Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind,Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g^?1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g^?1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.     

High-temperature annealing of amoeboid olivine aggregates: Heating experiments on olivine–anorthite mixtures

Amoeboid olivine aggregates (AOAs) are composed of forsteritic olivine, Fe,Ni-metal, and Ca,Al-rich nodules consisting mainly of Al-diopside, spinel, and anorthite. Although the textures, shapes, and mineralogy of AOAs are consistent with their being aggregates of nebular condensates, some textures are in conflict with equilibrium condensation calculations, indicating that AOAs were not produced by a simple one-stage condensation. To examine the origin of the constituent minerals within AOAs and their textural relationships, we performed heating experiments using mineral mixtures analogous to those in AOAs. Isothermal and cooling experiments on forsterite + anorthite mixtures reveal that a high-Ca pyroxene phase forms via the incipient melting of the two minerals. Comparative studies of heating experiments performed using the mineralogy of AOAs suggest that Al-diopside in AOAs can be produced from a small degree of melting of forsterite and anorthite. The formation of Al-diopside in this way is consistent with the annealing textures observed in AOAs, and it may account for the discrepancy between the observed mineralogy of AOAs and the results of equilibrium condensation calculations, the occurrence of two types of diopside (Al,Ti-rich diopside and Al-diopside), and the variable Al₂O₃ content of Al-diopside.     

Seismic evidence for a metastable olivine wedge in the subducting Pacific slab under Japan Sea

We apply a forward-modeling approach to high-quality arrival time data from 23 deep earthquakes greater than 400 km depth to investigate the detailed structure of the subducting Pacific slab beneath the Japan Sea. Our results show that a finger-like anomaly exists within the subducting Pacific slab below 400 km depth, which has a P-wave velocity 5% lower than the surrounding slab velocity (or 3% lower than that of the normal mantle), suggesting the existence of a metastable olivine wedge (MOW) in the slab. The MOW top and bottom depths are 400 and 560 km, respectively. The MOW is estimated to be about 50 km wide at 400 km depth and close to the slab upper boundary. At 560 km depth the MOW is located at about 25 km below the slab upper boundary. Most of the deep earthquakes are located in the MOW. Our results favor transformational faulting as the mechanism for deep earthquakes.     

亚稳态橄榄石相变与深源地震研究进展

由于岩石圈俯冲板块内部温度低, 在400km左右的深度橄榄石不发生相变, 低压相的橄榄石便以亚稳态的形式进入更深的深度。 高温高压实验研究表明, 亚稳态橄榄石相变机制以相变形成的超塑性透镜状尖晶石反裂纹破裂为深源地震的触发机制, 能很好的解释深源地震的特征。 亚稳态橄榄石在俯冲带中存在的范围,是制约亚稳态相变机制的重要因素。 然而亚稳态橄榄石在俯冲带存在的范围尚存争议, 不同模型给出结果相差较大, 文中给出一些解决这个问题的建议。     

Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction

 The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal diffraction method. The crystal data are (Co_0.377Ni_0.396Zn_0.227)₂SiO₄, M _r  = 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm³, Z = 4, D _x  = 4.864 g cm⁻³, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)_M1/(A/B)_M2] = −0.272 (IR _A -IR _B ) + 3.65 (EN _A −EN _B ), where IR (pm) and EN are ionic radius and electronegativity, respectively. Received: 8 April 1999 / Revised, accepted: 7 September 1999     

Subdivision of petrologic type of unequilibrated ordinary chondrites from Antarctica

We report results of petrologic and mineralogical studies of 25 unequilibrated ordinary chondrites (19 Chinese Antarctic meteorites) using electron microprobe, scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDS) techniques. With increasing degree of thermal metamorphism, chemical zoning of olivine was erased; plessite was transformed into intergrowths of coarser-grained kamacite and Ni-rich metal; Cr exsolved from ferroan olivine, produced needle-like crystals and coarsened into equant chromite grains; and feldspar crystallized during devitrification of glass and recrystallization of matrix. These features can help to identify different metamorphic grades. Based on the scheme by Sears et al (1982), we subdivided type 3 Chinese Antarctic ordinary chondrites into petrologic type 3.3 to 4 (3 type 3.3, 3 type 3.4, 1 type 3.5, 2 type 3.6, 2 type 3.7, 5 type 3.8, 3 type 4). This classification scheme is a quite effective way to subdivide Antarctic meteorites. Additionally, we propose to revise the chemical groups of GRV 020032 and GRV 020104 to L and H, respectively.     

江山-广丰地区早白垩世晚期玄武岩的岩石地球化学及其构造意义

江山-广丰地区所在的信江红色盆地与金衢红色盆地同属于NEE向赣杭断陷盆地带的组成部分.赣杭构造带自早白垩世晚期开始强烈拉张,红色盆地形成.红层下部夹有层状玄武岩,全岩K-Ar年龄为98～105 Ma,属早白垩世晚期.岩石地球化学特征表明研究区有两类玄武岩:江山陈塘坞一带的拉斑玄武岩,礼贤、广丰一带的碱性橄榄玄武岩.Nd、Sr同位素组成分析显示,拉斑玄武岩类(87Sr/86Sr)i值为0.705 4～0.707 0,εNd(t)值为1.69～0.70(接近于0),表明源区为基本未受壳源物质混染的原始地幔,在弧后陆缘环境下快速拉张而上升,呈熔岩被形式分布于信江盆地东部;碱性橄榄玄武岩(87Sr/86Sr)i值为0.707 6～0.708 0,而εNd(t)值偏低(-6.43～-5.18),表明来源于已受壳源物质混染的富集地幔,在拉张加剧、裂陷加深的构造背景下喷发,相对集中分布于盆地中部,范围小于拉斑玄武岩.二者的差别主要是地幔源区受到不均匀混染所致.研究表明,早白垩世晚期至晚白垩世期间,太平洋板块俯冲的角度由缓变陡以及向东南方向的后退作用,对弧后陆缘的快速拉张并形成赣杭带红色断陷盆地及其玄武岩起着关键性作用.     

