/extension of CO₂ varies as a function of heterogeneity both in the layers and in the reservoir. The investigation of CO₂ extension and pressure propagation suggested no breakthrough of CO₂ at the prospective production well during the 3-year injection period studied.     

Basin formation during the post-collisional evolution of the Eastern Alps: the example of the Lavanttal Basin

The Miocene Lavanttal Basin formed in the Eastern Alps during extrusion of crustal blocks towards the east. In contrast to basins, which formed contemporaneously along the strike-slip faults of the Noric Depression and on top of the moving blocks (Styrian Basin), little is known about the Lavanttal Basin. In this paper geophysical, sedimentological, and structural data are used to study structure and evolution of the Lavanttal Basin. The eastern margin of the 2-km-deep basin is formed by the WNW trending Koralm Fault. The geometry of the gently dipping western basin flank shows that the present-day basin is only a remnant of a former significantly larger basin. Late Early (Karpatian) and early Middle Miocene (Badenian) pull-apart phases initiated basin formation and deposition of thick fluvial (Granitztal Beds), lacustrine, and marine (Mühldorf Fm.) sediments. The Mühldorf Fm. represents the Lower Badenian cycle TB2.4. Another flooding event caused brackish environments in late Middle Miocene (Early Sarmatian) time, whereas freshwater environments existed in Late Sarmatian time. The coal-bearing Sarmatian succession is subdivided into four fourth-order sequences. The number of sequences suggests that the effect of tectonic subsidence was overruled by sea-level fluctuations during Sarmatian time. Increased relief energy caused by Early Pannonian pull-apart activity initiated deposition of thick fluvial sediments. The present-day shape of the basin is a result of young (Plio-/Pleistocene) basin inversion. In contrast to the multi-stage Lavanttal Basin, basins along the Noric Depression show a single-stage history. Similarities between the Lavanttal and Styrian basins exist in Early Badenian and Early Sarmatian times.     

The Antarctic viewpoint of the Central Paratethys: cause, timing, and duration of a deep valley incision in the Middle Miocene Alpine–Carpathian Foredeep of Lower Austria

Global, glacio-eustatic sea-level changes massively influenced the depositional history of the Central Paratethyan region. Here, we correlate Middle Miocene global δ¹⁸O-shifts with ice volume changes on Antarctica and sea-level changes with corresponding phases of erosion (valley incision) and deposition in the Lower Austrian part of the Alpine–Carpathian Foredeep. This allows the exact dating of the valley formation. Two periods of positive δ¹⁸O-shifts resulted in sea-level drops of about 60 and 40 m, respectively. The first drop in the late Langhian (middle Badenian) at c. 13.9 Ma (Mi3b) was fast and caused severe erosion on the emerged foredeep. In a second, less pronounced step around 13.0 Ma (Mi4) in the middle Serravallian (late Badenian), the base level was further deepened after a period of alternating erosion and deposition. The combined sea-level change (80–120 m) fits well with the maximum thickness of Sarmatian sediments drilled within incised valley (110 m). The global sea-level falls affected not only the geological history of the foredeep. The intensive erosion (valley incision) is combined with delta progradation in the adjacent Vienna Basin. Due to this massive sea-level drop, the interruption of marine connections resulted in vast salt deposits and faunal crises within the Central Paratethys during this time.     

