Thermal evolution of the Lesser Himalaya, central Nepal: Insights from K-white micas compositional variation

The Lesser Himalayan low- to medium-grade metamorphic rocks in central Nepal are rich in K-white micas occurring as porphyroclasts and in matrix defining S₁ and S₂. Porphyroclasts are usually zoned with celadonite-poor cores and celadonite-rich rims. The cores are the relics of igneous or high grade metamorphic muscovites, and the rims were re-equilibrated or overgrown under lower T metamorphic conditions. The matrix K-white micas defining S₁, pre-dating the Main Central Thrust activity, are generally celadonite-rich. They show heterogeneous compositional zoning with celadonite-rich cores and celadonite-poor rims. They were recrystallized at lower T condition prior to the Main Central Thrust activity, most probably prior to the India–Asia collision (pre-Himalayan metamorphism). The matrix K-white micas along S₂, synchronous to the Main Central Thrust activity (Neohimalayan metamorphism), are relatively celadonite-poor and were recrystallized under relatively higher T condition. K-white micas defining S₁ also were partially re-equilibrated during the Neohimalayan metamorphism. The average compositions of recrystallized K-white micas defining both S₁ and S₂ become gradually poor in (Fe + Mg)- and Si-contents and rich in Al- and Ti-contents from south to north showing an increase of metamorphic grade from structurally lower to higher parts in the Lesser Himalaya. This shows that the metamorphism is inverted throughout the inner Lesser Himalaya. The tectono-metamorphic significance of the published K–Ar and ⁴⁰Ar / ³⁹Ar K-white micas ages from the Lesser Himalaya need re-evaluation in the context of observed intrasample compositional variation and zoning, and possible higher closure temperature (500 °C) for K–Ar system.     

The evolution of the fluid phase during the crystallization of granite types: Salmi pluton,Karelia, Russia

Summary Two main geochemiscl types of granites are distingushed in the Salmi pluton: 1) ovoid biotite-hornblende granites, 2) non-ovoid biotite granites. The first one is characterized by higher CO₂, CO and CH₄ concentrations. The second type is rich in fluorine and shows similarities with rare metal Phanerozoic granites. Both granite types began to crystallize when P_f, < P_tot, but non-ovoid granites, which crystallized in a wider temperature range, reached conditions P_f, > PO_tot at the final stage. The mole fraction of carbon group gases (CO₂, CO and CH₄) decreases and that of H₂O increases in all granites from early crystallizing minerals to those of late crystallization.Compositional differences between ovoid biotite-hornblende and non-ovoid biotite granites are due to differences in the protolith composition.

---

Die Evolution der fluiden Phase während der Kristallisation von Graniten, Salmi Pluton, Karelia, Russland

Zusammenfassung Zwei geochemisch charakterisierte Granittypen können innerhalb des Salmi Plutons unterschieden werden: 1) ein ovoidaler Biotit-Hornblende-Granit, und 2) ein nichtovoidaler Biotit-Granit. Der erste Typ ist durch höhere Konzentrationen von CO₂, CO und CH₄ charakterisiert; der zweite Granittyp ist reich an Fluor und zeigt Ähnlichkeiten mit phanerozoischen Graniten, die seltene Metalle führen. Beide Granittypen beginnen bei P_fl, < P_tot, zu kristallisieren, nicht-ovoidale Granite jedoch, deren Kristallisation in einem weiteren Temperaturbereich abläuft, erreichen im Finalstadium der Kristallisation P_fl > P_tot,-Bedingungen. In allen Graniten sinkt die Molfraktion der Kohlenstoffgasgruppe (CO₂, CO und CH₄) bei gleichzeitigem Anstieg von H₂O, wenn man frühe Kristallisationsphasen mit späten vergleicht.Die Unterschiede in der Zusammensetzung zwischen den ovoidalen und nichtovoidalen Graniten sind auf Unterschiede in der Protolith-Zusammensetzung zurückzuführen.

