西拉沐伦钼矿带车户沟斑岩型钼-铜矿床成矿流体特征及其地质意义

车户沟钼-铜矿床是华北克拉通北缘西拉沐伦钼矿带上典型的斑岩型Mo-Cu矿床,位于华北克拉通北缘断裂南侧。矿床赋存于成矿母岩花岗斑岩及其围岩中,矿化类型以细脉浸染状矿化为主,还存在隐爆角砾岩型矿化和石英脉型矿化。根据脉体类型和矿物组合将车户沟钼-铜矿床划分为四个成矿阶段,分别为(1)辉钼矿-黄铁矿-石英阶段、(2)黄铜矿+黄铁矿±辉钼矿+石英阶段、(3)黄铁矿+石英阶段、(4)石英+碳酸盐±萤石阶段。成矿流体寄主矿物石英中发育Ⅰ型含CO2三相包裹体(LCO2+VCO2+LH2O)、Ⅱ型含子晶三相(V-L+S)包裹体、Ⅲ型富气相(V-L)包裹体、Ⅳ型富液相(L-V)包裹体、Ⅴ型纯气相(V)包裹体和Ⅵ型纯液相(L)六种类型。流体包裹体类型从早到晚具有规律性演化特征,表现为阶段(1)、(2)以发育Ⅰ型含CO2三相包裹体(LCO2+VCO2+LH2O)和Ⅱ型含子晶三相(V-L+S)包裹体为特征,成矿晚期阶段(3)、(4)以发育Ⅲ型富气相(V-L)包裹体、Ⅳ型富液相(L-V)水溶液包裹体为特征。从早阶段到晚阶段成矿流体温度及盐度具有规律性演化特征。均一温度峰值分别为270～400℃、230～370℃、160～290℃、120～230℃,成矿温度逐渐降低;流体盐度,阶段(1)流体盐度分两组:3.39%～14.25%NaCleqv和31.01%～66.75%NaCleqv、阶段(2)流体盐度分两组:1.23%～12.85%NaCleqv和31.14%～64.33%NaCleqv、阶段(3)、(4)盐度分别介于1.05%～21.47%NaCleqv和2.07%～10.73%NaCleqv,盐度逐渐降低。激光拉曼显微探针(LRM)及群体包裹体成分分析结果表明,流体体系成分以H2O、CO2、Cl-、SO42-、Na+为主,贫F-、Ca2+、Mg2+为特征,特征离子比值暗示流体来源于岩浆流体。包裹体岩相学及包裹体测温表明,流体由早期的高温、高盐度、含二氧化碳NaCl-H2O-CO2体系岩浆流体在主成矿阶段(1)、(2)发生流体包裹体的沸腾作用和相分离,伴随流体沸腾、CO2逸失、温度降低等过程导致大量金属硫化物沉淀。成矿晚期阶段(3)、(4),成矿体系趋于开放,流体存在大气降水混入演化为晚期中-低温、中-低盐度贫CO2的NaCl-H2O流体体系。成矿作用机制上沸腾作用是导致主成矿期辉钼矿、黄铜矿沉淀成矿的重要机制。成矿作用晚期阶段(3)、(4)流体混合作用成为成矿作用的主导机制。     

黑龙江省多宝山斑岩型铜(钼)矿床成矿流体特征及演化

黑龙江省多宝山斑岩铜(钼)矿床位于小兴安岭西北部,是中亚-兴蒙造山带北东段最大的斑岩型铜(钼)矿床,矿体产于加里东期花岗闪长岩和中奥陶世多宝山组安山岩、凝灰岩中。铜矿化与绢英岩化关系密切,而钼矿化主要产于钾硅化带中。矿区内脉体广泛发育,从早到晚依次为:石英+钾长石脉、早阶段石英+辉钼矿脉、晚阶段石英+辉钼矿脉、石英+黄铜矿+黄铁矿脉、石英+黄铁矿脉和方解石+石英脉。脉石英中广泛发育流体包裹体,包括气液两相水溶液包裹体(W型)、纯气相包裹体(G型)、含CO2三相包裹体(C型)及含子矿物多相包裹体(S型)。石英+钾长石脉中仅发育气液两相包裹体,均一温度峰值﹥550℃、盐度为16.2%～18.1%NaCleqv;早阶段石英+辉钼矿脉中发育大量气液两相包裹体和含子矿物多相包裹体,并见少量含CO2三相包裹体,均一温度集中在350～450℃、盐度变化于1.1%～﹥65.3%NaCleqv;晚阶段石英+辉钼矿脉体发育大量含CO2三相包裹体和含子矿物多相包裹体,另有少量气液两相包裹体,均一温度集中在270～350℃、盐度为0.8%～42.4%NaCleqv;石英+黄铜矿+黄铁矿脉中发育丰富的气液两相包裹体,见少量含子矿物多相包裹体、含CO2三相包裹体和纯气相包裹体,均一温度峰值在230～330℃、盐度为0.8%～42.4%NaCleqv;石英+黄铁矿脉和方解石+石英脉中仅发育气液两相包裹体,均一温度变化于110～200℃、盐度为3.9%～8.4%NaCleqv。成矿流体在古深度4.1km左右,温度在230～450℃之间、压力在10～41MPa之间,发生了强烈的流体沸腾作用,大量CO2等气体从流体中释放出来,黄铜矿、斑铜矿和辉钼矿等巨量沉淀下来,形成了铜(钼)矿体。成矿流体总体上属H2O-CO2-NaCl体系,多期次的流体沸腾作用是该矿床的主要成矿机制。     

