Towards a Li barometer for bimineralic eclogites: experiments in CMAS

An eclogite barometer has profound importance in the study of upper mantle processes and potential application to diamond prospecting. Studies on the partitioning of Li between clinopyroxene (cpx) and garnet (grt) in natural samples have shown that this particular element is very sensitive to changes in pressure and could be calibrated as the barometer demanded for bimineralic eclogites. Experiments were performed from 4 to 13 GPa and 1,100–1,400°C in the CMAS (CaO, MgO, Al₂O₃, SiO₂) system with Li added as Li₃PO₄ to quantify this pressure dependence into a barometer expressed in the following equation: P = (0.00255T – ln K _d)/0.2351 where P is in GPa, T is in °C and K _d is defined as the partition coefficient of Li (in ppm) between clinopyroxene and garnet. The experimental pressures are reproduced to ±0.38 GPa (1σ) by this equation. This barometer is strictly applicable only to CMAS. Experiments at 1,300°C, 8–12 GPa showed that Henry’s Law is fulfilled for Li partitioning between cpx and grt in the concentration range of approximately 0.01–1 wt% Li. Direct application of the equation to experiments in natural systems performed at 1,300°C from 4 to 13 GPa consistently overestimates pressures by approximately 2 GPa. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Monomineral universal clinopyroxene and garnet barometers for peridotitic,eclogitic and basaltic systems

New versions of the universal Jd-Di exchange clinopyroxene barometer for peridotites,pyroxenites and eclogites,and also garnet barometer for eclogites and peridotites were developed.They were checked using large experimental data sets for eciogitic(~530) and peridotitic systems(650).The precision of the universal Cpx barometer for peridotites based on Jd-Di exchange is close to Cr-Tschermalite method produced by Nimis and Taylor(2000).Cpx barometer was transformed by the substitution of major multiplier for K_D by the equations dependent from Al-Na-Fe.Obtained equation in combination with the thermometer of Nimis and Taylor(2000) allow to reconstruct position of the magma feeder systems of the alkali basaltic magma within the mantle diapirs in modern platforms like in Vitim plateau and other Southern Siberia localities and several localities worldwide showing good agreement of pressure ranges for black and green suites.These equations allow construct PTX diagrams for the kimberlite localities in Siberia and worldwide calculating simultaneously the PT parameters for different groups of mantle rocks.They give very good results for the concentrates from kimberlite lamproites and placers with mantle minerals.They are useful for PT estimates for diamond inclusions.The positions of eclogite groups in mantle sections are similar to those determined with new Gar—Cpx barometer produced by C.Beyer et al.(2015).The Fe rich eclogites commonly trace the boundary between the lower upper parts of subcontinental lithospheric mantle(SCLM) at 3-4 CPa marking pyroxenite eclogites layer.Ca-rich eclogites and especially grospydires in SCLM beneath Precambrian kimberlites occurs near pyroxenite layer but in younger mantle sections they became common in the lower parts.The diamondiferous Mg Cr-less group eclogites referring to the ancient island arc complexes are also common in the middle part of mantle sections and near 5-6 GPa.Commonly eclogites in lower apart of mantle sections are remelted and trace the high temperature convective branch.The Mg-and Fe-rich pyroxenites also show the extending in pressure trends which suggest the anatexic melting under the influence of volatiles or under the interaction with plums.     

Characterization of synthetic hedenbergite (CaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)–petedunnite (CaZnSi<Subscript>2</Subscript>O<Subscript>6</Subscript>) solid solution series by X-ray powder diffraction and <Superscript>57</Superscript>Fe Mössbauer spectroscopy

Clinopyroxenes along the solid solution series hedenbergite (CaFeSi₂O₆)–petedunnite (CaZnSi₂O₆) were synthesized under hydrothermal conditions and different oxygen fugacities at temperatures of 700 to 1200 °C and pressures of 0.2 to 2.5 GPa. Properties were determined by means of X-ray diffraction, electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy at 298 K. Unit-cell parameters display a linear dependency with changing composition. Parameters a₀ and b₀ exhibit a linear decrease with increasing Zn content while the monoclinic angle increases linearly. Parameter c₀ is not affected by composition and remains constant at a value of 5.248 Å. The molar volume can be described according to the equation V_mol (ccm mol^–1)=33.963(16)–0.544(31)*Zn pfu. The isomer shifts of ferrous iron on the octahedral M1 site in hedenbergite are not affected by composition along the hedenbergite–petedunnite solid solution series and remain constant at an average value of 1.18 mm s^–1. Quadrupole splittings of Fe²⁺ on the M1 are, however, strongly affected by composition, and they decrease linearly with increasing petedunnite component in hedenbergite, ranging from 2.25 mm s^–1 for pure hedenbergite end member to 1.99 mm s^–1 for a solid solution containing 84 mole% petedunnite. The half-widths of intermediate solid solutions vary between 0.26 and 0.33 mm s^–1, indicating, in accordance with the microprobe analyses and X-ray diffraction, that samples are homogeneous and well-crystallized. The data from this study demonstrate that the crystallinity of hedenbergitic clinopyroxenes can be improved by using oxide mixtures as starting materials. Crystal sizes for intermediate compositions range up to 70 m, suitable for standard single-crystal X-ray analysis.This paper is dedicated to Prof. Dr. Georg Amthauer, Salzburg, on occasion of his 60th birthday     

