胶东三甲金矿床流体包裹体特征

三甲金矿是胶东牟平-乳山金成矿带内重要的石英脉型金矿,金主要产于黄铁矿和多金属硫化物石英脉中。流体包裹体研究表明,三甲金矿蚀变岩石和各成矿阶段金矿石中的流体包裹体主要有三种类型：H2O-CO2包裹体、富CO2包裹体和H2O溶液包裹体。早期乳白色石英中主要赋存原生的H2O-CO2包裹体;成矿期黄铁矿石英脉和多金属硫化物石英脉中的富CO2包裹体主要为原生,随机分布,气液比变化较大,常与早期H2O溶液包裹体共生且均一温度接近,显示不混溶流体包裹体组合特征;在成矿晚期的石英和方解石中主要发育原生H2O溶液包裹体。显微测温结果显示,成矿前（第1阶段）H2O-CO2包裹体的完全均一温度（Tb．TOT,至液相）为280℃至416℃,成矿期（第Ⅱ和Ⅲ阶段）富CO2包裹体的完全均一温度为210—330℃,同期的H2O溶液包裹体均一温度为253～377℃,成矿后（第Ⅳ阶段）H2O溶液包裹体的均一温度为176—207℃。成矿流体为低盐度的CO2-H2O-NaCl型热液,成矿应力场转变导致的流体减压沸腾作用可能是三甲金矿金沉淀成矿的主要原因。     

新疆克因布拉克铜锌矿床富CO_2-N_2流体及地质意义

克因布拉克铜锌矿床位于新疆阿尔泰山南缘冲乎尔盆地。矿体主要赋存于早二叠世花岗岩外接触带的下泥盆统康布铁堡组上亚组内。克因布拉克矿床经历了两个成矿期:海相火山喷流沉积成矿期和变质热液叠加成矿期。变质热液叠加成矿期可包括2个阶段:早阶段顺层透镜状石英脉(Q1)和晚阶段切层含黄铁矿?黄铜矿石英脉(Q2)。石英脉中流体包裹体以富CO_2-N_2为特征,流体包裹体组合(FIA)发育。流体包裹体类型包括CO_2-N_2包裹体、H_2O-CO_2(±N_2)包裹体和水溶液包裹体(L-V型)。显微测温结果显示,Q1中CO_2-N_2包裹体三相点温度(T_(m,CO_2))范围在-61.2~-59.1℃,部分均一温度(T_(h,CO2))的范围是-42.3~-36.0℃。Q2中CO_2-N_2流体包裹体的T_(m,CO_2)为-61.6~-58.1℃,T_(h,CO_2)范围是-30.0~10.4℃;Q2中H_2O-CO_2(±N_2)包裹体的T_(m,CO_2)为-61.4~-58.1℃,T_(h,CO_2)为-11.9~5.3℃,CO_2笼合物融化温度(T_(m,clath))范围是2.9~13.1℃,完全均一温度(T_(h,total))为312℃,伴生的L-V包裹体T_(h,total)为201~389℃,求得CO_2相密度为0.91~0.97 g/cm~3,盐度为1.62%~12.02%NaCl_(eqv)。计算得到流体包裹体的最低捕获压力范围为250~320 MPa,具有极富CO_2-N_2、低盐度的特点,属于变质流体。变质热液期早阶段石英脉δD值为-90.5‰,δ~(18)O_(H_2O)值为7.8‰;晚阶段石英脉δD值为-82.1‰~-80.4‰,δ~(18)O_(H_2O)为6.2‰~8.6‰。海相火山沉积期硫化物的δ~(34)S为0.9‰~2.1‰,硫来自火山岩浆活动;变质热液叠加期硫化物的δ~(34)S为0.1‰~1.1‰,显示了与造山变质深源流体有关的来源。克因布拉克铜锌矿床矿石变形变质结构特征以及石英脉中富CO_2-N_2流体的大量出现,说明变质流体对矿床具有一定的叠加改造,矿床具有多阶段的特点。     