大兴安岭中南段布敦化铜矿床金鸡岭矿段流体包裹体研究

内蒙古布敦化铜矿床位于大兴安岭中南段,包括金鸡岭和孔雀山2个矿段,前者属于斑岩型,后者属于热液脉型,文章对金鸡岭矿段开展了详细的流体包裹体研究。金鸡岭矿段成矿过程可分为早、中、晚3个阶段,即毒砂-黄铁矿(黄铜矿)-石英阶段(早)、黄铜矿-磁黄铁矿-石英阶段(中)、碳酸盐-黄铁矿-石英脉阶段(晚)。其中,中阶段为主成矿阶段。流体包裹体研究表明,早阶段主要发育富气相包裹体、气液两相包裹体和含子矿物多相包裹体,中阶段以气液两相包裹体为主,并发育少量含子矿物多相包裹体,晚阶段仅发育气液两相包裹体。早、中、晚阶段流体包裹体的均一温度和w(NaCleq)变化范围分别为320~550℃、240~550℃、140~300℃和12.2%~43.2%、6.3%~17.2%、0.5%~9.7%。激光拉曼探针分析显示,早、中阶段包裹体气相成分为CH4和H2O,而晚阶段的包裹体气相成分只含H2O。早阶段多种类型包裹体共生,且均一温度相近,指示早阶段流体发生过沸腾作用。笔者认为早阶段成矿作用主要与高温、高盐度、含CH4流体的沸腾作用有关,中阶段的成矿作用则主要是流体混合而导致黄铜矿等金属硫化物的析出,晚阶段基本不成矿,只形成少量的黄铁矿。     

内蒙古鸡冠山斑岩钼矿床成矿时代和成矿流体研究

内蒙古鸡冠山钼矿床是西拉沐伦钼成矿带上的典型斑岩矿床。矿床产于火山侵入杂岩中,矿化类型以细脉浸染状矿化为主。对矿床5件辉钼矿样品进行了铼-锇同位素分析,获得了151.1±1.3Ma的等时线年龄,表明成矿作用发生在晚侏罗世。成矿作用可划分为三个阶段:早阶段为石英-黄铁矿阶段,发育乳白色石英和粗粒浸染状黄铁矿;中阶段包括早期石英-多金属硫化物亚阶段和晚期石英-萤石-金属硫化物亚阶段;晚阶段为石英-碳酸盐细脉,穿切早、中阶段脉体和矿物组合。鸡冠山钼矿床流体包裹体岩相学研究表明,与成矿有关的包裹体主要有六种类型:富液相、富气相、含子晶多相、含CO2三相、纯CO2及纯液相包裹体。其中,早阶段以富气和富CO2包裹体为主,中阶段多种包裹体共存,晚阶段则主要为富液包裹体。冷热台显微测温和激光拉曼显微探针(LRM)成分分析结果表明,早阶段石英中原生包裹体的均一温度480℃,盐度最高66.75%NaCleqv,包裹体气相成分富含水和CO2,液相成分则以水为主,子晶矿物有石盐、黄铜矿以及指示氧化条件的赤铁矿等,同时也说明成矿流体是富含成矿金属元素的。中阶段早期石英中的流体包裹体均一温度为320～480℃,晚期石英和萤石中的流体包裹体的均一温度为180～320℃。中阶段流体盐度介于4.65%～56.76%NaCleqv。中阶段包裹体含石盐、方解石、黄铜矿、赤铁矿等子矿物,富气相、富液相与含子晶多相包裹体共存,且具有相近的均一温度,而盐度相差悬殊,指示流体发生了沸腾。晚阶段流体的温度降低至100～180℃,盐度则低于10.86%NaCleqv,流体包裹体成分主要为水。鸡冠山钼矿成矿流体演化从早至晚为:从早阶段高温、高盐度、高氧逸度、富CO2、富成矿物质以岩浆热液为主成矿流体,演化至晚期低温、低盐度、无子晶、贫CO2、以大气降水为主的流体。沸腾作用是鸡冠山钼矿形成的重要机制。     