---

---

With 2 figures     

青藏高原拉萨地块松多榴辉岩的岩相学特征和变质演化过程

松多榴辉岩出露于拉萨地块的石英片岩中,主要由较为基性的金红石榴辉岩和较为酸性的石英榴辉岩组成。榴辉岩相矿物组合为石榴子石 绿辉石 绿帘石±多硅白云母±石英±金红石。岩石发生了较强烈的退变质作用,退变质矿物有角闪石、绿帘石、石英、钠长石及绿泥石。石榴子石变斑晶具有生长环带结构,变斑晶和基质石榴子石主要落入C类榴辉岩区,少数石榴子石变斑晶边部和基质石榴子石落入B类榴辉岩区;单斜辉石主要为绿辉石,少数Ⅰ世代和Ⅲ世代为普通辉石;角闪石均为钙质角闪石。根据石榴子石-绿辉石-多硅白云母矿物温压计计算,获得的温压范围为630～777℃和2.58～2.70GPa,峰期变质条件接近于石英-柯石英转变线。榴辉岩的原岩经历了从高绿片岩相、角闪岩相、榴辉岩相、角闪岩相到高绿片岩相的变质过程,这反映了与古特提斯洋闭合有关的俯冲进变质作用和随后的折返退变质作用。     

西南天山东德沟橄榄岩的岩相学、矿物学演化特征及其地质意义

中国西南天山东德橄榄岩出露于天山伊犁-中天山板块和塔里木板块碰撞造山带北缘,普遍经历了复杂多期的含水流体(熔体)交代作用.主要矿物为橄榄石、斜方辉石、尖晶石、角闪石、金云母和单斜辉石,研究发现,橄榄石和斜方辉石与地幔楔橄榄岩中橄榄石和斜方辉石成份相近,原生铬尖晶石具有SSZ环境橄榄岩的特征,次生绿色尖晶石形成于麻粒岩相-角闪相环境.岩相学、矿物转变结构分析和矿物组合及矿物成分变化表明,东德沟橄榄岩记录了复杂的演化历史,先后经历了地幔交代、麻粒岩相-角闪相退变质作用和蛇纹石化等阶段的演化.研究认为东德沟橄榄岩最初可能形成于915～961℃的地幔环境,而发生地幔交代时的温压条件约为770 ～ 900℃,10～18kbar.该橄榄岩全岩较低的TiO2含量和尖晶石中较低TiO2含量,以及矿物组合显示出因俯冲板块脱水而造成的快速冷却特征,表明东德沟橄榄岩极有可能是SSZ环境俯冲板片上地幔楔橄榄岩残片.     

新疆白石头泉高铷氟花岗岩不同相带云母成分及其演化

白石头泉含黄玉花岗岩体在露头上显示很好的岩性分带,从下至上依次为:淡色花岗岩(a带)、含天河石花岗岩(b带)、天河石花岗岩(c带)、含黄玉天河石花岗岩(d带)和黄玉钠长花岗岩(e带).岩体组成矿物主要为石英、钾长石(部分富铷的为天河石)、钠长石、黄玉和云母,副矿物为锰铝榴石和萤石.总体说来,从a带到c带,云母的Al、Mn、F和Rb含量递增,Fe、Mg和Ti含量递减;Li含量从a带到b带和c带递增,但b带和c带之间变化不明显.从c带到e带,随着Fe、Mg和Ti的减少,总体上表现为Al、Li递增,F、Mn和Rb递减的演化方向,但Li、F、Mn和Rb在c带和d带之间变化不明显,d带和e带之间却表现出急剧的变化.e带中的次生云母与原生云母相比,前者F、Li高而Al低,从a带到e带,Na K变化不明显.云母成分的这些变化特征与岩体的演化趋势相一致.白石头泉岩体与世界上其他地方类似花岗岩相比,没有出现锂云母这种高度富锂矿物,这可能与岩体中锂含量较低有关.     

A zircon study from the Rhodope metamorphic complex, N-Greece: Time record of a multistage evolution

Zircons from an eclogite and a diamond-bearing metapelite near the Kimi village (north-eastern Rhodope Metamorphic Complex, Greece) have been investigated by Micro Raman Spectroscopy, SEM, SHRIMP and LA-ICPMS to define their inclusion mineralogy, ages and trace element contents. In addition, the host rocks metamorphic evolution was reconstructed and linked to the zircon growth domains.