极富CO_2流体的造山型金矿:苏丹哈马迪金矿

哈马迪金矿位于苏丹东北部,矿床产于阿拉伯-努比亚地盾新元古界变质岩系中,属于受剪切带控制的造山型金矿床。金矿体赋存在角闪片岩内近南北向的片理化蚀变带中,围岩蚀变主要为黄铁绢英岩化,以及绿泥石化和碳酸盐化等。在含矿石英细脉中赋存有大量的极富CO2的碳质流体包裹体。这些包裹体几乎不含水,含有少量CH4(XCH4=0~0.10)。脉石英中碳质流体包裹体既有孤立或随机分布的原生包裹体,也有呈线性分布的次生包裹体,最晚期还有次生水溶液包裹体的分布。碳质流体包裹体的三相点(Tm,CO2)范围变化不大(-58.4~-57.0℃),但均一温度(Th,CO2)范围变化较大(-19℃~+29℃)。捕获的P-T条件可由LCO2包裹体的ρ值或Th,CO2值,以及与其伴生的CO2-H2O包裹体最终均一温度Th,TOT值,从有关相图中估算。早期碳质流体包裹体的捕获P-T条件范围为280~360℃、80~320MPa。金矿化发生在变质峰期之后的退变质作用晚期。广泛发育的热液蚀变说明碳质流体并非来自单一的流体源,寄主石英变形很弱也不能解释水从H2O-CO2-盐流体包裹体中优先淋失、残留大量的CO2±CH4包裹体。碳质流体包裹体可能的成因是:在金成矿的退变质时期,来自深部的H2O-CO2-盐流体,由于P-T下降而发生不混溶,H2O在热液蚀变中被大量消耗,而CO2则以碳质流体包裹体的形式被得捕获在脉石英中。     

胶西北新城金矿成矿流体与矿床成因

新城金矿是胶东招远-莱州成矿带内重要的蚀变岩型金矿.流体包裹体研究表明,新城金矿蚀变岩石和各成矿阶段金矿石中的流体包裹体主要有3种类型:H2O-CO2包裹体、富CO2包裹体和H2O溶液包裹体.早期乳白色石英中主要赋存原生的H2O-CO2包裹体;成矿期黄铁矿石英脉中的富CO2包裹体主要为原生,随机分布,常与同时期的H2O...     

新疆准噶尔北缘阿克希克铁金矿流体包裹体研究

阿克希克铁金矿床位于准噶尔北缘,矿体呈似层状、脉状、透镜状赋存于南明水组火山岩及凝灰岩的接触带上。围岩蚀变不发育,主要为硅化、绢云母化、绿泥石化、黄铁矿化、碳酸盐化等。矿床的形成经历了火山沉积期和热液期,铁矿化主要形成于火山沉积期,金矿化主要形成于热液期。火山沉积期石英以发育液体包裹体和少量含CO2包裹体为特征,热液期石英以发育含CO2和碳质(CH4和C4H6)包裹体为特征。火山沉积期成矿流体为中温(集中于180~320℃)、低盐度(集中于6~10 wt%Na Cleq)、中-低密度(0.59~0.98 g/cm3)的Na Cl-H2O-CO2体系。热液期成矿流体为中温(集中于220~320℃),低盐度(集中于2~10 wt%Na Cleq),中-低密度(0.55~1.03 g/cm3)的Na Cl-H2O-CO2-CH4型流体。火山沉积期石英的δDSMOW为-129.9‰~-97.9‰,δ18OSMOW值介于7.9‰~12.3‰,δ18OH2O值为-2.6‰~4.4‰,推测成矿流体为海水与岩浆水的混合。热液期石英的δDSMOW介于-129.8‰~-102.6‰,δ18OSMOW值介于11.2‰~16.1‰,δ18OH2O变化于3.1‰~7.4‰,推测成矿流体为变质水混合深循环的大气降水。结合矿床地质特征、流体成分和性质,本文认为热液期金矿化与CO2-CH4流体有关。     

山东招远九曲金矿床成矿流体地球化学特征

九曲金矿位于招远—平度成矿带内,地处胶东金矿集中区的西北部。矿区内出露的岩浆岩为黑云母二长花岗岩、浅色细粒花岗岩及似斑状花岗闪长岩,矿体受断裂构造控制,属石英脉型金矿床。矿化分为四个阶段:石英-黄铁矿阶段、黄铁矿-石英阶段、石英-多金属硫化物阶段及碳酸盐阶段。流体包裹体研究表明,矿体中含金石英脉发育含CO2三相包裹体(Ⅰ型)、气液两相包裹体(Ⅱ型)和纯CO2包裹体(Ⅲ型)3种类型。成矿流体具有由早阶段到晚阶段,温度从中高温(301℃~365℃)到中低温(200℃~256℃)逐渐降低,CO2从富到贫逐渐减少,整体上具有低盐度(3.53%~10.74%Na Cleqv)和低密度(0.55~0.96 g·cm-3)的特点,成矿压力为75~129 MPa,成矿深度为7.04~9.46 km,成分以CO2、H2O为主。δD=-51×10-3~-64.2×10-3,δ18O水=0.9×10-3~7.1×10-3。笔者认为成矿流体以地幔流体为主,后期有大气降水参与;δ34S变化范围为6.4×10-3~7.4×10-3,显示成矿物质为深源含矿岩浆,上涌过程中与赋矿围岩发生重熔。矿床属幔源流体参与成矿的中温热液脉型金矿床。     

