钙钛矿型结构亚硝酸盐和氰化物的分子体积          下载免费PDF全文

董麒  叶大年 《地质科学》1993,28(1):44-51

绝大部分的亚硝酸盐和氰化物属于钙钛矿型结构,但有部分化合物为“反”钙钛矿型结构,充填空洞A位的阳离子的拓扑体积为0。阴离子团NO₂^-和CN^-的拓扑体积都近乎常数,分别为41.73ų和40.03ų,标准方差σ_n-1=1.516和σ_n-1=1.25。由此,进一步证明了原来的一套离子拓扑体积数值的普适性。“反”钙钛矿型结构中A位阳离子的平均半径r_A>1.00Å时,三价阳离子会产生扩容效应,其扩容系数大约是其本身拓扑体积的2倍;正钙钛矿型结构中,当A位是由半径较大的Cs⁺充填时,Cs⁺也会产生扩容效应,其扩容系数约为24ų。氰化物中结晶水分子的拓扑体积近乎常数,为24ų或0。  相似文献   

天山东部冰川雪坑离子浓度特征的对比研究     

李向应  刘时银  韩添丁  李忠勤  卢爱刚 《地球科学进展》2008,23(12):1268-1276

对2004年获取的天山奎屯河哈希勒根51号冰川1个雪坑和哈密庙尔沟平顶冰川4个雪坑的离子浓度特征进行了研究,结果表明：Ca²⁺、NO^-3和SO₄^2-是哈密庙尔沟平顶冰川雪坑雪层和积累区雪坑底部冰中的主要离子（尤其是Ca²⁺ ）,其雪层中的主要阳离子关系可在底部冰中得以较好的反映,但雪层中各离子浓度与海拔的相关性不明显,可能与海拔的跨度较小和挖取的雪坑较疏有关;雪坑底部冰中的离子浓度与海拔间明显的相关性说明淋融作用随着海拔升高、气温降低而逐渐减弱。SO₄^2-和Ca²⁺是奎屯河哈希勒根51号冰川雪坑中的主要离子（尤其是SO₄^2-）,其雪坑离子化学特征与哈密庙尔沟平顶冰川差别较大,可能与哈密庙尔沟平顶冰川处于塔克拉玛干沙漠、古尔班通古特沙漠和鄯善沙漠的下风向相关,还可能与雪层内淋融作用的强弱和沉积通量的高程效应有关。哈密庙尔沟平顶冰川积累区雪坑中NH₄⁺、NO₃^-和K⁺的Cs/Ci较Ca²⁺、Mg²⁺和Na⁺要大,奎屯河哈希勒根51号冰川Na⁺和NH4⁺的“雪冰比”较Cl-、SO₄^2-、Mg²⁺和Ca²⁺要大,说明这两条冰川雪坑中的Ca²⁺和Mg²⁺信号较其它离子可能更易于在冰芯记录中保存下来,为冰芯研究和古气候记录的恢复提供了保障。  相似文献   

矿山环境土壤重金属污染潜在生态风险评价模型探讨   总被引：9，自引：0，他引：9  

李泽琴  侯佳渝  王奖臻 《地球科学进展》2008,23(5):509-516

Weeks(2005)提出有关土壤污染的生态风险“层叠式 (Tiered approach)”评价框架,有关各层次的评价技术是当前环境科学研究的热点。针对矿山环境土壤重金属污染生态风险特征,提出矿山环境土壤重金属污染潜在生态风险评价模型,属于Tire 1层次评价模型。根据矿山环境土壤重金属污染生态风险特征,遵循生态风险评价中的熵原理和证据权重原则,用土壤中重金属的浓度风险表征污染指数（Cⁱ_f）;以其环境生物可利用性表征毒性响应系数（Tⁱ_b）,以对污染指数进行修正;以重金属元素的生物毒性响应因子（T^i_e）为权重,提出矿山环境土壤重金属污染潜在生态风险评价模型：RI=∑^m_i=1Er_i其中,E^r_i= Tⁱ_e×Tⁱ_b×Cⁱ_f;RI表示土壤中多种重金属潜在生态风险指数;E^r_i为元素i的潜在风险因子;Cⁱ_f=Cⁱ/Cⁱ_o ,Cⁱ为土壤中重金属浓度实测值,Cⁱ_o为计算所需要的参照值。Tⁱ_b=（Rⁱ_b/ Pⁱ_b）1/2,Rⁱ_b为样品中某元素生物可利用相态占总含量的百分比,Pⁱ_b为参照土壤的相应比值。  相似文献   