The eclogite contains relicts of a high pressure stage (ca. 700 °C and > 17.5 kbar) characterised by matrix omphacite with Jd_40–35. This assemblage was overprinted by a lower pressure, higher temperature metamorphic event (ca. 820 °C and 15.5–17.5 kbar), as indicated by the presence of clinopyroxene (Jd_35–20) and plagioclase. Biotite and pargasitic amphibole represent a later stage, probably related to an influx of fluids. Zircons separated from the eclogite contain magmatic relicts indicating Permian crystallization of a quartz-bearing gabbroic protolith. Inclusions diagnostic of the high temperature, post-eclogitic overprint are found in metamorphic zircon domain Z2 which ages spread over a long period (160 – 95 Ma). Based on zircon textures, zoning and chemistry, we suggest that the high-temperature peak occurred at or before ca. 160 Ma and the zircons were disturbed by a later event possibly at around 115 Ma. Small metamorphic zircon overgrowths with a different composition yield an age of 79 ± 3 Ma, which is related to a distinct amphibolite-facies metamorphic event.

The metapelitic host rock consists of a mesosome with garnet, mica and kyanite, and a quartz- and plagioclase-bearing leucosome, which formed at granulite-facies conditions. Based on previously reported micro-diamond inclusions in garnet, the mesosome is assumed to have experienced UHP conditions. Nevertheless, (U)HP mineral inclusions were not found in the zircons separated from the diamond-bearing metapelite. Inclusions of melt, kyanite and high-Ti biotite in a first metamorphic zircon domain suggest that zircon formation occurred during pervasive granulite-facies metamorphism. An age of 171 ± 1 Ma measured on this zircon domain constrains the high-temperature metamorphic event. A second, inclusion-free metamorphic domain yielded an age of 160 ± 1 Ma that is related to decompression and melt crystallization.

The similar age data obtained from the samples indicate that both rock types recorded a high-T metamorphic overprint at granulite-facies conditions at ca. 170 – 160 Ma. This age implies that any high pressure or even ultra-high pressure metamorphism in the Kimi Complex occurred before that time. Our findings define new constraints for the geodynamic evolution for the Alpine orogenic cycle within the northernmost Greek part of the Rhodope Metamorphic Complex. It is proposed that the rocks of the Kimi Complex belong to a suture zone squeezed between two continental blocks and result from a Paleo-ocean basin, which should be located further north of the Jurassic Vardar Ocean.     

The isotopic composition of zircon and garnet: A record of the metamorphic history of Naxos, Greece

Growth of zircon with respect to that of garnet has been studied using a combination of petrography, U–Pb dating and oxygen isotope analysis. The aim is to document the mechanism and pressure–temperature conditions of zircon growth during metamorphism in order to better constrain the Tertiary metamorphic history of Naxos, Greece. Two metamorphisms are recognised: (1) an Eocene Franciscan metamorphism (M1) and (2) a widespread Miocene Barrovian metamorphism (M2) that increases from greenschist facies up to partial melting. An amphibolite sample contains zircon crystals characterised by a magmatic core and two metamorphic rims, denoted as A and B, dated at 200–270, 42–69, and 14–19 Ma, respectively. The first metamorphic rim A (δ¹⁸O = 7 ± 1‰) preserves the δ¹⁸O value of the magmatic core (6.2 ± 0.8‰), whereas rim B is characterised by higher δ¹⁸O values (7.8 ± 1.8‰). These observations indicate the formation of A rims by solid-state recrystallisation in a closed system with regard to oxygen and those of B in an open system. Compositional zoning in garnet is interpreted as the result of decompressional heating. Zircon B rims and garnet rims display similar δ¹⁸O values which indicates a contemporaneous growth of garnet and zircon rims during the Miocene Barrovian event (M2). Calcic gneiss and metapelite samples contain zircon crystals with single metamorphic overgrowths aged 41–57 Ma. δ¹⁸O values measured in zircon overgrowths (11.8 ± 1.4‰) from the calcic gneiss are similar to those measured in garnet rims (11.4 ± 1.1‰) from the same rock. This suggests that garnet rims and zircon overgrowths grew during the high pressure–low temperature event in equilibrium with prograde fluids. In the metapelite sample, δ¹⁸O values are similar in garnet cores (14.8 ± 0.2‰) and in zircon metamorphic overgrowths (14.2 ± 0.5‰). As zircon overgrowths have been dated at ca. 50 Ma by U–Pb, garnet cores and zircon overgrowths are interpreted to have grown during the high pressure event.