河南省新县姚冲钼矿床流体包裹体研究

河南省新县姚冲钼矿床产于大别造山带,属于陆-陆碰撞体制的斑岩型矿床,其流体成矿过程可以分为早、中、晚三个阶段,分别以石英+钾长石±黄铁矿±磁铁矿、石英±钾长石+辉钼矿±其他硫化物和石英±碳酸盐±萤石组合为标志.热液石英和萤石中发育纯CO2包裹体(PC型)、CO2-H2O型包裹体(C型)、水溶液包裹体(W型)和含子晶多相包裹体(S型).早阶段石英中发育纯CO2包裹体、CO2-H2O型包裹体和含子晶多相包裹体,中阶段的石英则发育CO2-H2O型包裹体、水溶液包裹体和含子晶多相包裹体,在晚阶段的无矿石英脉中发育水溶液包裹体和少量的CO2-H2O型包裹体,石英-碳酸盐-(萤石)脉石英与萤石中只发育水溶液包裹体.早阶段流体包裹体的均一温度为277～ 380℃,集中于300～ 360℃,盐度变化于3.0％～10.3％ NaCleqv之间.中阶段包裹体均一温度介于185 ～ 351℃之间,集中在260～ 320℃,盐度介于2.4％ ～9.3％NaCleqv;晚阶段包裹体均一温度为139 ～245℃,盐度介于0.7％ ～6.3％ NaCleqv之间.中阶段多相包裹体中常见黄铜矿和其他透明子矿物,表明流体具有还原性、过饱和的特征,是矿石矿物沉淀的主要阶段.估算早、中阶段流体捕获压力分别集中于47 ～ 131MPa和26 ～118MPa,所对应的成矿深度分别约为4.7km和2.6～4.2km.上述流体包裹体的研究表明姚冲钼矿床的初始成矿流体具有高温、高盐度、富CO2的特征,同时预测了深部找矿潜能.     

滇西北雪鸡坪铜矿床流体包裹体特征研究及矿床成因讨论

雪鸡坪铜矿床产于印支晚期石英二长闪长玢岩-石英闪长玢岩-石英二长斑岩复式侵入体内,为一斑岩型铜矿床。矿床形成经历了多阶段热液成矿作用,主要有微细脉浸染状黄铁矿±黄铜矿-石英、细脉状辉钼矿±黄铁矿±黄铜矿-石英及微细脉状贫硫化物-石英-方解石等。流体包裹体岩相学、显微测温、激光拉曼及碳、氢、氧同位素综合研究表明,微细脉浸染状黄铁矿±黄铜矿-石英阶段石英中主要发育含Na Cl子矿物三相及气液两相包裹体,与含矿的石英二长斑岩石英中发育的流体包裹体特征相似,表明成矿流体主要为中高温、高盐度Na Cl-H2O体系热液,可能主要来源于印支期石英二长斑岩侵入体;辉钼矿±黄铁矿±黄铜矿-石英中主要发育含CO2三相及气液两相包裹体,成矿流体为中温、低盐度Na Cl-CO2-H2O体系热液,与前者来源明显不同;贫硫化物-石英-方解石石英中主要发育气液两相包裹体,成矿流体为中低温、低盐度Na Cl-H2O体系热液,推测其可能较多来自于大气降水。因此,雪鸡坪铜矿床为不同来源、不同地球化学性质热液叠加成矿作用的结果。     