祁连山大雪山地区大气PM_2.5细粒子中可溶性离子特征     

王泽斌  徐建中  余光明  崔晓庆  任贾文 《冰川冻土》2013,35(2):336-344

为了研究祁连山大雪山地区大气PM_2.5细粒子中可溶性无机离子组分的变化特征, 于2010年7月至2011年7月在祁连山冰川与生态环境综合观测站附近采集46个大气PM_2.5的Telfon滤膜样品, 并应用离子色谱对可溶性离子进行了分析.结果显示: 所测样品的阴、 阳离子中, SO₄^2-、 NO^-₃、 Ca²⁺和NH⁺₄的质量浓度分别为1.54μg·m^-3、 0.38μg·m^-3、 0.73μg·m^-3和0.22μg·m^-3, 累计约占到水溶性离子总量的88%.可溶性离子浓度呈现出春夏季节明显高于秋冬季节的特征, 夏季的浓度最高, 其次是春季、 冬季和秋季. Cl^-、 Ca²⁺、 Na⁺和Mg²⁺之间的相关性极高, SO₄^2-和NO^-₃与大部分阳离子的相关性都很高, 说明大部分硫酸盐是来自于中亚沙尘源区的自然源, 而并非是通过人类活动造成的一次污染物通过二次反应过程得到的. NH⁺₄仅与SO₄^2-通过相关性检验说明, 该地区NH₃主要中和了大气中硫酸并生成(NH₄)₂SO₄.该地区的大气环境主要来源于自然源的影响, 但夏季风期间人为污染排放已经不可忽视, 这也得到HYSPLIT后向轨迹模式的计算验证.  相似文献   

安徽马鞍山市当涂地区地下水水化学特征及演化机制          下载免费PDF全文

李状  苏晶文  董长春  叶永红  杨洋 《中国地质》2022,49(5):1509-1526

【研究目的】 了解长江中下游平原地区地下水流系统并深入分析其地下水水化学特征及其演化机制。【研究方法】 综合马鞍山市当涂地区的水文地质条件、水动力场等,基于研究区水化学基本特征,运用多元统计分析、水化学图件、离子比值和反向水文地球化学模拟等方法对该地区浅层地下水水化学演化进行分析。【研究结果】 结果表明：（1）研究区地下水主要为低矿化度偏碱性水,地下水组分中阳离子以Ca²⁺和Mg²⁺为主,阴离子以HCO₃^-和SO₄^2-为主。（2）研究区地下水水化学类型主要可分为7类,其中松散岩类孔隙含水岩组和碎屑岩类孔隙裂隙含水岩组的水化学类型主要为HCO₃^-Ca型、HCO₃^-Ca·Na型、HCO₃·Cl-Ca·Na型以及HCO₃^-Ca·Mg型;基岩类裂隙含水岩组的化学类型主要为HCO₃·SO₄-Ca·Mg型和SO₄·HCO₃^-Ca·Mg型。（3）研究区浅层地下水水样超标率为46%,总体水质较差,超标率较高的组分依次为Mn、高锰酸盐指数（COD_Mn）、硝酸盐（以N计）、Fe、As、氨氮（以N计）等。（4）研究区地下水的化学组分主要受到岩石风化作用的控制;此外,还存在Na-Ca的正向阳离子交替吸附作用。反向水文地球化学模拟结果进一步定量论证了水岩相互作用对本区浅层地下水组分的形成和演化起着主导作用。【结论】 研究区地下水主要为低矿化度偏碱性,主要可分为松散岩类孔隙水、碎屑岩类孔隙裂隙水和基岩类裂隙水。主要离子比例和反向水文地球化学模拟揭示了本区浅层地下水化学组分主要是地下水溶滤方解石、白云石等碳酸盐矿物、石英、长石等硅酸盐矿物,高岭土等黏土矿物以及岩盐、石膏等达到过饱和之后形成的。  相似文献   

