Local distribution of oxygen isotopes and fluid exchange during genesis of the corundum-bearing rocks of Khitostrov Island

New data are presented on the distribution of oxygen isotopes and conditions of the local isotope equilibrium in high-Al rocks rocks of Khitostrov Island showing abnormally low δ¹⁸O values (below–25‰). The temperatures of isotope equilibrium are within 400–475°C. The minimum δ¹⁸O values have been registered in the in plagioclase, whereas the same phases in kyanite-bearing rocks lacking corundum demonstrate δ¹⁸O values usually 3–5‰ higher. The fluid δ¹⁸O value varies from–22 to–16‰ at 475 ± 15°C, from–18 to–23‰ at 425 ± 25°C, and from–17 to–22‰ at 380 ± 15°C. The results obtained do not require abnormal depletion of δ¹⁸O values owing to the infiltration of an external fluid under the Svecofennian transformations. The association of corundum-bearing rocks with the basic intrusions, the presence of zircon cores of older ages compared to these rocks, and the peculiarities of rock chemistry may be ascribed to the fact that lower crustal layers of ancient rocks depleted in δ¹⁸O before metamorphism were captured by basite melts.     

Age and origin of the corundum-bearing rocks of Khitostrov Island, Northern Karelia

The Chupa nappe of the Belomorian Complex contains aluminous silica-undersaturated rocks with corundum, which are characterized by extremely low ¹⁸O/¹⁶O (whole-rock δ¹⁸O up to −21‰). Revealed isotopic anomalies are explained by the influence of meteoric waters that were modified through evaporation-precipitation cycles (Rayleigh distillation) under cold climatic conditions. In order to estimate whether the decrease in δ¹⁸O occurred prior to metamorphism of the protoliths of the Chupa Sequence or during water percolation in the course of metamorphic or postmetamorphic transformations, we studied oxygen composition in the rocks and minerals and conducted U-Pb dating on single zircons from corundumbearing rocks of Khitostrov.     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

阿拉善北部杭乌拉地区早二叠世火山岩地球化学、Nd-Hf同位素特征及其构造意义

位于阿拉善恩格尔乌苏蛇绿岩带北侧的珠斯楞-杭乌拉构造带,分布较完整的早二叠世方山口组火山岩,对解析阿拉善地块晚古生代晚期的构造演化具有重要意义。方山口组以灰绿色安山岩、安山质角砾熔岩为主,局部含集块。安山岩SiO2含量为54.23%~60.81%,Al2O3为13.67%~15.96%,MgO为4.26%~5.76%,Mg#值为42~50;Na2O含量（2.21%~3.48%）与K2O（2.51%~3.49%）相当,具较高的TFe2O3（7.98%~11.24%）,低的CaO（2.52%~3.36%）和TiO2（0.75%~1.32%）,为过铝质钙碱性安山岩;安山岩在稀土元素球粒陨石标准化配分图上,轻稀土元素略富集,（La/Yb）N=3.73~9.86,具负Eu异常（δEu=0.52~0.75）;在微量元素原始地幔标准化蛛网图上,富集Rb、K,亏损Nb、Ta、Ti等;变化范围非常大的εNd（t）（-4.3~-14.2）、εHf（t）（-19.8~+1.4）。上述特征表明,安山岩属于壳幔物质混合的产物,形成于板内裂谷环境。结合区域地质背景研究资料,进一步指出,恩格尔乌苏蛇绿岩带所代表的大洋在晚石炭世之前已经闭合;晚石炭世-早二叠世北山-阿拉善-内蒙古中部地区已进入板内构造岩浆-沉积阶段。     

Geochemistry and cosmochemistry of potassium stable isotopes

Stable potassium isotopes are one of the emerging non-traditional isotope systems enabled in recent years by the advance of Multi-Collector Inductively-Coupled-Plasma Mass-Spectrometry (MC-ICP-MS). In this review, we first summarize the geochemical and cosmochemical properties of K, its major reservoirs, and the analytical methods of K isotopes. Following this, we review recent literature on K isotope applications in the fields of geochemistry and cosmochemistry. Geochemically, K is a highly incompatible lithophile element, and a highly soluble, biophile element. The isotopic fractionation of K is relatively small during magmatic processes such as partial melting and fractional crystallization, whereas during low-temperature and biological processes fractionation is considerably larger. This resolvable fractionation has made K isotopes promising tracers for a variety of Earth and environmental processes, including chemical weathering, low-temperature alteration of igneous rocks, reverse weathering, and the recycling of sediments into the mantle during subduction. Sorption and interactions of aqueous K with different clay minerals during cation exchange and clay formation are likely to be of fundamental significance in generating much of the K isotope variability seen in samples from the Earth surface and samples carrying recycled surface materials from the deep Earth. The magnitude of this fractionation is process- and mineral-dependent. Comprehensive quantification of pertinent K isotope fractionation factors is currently lacking and urgently needed. Significant fractionation during biological activities, such as plant uptake, demonstrates the potential utility of K isotopes in the study of the nutrient cycle and its relation to the climate and various ecosystems, enabling new and largely unexplored avenues for future research.Of significant importance to the cosmochemistry community, K is a moderately volatile element with large variations in K/U ratio observed among chondrites and planetary materials. As this indicates different degrees of volatile depletion, it has become a fundamental chemical signature of both chondritic and planetary bodies. This volatile depletion has been attributed to various processes such as solar nebula condensation, mixing of volatile-rich and -poor reservoirs, planetary accretional volatilization via impacts, and/or magma ocean degassing. While K isotopes have the potential to distinguish these different processes, the current results are still highly debated. A good correlation between the K isotope compositions of four differentiated bodies (Earth, Mars, Moon, and Vesta) and their masses suggests a ubiquitous volatile depletion mechanism during the formation of the terrestrial planets. It is still unknown whether any of the K isotopic variation among chondrites and differentiated bodies can be attributed to inherited signatures of mass-independent isotopic anomalies.     