As demonstrated here for the island of Naxos, correlating the crystallisation of zircon with that of metamorphic index minerals such as garnet using stable isotope composition and U–Pb determination is a powerful tool for deciphering the mechanism of zircon growth and pin-pointing zircon crystallisation within the metamorphic history of a terrain. This approach is potentially hampered by an inability to verify the degree of textural equilibrium of zircon with other mineral phases, and the possible preservation (in metamorphic rims) of isotopic signatures from pre-existing zircon when they form by recrystallisation. Nevertheless, this study illustrates the application of this approach in providing key constraints on the timing and mechanism of growth of minerals important to understanding metamorphic petrogenesis.     

Mechanisms of formation of barium-rich phlogopite and strontium-rich apatite during the final stages of alkaline magma evolution

Carbonatite veinlets in fergusite from the Dunkeldyk potassium-rich basaltoid complex (southeastern Pamirs) are composed of clinopyroxene, phlogopite, and apatite phenocrysts embedded in a crystallized calcite-bearing groundmass. The examination of back-scattered electron images revealed areas of significantly different compositions in fluorapatite and fluorphlogopite. The content of BaO in the phlogopite ranges from 0.68 to 10.9 wt %. There are also variations in MgO and F contents. The maximum BaO content corresponds to high mole fractions of the Ba end member kinoshitalite (up to 0.24) in the phlogopite. The zoned fluorapatite phenocrysts are rich in SrO (0.77–25.4 wt %). An increase in SrO content is accompanied by an increase in Ce₂O₃, La₂O₃, and BaO and a distinct decrease in CaO. Most of the apatite grains are rimmed by elongated colorless crystals showing the maximum SrO contents. Based on the experimentally determined Ba and Sr partition coefficients between these minerals, silicate and carbonate melts, and fluid, a model was proposed for the enrichment of phases in these trace elements. It was shown that the mineral-forming media of the Ba-rich phlogopites was a residual melt enriched in volatiles (including F) and fluid-mobile elements. During that stage, the decomposition reactions of early Ba-bearing feldspars with subsequent incorporation of BaO in Ba-rich phlogopites played an important role. The mechanism of formation of Sr-rich apatites is fundamentally different: early apatite grains with moderate Sr contents recrystallized under the influence of Sr-rich fluids released during the late magmatic stage. Thus, despite their close association in a single rock, the Ba-bearing phlogopite and Sr-rich apatite were formed by significantly different mechanisms. Our previous investigations of melt and fluid inclusions in minerals from the rocks of the Dunkeldyk complex and the results obtained in this study allowed us to suggest that the barium, fluorite-carbonatite, and rare metal mineralization occurring in the region developed owing to the prolonged evolution of primary magmas, resulting in the formation of melt-solutions (brines) and hydrothermal systems.     