浙江宁波平原地下水水化学特征及其生态环境效应          下载免费PDF全文

金阳  姜月华  董贤哲  杨国强  刘红樱  雷长征  周权平  张鸿  梅世嘉  杨辉  吕劲松  李云 《中国地质》2022,49(5):1527-1542

【研究目的】 为查明浙江宁波平原地下水特征及成因演化,促进宁波地区地下水环境优化。【研究方法】 在野外调查和取样分析的基础上,充分利用前人资料,综合运用数理统计、相关性分析、Piper三线图、离子比例系数及环境同位素等方法手段,全面系统地分析了宁波平原地下水状况。【研究结果】 宁波平原地表水和潜水以淡水为主,Ⅰ承压水和Ⅱ承压水以微咸水、咸水为主,潜水中HCO₃^-占绝对优势,Cl^-、Ca²⁺、Na⁺次之,地表水和承压水中Cl^-、Na⁺占主导地位,HCO₃^-次之。4种水共划分23种水化学类型,地表水和潜水受大气降水影响明显,深层承压水以封存型为主,与浅表水体天然联系不密切,受地质历史时期海侵影响较大。【结论】 与20世纪70年代相比,宁波城区Ⅰ承压淡水体分布范围无明显变化,Ⅱ承压水在人类生产生活和水体自然循环双重影响下,原淡水区演化出孤岛状咸水体,但淡水体整体分布范围外扩,面积增加了约12 km₂,其生态环境效应趋于正向发展。  相似文献   

河南省安林地区接触交代型铁矿稀土元素地球化学特征          下载免费PDF全文

刘海鹏  柳阳阳  李普轩  张旭  董寒杰 《地质找矿论丛》2023,38(1):29-36

安林地区铁矿属典型的接触交代型铁矿，与成矿作用有关的岩浆岩为燕山期闪长岩，奥陶系马家沟组第三岩性段是主要的赋矿地层。通过对该矿区与成矿相关的岩矿石稀土元素地球化学研究表明：闪长岩w（ΣREE）_平均=114.12×10^-6，灰岩w（ΣREE）_平均=11.98×10^-6，磁铁矿石w（ΣREE）_平均=26.13×10^-6，矽卡岩w（ΣREE）_平均=65.67×10^-6，磁铁矿石和矽卡岩的稀土总量介于闪长岩与灰岩之间；稀土配分曲线总体上都表现为轻稀土相对富集的右倾型；闪长岩一般具有极弱的正Eu异常，灰岩具有较明显的负Eu异常，矽卡岩具有较弱的负Eu异常，磁铁矿石具弱的正Eu异常或Eu异常不明显；岩矿石的δCe值非常接近，且均不显示或显示极弱的负Ce异常；铁矿石和矽卡岩继承了来自闪长岩和灰岩的稀土元素特征，结合S、Pb同位素特征，认为闪长岩提供了主要成矿物质，赋矿地层也可能提供了部分成矿物质。  相似文献   

我国海洋地质分析测试技术   总被引：1，自引：0，他引：1  

陈道华  刁少波  张欣 《岩矿测试》2013,32(6):850-859

21世纪是海洋开发和利用的新世纪,随着国家对海洋地质调查工作的日益重视,海洋地质分析测试技术迎来了快速发展时期。本文对我国海洋地质分析测试技术的最新进展进行了简要评述:为满足海洋区域调查、海岸带地质调查的需要,建立了以大型分析仪器为主的多元素同时分析海洋地质样品的快速高效分析方法体系;针对新能源天然气水合物样品,开展了异常识别测试技术和应用测试技术研究,建立了用离子色谱法快速测定孔隙水中阴离子Cl^-、Br^-、SO₄^2-和阳离子Na⁺、NH₄⁺、K⁺、Ca²⁺、Mg²⁺ 的方法,开发出了以声学、电阻、时域反射(Time Domain Reflectometry, 简称为TDR)三种探测技术为主的适用于天然气水合物模拟实验的探测新技术;对于海洋沉积物中有机污染物样品,采用复合固相萃取净化柱,对海洋沉积物萃取液样品进行净化分离,依次选用正己烷和正己烷－二氯甲烷混合液淋洗固相萃取净化柱,可有效保留基体杂质,实现了海洋环境地质调查中基质复杂沉积物样品的同时净化、分离与测试,可显著提高实验效率;同时在大洋矿产样品分析技术、海洋地质标准物质研制、船载与原位化学探测技术等方面也取得了重要进展。本文还提出在海洋调查和监测的应用中,船载及原位测试技术将愈趋重要,加强海洋化学传感器的性能和检测集成化技术是今后的一个重要发展方向。  相似文献   

