应用电子探针技术研究北京密云放马峪铬铁矿床成因——来自含铬尖晶石矿物化学的证据

似层状铬铁矿床长期以来被认为是岩浆分异成因,但近年来有学者提出其中个别产在蛇绿岩中。本文选择北京放马峪似层状铬铁矿床中纯橄岩、辉橄岩和辉石岩中不同类型的含铬尖晶石进行了电子探针分析。研究表明,岩浆早期的纯橄岩和辉橄岩中的铬尖晶石富铬(Cr2O3平均43.32%),而岩浆晚期辉石的结晶消耗了大量Cr3+,由于氧逸度的升高,在辉石岩的单斜辉石中出溶贫铬的铬磁铁矿(Cr2O3平均10.32%)和富铝尖晶石(Cr2O3平均15.77%)。与世界上不同类型铬尖晶石的矿物化学特征进行对比,可以认为放马峪铬铁矿床是产在阿拉斯加型岩体中的早期岩浆矿床,而与蛇绿岩无关。本文对放马峪铬铁矿床成因和成矿专属性的限定,为这类镁铁-超镁铁岩体的铬、铜镍、铂族元素的找矿勘查提供了依据。     

云南宾川-永胜-丽江地区低钛玄武岩和苦橄岩的岩石成因与源区性质

云南宾川-永胜-丽江地区是峨眉山玄武岩厚度最大、喷发最早的地区,最主要的岩石类型是低钛和高钛玄武岩,并有少量摘要云南宾川—永胜—丽江地区是峨眉山玄武岩厚度最大、喷发最早的地区,最主要的岩石类型是低钛和高钛玄武岩,并有少量的苦橄质玄武岩、苦橄岩和麦美奇岩。大部分火山岩的岩石化学组成属于拉斑玄武岩系列,少数低钛玄武岩属碱性玄武岩系列。它们不同程度地富集大离子亲石元素和轻稀土元素,相对亏损重稀土元素,稀土元素分馏明显,显著亏损相容元素(Co,V,Cr,Ni)。陆壳物质对低钛玄武岩浆的混染程度明显大于对苦橄质岩浆的影响程度。而且混染作用对于Sr同位素和大离子亲石元素的影响程度明显大于对Nd同位素和稀土元素的影响程度。Nd和Sr同位素证明,混染物主要是下地壳变质岩,也有少量上部陆壳物质。未受混染的样品具有适度亏损的Nd、Sr同位素组成。低钛玄武岩和苦橄岩类岩石是不同原生岩浆分异演化的产物。低钛玄武岩的原生岩浆是高镁拉斑玄武岩浆,原生苦橄质岩浆以EM-55为代表(MgO= 16.56%)。此外,还有一种比EM-55更富镁的原生岩浆。高镁拉斑玄武岩浆分异过程中的主要分离结晶相/堆晶相是单斜辉石,并有少量斜长石。苦橄岩浆分异过程中的主要分离结晶相/堆晶相是橄榄石,并有少量单斜辉石。参考相关的实验岩石学成果,可以证明,地幔柱源区由两种岩石组成:一种是50%榴辉岩和50%橄榄岩反应形成的石榴石辉石岩,另一种是橄榄岩。在地幔柱绝热上升过程中,位于其轴部的石榴石辉石岩的熔融作用始于≈165km,主要的熔融作用发生于165～128km,持续到66km,熔融产物为苦橄岩浆。橄榄岩的部分熔融始于≈150km,持续到66km,熔融产物是比EM-55更富镁的岩浆。地幔柱头部的熔融作用始于≈100km,终止于66km,主要的熔融作用发生于尖晶石稳定域,熔融产物为低钛玄武岩浆。     