显生宙全球海水化学成分演化及其对蒸发岩沉积的约束

通过搜集显生宙以来不同地质时期内海相碳酸盐岩鲕粒及胶结物矿物成分、钾盐矿床矿物种类及组合特征、蒸发岩盆地中石盐流体包裹体成分,并利用这些资料与人工海水模拟实验得到的石盐中Br分配特征的对比,得出海水成分在5.5亿年以来的显生宙期间,经历了五个阶段:其中晚元古代至寒武纪早期、二叠纪早期至中生代早期、新生代早期至现今,这些时期的原始海水组成特征系数m(SO_4~(2-))+m(HCO_3~-)/2m(Ca~(2+)),为Na-Mg-K-SO_4-Cl型海水,此期间沉积的钾盐矿床的钾镁盐矿物主要为钾盐镁矾、无水钾镁矾、杂卤石、硫酸镁石等含MgSO_4矿物,海相鲕粒和碳酸盐胶结物矿物成分为文石;而寒武纪早期至石炭纪、中生代早期至新生代早期,原始海水组成特征系数m(Ca~(2+))m(SO_4~(2-))+m(HCO_3~-)/2,为Na-Mg-KCa-Cl型海水,此期间沉积的钾镁盐矿物主要为光卤石和钾石盐,甚至含有溢晶石,海相鲕粒和碳酸盐胶结物矿物成分为方解石。根据石盐流体包裹体成分计算得出:显生宙期间,海水K+含量大部分时间变化幅度较小,为9.3～11.5mmol/kg H_2O(除了石炭纪和晚元古代),平均为10.55mmol/kg H_2O。Mg~(2+)含量在早寒武世≥67mmol/kg H_2O、晚志留世至中泥盆世31～41mmol/kg H_2O、晚古生代≥48mmol/kg H22O、晚白垩世34mmol/kg H_2O和现代55.1mmol/kg H_2O。Ca~+含量在晚元古代至古生代早期≤11mmol/kg H_2O、古生代早期至石炭纪22～35mmol/kg H_2O、石炭纪至中生代早期≤17mmol/kg H_2O、中生代早期至新生代早期19～39mmol/kg H_2O及新生代早期至今7～21mmol/kg H_2O。SO_4~(2-)含量在晚元古代至古生代早期≥23mmol/kg H_2O、古生代早期至石炭纪5～17mmol/kg H_2O、石炭纪至中生代早期13～22mmol/kg H_2O、中生代早期至新生代早期5～19mmol/kg H_2O及新生代早期至今12～29.2mmol/kg H_2O。海水Ca~(2+)与SO_4~(2-)含量的相对变化是控制海相钾盐矿床钾镁盐矿物类型的基本因素。同时,利用以上数据计算得到的显生宙各时期海水[m(Mg~(2+))+m(SO_4~(2-))]/[m(K~+)+m(Ca~(2+))]的变化与各时期海相蒸发岩系石盐层底部的Br含量变化具有同步性,进一步验证了显生宙期间海水成分是不断变化的,是约束海相蒸发岩钾盐矿物类型的主要因素。海水成分变化的控制因素为洋中脊热液和陆地水,其中洋中脊热液起主要作用,而控制这些因素变化的根本原因为板块构造运动。     

Melt evolution during the crystallization of basanites of the Tergesh pipe,northern Minusinsk Depression

In this paper we describe the mineralogy and geochemistry of basanites and melt inclusions in minerals from the Tergesh pipe, northern Minusinsk Depression. The rocks are composed of olivine and clinopyroxene phenocrysts and a groundmass of olivine, clinopyroxene, titanomagnetite, plagioclase, apatite, ilmenite, and glass. Melt inclusions were found only in the olivine and clinopyroxene phenocrysts. Primary melt inclusions in olivine contain glass, rh?nite, clinopyroxene, a sulfide globule, and low-density fluid. The phase composition of melt inclusions in clinopyroxene is glass + low-density fluid ± xenogenous magnetite. According to thermometric investigations, the olivine phenocrysts began crystallizing at T = 1280–1320°C and P > 3.5 kbar, whereas groundmass minerals were formed under near-surface conditions at T ≤ 1200°C. The oxygen fugacity gradually changed during basanite crystallization from oxidizing (NNO) to more reducing conditions (QFM). The investigation of glass compositions (heated and unheated inclusions in phenocrysts and groundmass) showed that the evolution of a basanite melt during its crystallization included mainly an increase in SiO₂, Al₂O₃, and alkalis, while a decrease in femic components, and the melt composition moved gradually toward tephriphonolite and trachyandesite. Geochemical evidence suggests that the primary basanite melt was derived from a mantle source affected by differentiation. Original Russian Text ? T.Yu. Timina, V.V. Sharygin, A.V. Golovin, 2006, published in Geokhimiya, 2006, No. 8, pp. 814–833.     