阿勒泰恰夏铜矿床的富CO2流体与矿床成因

恰夏铜矿床位于新疆阿尔泰山南缘克兰火山-沉积盆地内,赋矿地层主要为下泥盆统康布铁堡组上亚组变质岩系.脉状铜矿化主要特征为:早期顺层石英脉,呈脉状或透镜状沿变质片理分布,有星点状黄铁矿产出;晚期含铜黄铁矿-石英脉,斜切变质围岩,黄铜矿以浸染状分布于石英脉裂隙中.石英脉中流体包裹体主要为富CO2包裹体,其次为水溶液包裹体,同时含有少量的碳质流体包裹体.显微测温研究表明,早期顺层石英中原生富CO2流体包裹体,CO2三相点温度(tm,CO2)集中在-61.5～-57.5℃,CO2部分均一温度(th,CO2)集中在25～27℃,完全均一温度(th,tot)集中于223～280℃,流体密度为0.82～0.90 g/cm3;含铜黄铁矿-石英脉中原生富CO2包裹体的tm,CO2集中于-61.5～-58.7℃,th,CO2集中在23.5～28.7℃,th,tot集中在230 ～ 310℃,流体密度0.81～0.86 g/cm3.成矿流体为中高温、中低盐度、富CO2的CO2-H2O-NaCl±CH4±N2体系.恰夏铜矿脉状铜矿化的成矿流体特征与造山型金矿床的流体包裹体特征类似,结合矿床产出的地质背景、控矿构造特征,认为脉状铜矿化的成因与造山-变质热液有关,是阿尔泰山南缘晚泥盆世一二叠纪造山-变质作用的产物.SRXRF测试富CO2流体包裹体中金属微量元素,显示其富集Au,可能表明富CO2流体对金的富集起到一定作用.     

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。     

北山金窝子金矿床流体包裹体特征及成矿流体演化

金窝子金矿床为于甘肃北山中成矿带。包裹体测温研究表明，从成矿初期到主成矿阶段，石英捕获了H2O—NaCl，H2O-CO2-CH4-NaCl，或H2O-CO2-NaCl体系的流体。大脉型金矿成矿初期，热液成矿流体由高温中盐度H2O-NaCl-CO2-CH4四端元组份混溶的均一相热液流体；石英-黄铁矿和多金属硫化物阶段，石英捕获两成分和温度都不相同的热液组份：低盐度、富水溶液、较冷的热液和高盐度、富挥发份CO2、CH4和水蒸气、较热的热液。主成矿阶段石英捕获的两类型包裹体的完全均一温度相差近100℃，而且富挥发份流体盐度相对于贫挥发份流体盐度高，上述特征表明主成矿期3号脉大规模金成矿并非流体沸腾作用结果。网脉型金矿（210号脉）黄铁矿-石英成矿阶段、石英．黄铁矿和多金属硫化物成矿阶段石英捕获的地质流体的温度-成分特征无明显差异，均捕获了两种组份不同、成矿温度一 致的地质流体（高盐度富水溶液流体和富堤盐度CO2＋CH4流体），与许多金矿的流体不混溶金成矿机制矛盾。     

广西栗木钽铌锡多金属矿床的成矿流体演化及其对成矿过程的制约

广西栗木钽铌锡多金属矿床既产具明显垂直分带的花岗岩型钽铌锡矿体,又有石英脉型钨锡矿体,是研究岩浆-热液演化过程的典型实例。本次研究对栗木矿区中水溪庙和金竹源两个矿床开展了系统成矿流体研究。研究表明栗木矿区中的包裹体类型主要有盐水溶液包裹体、H2O-CO2-Na Cl包裹体和熔体包裹体三类。自云英岩化钠长石花岗岩→似伟晶岩→长石石英脉型→锂云母萤石脉,盐水溶液包裹体逐渐由定向分布的次生包裹体特征,转变为面状孤立分布的原生包裹体特征,而且均一温度、盐度和密度逐渐降低,具有低均一温度(150~210℃)、低盐度(1.0%~9.0%NaC leqv)和低密度(0.83~1.05g/cm3)的特点。H2O-CO2-NaC l包裹体和熔体包裹体主要产在钠长石花岗岩和似伟晶岩中,H2O-CO2-NaC l包裹体孤立分布,均一温度为260~350℃,盐度为0.8%~8.5%NaC leqv;熔体包裹体的固相初熔温度为560~600℃,完全均一温度为704~853℃,流体相具有与盐水溶液包裹体相近的均一温度和盐度。根据以上资料,本文把栗木矿区的成矿作用分为岩浆阶段的钽铌锡成矿作用和岩浆热液阶段的钨锡成矿作用,估算成岩成矿压力约为270MPa,这有利于栗木矿区的钽铌锡在花岗岩浆阶段发生了相对贫化的富集作用,钽、铌、锡、钨等元素在熔体/流体的分配系数制约了钽铌成矿作用发生在岩浆阶段,而钨锡成矿作用主要发生在热液阶段。     

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.     

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.     

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.     

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.