吉林省长白山地区新生代火山岩的特点及其成因

长白山地区新生代火山岩是一套玄武岩、粗面岩和钠闪碱流岩的双峰式火山岩组合。玄武岩类分别属于碱性玄武岩系列和拉斑玄武岩系列。奶头山期玄武岩是幔源原生岩浆直接喷发于地表的产物,其他各期玄武岩是幔源原生岩浆经历了一定程度分异作用的产物。粗面岩和钠闪碱流岩与玄武岩有成因联系,可能是玄武岩浆通过分离结晶作用而形成的。本区新生代火山岩是大陆裂谷构造环境下的产物,是在地幔增温和底辞上升过程中形成的。     

Plastic deformation of orthoenstatite and the ortho- to high-pressure clinoenstatite transition: a metadynamics simulation study

Atomic-scale mechanisms of plastic deformation in orthoenstatite, MgSiO₃ are studied by computer simulation methods. The combined use of metadynamics and molecular dynamics allows a direct observation of the structural changes during the creation of stacking faults in the (100) plane. A sequence of slip deformations in two different (100) planes at P = 15 GPa and T = 1,000 K reveals a probable transformation mechanism for the ortho- to high-pressure clinopyroxene transition. Each of the observed slips consists of at least four partial deformations crossing high-energy intermediate structures. In agreement with experimental studies, both (100)[010] and (100)[001] slip systems are activated in the deformation process. The observation of a dominant (100)[001] single slip system in pyroxenes may be related to the fact that high-energy intermediate dislocations with (100)[010] component are not stable on geological or experimental timescales.     

Sr–barite droplets associated with sulfide blebs in clinopyroxene megacrysts from basaltic tuff (Szentbékkálla, western Hungary)

A unique occurrence of strontian barite droplets associated with oriented planes of primary sulfide blebs in several clinopyroxene megacrysts was found in the Plio-Pleistocene basaltic tuff of Szentbékkálla (Bakony–Balaton Highland, western Hungary). The barite droplets contain 3.22–14.7 wt.% SrO, variable amount of FeO (up to 3.25 wt.%), minor CaO, CuO and NiO. Textural arrangements of oriented sulfide planes show that they were trapped as immiscible sulfide melt during crystallization of the clinopyroxene. Temperature and pressure estimation (978–1094 °C and 1.0–1.1 GPa) of the host clinopyroxenes indicate that formation of clinopyroxene megacrysts and entrapment of sulfide blebs happened under upper mantle conditions.

A genetic relationship between the sulfate and sulfide blebs is doubtful. Textural features suggest that the barite droplets might have been trapped together with the sulfide blebs from immiscible sulfide melts. However, it cannot be excluded that the barite formed during metasomatic event following the sulfide formation.     

大别山碧溪岭和黄镇榴辉岩中绿辉石的结构水：对原岩性质和动力学过程的制约

运用傅立叶变换红外光谱(FTIR)技术,对大别山碧溪岭和黄镇榴辉岩中的绿辉石进行了详细的结构水观察。绿辉石中普遍含有结构水,以OH~-的形式存在,含量可达～2000ppm(H_2O wt.)。碧溪岭绿辉石的水含量在露头尺度(-150km)上是不均一的,而黄镇绿辉石是均一的(至少在3km的尺度上)。碧溪岭绿辉石水含量的不均一分布和黄镇绿辉石水含量的均一分布都反映的是原岩特征,碧溪岭榴辉岩原岩经历的水-岩相互作用是“隧道式”的而黄镇是“弥散式”的碧溪岭榴辉岩的原岩可能是基性的侵入岩而黄镇榴辉岩的原岩可能是玄武岩。碧溪岭绿辉石的水含量(<1400ppm)明显低于黄镇绿辉石(～1850ppm),这是原岩水含量差异的体现,原岩性质的不同和经历的水-岩相互作用方式的不同造成了原岩水含量的差异。     

拉萨地块中南部新生代超钾质岩中单斜辉石斑晶的环带成分研究

在青藏高原拉萨地块中南部的米巴勒、麦嘎乡、赛利普地区分布有新生代的超钾质火山岩,这些火山岩的斑晶中广泛发育单斜辉石正环带,其记录了超钾质岩浆的早期结晶历史.这些单斜辉石的正环带核部到边部Mg*和镁、铬的氧化物含量降低,而铁、钠、铝、钛的氧化物含量升高,它反映了岩浆正常结晶的顺序.米巴勒地区超钾质岩中的单斜辉石还出现反环带和少量的韵律环带,可能与该地区所发现的共生钠质过碱性火山岩有关,韵律环带揭示了其可能是相同成分的超钾质母岩浆从岩浆源区多次补给形成,而反环带则可能是与钠质过碱性火山岩岩浆存在一定程度的混合造成的.尽管三个地区超钾质火山岩的喷发时间稍不同,但是三地区的单斜辉石正环带核部成分基本相同,它们具有相似的Al-Ti值,指示出超钾质岩形成在相同的构造环境并具有相同的岩浆成因.     

辽西义县组玄武岩捕虏晶的发现及其意义

辽西早白垩世义县组底部有一套镁含量较高（MgO=8％～10％）的橄榄玄武岩，有人称之为“高镁玄武岩”。通过这些玄武岩所含的橄榄石、单斜辉石的形态特征、环带结构以及所包含不透明矿物的研究，笔者认为它们属于地幔捕虏晶。捕虏晶和玄武质熔体反应的结果形成了环带结构，由于捕虏晶比玄武质熔体富Mg、Ni、Cr，贫Fe、Mn、Ca，因此作用结果提高了熔体的镁含量。此外，辉石的反环带以及复杂环带结构反映了两种熔体的混合作用。因此上述橄榄石、辉石捕虏晶的发现有助于揭示：1）岩石圈地幔和熔体相互作用以及高镁岩石的成因；2）两种熔体的混合作用。这一发现对进一步研究华北中生代岩石圈地幔的改造与破坏，理解华北克拉通东部中生代地球动力学背景和构造环境是有意义的。     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.