High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

南秦岭早古生代玄武岩的岩浆源区及演化过程

南秦岭地区早古生代玄武岩中发育的大量单斜辉石斑晶为研究火山岩的深部演化过程及源区属性提供了重要的载体。本文通过对早古生代玄武岩及其中的单斜辉石斑晶进行矿物学、岩石学及地球化学分析,讨论火山岩的演化历程及源区属性。电子探针分析结果表明玄武岩中单斜辉石斑晶属于透辉石,其成分与全岩成分并不平衡,暗示岩石经历了单斜辉石的堆晶作用。通过质量平衡计算得到了与单斜辉石斑晶平衡的熔体并计算了单斜辉石结晶的温压条件,结果显示单斜辉石斑晶结晶压力为7.6～14.0kbar,温度为1201～1268℃。高压下的分离结晶作用导致了单斜辉石成为主要的结晶相。重建后的玄武岩具有高镁、高钙、富钛,富集高场强元素Nb、Ta,亏损Rb、K、Sr和P,Dy/Yb比值高的地球化学特征,指示其源区为含单斜辉石、磷灰石及石榴石的交代岩石圈地幔。同地区发现的玄武质角砾也具高镁及高钙的特征,其富集Ba、Nb、Ta、Ti及低Dy/Yb比值表明源区为含单斜辉石、角闪石及尖晶石的交代岩石圈地幔。     

河北矾山杂岩体中单斜辉石的研究

河北矾山杂岩体属于二氧化硅不饱和的超钾质碱性-过碱性岩浆系列,由单斜辉石岩、辉石正长岩和碱长正长岩等不同类型岩石组成。各类型岩石主要组成矿物为单斜辉石、黑云母、石榴石和正长石。本文利用电子探针对单斜辉石进行了详细研究,发现所有单斜辉石属于高钙透辉石,随着岩浆的演化,主要表现为Fe²⁺对Mg²⁺的替代关系,结晶趋势为透辉石→钙铁辉石,这揭示矾山杂岩体岩浆体系的特点是高温、中等大小的氧逸度、贫硅、富碱（尤其是钾）。辉石中的Al^IV含量取决于岩浆的硅饱和度,硅越不饱和,Al^IV含量越高;Al^VI含量则与体系中的Al含量呈正相关关系。由Al对Si的替代引起的电荷不平衡主要由八面体位置的Fe³⁺来补偿,其次为少量的Ti⁴⁺和更少量的Al³⁺。体系中的Ti含量与体系的温度呈正相关关系,而Na含量则与辉石中的Ti和Fe³⁺含量成正相关关系。不同类型岩石中单斜辉石从核部到边部随着Mg^#的降低,Al、Ti含量呈现不同的演化趋势,这是因为它们于岩浆演化的不同阶段开始结晶,经历了不同的岩浆演化史。碱性岩中高钙辉石的出现和成分环带的普遍发育是由岩浆的贫硅富钾特征决定的。单斜辉石的成分不仅受控于结晶时的温度、压力条件,也受控于岩浆的总成分及其变异。     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

北大巴山志留系滔河口组碱质斑状玄武岩的岩浆源区及形成环境——来自全岩和辉石斑晶地球化学的约束

北大巴山志留系滔河口组火山-沉积地层发育有粗粒玄武岩、细粒玄武岩、杏仁构造玄武岩和枕状玄武岩四种斑状玄武岩相。它们都属于碱性玄武岩,并具有相似的地球化学特征,富Ti、贫Si,富集大离子亲石元素(LILE,如Th、Rb、Ba)和LREE,轻重稀土分异明显。稀土和微量元素标准化配分型式具有与洋岛玄武岩(OIB)类似的特征。斑晶主要属于单斜辉石族中的次透辉石-透辉石,具有与全岩相似的微量和稀土元素配分形态,表明四种玄武岩相由同一岩浆源区形成。由单斜辉石-熔体平衡温压计计算获得的初始岩浆深度大于67.65km,表明岩浆源区来自地幔。岩浆在上升过程中在39.93～67.65km、14.52～20.46km、4.62～9.24km三个深度范围发生了储积结晶,最后喷出到地表分别形成粗粒玄武岩、细粒和枕状玄武岩、杏仁构造玄武岩。粗粒玄武岩中富含金云母表明岩浆源区遭受了富不相容元素流体的交代作用。玄武岩全岩、单斜辉石地球化学特征以及火山-沉积序列共同表明,滔河口组碱性玄武岩形成于大洋板内环境。     

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。     

Elastic constants of chrome-diopside: application of resonant ultrasound spectroscopy to monoclinic single-crystals