河南嵩县纸房钼矿床流体包裹体研究及矿床成因

河南嵩县纸房钼矿床位于秦岭造山带北部的熊耳地体,矿体以石英脉形式产于熊耳群火山岩,并受熊耳地体南边界断裂马超营断裂的次级断裂构造控制。成矿过程包括早、中、晚三个阶段,分别以石英-黄铁矿、石英-多金属硫化物和石英-碳酸盐组合为标志,早阶段石英脉或矿物组合遭受了构造变形和角砾岩化。早、中阶段的石英中可见CO2-H2O型、NaCl-H2O型及含子晶型等3类流体包裹体,而晚阶段碳酸盐只发育NaCl-H2O型包裹体。早、中、晚阶段的流体包裹体均一温度分别为467—380℃、360—250℃和240～137℃,从早到晚逐渐降低;早、中、晚3个阶段流体包裹体盐度分别为0．18％～13．13％NaCl．eqv、0．01％～20．70％NaCl．eqv和0．35％～12．85％NaCl．eqv,早、中阶段含子晶包裹体的盐度为28．04％～31．35％NaCl．eqv。早阶段含子晶包裹体系捕获的不饱和溶液,中阶段含子晶包裹体既捕获自过饱和溶液,也捕获自不饱和溶液。早、中阶段的流体包裹体均一压力集中在180—220MPa和40～80MPa两个范围,表明成矿流体是在6km～8km深处交替于静岩和静水压力体系之间的流体系统;晚阶段流体包裹体均一压力为50～80MPa,代表张性构造内充填的静水压力流体。静岩和静水压体系之间的振荡性交替现象,与针对造山型金矿建立的断层阀模型吻合,是振荡性流体沸腾或同震愈合-破裂的结果。沸腾导致的CO2等挥发组分的逃逸使流体浓缩甚至过饱和,增高了流体的pH值和还原性,促进辉钼矿等成矿物质快速沉淀。总之,纸房钼矿床是陆陆碰撞体制发育的造山型成矿系统。考虑到早、中阶段石英中多数流体包裹体均一至气相,预测现行勘探深度之下具有较大的寻找高品位钼矿床的潜力。     

大兴安岭中南段布敦化铜矿床金鸡岭矿段流体包裹体研究

内蒙古布敦化铜矿床位于大兴安岭中南段,包括金鸡岭和孔雀山2个矿段,前者属于斑岩型,后者属于热液脉型,文章对金鸡岭矿段开展了详细的流体包裹体研究。金鸡岭矿段成矿过程可分为早、中、晚3个阶段,即毒砂-黄铁矿（黄铜矿）-石英阶段（早）、黄铜矿-磁黄铁矿-石英阶段（中）、碳酸盐-黄铁矿-石英脉阶段（晚）。其中,中阶段为主成矿阶段。流体包裹体研究表明,早阶段主要发育富气相包裹体、气液两相包裹体和含子矿物多相包裹体,中阶段以气液两相包裹体为主,并发育少量含子矿物多相包裹体,晚阶段仅发育气液两相包裹体。早、中、晚阶段流体包裹体的均一温度和w（NaCl_eq）变化范围分别为320~550℃、240~550℃、140~300℃和12.2%~43.2%、6.3%~17.2%、0.5%~9.7%。激光拉曼探针分析显示,早、中阶段包裹体气相成分为CH₄和H₂O,而晚阶段的包裹体气相成分只含H₂O。早阶段多种类型包裹体共生,且均一温度相近,指示早阶段流体发生过沸腾作用。笔者认为早阶段成矿作用主要与高温、高盐度、含CH₄流体的沸腾作用有关,中阶段的成矿作用则主要是流体混合而导致黄铜矿等金属硫化物的析出,晚阶段基本不成矿,只形成少量的黄铁矿。     