福建龙岩大洋-莒舟花岗岩锆石U-Pb年龄和Sr-Nd-Pb同位素特征及其地质意义   总被引：13，自引：3，他引：10  

张承帅  苏慧敏  于淼  胡兆国 《岩石学报》2012,28(1):225-242

马坑铁矿是一个大型层控矽卡岩型矿床,大洋、莒舟花岗岩分布于铁矿东西两侧,与铁矿关系密切。本文利用LA-ICP-MS锆石U-Pb定年法测得莒舟花岗岩年龄为129.6±0.8Ma,MSWD=2.3,利用SHRIMP锆石U-Pb定年法测得大洋花岗岩年龄为132.6±1.3Ma,MSWD=1.3,它们都形成于早白垩世,与马坑铁矿辉钼矿Re-Os年龄(130~133Ma)一致。大洋-莒舟花岗岩具高硅、富碱、贫钙镁和高分异指数等特点,属弱过铝或准铝质花岗岩;岩石稀土元素含量较高,配分模式呈轻稀土富集并缓向右倾斜,呈明显铕负异常的"V"型展布;微量元素具有Rb、U、Th、La等元素强烈富集而Ba、Sr、P、Ti 等元素相对亏损的特点;大洋岩体的(⁸⁷Sr/⁸⁶Sr)_ⅰ值变化于0.70878~0.71349之间;ε_Nd(t)值变化于-7.2~-8.6之间,f_Sm/Nd=-0.27~0.16,t_2DM =1511~1637Ma,(²⁰⁶Pb/²⁰⁴Pb)_i=18.588~18.955,(²⁰⁷Pb/²⁰⁴Pb)_i=15.660~15.682,(²⁰⁸Pb/²⁰⁴Pb)_i=38.935~39.168,μ值介于9.54~9.59,ω值介于36. 77~38.13。岩石地球化学和同位素组成特征表明大洋-莒舟花岗岩属于高分异壳源型花岗岩,形成于岩石圈减薄的背景下。花岗岩主要来源于元古代地壳物质,有EMⅡ型富集地幔组分的参与,使花岗岩的地壳留存年龄的降低(1.51~1.63Ga)。  相似文献   

大别硬玉石英岩中金红石原位高温高压下晶体结构和OH的研究     

陈菲  苏文  李晓光  胡鑫蒙  高静 《岩石学报》2021,37(12):3893-3902

本文通过金刚石对顶砧与拉曼光谱、红外光谱联用技术,原位模拟了金红石在高温高压下晶体结构及其OH的变化,从而了解俯冲带流体中金红石在地质过程中的行为及作用。实验证明,金红石在压力的作用下经历两次相变,分别为金红石型TiO₂结构→斜锆石型TiO₂结构（P=23.43GPa）→萤石型TiO₂结构（P=34.98GPa）,其结构在经历过超深俯冲后、折返过程中则以ɑ-PbO₂型TiO₂结构稳定存在。并且金红石晶体中的OH红外特征峰强度随着压力的增加而降低,从而显示在加压过程中金红石中OH含量降低,但直至地球深部超过600km（37.28GPa,约1200km）,其晶体中的OH也并未完全脱去。在高温高压实验中,金红石样品从常温常压条件加压、加温至P=4.01~4.08GPa和T=700℃时,金红石晶体的有序度、OH含量随着温度增加而降低,但至实验最高温压,晶体内部仍保留OH,其结构也稳定存在,因此金红石可以将水携带至深部约120km处。在降至常温常压的过程中,金红石中OH含量虽然增加,但并未恢复至实验开始时的含量,因此经历过快速俯冲、折返后的金红石中的OH含量无法代表金红石形成时的OH含量。  相似文献   