Petrography,chemical composition,and Raman spectra of chrome spinel: Constraints on the diamond potential of the No. 30 pipe kimberlite in Wafangdian,North China Craton

Conventional diamond exploration seldom searches directly for diamonds in rock and soil samples. Instead, it focuses on the search for indicator minerals like chrome spinel, which can be used to evaluate diamond potential. Chrome spinels are preserved as pristine minerals in the early Paleozoic (∼465 Ma), hydrothermally altered, Group I No. 30 pipe kimberlite that intruded the Neoproterozoic Qingbaikou strata in Wafangdian, North China Craton (NCC). The characteristics of the chrome spinels were investigated by petrographic observation (BSE imaging), quantitative chemical analysis (EPMA), and Raman spectral analysis. The results show that the chrome spinels are mostly sub-rounded with extremely few grains being subhedral, and these spinels are macrocrystic, more than 500 µm in size. The chrome spinels also have compositional zones: the cores are classified as magnesiochromite as they have distinctly chromium-rich (Cr₂O₃ up to 66.56 wt%) and titanium-poor (TiO₂ < 1 wt%) compositions; and the rims are classified as magnetite as they have chromium-poor and iron-rich composition. In the cores of chrome spinels, compositional variations are controlled by Al³⁺-Cr³⁺ isomorphism, which results in a strong Raman spectra peak (A_1g mode) varying from 690 cm⁻¹ to 702.9 cm⁻¹. In the rims of chrome spinel, compositional variations result in the A_1g peak varying from 660 cm⁻¹ to 672 cm⁻¹. The morphology and chemical compositions indicate that the chrome spinels are mantle xenocrysts. The cores of the spinel are remnants of primary mantle xenocrysts that have been resorbed, and the rims were formed during kimberlite magmatism. The compositions of the cores are used to evaluate the diamond potential of this kimberlite through comparison with the compositions of chrome spinels from the Changmazhuang and No. 50 pipe kimberlites in the NCC. In MgO, Al₂O₃ and TiO₂ versus Cr₂O₃ plots, the chrome spinels from the Changmazhuang and No. 50 pipe kimberlites are mostly located in the diamond stability field. However, only a small proportion of chrome spinels from No. 30 pipe kimberlite have same behavior, which indicates that the diamond potential of the former two kimberlites is greater than that of the No. 30 pipe kimberlite. This is also supported by compositional zones in the spinel grains: there is with an increase in Fe³⁺ in the rims, which suggests that the chrome spinels experienced highly oxidizing conditions. Oxidizing conditions may have been imparted by fluids/melts that have a great influence on diamond destruction. Here, we suggest that chrome spinel compositions can be a useful tool for identifying the target for diamond potential in the North China Craton.     

The last interglacial as represented in the glaciochemical record from Mount Moulton Blue Ice Area,West Antarctica

Understanding climate during the last interglacial is critical for understanding how modern climate change differs from purely naturally forced climate change. Here we present the first high-resolution ice core record of the last interglacial and transition to the subsequent glacial period from Antarctica and the first glaciochemical record for this period from West Antarctica. Samples were collected from a horizontal ice trench in the Mt. Moulton Blue Ice Area (BIA) in West Antarctica and analyzed for their soluble major anions (Cl^?, NO₃^?, SO₄^2-), major and trace elements (Na, Mg, Ca, Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Al, S, Ti, V, Cr, Mn, Fe, Co, Cu, Zn) and water hydrogen isotopes (δD). The last interglacial is characterized by warmer temperatures (δD), weakened atmospheric circulation (dust elements, seasalts aerosols), decreased sea ice extent (Na, nssSO₄^2-) and decreased oceanic productivity (nssSO₄^2-). A combined examination of Mt. Moulton seasalts, dust, nssSO₄^2- and δD records indicates that the last interglacial was extremely stable compared to glacial age climate events and it ended through a long period of gradual cooling unlike that projected for future Holocene climate.     

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H₂O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for ^[6]Mg _m ^[4] Si _n O_(m+2n) and MgSO₄(H₂O) _n .     