Origins of yttrium and rare earth element distributions in metamorphic garnet

Highly variable distributions of yttrium and rare earth elements (Y+REEs) are documented in pelitic garnet from the Picuris Mountains, New Mexico, and from Passo del Sole, Switzerland, and in mafic garnet from the Franciscan Complex, California. The wide variety of these Y+REE zoning patterns, and those described previously in other occurrences, imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth. In the Picuris Mountains, large, early‐nucleating crystals have radial profiles of Y+REE dominated by central peaks and annular maxima, in patterns that vary systematically with atomic number. Superimposed on these features are narrow spikes in HREEs and MREEs, located progressively rimward with decreasing atomic number. In contrast, profiles in small, late‐nucleating crystals contain only broad central maxima for all Y+REEs. In garnet from Passo del Sole, Y+REE zoning varies radically from sample to sample: in some rocks, crystals of all sizes display only central peaks for all Y+REEs; in others, profiles exhibit irregular fluctuations in Y+REE contents that match up with small‐scale patchy zoning in Y and Ca X‐ray maps. In the Franciscan Complex, Y+REE in garnet cores fluctuate unsystematically, but mantles and rims display concentric oscillatory zoning for both major elements and Y+REEs. Our interpretation of the complexity of Y+REE distributions in metamorphic garnet centres on the concept that these distributions vary primarily in response to the length scales over which these elements can equilibrate during garnet growth. Very short length scales of equilibration, due to low intergranular mobility, produce overprint zoning characterized by small‐scale irregularities. Higher but still restricted mobility yields diffusion‐controlled uptake, characterized by patterns of central peaks and annular maxima that vary with atomic number and are strongly influenced by T–t paths during garnet growth. Still greater mobility permits progressively greater, potentially rock‐wide, equilibration with major‐ and accessory‐phase assemblages, leading to mineralogical controls: an unchanging mineral assemblage during garnet growth produces bell‐shaped profiles resembling those produced by Rayleigh fractionation, whereas changes in major‐ and/or accessory‐phase assemblages produce profiles with distinct annuli and sharp discontinuities in concentration. The very high mobility associated with influxes of Y+REE‐bearing fluids can cause these element distributions to be dominated by factors external to the rock, yielding profiles characterized by abrupt shifts or oscillations that are not correlated to changes in mineral assemblages.     

The formation of phosphoran olivine and stanfieldite from the pyrometamorphic breakdown of apatite in slags from a prehistoric ritual immolation site (Goldbichl, Igls, Tyrol, Austria)

In this study we report P-rich olivine and the tric-calcium phosphate (TCP) stanfieldite in partially molten quartzphyllites from the ritual immolation site at the Goldbichl, near Innsbruck in the Tyrol, Austria. During partial melting, foamy patches of dark glassy material formed at the surface of the rocks and also as layers within the rocks. The pyrometamorphic rocks contain mostly the mineral assemblage olivine + orthopyroxene + plagioclase + spinel + glass. During the investigation of slag samples from this prehistoric ritual immolation site, extremely P-rich, apatite-bearing micro-domains were found. In these domains phosphoran olivine was found whose P contents are approaching the maximum P contents in olivine according to the experimental investigations of Boesenberg and Hewins (Geochim Cosmochim Acta 74:1923–1941, 2010). The textures within these domains indicate strongly disequilibrium conditions. The phosphoran olivines formed due to reactions involving apatite and the mineral assemblage of the quartzphyllites, and coexist with plagioclase and a tri-calcium phosphate phase (TCP) showing stanfieldite Ca₄(Mg, Fe²⁺, Mn²⁺)₅(PO₄)₆ composition. In terms of its chemical composition, olivine shows a wide range in composition with P ranging from 0.3 to 0.54 a.p.f.u, which corresponds to maximal 23 wt.% P₂O₅. These are the highest P-contents in olivine reported from rocks so far. The incorporation of P correlates with decreasing Si contents according to the charge balancing scheme $ 2{{\mathrm{P}}^{5+ }}+□{{\mathrm{M}}_{1,2 }}=2\mathrm{S}{{\mathrm{i}}^{4+ }}+{{\left( {\mathrm{M}\mathrm{g},\mathrm{Fe}} \right)}^{2+ }}{{\mathrm{M}}_{1,2 }} $ . Therefore P can only be incorporated in combination with a vacancy on the M_1,2 position. Micro-Raman spectroscopy of phosphoran olivines indicates that these olivines can easily be identified with this method due to the strong signals of the SiO₄ and PO₄ vibrations. The external vibrations of the M_1,2 sites at low wave-numbers are more complex than for P-free olivine. This might be due to the effect of P⁵⁺ on the M₁ ²⁺ and M₂ ²⁺ positions and the formation of vacancies on these sites. Since micro-Raman investigations of the TCP phase yielded no conclusive match with a known Raman spectrum of a phosphate mineral so far, therefore it is most likely that the TCP phase is stanfieldite, whose Raman spectrum has not been obtained yet. Schematical Schreinemakers analysis in the system CaO-Al₂O₃-FeO-SiO₂-P₂O₅-H₂O shows that P-rich olivine (fayalite-sarcopside solid solution) can form from mineral reactions involving chlorite, apatite and quartz and show that the occurrence of P-rich Fe-olivines spans a large T-range but is restricted to domains with high aSiO₂. The mineral assemblage in the P-rich micro-domains shows that the formation of phosphoran olivine is not only restricted to the interaction between bone material and rocks in slags from ritual immolation sites as suggested by Tropper et al. (Eur J Mineral 16:631–640, 2004) from the immolation site in Oetz but can form locally due to the pyrometamorphic breakdown of a P-rich accessory precursor phase such as apatite.     