Rare-earth and rare elements in zircons of different ages from corundum-bearing rocks of Khitoostrov (Northern Karelia)

Doklady Earth Sciences -     

Distribution of oxygen isotopes in rocks and minerals from the critical zone of the Ioko-Dovyren pluton

The oxygen isotopic composition was studied in minerals and rocks from the critical zone of the Ioko-Dovyren layered pluton. The δ¹⁸O values vary from +5.4 to +6.1‰ in rocks, from +4.8 to +5.8‰ in olivine, from +5.5 to 6.5‰ in pyroxene, and from +5.8 to +6.9‰ in plagioclase and fall into the interval of mantle values for continental mafic and ultramafic rocks. A decrease in δ¹⁸O could have been caused by penetration of meteoric water. Postmagmatic (retrograde) oxygen isotopic redistribution in the slowly cooling rocks is responsible for disturbance of oxygen isotope equilibria in the coexisting minerals, which were crystallized from the same magma at a high temperature. The nonequilibrium oxygen isotopic composition in the associated minerals and calculated temperature of the final isotopic equilibration do not contradict the model of “fluid” formation of low-sulfide PGE mineralization in the Ioko-Dovyren layered pluton.     

Analysis of carbon and oxygen stable isotopes in carbonate rocks by the laser micro-sampling technique

The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses laser beams with sufficient energy on a micro area of a thin section in a vacuum sample box via microscope. CO 2 produced by heating decomposition of carbonate was purified by the vacuum system, and the stable isotopic values of carbon and oxygen were calculated and analyzed on a mass spectrometer. This paper adopted the laser micro-sampling technique to analyze the stable isotopes of carbon and oxygen in dolomite, carbonate cement, stromatolite and different forms of dawsonite (donbassite). Results indicated that the laser micro-sampling method is effective in analyzing carbonate composition and could be a convincing proof for justification on carbonate composition analysis.     

Geochemistry of coexisting aplites and pegmatites and of their minerals from central northern Portugal

The major-, minor- and trace-elements chemistry of Hercynian granitoids and their minerals from the central area of northern Portugal indicates that the composition of the rocks and also of their minerals varies in the comagmatic sequence of granite, aplite and pegmatite. The compositional variation appears to be the result of a magmatic fractionation process and the minor and trace elements play an important role mainly in the trend aplite→pegmatite coexisting in the same vein, particularly for the minerals. A subsequent recrystallization of granites and aplites apparently did not alter the chemistry.     

Geochemistry of hybrid granitoid rocks and of their biotites from central northern Portugal and their petrogenesis

In the area of Franzilhal, S. Lourenço and Pombal, central northern Portugal, occur rocks ranging from hornblende-biotite tonalite to muscovite-biotite granite. The distribution of some major and trace elements in the rocks and in the biotite shows an apparent calc-alkalic trend of differentiation. The behaviour of K, Li, Rb, Cs and K/Rb, Cr.10³/Fe³⁺, Ni.10³/Mg, Li.10³/Mg, Cs.10³/K ratios of the rocks and of F of biotite cannot be explained by mineral fractionation, but can be described in terms of hybridization. The tonalite, granodiorites and biotite-muscovite granite are hybrid rocks formed by assimilation of pelitic sediments and dolomitic marbles by the granite magma. The fO₂ values range from 10^?14.8 to 10^?16.3; fO₂ attains higher values during the crystallization of hybrid rocks than in the uncontaminated muscovite-biotite granite (GIII) magma. The fH₂O and PH₂O values generally increase and the fH₂O/fHF ratio decreases in the hybrid rocks from tonalite to biotite-muscovite-bearing granodiorite and is smaller than in the uncontaminated granite magma.     

Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen.Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H₂O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks.Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism.Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.