高Cr地质样品的Mg同位素分析方法

使用多接收等离子体质谱仪测定Mg同位素比值时,Cr元素会干扰测定结果。高Cr地质样品如铬尖晶石和铬铁矿中的Cr/Mg值可高达5︰1。针对这些样品,本研究检测了Cr对Mg同位素测试的干扰程度,评估了实验室流程中Cr和Mg的分离效果,探讨了Cr在淋洗过程中的行为。实验采用1mol/L HNO_3及2.3mL AG50W-X8型阳离子树脂,仅通过一次分离纯化便能将Mg与Cr等其他基质元素有效分离,且Mg的回收率可达99.8%,测试结果可靠。此外,Cr在分离过程中分为两阶段被洗脱,这与其在样品中不同的赋存价态有关。     

钙同位素化学分离方法研究

报道了在本实验室建立的地质样品钙同位素化学分离方法。通过对比不同离子交换柱类型、树脂体积、淋洗酸浓度及类型、上样量及样品岩性等影响化学分离效果的因素,确定了采用AG MP-50(100-200目)树脂及HCl淋洗的化学分离流程。该流程在确保高回收率的条件下实现了Ca与K、Sr等干扰元素的有效分离和质谱测量过程中基体效应的有效控制,经这套化学分离方法提纯的NIST SRM 915a、IAPSO大西洋标准海水及一些USGS标样的测试结果与文献值在误差范围内一致,表明本文建立的化学分离流程可满足热电离质谱(TIMS)高精度测定地质样品钙同位素的要求。     

地质样品中高精度铬同位素分析纯化技术研究进展

随着多接收器热电离质谱仪(MC-TIMS)和多接收器电感耦合等离子体质谱仪(MC-ICP-MS)的发展,高精度铬(Cr)同位素测试已成为可能。铬同位素在地球、环境、农业生态和宇宙化学等科学领域中已显示出良好的应用潜力。然而,样品的纯化分离、干扰和仪器质量分馏的校正,依然是制约铬同位素高精度测试的重要因素。本文在近年来铬同位素分析技术最新进展的基础上,结合本课题组已有的研究,对陨石、地质和环境等各类样品中铬同位素的分离纯化方法、MC-ICP-MS测试中干扰与质量歧视校正等进行了详细综述。本文认为,阴阳离子树脂交换联用与过硫酸钾等强氧化剂的结合,可以进行低铬高基质样品的有效纯化,是一种较为普适性的纯化方法。使用铬同位素双稀释剂校正质量歧视效应,在MC-ICP-MS的中高分辨与静态测量模式下,不仅可以有效分开多原子离子的干扰,而且也可以进行高精度铬同位素分析,其δ~(53/52)Cr的分析精度与TIMS相当,可以达到0.04‰(2SD),且最低测试浓度可低至10ng,能够实现超微量铬的同位素分析。     

峨眉火成岩省地幔热柱的主要元素及Cr、Ni地球化学特征

峨眉山玄武岩省晚古生代镁铁超镁铁岩可分为苦橄岩—橄榄玄武岩系和玄武岩系等两个岩石系列。它们的常量及微量元素特征均存在区别,这些区别可以通过对比两个岩系的Ni与Cr、MgO、Al2O3的相关关系加以明确。据此估算了峨眉火成岩省地幔、地幔热柱不同部位主元素、Mg#值和Cr、Ni含量,推算出成分接近原始岩浆的玄武岩、苦橄岩类和橄榄岩类分别为地幔7%～15%、25%～40%和 >50%的部分熔融产物。     

北大巴山笔架山—铜洞湾碱性镁铁质熔岩的岩石学研究

笔—铜碱性镁铁质火山岩体由碎屑岩和熔岩组成。熔岩的主要岩石类型有苦橄岩(富橄辉玄岩)和碱性玄武岩。所有样品都富集不相容元素,REE显示出高度分离的分配型式,其(La/Yb)_(CN)比值多数在15和20之间,而相容元素(Co、Cr和Ni)则明显亏损,计算表明,碱性镁铁质熔岩不可能由球粒陨石型地幔分离出的橄榄岩部分熔融产生,而可能是由交代地幔适度部分熔融产物。     