Chromite in the Platreef (Bushveld Complex, South Africa): occurrence and evolution of its chemical composition

The regional distribution and chemical composition of massive and disseminated chromitites through a Platreef sequence and along a strike distance of over ∼20 km were investigated to correlate them both within the framework of the northern limb and to the eastern and western limbs of the Bushveld Complex. The chromitite layers and seams of the Platreef form two main chromite-bearing zones: the Upper Chromitite that occurs as two to three discontinuous seams in feldspathic pyroxenite at approximately 20 m below the Platreef top contact and the Lower Chromitite that is composed of multiple seams in feldspathic harzburgite, pyroxenite and norite close to the bottom contact of the Platreef with footwall. Electron micro-probe analyses reveal that the chemical composition of chromite depends on the host rock type. Norite and pyroxenite host chromite with the highest Cr₂O₃ content while harzburgite-hosted chromites are Cr and Mg poor. The wide range in chromite compositions is explained by the influence of late-magmatic processes including post-cumulus growth and re-equilibration, interaction with fluid- and sulphide-saturated magmatic liquid and contact metamorphism. Each of these processes is characterised by its own distinct geochemical signature, but generally they lead to a decrease in Mg and Al and an increase in both di- and tri-valent Fe in the chromite. The occurrence of chromitite locally on the different distance from the contact between the upper Platreef sills and the overlying Main Zone magma suggests erosion of the upper Platreef by the Main Zone as it was emplaced. The localisation of chromitites supports an independent development of the northern limb during the Critical Zone emplacement although the chemical composition of chromite and co-existing silicates from ultramafic rocks suggest a Critical Zone affinity with the eastern and western limbs of the Bushveld Complex.     

Ilmenite composition in the Tellnes Fe–Ti deposit,SW Norway: fractional crystallization,postcumulus evolution and ilmenite–zircon relation

Major and trace element XRF and in situ LA-ICP-MS analyses of ilmenite in the Tellnes ilmenite deposit, Rogaland Anorthosite Province, SW Norway, constrains a two stage fractional crystallization model of a ferrodioritic Fe-Ti-P rich melt. Stage 1 is characterized by ilmenite-plagioclase cumulates, partly stored in the lower part of the ore body (Lower Central Zone, LCZ), and stage 2 by ilmenite-plagioclase-orthopyroxene-olivine cumulates (Upper Central Zone, UCZ). The concentration of V and Cr in ilmenite, corrected for the trapped liquid effect, (1) defines the cotectic proportion of ilmenite to be 17.5 wt% during stage 1, and (2) implies an increase of D _V^Ilm during stage 2, most likely related to a shift in fO₂. The proportion of 17.5 wt% is lower than the modal proportion of ilmenite (ca. 50 wt%) in the ore body, implying accumulation of ilmenite and flotation of plagioclase. The fraction of residual liquid left after crystallization of Tellnes cumulates is estimated at 0.6 and the flotation of plagioclase at 26 wt% of the initial melt mass. The increasing content of intercumulus magnetite with stratigraphic height, from 0 to ca. 3 wt%, results from differentiation of the trapped liquid towards magnetite saturation. The MgO content of ilmenite (1.4–4.4 wt%) is much lower than the expected cumulus composition. It shows extensive postcumulus re-equilibration with trapped liquid and ferromagnesian silicates, correlated with distance to the host anorthosite. The Zr content of ilmenite, provided by in situ analyses, is low (<114 ppm) and uncorrelated with stratigraphy or Cr content. The data demonstrate that zircon coronas observed around ilmenite formed by subsolidus exsolution of ZrO₂ from ilmenite. The U-Pb zircon age of 920 ± 3 Ma probably records this exsolution process. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Palaeoenvironmental record of glacial lake evolution during the early Holocene at Sokli,NE Finland