The right-rectangular parallelepiped resonance (RPR) form of resonant ultrasound spectroscopy (RUS) is applied to monoclinic crystal symmetry to determine the 13 adiabatic elastic constants, C_ij, of single-crystal chrome-diopside Di_0.93Hd_0.03Ur_0.02X_0.02 (Di, diopside; Hd, hedenbergite; Ur, ureyite; X, other or unknown). These data represent the first published values of the elastic tensor for a monoclinic single-crystal determined by the RPR method, thus demonstrating the feasibility of this method for studying elasticity of low-symmetry crystals. The lowest 62 modal frequencies of a gem-quality specimen were measured and identified at ambient temperature and pressure. Inverting the modal frequencies results in, respectively C₁₁, C₂₂, C₃₃, C₄₄, C₅₅, C₆₆, C₁₂, C₁₃, C₂₃, C₁₅, C₂₅, C₃₅, C₄₆ values (GPa) of 228.1(1.0), 181.1(0.6), 245.4(1.3), 78.9(0.3), 68.2(0.2), 78.1(0.2), 78.8(0.5), 70.2(0.7), 61.1(0.7), 7.9(0.5), 5.9(0.5), 39.7(0.4), and 6.4(0.2), where numbers in parentheses indicate experimental uncertainty. The corresponding isotropic bulk, K_S, and shear, G, moduli are 116.5 (0.9) and 72.8(0.4) GPa, respectively. When comparing these results with other pyroxene data, we find systematic correlations between M2 site composition and C_ij values for most, but not all, moduli. Unusual compositional dependence near end-member diopside is seen for a few moduli, and is propagated to the K_S and G moduli, which should prompt a reexamination of some C_ij values of end-member diopside.     

Computer modelling of hydrogen defects in the clinopyroxenes diopside and jadeite

Atomistic computer simulation techniques have been employed to model mechanisms of hydrogen incorporation in the clinopyroxenes diopside and jadeite. Calculation of solution reaction energies for the pure phases indicates that hydrogen is most easily incorporated via the formation of [V_Si(OH)₄] ^x hydrogarnet type defects. When components of the two phases are mixed, then solution energies can become exothermic. The substitution of Al for Si in diopside and of Mg or Ca for Al in jadeite, provides favourable routes for hydrogen incorporation, with exothermic values of solution energy. Thus the amount of water present in these minerals in the Earth’s upper mantle will vary with composition. Simulation of IR frequencies associated with O–H stretching at specific defect clusters has also been carried out. An analysis of hydrogen–oxygen bond lengths gives good agreement, although comparison of experimental and calculated IR frequencies are problematic. This is partly due to the complexity of experimental spectra, but may also be due in part to deficiencies in the ability of the model to accurately describe the O–H stretching frequency.     

The elastic constants of monoclinic single-crystal chrome-diopside to 1,300 K

Values of the complete adiabatic elastic tensor for single-crystal chrome-diopside (a monoclinic pyroxene mineral) are presented from 298 to 1,300 K. The data were obtained using resonant ultrasound spectroscopy (RUS). They are the first published results for the temperature T dependences of the 13 individual elastic constants C _ij of any clinopyroxene mineral. Each C _ij is appropriately described by a linear function in T throughout the range of T. Values for each (∂C _ij /∂T) _P in GPa K⁻¹ are as follows: C ₁₁, −0.0291; C ₂₂, −0.0248; C ₃₃, −0.0179; C ₄₄, −0.0103; C ₅₅, −0.0077; C ₆₆, −0.0152; C ₁₂, −0.0119; C ₁₃, −0.0064; C ₂₃, 0.0000; C ₁₅, 0.0025; C ₂₅, 0.0022; C ₃₅, −0.0046; and C ₄₆, 0.0026. Values of (∂M/∂T) _P in GPa K⁻¹, where M represents an isotropic bulk property calculated from the C _ij data, are as follows: adiabatic bulk modulus K _S , −0.0123; isothermal bulk modulus K _T , −0.0178; and shear modulus G, −0.00998. Some diopside derivatives, notably (∂K _S /∂T) _P , (∂K _T /∂T) _P , and (∂V _P /∂T) _P , where V _P is the compressional wave velocity, have smaller magnitudes than all other minerals of importance in Earth’s mantle, thus, confirming predictions from systematics studies. We find several dimensionless quantities for this monoclinic mineral have normal values compared to other mantle minerals. Further, αK _T (α is the volume coefficient of thermal expansion) for diopside is approximately independent of both T and volume V at elevated temperature, so its equation of state is accurately expressed in simplified form.     

High-Mg diorites derived from sanukitic HMA magmas, Kyushu Island, southwest Japan arc: evidence from clinopyroxene and whole rock compositions

High-Mg diorites that have similar whole rock composition to high-Mg andesites (HMAs) should not be simply interpreted as rocks solidified from the HMA magmas, because the high-Mg diorites may be mafic cumulates derived from a different magma from the HMAs.

The HMAs contain unique clinopyroxenes with higher Mg# and Si than those of other sub-alkaline series igneous rocks. The Mg# and Si are controlled by the source magma composition rather than its crystallized conditions such as pressure and temperature. The chemical composition of clinopyroxenes would present important information for the investigation of the source of high-Mg diorites.

We considered the source of Early Cretaceous high-Mg diorites on Kyushu Island, southwest Japan arc, based on their clinopyroxene and whole rock compositions. The clinopyroxenes have similar chemical characteristics to those in HMAs rather than those in other sub-alkaline rocks. Moreover, the whole rock compositions are equivalent to the sanukitic HMA and do not show features of mafic cumulates. This indicates that the high-Mg diorites solidified from sanukitic HMA magmas. It is generally believed that the sanukitic HMA magmas involve the subduction of a young and/or hot oceanic slab was situated in their genesis. Therefore, the occurrence of the high-Mg diorites suggests that Kyushu was situated in the tectonic setting of young and/or hot slab subduction in the Early Cretaceous.