Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

Cryptic crustal contamination of MORB primitive melts recorded in olivine-hosted glass and mineral inclusions

The origin of compositional heterogeneities among the magmas parental to mid-ocean ridge basalts (MORB) was investigated using a single rock piece of the olivine-phyric basalt from 43°N, Mid-Atlantic Ridge (AII D11-177). The exceptional feature of this sample is presence of very primitive olivine crystals (90–91 mol% Fo) that are significantly variable in terms of CaO (0.15–0.35 wt%). A population of low-Ca olivine (0.15–0.25 wt% CaO) is also notably distinct from high-Ca olivine population in AII D11-177, and primitive MORB olivine in general, in having unusual assemblage of trapped mineral and glass inclusions. Mineral inclusions are represented by high-magnesian (Mg# 90.7–91.1 mol%) orthopyroxene and Cr-spinel, distinctly enriched in TiO₂ (up to 5 wt%, c.f. <1 wt% in common MORB spinel). Glass inclusions associated with orthopyroxene and high-Ti Cr-spinel have andesitic compositions (53–58 wt% SiO₂). Compared to the pillow-rim glass and “normal” MORB inclusions, the Si-rich glass inclusions in low-Ca olivine have strongly reduced Ca and elevated concentrations of Ti, Na, K, P, Cl, and highly incompatible trace elements. Strong variability is recorded among glass inclusions within a single olivine phenocrysts. We argue that the observed compositional anomalies are mineralogically controlled, and thus may arise from the interaction between hot MORB magmas and crystal cumulates in the oceanic crust or magma chamber.     

东疆二叠纪镁铁-超镁铁岩体中辉石的成分特征及其对成岩和Ni-Cu成矿的指示

新疆东部早二叠世镁铁-超镁铁岩体主要分布在天山东段觉罗塔格构造带、中天山地块和北山地区,与这类岩体相关的Ni-Cu矿床主要产出在觉罗塔格带和中天山地区,北山目前并未发现典型Ni-Cu矿床。这些岩体中的斜方辉石主要为古铜辉石,少量为紫苏辉石;单斜辉石属透辉石、次透辉石或普通辉石。矿物成分系统变化显示橄榄石Fo值北山最高、觉罗塔格带到中天山逐次降低的特点,橄榄石Fo值在78~86和Ni含量低于1800×10-6范围内更有利于Cu-Ni成矿;斜方辉石En端元和单斜辉石Wo端元极差值也显示北山最高、觉罗塔格带和中天山较低的规律,且相对小的极差值更有利于成矿。单斜辉石AlⅣ/AlⅥ比值结果显示北山岩体在矿物结晶过程中压力较低,硫溶解度较大,可能是其矿化程度弱于觉罗塔格带和中天山的一个重要因素。觉罗塔格带、中天山和北山镁铁-超镁铁质岩体的母岩浆为非碱性系列、大陆拉斑玄武质岩浆。根据北山和觉罗塔格带岩体单斜辉石微量元素成分估算的母岩浆具有LREE富集以及Nb、Ta、Zr、Hf负异常的特征,指示出两者源区为受俯冲板片交代的地幔,且坡北源区俯冲交代程度更低。觉罗塔格带和中天山单斜辉石Alz vs.Ti显示裂谷堆晶趋势向弧堆晶趋势演化,而北山单斜辉石Alz vs.Ti则显示明显的裂谷堆晶趋势,这说明俯冲交代作用在觉罗塔格带和中天山地区表现的更为强烈。北山镁铁-超镁铁岩体中发现单斜辉石Ti的高异常及矿物温压计算结果显示,表明北山地区具有比觉罗塔格带和中天山更高的岩浆温度,这可能与塔里木二叠纪地幔柱的活动有关。     

Ultrahigh temperature deformation microstructures in felsic granulites of the Napier Complex, Antarctica

Detailed electron microscope and microstructural analysis of two ultrahigh temperature felsic granulites from Tonagh Island, Napier Complex, Antarctica show deformation microstructures produced at  1000 °C at 8–10 kbar. High temperature orthopyroxene (Al 7 wt.% and  11 wt.%), exhibits crystallographic preferred orientation (CPO) and frequent subgrain boundaries which point to dislocation creep as the dominating deformation mechanism within opx. Two different main slip systems are observed: in opx bands with exclusively opx grains containing subgrain boundaries with traces parallel to [010] and a strong coupling of low angle misorientations (2.5°–5°) with rotation axes parallel to [010] the dominating slip system is (100)[001]. Isolated opx grains and grain clusters of 2–5 grains embedded in a qtz–fsp matrix show an additional slip system of (010)[001]. The latter slip system is harder to activate. We suggest that differences in the activation of these slip systems is a result of higher differential stresses imposed onto the isolated opx grains and grain clusters. In contrast to opx, large qtz grains (up to 200 μm) show random crystallographic orientation. This together with their elongate and cuspate shape and the lack of systematic in the rotation axes associated with the subgrain boundaries is consistent with diffusion creep as the primary deformation mechanism in quartz.Our first time detailed microstructural observations of ultrahigh temperature and medium to high pressure granulites and their interpretation in terms of active deformation mechanisms give some insight into the type of rheology that can be expect at lower crustal conditions. If qtz is the mineral phase governing the rock rheology, Newtonian flow behaviour is expected and only low differential stress can be supported. However, if the stress supporting mineral phase is opx, the flow law resulting from dislocation creep will govern the rheology of the rock unit; hence, an exponential relationship between stress and strain rate is to be expected.     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