阿尔泰南缘托库孜巴依金矿床流体包裹体特征及成矿流体演化

新疆西北部的托库孜巴依(巴依)金矿床位于西伯利亚古板块南缘,阿尔泰陆缘活动带克兰弧后盆地与哈巴河弧间盆地接壤处。本次研究在前人成果基础上,通过详细的野外调查、室内显微观察、流体包裹体测温、激光拉曼成分分析和氢-氧同位素分析等多种方法,揭示了巴依金矿各成矿阶段流体特征、成矿热液来源和流体演化过程。根据野外矿脉空间分布、穿插关系、矿物组合及结构构造等特征,结合流体包裹体研究,本文将巴依金矿的成矿作用划分为4个阶段:石英-磁铁矿阶段(Ⅰ),主要发育富液相包裹体,均一温度范围在3529～4134℃区间,盐度范围为73%～147%NaCleqv,平均为104%NaCleqv;石英-黄铁矿阶段(Ⅱ),该阶段主要发育富液相包裹体、富气相包裹体以及含子晶包裹体,均一温度范围为1860～3398℃,盐度变化范围为27%～443%NaCleqv,平均为92%NaCleqv;石英-黄铁矿-黄铜矿阶段(Ⅲ)主要发育富液相包裹体和含(富)CO_2三相水溶液包裹体,均一温度范围为1410～1864℃(富液相包裹体),盐度范围较大,介于0～88%NaCleqv之间;石英-方解石阶段(Ⅳ),流体包裹体以富液相为主,均一温度范围1020～1400℃,盐度范围为02%～43%NaCleqv。该矿床从成矿早阶段到成矿晚阶段温度-盐度整体呈下降趋势,在主要成矿阶段(Ⅱ、Ⅲ)出现流体沸腾现象。各成矿阶段δ~(18)O、δD同位素变化范围分别为:成矿早阶段(Ⅰ)531‰和-8510‰;主要成矿阶段(Ⅱ、Ⅲ)-153‰～150‰和-974‰～-811‰;成矿晚阶段(Ⅳ)-352‰～-342‰和-939‰～-871‰,成矿流体主要是早阶段的变质水与中晚阶段加入的大气水混合而成。巴依金矿成矿流体表现为一套中低盐度NaCl-H_2O-CO_2流体体系,符合造山型金矿成矿流体特征。综合矿床地质研究,本文认为在晚石炭世-二叠纪喀拉通克岛弧与西伯利亚板块碰撞造山构造体制下,流体混合、压力降低和沸腾作用是巴依金矿床富集成矿的主要机制。     

内蒙古西拉沐伦成矿带羊场石英脉型钼矿床成矿流体地球化学特征研究

内蒙古羊场钼矿床产于华北克拉通北缘西拉沐伦钼多金属成矿带内,矿体主要以石英脉形式产于燕山期黑云母二长花岗岩内,受NW、NNW向断裂构造控制。成矿过程包括石英大脉阶段(Ⅰ)、石英-黄铁矿亚阶段(Ⅱ-1)、石英-黄铁矿-辉钼矿-黄铜矿-方铅矿-闪锌矿亚阶段(Ⅱ-2)、碳酸岩化阶段(Ⅲ)。流体包裹体研究发现,按照气相比不同可将包裹体分为WL型(<50%)、WV型(50%～90%)、G型(100%)。Ⅰ、Ⅱ-1、Ⅱ-2阶段包裹体均一温度分别为173～280℃、180～467℃、151～366℃,不具有继承演化关系,可能是成矿作用过程中加入有岩浆热液的结果;盐度分别为4.03%～10.61%NaCleqv、2.07%～10.36%NaCleqv和2.41%～9.98%NaCleqv。各阶段流体成分均以H2O为主(>94.39mol%),含少量挥发份CO2、N2、CH4、C2H6、Ar、H2S等还原性气体,阳离子以Na+为主,阴离子以HS-、Cl-为主,属含少量CO2的NaCl-H2O体系;各阶段石英氢、氧同位素δ18OH2O介于-0.08‰～1.90‰、δD介于-119.66‰～-98.79‰。上述特征说明该矿床的成矿流体是岩浆热液与古大气降水混合而成。不同来源、不同性质的流体混合作用是造成羊场辉钼矿沉淀成矿的主要原因。     

Elastic and thermoelastic properties of synthetic Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (åkermanite) and Ca<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (hardystonite)

Elastic and thermoelastic constants of large single crystals of Ca₂MgSi₂O₇ and Ca₂ZnSi₂O₇ have been derived from ultrasonic resonance frequencies of plane-parallel plates and their shift upon variation of temperature, respectively. In addition, coefficients of thermal expansion and dielectric constants were determined. Both species possess quite similar properties. As observed in other isotypic magnesium and zinc compounds, the mean elastic stiffness and the deviation from the Cauchy relations are significantly larger in the zinc compound, due to a covalent contribution of the Zn–O bond. Positive thermoelastic constants T₄₄ and T₆₆ in Ca₂MgSi₂O₇ allow temperature-independent ultrasonic generators and oscillators to be manufactured.     

硅酸盐玻璃中的Na和K含量电子探针分析条件设定探讨

含Ti硅酸盐玻璃在基础科学研究和应用技术开发上均有重要价值,亟需对其进行准确的成分分析,为进一步的科研工作提供重要的数据支撑.对玻璃进行电子探针分析时,由于样品的易损性和其中(Na和K)阳离子在电子束轰击下极易发生迁移和扩散,因此往往需要经过条件实验来确定合适的分析条件,确保样品在该条件下能够保持尽量稳定的状态,才能获...     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.