The development of a glacial lake impounded along the retreating, northeastern ice margin of the Fennoscandian Ice Sheet during the last deglaciation and environmental conditions directly following the early Holocene deglaciation have been studied in NE Finland. This so‐called Sokli Ice Lake has been reconstructed previously using topographic and geomorphologic evidence. In this paper a multiproxy approach is employed to study a 3‐m‐thick sediment succession consisting of laminated silts grading into gyttja cored in Lake Loitsana, a remnant of the Sokli Ice Lake. Variations in the sediment and siliceous microfossil records indicate distinct changes in water depth and lake size in the Loitsana basin as the Sokli Ice Lake was drained through various spillways opening up along the retreating ice front. Geochemical data (XRF core‐scanning) show changes in the influence of regional catchment geochemistry (Precambrian crystalline rocks) in the glacial lake drainage area versus local catchment geochemistry (Sokli Carbonatite Massif) within the Lake Loitsana drainage area during the lake evolution. Principal component analysis on the geochemical data further suggests that grain‐size is an additional factor responsible for the variability of the sediment geochemistry record. The trophic state of the lake changed drastically as a result of morphometric eutrophication once the glacial lake developed into Lake Loitsana. The AMS radiocarbon dating on tree birch seeds found in the glaciolacustrine sediment indicates that Lake Loitsana was deglaciated sometime prior to 10 700 cal. a BP showing that tree Betula was present on the deglaciated land surrounding the glacial lake. Although glacial lakes covered large areas of northern Finland during the last deglaciation, only few glaciolacustrine sediment successions have been studied in any detail. Our study shows the potential of these sediments for multiproxy analysis and contributes to the reconstruction of environmental conditions in NE Finland directly following deglaciation in the early Holocene.     

碳酸岩岩浆演化的指示性矿物—环带金云母——以山东西部雪野碳酸岩为例

山东西部莱芜－淄博地区的中生代雪野碳酸岩中发育有大量罕见的反环带云母,云母的电子探针分析表明,云母斑晶的核心为黑云母,过渡带和边缘是金云母,基质中云母为金云母,核心黑云母与过渡带的金云母界限清晰,成分突变以及核心黑云母的溶蚀结构表明,核心黑云母和过渡带与边缘带金云母不是同一岩浆体系结晶的产物,核心黑云母可能是碳酸岩岩浆捕获的外来黑云母,过渡带与边缘带金云母同基质中金云母具有相似的化学成分,从过渡带到边缘带,金云母的Mg(Mg Fe)逐渐降低,反映了碳酸岩岩浆的不断结晶演化过程,TiO2的不断降低,一方面是由于岩浆的分异结晶,另一方面则是岩浆上升期间去气作用导致岩浆内CO2／H2O值降低所致。云母斑晶从过渡带向边缘带Al2O3含量逐渐减少,表明碳酸岩浆自过渡带云母结晶后没有富Al的圈岩物质加入。     

Crystal chemical and energy analysis of partition coefficients of impurities during melt crystallization: The case of olivine

Partition coefficients (K) between forsterite crystal and melt are experimentally determined for many univalent, bivalent, trivalent, and tetravalent trace elements. Using numerical modeling, we calculated the energies of intrinsic and impurity defects in forsterite (E _df) and the energies of dissolution of univalent, bivalent, trivalent, and tetravalent impurities (E _ds). These results are compared with literature data. A linear dependence is established for the energy of defects on the charge of the impurity ion and the relative difference in the radii of the impurity and matrix ions Δr/d, where d is the average interatomic distance in the matrix. Partition coefficients are described by parabolic dependences on Δr/d and charge of the impurity ion using literature data on K of impurity elements in olivines and impurity ion dissolution energies. Linear dependences-RTlnK-(Δr/d)² and E _ds-(Δr/d)² pass through the origin for isovalent substitutions and are well apart from it for heterovalent substitutions. Linear dependence (Δr/d)² has a free term of about 200 kJ/mol, which is approximately equal to a half of the energy of formation of the Frenkel defect in forsterite; this defect maintains electroneutrality. If valency is compensated due to addition into the melt of an ion with another charge (than that of the impurity ion), E _ds-(Δr/d)² and-RTlnK-(Δr/d)² lines at low (Δr/d)² shift to the origin. This means that energy consumption for coupled isomorphism is lower than that for the formation of intrinsic structural defects. Correlation dependences are proposed for the distribution of impurities and the energy of their dissolution. They indicate the increasing contribution of the entropy components of impurity ion dissolution energy during heterovalent isomorphism.     

Calcium isotope record of Phanerozoic oceans: Implications for chemical evolution of seawater and its causative mechanisms

A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ^44/40Ca_SW) over the Phanerozoic. The compiled δ^44/40Ca_SW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ^44/40Ca_SW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine ⁸⁷Sr/⁸⁶Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO₂, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ^44/40Ca_SW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ^44/40Ca_SW. As to the causes of the short-term oscillations recorded in the secular δ^44/40Ca_SW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.