硫酸盐化合物分子体积的加和性研究     

张振禹  叶大年 《地质科学》1985,(2):180-190

自然界中已发现的硫酸盐矿物主要是表生作用和热液后期的产物,均是在低温、低压条件下形成的。因此,对于硫酸盐化合物来说,由于其结晶条件相似,那么,各种离子(或离子团)在不同的硫酸盐化合物中是否占有大致相同的体积。  相似文献   

Crystal structure of K-substituted gonnardite: separation of local water–cation assemblages     

Yurii V. Seryotkin  V. V. Bakakin 《Physics and Chemistry of Minerals》2014,41(3):173-180

K-substituted gonnardite, K_2.18Na_0.04Ca_0.02[Al_2.26Si_2.74O₁₀]·2.2H₂O, was studied by X-ray powder diffraction method. The structure was refined with the Rietveld technique in the tetragonal space group $I\overline{4} 2d$ with a = 13.65409(16), c = 6.56928(11) Å, V = 1224.74(2) ų, Z = 4. Most of K⁺ cations (1.94 apfu) statistically occupy three nearest positions to be considered as the split one. “Excess” cations are located in the position non-typical for K⁺. Statistics in the cation distribution is defined by the occupation of the additional position. Based on a crystal chemical positional model (C₂R₂A₂) [T₅O₁₀], the separation of the local water–cation assemblages from an average statistical pattern has been suggested.  相似文献   

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr)     

Hongwu Xu  Alexandra Navrotsky  M. Lou. Balmer  Yali Su 《Physics and Chemistry of Minerals》2005,32(5-6):426-435

Wadeite K₂ZrSi₃O₉ and its analogues K₂TiSi₃O₉ and Cs₂ZrSi₃O₉, synthesized by high-temperature solid-state sintering, have been investigated using powder X-ray diffraction coupled with Rietveld analysis and high-temperature oxide melt solution calorimetry. The crystal chemistry and energetics of these phases, together with K₂Si^VISi₃ ^IVO₉, a high-pressure wadeite analogue containing both tetrahedral and octahedral Si, are discussed in term of ionic substitutions. As the size of the octahedral framework cation increases, Si⁴⁺ → Ti⁴⁺ → Zr⁴⁺, the cell parameter c increases at a much higher rate than a. In contrast, increasing the interstitial alkali cation size (K⁺ → Cs⁺) results in a higher rate of increase in a compared with c. This behavior can be attributed to framework distortion around the interstitial cation. The enthalpies of formation from the constituent oxides (ΔH_f,ox⁰) and from the elements (ΔH_f,el⁰) have been determined from drop-solution calorimetry into 2PbO·B₂O₃ solvent at 975 K. The obtained values (in kJ/mol) are as follows: ΔH_f,ox⁰ (K₂TiSi₃O₉) = −355.8 ± 3.0, ΔH_f,el⁰ (K₂TiSi₃O₉) = −4395.1 ± 4.8, ΔH_f,ox⁰ (K₂ZrSi₃O₉) = −374.3 ± 3.3, ΔH_f,el⁰ (K₂ZrSi₃O₉) = −4569.9 ± 5.0, ΔH_f,ox⁰ (Cs₂ZrSi₃O₉) = −396.6 ± 4.4, and ΔH_f,el⁰ (Cs₂ZrSi₃O₉) = −4575.0 ± 5.5. The enthalpies of formation for K₂Si^VISi₃ ^IVO₉ were calculated from its drop-solution enthalpy of an earlier study (Akaogi et al. 2004), and the obtained ΔH_f,ox⁰ (K₂SiSi₃O₉) = −319.7 ± 3.4 and ΔH_f,el⁰ (K₂SiSi₃O₉) = −4288.7 ± 5.1 kJ/mol. With increasing the size of the octahedral framework cation or of the interstitial alkali cation, the formation enthalpies become more exothermic. This trend is consistent with the general behavior of increasing energetic stability with decreasing ionic potential (z/r) seen in many oxide and silicate systems. Further, increasing the size of the octahedral framework cation appears to induce more rapid increase in stability than increasing the interstitial alkali cation size, suggesting that framework cations play a more dominant role in wadeite stability.  相似文献   

