Ternary feldspars: Kinetics and possible equilibria at 800° C

The ternary feldspar system KAlSi₃O₈ - NaAlSi₃O₈ - CaAl₂Si₂O₈ was reinvestigated at 650 ° C and 800 ° C (P _H2O = 1 kb) using mixtures of crystalline plagioclases and alkali feldspars as starting materials. The compositions of plagioclases and alkali feldspars of the run products were determined by X-ray means. The Or-content of the feldspar phases was determined by measuring the position of the (201) X-ray peak of the unexchanged feldspars, whereas the An-content was determined by measuring the same X-ray peak of the K-exchanged feldspars. The reaction rate of a reaction leading to a more An-rich plagioclase (type II reaction) is much faster than a reaction producing a more Ab-rich plagioclase (type I). In a type II reaction run times of approximately 20 days are needed to reach new constant plagioclase and alkali feldspar compositions at 650 ° C, and 10 days are needed to reach constant compositions at 800 ° C. In a reaction of type I only the outer zone of the plagioclases reacts to more Abrich compositions. A diffuse zone with a wide range of compositions was observed in 650 ° C runs. Equilibrium could not be reached in these experiments within 45 days. At 800 ° C a new zone having a specific composition develops in 42 days. This new zone is believed to be in equilibrium with the coexisting alkali feldspar. The depth of reaction is calculated as 0.03 μm after 42 days (800 ° C, P _f= 1 kb). The reaction between the two feldspar phases could be reversed at 800 ° C. The following compositions are considered to represent equilibrium data at 800 ° C and P _t = 1 kb:

An 43 Ab 51 Or 6 coexisting with Or 79 Ab 20 An 1, and

An 40 Ab 54 Or 6 coexisting with Or 75 Ab 24 An 1.

Recent data obtained with gels of ternary feldspar composition as starting materials do not agree with the results presented in this paper. Gels obviously crystallize spontaneously forming coexisting feldspars of non - equilibrium composition - alkali feldspars too rich in Ab and plagioclases too rich in An.     

Black carbon decomposition under varying water regimes

The stability of biomass-derived black carbon (BC) or biochar as a slow cycling pool in the global C cycle is an important property and is likely governed by environmental conditions. This study investigated the effects of water regimes (saturated, unsaturated and alternating saturated–unsaturated conditions) and differences in BC materials, produced by carbonizing corn residues and oak wood at two temperatures (350 °C and 600 °C) on BC degradation at 30 °C over 1 year in a full factorial experiment. Effects of water regime on C loss and potential cation exchange capacity (CECp at pH 7) significantly depended on biomass type. Corn BC was both mineralized (16% C loss for the first year) and was oxidized [1000 mmole(+) kg^?1 C] significantly faster under unsaturated conditions than under other water regimes, whereas oak BC mineralized most rapidly (12%) under alternating saturated–unsaturated conditions with similar oxidation, irrespective of water regime. Over 1 year of saturated incubation, the O/C ratio values did not significantly (P > 0.05) increase even though BC was mineralized by 9% and CECp increased by 170 mmole(+) kg^?1 C, in contrast to unsaturated and alternating saturated–unsaturated conditions. While mineralization and oxidation significantly decreased at higher charring temperature for corn, no difference was observed for oak (P > 0.05). Unsaturated and alternating conditions increased carboxylic and OH functional groups, while they decreased aliphatic groups. The pH increased by about one unit for corn BC, but decreased by 0.2 units for oak BC, indicating strong mineral dissolution of corn BC. Carbon loss strongly correlated with changes in O/C values of both corn BC and oak BC, indicating that oxidation of BC was most likely the major mechanism controlling its stability. However, under saturated conditions, additional mechanisms may govern BC degradation and require further investigation.     

Analysis of coprolites from the extinct mountain goat Myotragus balearicus

Humans colonized the Balearic Islands 5–4 ka ago. They arrived in a uniquely adapted ecosystem with the Balearic mountain goat Myotragus balearicus (Bovidae, Antilopinae, Caprini) as the only large mammal. This mammal went extinct rapidly after human arrival. Several hypotheses have been proposed to explain the extinction of M. balearicus. For the present study ancient DNA analysis (Sanger sequencing, Roche-454, Ion Torrent), and pollen and macrofossil analyses were performed on preserved coprolites from M. balearicus, providing information on its diet and paleo-environment. The information retrieved shows that M. balearicus was heavily dependent on the Balearic box species Buxus balearica during at least part of the year, and that it was most probably a browser. Hindcast ecological niche modelling of B. balearica shows that local distribution of this plant species was affected by climate changes. This suggests that the extinction of M. balearicus can be related to the decline and regional extinction of a plant species that formed a major component of its diet. The vegetation change is thought to be caused by increased aridity occurring throughout the Mediterranean. Previous hypotheses relating the extinction of M. balearicus directly to the arrival of humans on the islands must therefore be adjusted.     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

The deep Cretaceous aquifer in the Aleppo and Steppe basins of Syria: assessment of the meteoric origin and geographic source of the groundwater

