钙钛矿型结构亚硝酸盐和氰化物的分子体积

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。     

天山东部冰川雪坑离子浓度特征的对比研究

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。     

矿山环境土壤重金属污染潜在生态风险评价模型探讨

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。     

安徽马鞍山市当涂地区地下水水化学特征及演化机制

【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。     

江南钨矿带桂林郑富钼白钨矿稀土元素的富集机制及其地质意义

桂林郑钼钨多金属矿床位于江南钨矿带北部,其矿石矿物以富钼白钨矿为主。研究显示,该矿床富钼白钨矿中富集稀土元素。为探究其富集机制,文章对不同世代的富钼白钨矿进行原位LA-ICP-MS微量分析和面扫描分析。结果显示,富钼白钨矿的总稀土元素含量（∑REE）在28.59×10^-6~4863.82×10^-6之间,均值为789.21×10^-6（n=122）,从第一世代（Sch-Ⅰ）28.59×10^-6~1059.18×10^-6（平均值为203.19×10^-6,n=55）→第二世代（Sch-Ⅱ）533.54×10^-6~2536.51×10^-6（平均值=928.79×10^-6,n=30）→第三世代（Sch-Ⅲ）117.21×10^-6~4863.82×10^-6（平均值=1547.13×10^-6;n=37）逐渐增高。从Sch-Ⅰ→Sch-Ⅱ→Sch-Ⅲ,轻重稀土元素比值（LREE/HREE）13.99~143.90（平均值=53.53）→22.38~70.08（平均值=33.74）→7.44~69.86（平均值=27.54）逐渐降低。桂林郑富钼白钨矿形成于高氧逸度、富F的岩浆热液系统,REE主要以Ca²⁺+Mo⁶⁺=REE³⁺+(1-x) Mo⁵⁺+xNb⁵⁺(0≤x≤1）为主导方式进入富钼白钨矿中。成矿流体中Cl降低、F增高、氧逸度降低等是REE进入富钼白钨矿的有利条件。通过对江南钨矿带代表性矽卡岩型矿床综合对比分析显示,富钼白钨矿床相比贫钼白钨矿床具有更高的REE,说明桂林郑矿床富钼白钨矿在后续开采中具有稀土元素的综合利用前景。     

河北赞皇地区许亭花岗岩的时代及成因:对华北克拉通中部带构造演化的制约

许亭花岗岩出露于赞皇杂岩中,位于河北省赞皇县西部山区,呈岩基状侵入新太古代TTG片麻岩和变质地层中,SHRIMP 锆石U-Pb年龄为2090±10Ma。岩体主要由钾长-二长花岗岩组成,无暗色包体,偶见围岩的捕掳体。岩体组成不均匀,局部含石英和少量钾长石斑晶,构成似斑状结构。主要的矿物组合为石英+钾长石+斜长石+黑云母+绿帘石±白云母±角闪石,含萤石副矿物。岩石具有高硅(SiO₂＞75%)、富碱(ALK=6.90%~8.75%)、低铝(Al₂O₃ =10.32%~11.64%)、钛(TiO₂=0.26%~0.36%)和贫钙(CaO=0.18%~0.48%)、镁(MgO=0.16%~0.40%)、铁(Fe₂O^T₃=2.58%~3.46%)的特征,为偏铝质到弱过铝质的高钾钙碱性系列。岩石的稀土总量较高(293.8×10^-6 ~702.8×10^-6),轻稀土相对富集,有明显的负Eu异常(Eu/Eu^*=0.1~0.35)。微量元素中,富Zr、Nb和Y,而贫Ba、Sr和P等元素,Rb/Sr比值较高,介于1.45~7.52之间,平均4.31。岩石还具有高的Ga/Al值(3.04×10^-6~4.08×10^-6),具有A型花岗岩特征。在同位素组成方面,具有较低的ε_Nd(t)值(-14.29~-0.29,平均为-5.58)。许亭花岗岩具有板内花岗岩特征,可能与2.1Ga时岩浆板底垫托,导致新太古代TTG岩石部分熔融,并可能有少量古老地壳物质加入。根据岩体性质及岩石组合等特征推测赞皇、阜平、五台等地区的2.1Ga岩浆活动形成于统一的拉张裂解环境。     

西秦岭铧厂沟金矿床流体包裹体特征研究及矿床成因

铧厂沟金矿位于西秦岭勉略缝合带南侧,其产出受韧脆性剪切带控制,赋矿围岩为泥盆系细碧岩、凝灰质绢云千枚岩和灰岩。根据脉体穿切关系和矿物交代关系,可以将铧厂沟金矿分为早、中、晚3个成矿阶段。在铧厂沟金矿的石英中发育了CO₂-H₂O型、纯CO₂型、H₂O溶液型和含子矿物型四种类型流体包裹体。早期石英中原生包裹体主要是CO₂-H₂O型和纯CO₂型,其成分为CO₂+H₂O±N₂±CH₄±H₂S,均一温度集中在320~360℃,盐度为0.43%~5.14% NaCleqv;中阶段为主成矿阶段,该阶段石英中包含了所有四种类型的包裹体,其中H₂O溶液型包裹体占了大多数,CO₂-H₂O和水溶液包裹体均一温度集中在240~320℃,盐度为0.43%~11.19% NaCleqv;晚阶段石英仅发育水溶液型包裹体,具有较低的均一温度(118~228℃)和盐度(0.18%~6.59% NaCleqv)。根据CO₂-H₂O型包裹体计算主成矿阶段压力为70~195MPa,成矿深度为5~7km。总体而言,铧厂沟金矿的初始流体具有中高温、富CO₂、低盐度的变质流体特征,晚成矿阶段流体演化为低温、低盐度水溶液流体,流体的不混溶导致了主成矿期的矿质的大量沉淀,铧厂金矿为中浅成的造山型矿床。     