Hydrostatic compression of galenobismutite (PbBi<Subscript>2</Subscript>S<Subscript>4</Subscript>): elastic properties and high-pressure crystal chemistry     

Lars A. Olsen  Tonci Balic-Zunic  Emil Makovicky  Angela Ullrich  Ronald Miletich 《Physics and Chemistry of Minerals》2007,34(7):467-475

A single-crystal sample of galenobismutite was subjected to hydrostatic pressures in the range of 0.0001 and 9 GPa at room temperature using the diamond-anvil cell technique. A series of X-ray diffraction intensities were collected at ten distinct pressures using a CCD equipped 4-circle diffractometer. The crystal structure was refined to R1(|F₀| > 4σ) values of approximately 0.05 at all pressures. By fitting a third-order Birch-Murnaghan equation of state to the unit-cell volumes V ₀ = 700.6(2) ų, K ₀ = 43.9(7) GPa and dK/dP = 6.9(3) could be determined for the lattice compression. Both types of cations in galenobismutite have stereochemically active lone electron pairs, which distort the cation polyhedra at room pressure. The cation eccentricities decrease at higher pressure but are still pronounced at 9 GPa. Galenobismutite is isotypic with CaFe₂O₄ (CF) but moves away from the idealised CF-type structure during compression. Instead of the two octahedral cation sites and one bi-capped trigonal-prismatic site, PbBi₂S₄ attains a new high-pressure structure characterised by one octahedral site and two mono-capped trigonal-prismatic sites. Analyses of the crystal structure at high pressure confirm the preference of Bi for the octahedral site and the smaller one of the two trigonal-prismatic sites.  相似文献   

Eifelite,KNa3Mg4Si12O30, a new mineral of the osumilite group with octahedral sodium     

K. Abraham  W. Gebert  O. Medenbach  W. Schreyer  G. Hentschel 《Contributions to Mineralogy and Petrology》1983,82(2-3):252-258

Eifelite of variable composition is uniaxial positive withn ₀ near 1.543 andn _e near 1.544, a between 10.14 and 10.15 Å, andc about 14.22 Å, space groupP 6/m 2/c 2/c. There is a complete series of solid solution between the eifelite end member KNa₃Mg₄Si₁₂O₃₀ and roedderite, KNaMg₅Si₁₂O₃₀, following the 2 Na?Mg substitution. Both eifelite and roedderite have milarite-type structures, but Na is always in six-coordinated sites: In roedderite Na occupies solely a newly defined B′^[6]-position which is slightly displaced alongc from the ideal B_[9]-position lying on the (001/2)-mirror plane in K₂Mg₅Si₁₂O₃₀. In eifelite Na is located both inB′^[6] and in theA _[6]-positions, where it partially replaces Mg. Eifelite has the highest cation occupancy of all osumilite group minerals known thus far. Both eifelite and roedderite occur in vesicles of contact metamorphosed basement xenoliths ejected with the leucite tephrite lava of the Quaternary Bellerberg volcano in the Eifel, West Germany. They are considered to be precipitates from highly alkaline, MgSi-rich, but Al-deficient gas phases that originated through interaction of gaseous igneous differentiates with the xenoliths.  相似文献   

Calcium and Magnesium‐bearing Sabugalite from the Tono Uranium Deposit,Central Japan     

Masataka Nakata  Eiji Sasao  Kosei Komuro 《Resource Geology》2013,63(4):404-411

Calcium and magnesium‐bearing sabugalite occurs as aggregations of yellowish platy crystals in veinlets or druses in conglomerate from the oxidized parts of the Tono uranium deposit, Central Japan. X‐ray powder diffractometry of this mineral has reflections consistent with previous powder diffraction data of sabugalite. It is included in the monoclinic system with space group C2/m and calculated cell parameters of a = 19.68Å, b = 9.89Å, c = 9.82Å α = γ = 90°, β‐96.93° and V = 1897.83ų. Chemical analysis yields a formula of (Ca_0.10 Mg_0.09)_Σ0.19Al_0.53(UO₂)_2.04((PO₄)_1.99(AsO₄)_0.01)_Σ2.00·11.22H₂O. EMPA mapping shows that the mineral is compositionally uniform with no micron‐scale layering. Charge of cations including Ca and Mg in the cation‐H₂O layer is 1.98 being identical to that of autunite group minerals. This suggests that the charge balance in the cation‐H₂O layer of the mineral could be made by the alkaline earth or alkaline elements rather than by hydrogen ions.  相似文献   