承德黑山斜长岩杂岩体辉石特征及其形成温度条件

本文对黑山斜长岩杂岩体中斜方辉石和单斜辉石的光学特征、化学成分及其演化规律作了系统研究的同时,也研究了两种辉石中Fe-Mg的分配,其分配系数K_D值多大于1.37。并用13对共生的二辉石矿物对的化学成分,计算了形成温度为800～980℃。该杂岩体是在平衡条件下缓慢结晶而成。     

汉诺坝地幔捕虏体中富硅熔体的成因及其意义

近年来地幔捕虏体中富硅熔体的研究受到广泛关注,富硅熔体不仅具有多种产出状态,其成因来源也具有多样性。本文选取汉诺坝地区地幔捕虏体矿物中的熔体包裹体和斜方辉石反应边中的熔体玻璃为研究对象,探索富硅熔体在岩石圈地幔演化中的作用。通过详细的岩相学观察并结合电子探针分析发现,二者成因不同。熔体包裹体玻璃成分富硅(SiO₂ 61%~65%),相对贫Na₂O(1%~3%)、K₂O(<1%),富含挥发份(约3%~6%),为地幔交代成因;斜方辉石反应边玻璃富硅(SiO₂ 64%~67%)、碱(Na₂O 5%~7%,K₂O 6%~9%),几乎不含挥发份,是地幔捕虏体被寄主玄武岩浆快速携带上升至地表的过程中两者反应的产物。地幔交代作用产生的富硅熔体包裹体深刻影响了岩石圈地幔的地球化学性质;而玄武岩浆在上升过程中与岩石圈地幔捕虏体中斜方辉石的反应,导致了岩石圈地幔由富硅向贫硅转变,为华北克拉通的破坏提供了证据。     

东天山岩浆铜镍硫化物矿床的多期次岩浆侵位与成矿作用——以黄山铜镍矿床为例

位于黄山-镜儿泉镁铁-超镁铁岩带西段的黄山铜镍矿田（包括黄山、黄山东、香山、黄山南矿床）,是北疆最重要的镍矿产地。矿田内各岩体都是多期岩浆侵位形成的杂岩体,且黄山东和香山铜镍矿床存在多期成矿作用。本文选取黄山大型隐伏铜镍矿床进行详细解剖,在此基础上探讨东天山地区多期成岩成矿作用及其勘查意义。黄山矿山开采揭露最新地质现象系统观察,不同岩相中橄榄石、辉石（粒径、成分）的垂向和平面剖面变化表明黄山铜镍矿床由多期岩浆侵位形成,且第三期次为主要成矿期。第三期次岩相主要由角闪二辉橄辉岩、角闪方辉橄辉岩和角闪橄榄岩组成。角闪二辉橄辉岩底部的橄榄石核部和边部具有明显的成分差异,其橄榄石的边部相对于核部Fo值和Ni含量升高,由于橄榄石结晶过程中与晶间硫化物发生Fe-Ni的交换反应所致。第三期次的角闪方辉橄辉岩和角闪橄榄岩岩相中橄榄石的Fo值与角闪二辉橄辉岩中橄榄石Fo值相近,但Ni含量（500×10^-6~2050×10^-6）高于第二侵入期次角闪二辉橄辉岩中的Ni含量（160×10^-6~1000×10^-6）,橄榄石和硫化物熔体的Fe-Ni交换反应或者不同的母岩浆性质是橄榄石Ni含量不同的主要原因。黄山岩体的斜方辉石都为古铜辉石,第三期次岩体角闪方辉橄辉岩和角闪橄榄岩中含有粗粒的古铜辉石,其最大粒径（4~8mm）大于角闪二辉橄辉岩中古铜辉石（2~4mm）。单颗粒古铜辉石的Mg^#值、CaO及Cr₂O₃含量从核部到边部有多次重复变化,反映岩浆成分存在多次变化。第三期次单斜辉石包裹的橄榄石的边部比核部具有更高的Ni含量（Fo值相似）,结合Cu、Ni、Co等元素的垂直剖面变化,本文提出新鲜岩浆补给是黄山主矿体（30号矿体）硫化物富集的重要控制因素。多次岩浆的补给暗示黄山为岩浆通道成矿系统。岩体变宽、局部膨大及岩体产状改变部位是硫化物有利的聚集部位。东天山黄山-镜儿泉地区铜镍矿床勘查过程中往往以超基性岩相为主要评价对象,根据黄山矿田其他岩体的岩石组合与矿化岩相分析,本文认为该区铜镍矿勘查过程中也要重视基性岩相（辉长岩、苏长岩、橄榄辉长岩等）的成矿潜力,对多期次岩浆作用及相对应的成矿作用应给予重视。     

Orthopyroxene–cordierite mafic gneiss from the Nomamisaki metamorphic rocks,Southern Kyushu,Japan: Implication for western continuation of the Usuki–Yatsushiro Tectonic Line

We describe an orthopyroxene–cordierite mafic gneiss from the Nomamisaki metamorphic rocks in the Noma Peninsula, southern Kyushu, Japan. The mineral assemblage of the gneiss is orthopyroxene, cordierite, biotite, plagioclase, and ilmenite. Thermometry based on the Fe–Mg exchange reaction between orthopyroxene and biotite yields a peak metamorphic temperature of 680°C. The stability of cordierite relative to garnet, quartz, and sillimanite defines the upper limit of the peak metamorphic pressure as 4.4 kbar. These features indicate that the Nomamisaki metamorphic rocks underwent low‐pressure high‐temperature type metamorphism. Although a chronological problem still remains, the Nomamisaki metamorphic rocks can be regarded as a western continuation of the Higo Belt. The Usuki–Yatsushiro Tectonic Line, which delineates the southern border of the Higo Belt, is therefore located on the east of the Nomamisaki metamorphic rocks in southern Kyushu.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.