Paleolimnological evidence of mining and demographic impacts on Lac Dauriat, Schefferville (subarctic Québec, Canada)

Qualitative and quantitative analysis of fossil diatoms and geochemical signals preserved in the sediments of Lac Dauriat (subarctic Quebec) were performed to evaluate the impacts of nearby mining activity and the expansion of the town of Schefferville on the water quality of the lake, and to reconstruct the changes of its trophic status. The presence of taxa typical of nutrient-enriched environments (e.g., Cyclostephanos invisitatus, Nitzschia gracilis, Nitzschia perminuta) and the low percentages of chrysophytes were indicative of the advanced state of eutrophication of the lake during the peak of mining activity, and were evidence of the negative impacts of municipal waste on the water quality of Lac Dauriat. Sedimentary analysis of metals, notably lead, mercury, cadmium, bismuth, cobalt, copper and zinc, showed maximum concentrations between 1940 and 1960 with mining era to pre-development enrichment factors ranging from 4.5 to 7.9. The changes seen in recent sediments reflected 3 distinct stages in the recent history of this ecosystem: (a) the non-perturbed, pre-mining (1882–1939), (b) the perturbed, mining period (1939–1977) with accelerated eutrophication, and (c) the post-mining period (1977–1999) with indications of natural recovery of the system after the installation of a water treatment plant in 1975, the closing of the mine in 1983, and the subsequent exodus of the town’s population. Despite the trajectory towards a return to the lake’s natural conditions, water resource managers and (paleo-)limnologists should be alarmed that the impacts of past human disturbance are still in evidence more than 20 years after the closure of the mines, and that Lac Dauriat has yet to reach its natural state of the period preceding extreme anthropogenic impact.     

Establishing Holocene sediment core chronologies for northern Ungava lakes, Canada, using humic acids (AMS C) and Pb

The absence of datable macrofossils in six sediment cores recovered from northern Ungava (Canada) lakes constituted a major challenge for the establishment of reliable lacustrine chronologies for the Holocene. Consequently, AMS radiocarbon dating of humic acids was used to assess age–depth in the cores. The reliability of the radiocarbon results near some of the core tops was evaluated through ²¹⁰Pb dating. The offset of sediment radiocarbon ages with their most probable time of formation and deposition in the lakes was found to be in the order of about 1000 years for recently deposited sediments. However, the basal dates in one core covering the entire postglacial period yielded a remarkable fit with previously established dates performed on marine shells at the maximum marine limit. Hence, the aim of this study was to describe how the two dating methods can be combined to address some of the problems paleolimnologists face when trying to assign ages to high-latitude lake sediment records. Suggestions are made for improving the quality of age–depth models developed in future studies for northernmost Québec and other comparable regions where paleolimnologists must deal with the combined challenges of very slow sediment accumulation rates in lakes, an extreme paucity of datable material and the sequestration of old carbon in the watersheds.