A drilling project was carried out in Syria to assess the potential of the deep groundwater resources of the Cretaceous aquifer, composed of Cenomanian-Turonian limestones and dolomites. In this context, isotope (¹⁴C, ³H, δ¹³C, δ¹⁸O, δ²H) and hydrochemical analyses were performed on wells in and around the Aleppo and Steppe basins. The interpretation includes complementary results from published and unpublished literature. The results provide evidence that many new wells pump mixed groundwater from the Cretaceous aquifer and the overlying Paleogene aquifer. Radiocarbon measurements confirmed dominating Pleistocene groundwater in the Cretaceous aquifer and mainly Holocene groundwater in the Paleogene aquifer. Most groundwater in the Cretaceous aquifer seems to be recharged in the western limestone ridges, stretching from Jebel az Zawiyah (south of Idlep) via Jebel Samane (south of Afrin and A’zaz) to the region north of Aleppo, and in the Northern Palmyrides mountain belt. Some recharge also occurs around the basalt plateau of the Jebel al Hass, south east of Aleppo. It is concluded that the Taurus Mountains and the Euphrates River do not recharge the Cretaceous aquifer. The sources of recharge seem to be occasionally occurring intensive winter storms that approach from Siberia.     

Equilibrium-disequilibrium relations in the Monte Rosa Granite,Western Alps: Petrological,Rb-Sr and stable isotope data

Nine samples from the Monte Rosa Granite have been investigated by microscopic, X-ray, wet chemical, electron microprobe, stable isotope and Rb-Sr and K-Ar methods. Two mineral assemblages have been distinguished by optical methods and dated as Permian and mid-Tertiary by means of Rb-Sr age determinations. The Permian assemblage comprises quartz, orthoclase, oligoclase, biotite, and muscovite whereas the Alpine assemblage comprises quartz, microcline, albite+epidote or oligoclase, biotite, and phengite. Disequilibrium between the Permian and Alpine mineral assemblages is documented by the following facts: (i) Two texturally distinguishable generations of white K-mica are 2 M muscovite (Si=3.1–3.2) and 2 M or 3 T phengite (Si=3.3–3.4). Five muscovites show Permian Rb-Sr ages and oxygen isotope fractionations indicating temperatures between 520 and 560 ° C; however, K-Ar ages are mixed or rejuvenated. Phengite always shows mid-Tertiary Rb-Sr ages, (ii) Two biotite generations can be recognized, although textural evidence is often ambiguous. Three out of four texturally old biotites show mid-Tertiary Rb-Sr cooling ages while the oxygen isotopic fractionations point to Permian, mixed or Alpine temperatures, (iii) Comparison of radiogenic and stable isotope relations indicates that the radiogenic isotopes in the interlayer positions of the micas were mobilized during Alpine time without recrystallization, that is, without breaking Al-O or Si-O bonds. High Ti contents in young muscovites and biotites also indicate that the octahedral (and tetrahedral) sites remained undisturbed during rejuvenation. (iv) Isotopic reversals in the order of O¹⁸ enrichment between K-feldspar and albite exist. Arguments for equilibrium during Permian time are meagre because of Alpine overprinting effects. Texturally old muscovites show high temperatures and Permian Rb-Sr ages in concordancy with Rb-Sr whole rock ages. For the tectonically least affected samples, excellent concordance between quartz-muscovite and quartz-biotite Permian temperatures implies oxygen isotope equilibrium in Permian time which was undisturbed during Alpine metamorphism. Arguments for equilibrium during the mid-Tertiary metamorphism are as follows: (i) Mid-Tertiary Rb-Sr mineral isochrons of up to six minerals exist, (ii) Oxygen isotope temperatures of coexisting Alpine phengites and biotites are concordant.The major factor for the adjustment of the Permian assemblages to Alpine conditions was the degree of Alpine tectonic overprinting rather than the maximum temperatures reached during the mid-Tertiary Alpine metamorphism. The lack of exchange with externally introduced fluid phases in the samples least affected by tectonism indicates that the Monte Rosa Granite stewed in its own juices. This seems to be the major cause for the persistence of Permian ages and corresponding temperatures.     

Multi‐scale stratigraphic forward modelling of the Surat Basin for geological storage of CO2

Underground geological storage of CO₂ (GSC) requires a high level of subsurface understanding that is often hindered by a lack of data. This study demonstrates the use of stratigraphic forward modelling (SFM) in generating and characterising a static reservoir model using limited well data, with multiple potential applications within the GSC workflow. Sedsim SFM software was used to create a static model of the Surat Basin, including a high‐resolution nested model of the EPQ‐7 GSC tenement within the basin. Deposition and burial of the Jurassic Precipice Sandstone, Evergreen Formation and Hutton Sandstone were simulated. Modelling results show a close match with gamma‐ray well logs in the tenement area, and the model can be considered a credible model of the subsurface. The Sedsim‐predicted formation thicknesses and porosity and permeability distributions meet criteria set for GSC, suggesting that the EPQ‐7 tenement may be a prospective GSC location.