北大巴山笔架山—铜洞湾碱性镁铁质熔岩的岩石学研究

笔-铜碱性镁铁质火山岩体由碎屑岩和熔岩组成。熔岩的主要岩石类型有苦橄岩(富橄辉玄岩)和碱性玄武岩。所有样品都富集不相容元素,REE显示出高度分离的分配型式,其(La/Yb)_(ON)比值多数在15和20之间,而相容元素(Co、Cr和Ni)则明显亏损,计算表明,碱性镁铁质熔岩不可能由球粒陨石型地幔分离出的橄榄岩部分熔融产生,而可能是由交代地幔适度部分熔融产物。     

峨眉山大火成岩省中高Os苦橄岩的发现及地质意义

本文对峨眉山大火成岩省中苦橄岩及其共生的玄武岩进行了铂族元素(PGE)分析,结果表明苦橄岩比玄武岩的PGE含量要高至少一个数量级,并且具有明显高的Os含量,不仅比熔融程度最高的科马提岩要高,而且比原始地幔还要高,另外,还显示出超球粒陨石的Os/Ir比值(2.84～3.88)。其高的Os/Ir比值可能与岩浆上升过程中混入黑色页岩有关。部分熔融计算表明,含有0.01%硫化物的原始地幔 0.5%的外核在7%的熔融程度下,然后又被约10%的黑色页岩混染可以模拟原始岩浆的PGE含量。其Os含量及其他地球化学特征与其同时代的西伯利亚暗色岩系的相似性可能暗示了这两个大火成岩省来自于同一个起源于核-幔边界的超级地幔柱。另外,还根据苦橄岩和玄武岩PGE的含量估算了该地区PGE的成矿潜力。     

新疆西准噶尔地区两类蛇绿岩中橄榄岩的矿物学研究

两类蛇绿岩中变质橄榄岩的矿物表现出的共同特征是:从二辉橄榄岩→斜辉橄榄岩→斜辉辉橄岩→纯橄岩→铬铁矿石,其橄榄石、斜方辉石和单斜辉石的Mg/(Mg+Fe)(矿物牌号)依次升高,表现出富Mg贫Fe的演化趋势;铬尖晶石的Cr/(Cr+Al)亦同时升高,表现为富Cr贫Al的演化特征。 变质橄榄岩中的矿物均是原始上地幔岩部分熔融的残余物。在部分熔融过程中,橄榄石与铬尖晶石是生成相矿物,而斜方与单斜辉石则是消失相矿物,正是通过两种辉石的不断消失,岩石才从二辉橄榄岩依次转化为纯橄岩,并造成纯橄岩与铬铁矿的紧密伴生。在此过程中,矿物成分时刻都在变化,造岩矿物向富Mg贫Fe,金属矿物向富Cr贫Al方向调整,这与实际测定结果是一致的。     

Chromium contamination from chromite mine

Among the dominant species of chromium, the trivalent form widely occurs in nature in chromite ores or in silicate minerals and is extremely immobile. The higher oxidation state Cr(VI), is, however, rarely found in nature, is more mobile, and several times more toxic than Cr(III). Cr(VI) occurs in chromates and dichromates manufactured from chromite ores. The hexavalent state is stable in an oxidizing alkaline environment, whereas the trivalent state is stable in a reducing acidic environment. Serpentinization and Mg release during deuteric alteration of ultramafic rocks create alkaline pore water and lateritization is an intensive oxidation process. Chromite ore bodies in oxidized serpentinite therefore may generate hexavalent chromium from the inert chromites and cause hazardous chromium pollution of the water. With this end in view, a combined field and laboratory study has been made on chromite-bearing oxidized serpentinite rocks of Sukinda in Orissa, India. Laboratory leaching studies on mine overburden samples, chemical analyses of streamwater, and hydrolysate incrustation on detrital grains taken from stream beds have indicated the possibility of chromium mobilization from the chromite ores into the waterbodies.     