First-principles study of (MgH2SiO4)? n (Mg2SiO4) hydrous olivine structures. I. Crystal structure modelling of hydrous olivine Hy-2 a (MgH2SiO4) ? 3(Mg2SiO4)

 Recently, the Hy-2a hydrous olivine (MgH₂ SiO₄)·3(Mg₂SiO₄) occurring as nanometre-sized inclusions in mantle olivines has been found by TEM, and has been suggested to be a new DHMS phase (Khisina et al. 2001). A model of the crystal structure of Hy-2a has been proposed as a 2a-superstructure of olivine with one Me²⁺ -vacant octahedral layer in the (1 0 0) plane per Hy-2a unit cell (Khisina and Wirth 2002). In the present study the crystal structure of Hy-2a hydrous olivine is optimized by ab initio calculations. The aims of this study are: (1) verification of the suggested models of Hy-2a hydrous olivine structure; (2) calculation of the most stable configurations for Hy-2a structure with minimum static lattice energy, by assuming a possible formation of Me²⁺ vacancies in either M1 or M2 octahedral sites; (3) determination of the position of protons and hydrogen bonds in the Hy-2a structure. Several different possible configurations of the Hy-2a structure are optimized. The results support the idea of a stable olivine structure with ordered planar-segregated OH-bearing defects oriented parallel to (1 0 0). The data obtained indicate a preferred stability of the Hy-2a structure with the protons associated with M1 vacancies and bonded with O1 and O2 oxygen sites. The relative energy values of the optimized Hy-2a structure configurations correlate as a rule with the average shifts of atoms from their positions in pure forsterite structure. Received: 7 February 2002 / Accepted: 23 October 2002     

Mg-Cr~(2+)橄揽石、辉石和尖晶石的晶胞参数测定及Cr~(2+)在各晶体结构中的占位

本文用Mg－Cr2+做榄石、辉石、尖晶石的粉晶X射线衍射数据，采取“整体图谱最小二乘Rietveld”方法计算了上述矿物的晶胞参数和摩尔体积，并对Cr2+在各晶体结构中的占位情况进行了研究。结果显示，各矿物的晶胞参数随含Cr2+量的增大而增大。据Vegard定律，推算出各端元组分铬橄榄石（Cr2SiO1）、铬辉石（Cr2SiO2O6）及立方铬尖晶石（Cr3O4）的摩尔体积分别为47．7，68．0，44．9cm3。精化结构参数指示，在橄榄石中，Cr2+随机分配在两个八面体（M1，M2）位置；在辉石中，Cr2+优先选择八面体M2位置；在尖晶石中，Cr2+占置四面体位置。这种晶体内离子分配可从离子半径差别或晶体场稳定能大小得到解释。     

金川岩浆铜镍（铂）硫化物矿床中两类橄榄石的发现及其成矿意义

金川铜镍硫化物矿床是世界第三大岩浆型铜镍硫化物矿床,其成因机制一直备受争议。主要成矿模型有以下两种:(1)岩浆通道堆积模型;(2)深部熔离-多次贯入模型。目前,二者均不能较好解释矿区中存在的各种地质现象。本文重点研究矿区橄榄石的特征,借此来探讨"硫化物矿浆"的迁移方式与侵位能力。本次研究在金川矿床中发现了两类橄榄石:LREE亏损型(Ⅰ型)与LREE富集型(Ⅱ型)。其中,Ⅰ型橄榄石为岩浆正常结晶的原始颗粒,常见复杂的成分环带,由原生橄榄石与晶间硅酸盐熔体/不混溶硫化物熔体发生物质交换所形成,继承了玄武质岩浆稀土含量低的特征,广泛分布于各类超基性岩石与矿石中;Ⅱ型橄榄石常见包裹斜方辉石的反序列包含关系,以稀土含量高(～2个数量级)且相对富Mg而显著区别于前者,为辉石堆晶颗粒经流体触发不一致熔融后再结晶形成的橄榄石,多见于硫化物矿石中。金川矿床硫化物矿石中广泛发育的原生富Cl含水矿物(金云母、角闪石、磷灰石)与Ⅰ型橄榄石边部活动性元素含量的剧增,暗示金川矿体形成过程受富Cl流体影响显著。实验岩石学与动力学模拟的新研究进展表明流体的加入可有效推动高密度硫化物的迁移,流体的加入可能是金川硫化物矿浆上侵运移的主要机制。结合硫化物Cu/Ni西高东低的空间演化规律,橄榄石Fo值西高东低的空间变化趋势与晶体粒度西细东粗的分布特征可以推测,金川铜镍硫化物矿床岩浆通道的前进方向为自西向东。