我国首次发现的天然硅铋石的矿物学研究

硅铋石是一种极为罕见的铋的硅酸盐矿物,本次报道的天然硅铋石产于我国内蒙古自治区东乌旗朝不楞矽卡岩型铁多金属矿床中,附生在蔷薇辉石晶洞或裂隙中的透闪石纤维上。常见四面体{111}及三角三四面体晶形,一般粒径为0.07～0.15mm,颜色多为浅黄色,透明,玻璃光泽,性脆,条痕为无色,维氏硬度VHN_（100g）=487～583kg/mm²,平均535kg/mm²,摩氏硬度5,计算密度7.11g/cm³,计算折射率N=2.15。矿物化学分子式为Bi₄Si₃O₁₂。X射线衍射强线[d（Å）（I）]为4.26（85）、3.29（100）、2.77（79）、2.11（45）和1.67（33）,结构精修晶胞参数a=10.116（2）Å,V=1035.2（7）ų,空间群为I43d,Z=4。本文还对硅铋石的成因进行了初步探讨。     

扬子陆块西缘中元古代晚期元谋花岗岩的时代、成因及构造意义

扬子陆块西缘晚中元古代地质演化史一直存在较大争议,本文选择以扬子西缘元谋杂岩中一套二长花岗岩为研究对象,开展岩相学、锆石U-Pb年代学、全岩地球化学等综合研究,为认识和理解扬子西缘晚中元古代地质演化提供支撑。两件元谋二长花岗岩样品的LA-ICP-MS锆石U-Pb年龄分别为1086±10 Ma（MSWD=1.4,n=50）和1099±10 Ma（MSWD=1.8,n=58）。所有样品具有高硅（SiO₂为69.44%~73.98%）、富碱（Na₂O+K₂O为6.11%~7.72%）、贫钙（CaO为0.39%~1.46%）、贫镁（MgO为0.52%~0.76%）、低钛（TiO₂为0.30%~0.59%）的特点,同时表现出强过铝质（A/CNK=1.19~1.35）及中钾钙碱性–钾玄岩系列特征。它们具有高的稀土元素总量（∑REE=211.60×10^-6~349.01×10^-6）,呈现轻稀土元素富集和重稀土元素亏损（（La/Yb）_N=4.32~7.36）;富集Rb、U、Th等大离子亲石元素和Zr、Th、Hf等,亏损Nb、Ta、Ba等元素,并具有明显的负Eu异常（δEu=0.46~0.59）,锆石饱和温度介于827~912℃之间,展示了A型花岗岩的属性。这些二长花岗岩可能是通过中上地壳的中酸性火成岩的部分熔融形成,结合前人的研究成果,它们最可能形成于弧后的伸展环境,综合扬子陆块周缘晚中元古代的岩浆记录,元谋杂岩中1.09 Ga二长花岗岩的形成应与扬子陆块开始参与Rodinia超大陆聚合有关。     

内蒙古道郎呼都格地区A型花岗岩年代学、地球化学及地质意义

道郎呼都格钾长花岗岩体位于华北克拉通北缘白乃庙构造带。SHRIMP锆石U-Pb定年获得139.6±1.7Ma岩体侵位年龄。岩体富硅(SiO₂=75.79%~78.07%)、富碱(K₂O+Na₂O=7.39%~8.29%)、贫钙(CaO=0.22%~0.59%);稀土配分曲线呈现"海鸥式"分布特征,显示强烈的Eu负异常(δEu =0.03~0.12);微量元素特征显示具有较高Ga(21.2×10^-6~26.6×10^-6)、Zr(173×10^-6~417×10^-6)、Nb(32.3×10^-6~42.4×10^-6)和Y(24.6×10^-6~53.9×10^-6)含量,较低的Sr(14×10^-6~44×10^-6)、Ba(18×10^-6~211×10^-6)含量,在微量元素原始地幔标准化蛛网图上显示明显的Ba、Sr、P、Eu和Ti的负异常。以上特征表明道郎呼都格钾长花岗岩为A型花岗岩,为高温低压下长英质地壳的部分熔融及其后长石、榍石等的分离结晶作用的产物。结合区域构造演化,本文认为该区钾长花岗岩形成于板内伸展背景。在晚中生代期间,华北板块北缘的构造体制经历了重要的转变,由挤压体制转变为岩石圈减薄和地壳伸展,在伸展体制下,软流圈地幔上涌对上覆长英质地壳的直接加热作用促使其部分熔融形成该区A型花岗岩。     

硫酸盐化合物分子体积的加和性研究

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。     

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

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.     

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

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.     

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

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.     

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

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.     

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

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.     

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

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.     

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

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.     

Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA

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.