Rhombohedral ilmenite group nickel titanates with Zn, Mg, and Mn: synthesis and crystal structures     

Ruslan P. Liferovich  Roger H. Mitchell 《Physics and Chemistry of Minerals》2005,32(5-6):442-449

Binary, ternary, and quaternary rhombohedral ordered titanates, Ni_1/2Mn_1/2TiO₃, Ni_1/2Mg_1/2TiO₃, Ni_1/3Zn_1/3Mg_1/3TiO₃, and Ni_1/4Zn_1/4Mg_1/4Mn_1/4TiO₃, were obtained by solid-state synthesis at 1095°C at ambient pressure in a nitrogen atmosphere. All of the compounds adopt ATiO₃ (A = Ni, Mn, Zn, and Mg) stoichiometry. Crystal structures were refined by the Rietveld method from powder X-ray diffraction data. Unit cell parameters and unit cell volumes decrease with decreasing average radius of the ^vi A ²⁺ cation. All the synthetic titanates adopt the space group and the ilmenite structure consisting of distorted AO₆ and TiO₆ octahedra. The divalent cations and Ti⁴⁺ are distributed in layers of octahedra alternating along c with no evidence for disorder. In common with pyrophanite, NiTiO₃, and ilmenite sensu stricto, the distortion of the AO₆ octahedra is less than that of the TiO₆ octahedra. The Ti⁴⁺ and A-site cations in the titanates are off-centred within the coordination polyhedra. Deviation of the z positional parameters from their theoretical values for the A and Ti atoms indicate that in the titanates with the larger A ²⁺ cations and Goldschmidt tolerance factors, t ≥ 0.745, the AO₆ octahedral layer is more “puckered” above and below planes parallel to (001) than that of the TiO₆ octahedra, and vice versa in the titanates with smaller R _A ²⁺ for which t≤0.745. Data are given for the volumes and distortion indices of all the coordination polyhedra. This study confirms the existence and stability of complex solid solutions between ordered rhombohedral titanates of Ni and first-row transition metals at ambient conditions over a range of t from 0.786 to 0.737. These experimental data suggest that the formation of ilmenite-type titanates enriched in Ni is possible in exotic mineral-forming systems at low pressure and/or in extraterrestrial rocks.  相似文献   

The thermal expansion of synthetic aluminosilicate-sodalites,M 8(Al6Si6O24)X 2     

C. M. B. Henderson  D. Taylor 《Physics and Chemistry of Minerals》1978,2(4):337-347

Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)₈(Al₆Si₆O₂₄)Cl₂ solid solution series, 3 members of the (Na,K)₈(Al₆Si₆O₂₄)Br₂ solid solution series and Na₈(Al₆Si₆O₂₄)I₂. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10^?6 °C^?1 below and 7.7×10^?6 °C^?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I^? or SO ₄ ^2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.  相似文献   

Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA   总被引：1，自引：0，他引：1  

John M Zachara  Steven C SmithChongxuan Liu  James P McKinleyR.Jeffrey Serne  Paul L Gassman 《Geochimica et cosmochimica acta》2002,66(2):193-211

The sorption of Cs⁺ was investigated over a large concentration range (10⁻⁹−10⁻² mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO₃ brine) is the carrier. Cs⁺ sorption was measured on homoionic sediments (Na⁺, K⁺, Ca²⁺) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na⁺ electrolyte, concentrations were extended to near saturation with NaNO_3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs⁺ for both high- and low-affinity sites according to the trend K⁺ >> Na⁺ ≥ Ca²⁺. At high salt concentration, Cs⁺ adsorption occurred only on high-affinity sites. Na⁺ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs⁺_(aq), and analyzed by electron microprobe to identify phases and features important to Cs⁺ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na⁺ in HLW and indigenous K⁺ displaced from the sediments may act to expedite the migration of strongly sorbing Cs⁺ in subsurface environments.  相似文献