The Chromium Resources of Albania

During the past three decades Albania has been a major world source of chromite-in terms of both mine production and exports. However, the recent steep decline in Albania's production and export of chromite and ferrochromium has raised the question of the country's future status as a supplier of these commodities to the world market. This report describes the salient characteristics of Albania's chromium resources; examines the raw material base, mining and processing facilities, foreign trade, and programs controlling their development; and assesses future development prospects for the industry.     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

Preparation of Four Chromium Ore Reference Materials

The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr₂O₃ ranged from 17.59 to 57.80% m/m. The contents of FeO and CO₂ were taken as reference values.     

用金属铬法分析微量水和有机质氢同位素组成

本文介绍一种用金属铬作还原剂分析微量水和有机分子中氢同位素组成的技术方法。该分析方法是利用金属铬在高温条件下的还原性，将微量水和有机分子中的氢转变成H2气的分析技术。金属铬还原法的流程简单、安全可靠、操作便捷，其分析精密度可达±2‰。     

Chromium Transformations in Natural Environments: The Role of Biological and Abiological Processes in Chromium(VI) Reduction

Chromium is a redox-dynamic element that has many industrial uses. As a consequence, it is often introduced at elevated levels into the surface environment through human activity. Additionally, ultramafic rocks such as serpentinite are commonly enriched in chromium, and thus can also lead to appreciable levels of this element within soils and waters. In the trivalent state, it poses little hazard to biological activity, but, unfortunately, in the hexavalent state it is very toxic to living matter. One must therefore assess the oxidation state of Cr in a given system and determine the potential for transformation between valence states. The objective of this paper to is review and provide new insight on reduction reactions of Cr(VI) within natural environments. A number of aerobic and anaerobic bacteria demonstrate the enzymatic ability to reduce Cr(VI) to Cr(III); two species can even grow using Cr(VI) as the terminal electron acceptor in respiration. The ability to reduce chromium in itself is not evidence that the process will take place at appreciable levels in natural environments, however. Reduced materials such as ferrous iron or hydrogen sulfide may compete with biological pathways in the reduction of Cr(VI). On the basis of measured reaction rates and derived rate expressions, we demonstrate that biological pathways are not likely to contribute to the reduction of chromate in anaerobic systems. Ferrous iron will dominate the reduction of chromate at pH values greater than ～ 5.5, whereas hydrogen sulfide will dominate at pH values below this value. In contrast, bacteria may be the principal means by which Cr(VI) is converted to Cr(III) in aerobic environments. Thus, the process by which Cr(VI) is reduced will depend primarily on the aeration status of the system, and secondarily on pH and the concentrations of specific reduced phases.     

离石黄土对Cr3+的去除及对Cr3+形态分布的影响

选取离石黄土中的黄土及黏土层和重金属铬作为研究对象,通过等温吸附实验及Tessier法形态提取实验,分析了Cr3 在离石黄土中的存在形态,并对其分布规律进行了比较,研究了离石黄土对Cr3 的去除机理.实验结果表明:黄土及黏土层对Cr5 均有很好的去除效果,吸附率超过98%.当初始质量浓度ρ0＜100 mg/L时,其等温吸附曲线属Henry型.形态提取研究发现:黄土及黏土层对Cr3 的吸附形态以碳酸盐结合态和铁锰氧化物结合态为主,两者的总和都在95%以上,有机质结合态较少且相对稳定.受黄土及黏土层化学成分差异的影响,它们对Cr3 的去除在形态分布上存在一定差异,黄土中Cr3 的形态分布:碳酸盐结合态＞铁锰氧化物结合态＞有机质结合态＞可溶态＞可交换态;黏土层中Cr3 的形态分布:铁锰氧化物结合态＞碳酸盐结合态＞有机质结合态＞可溶态＞可交换态.     

含铬蒙脱石中铬离子占位位置研究

采用提纯后的蒙脱石在不同浓度硫酸铬溶液中进行交换吸附制备了含铬蒙脱石,并利用包括粉末X射线衍射术 （XRD）、电子自旋共振谱术（ESR） 和傅里叶变换红外吸收光谱术（FTIR） 等分析测试手段对铬在蒙脱石中的吸附位置进 行了探索研究。研究结果显示铬离子不仅置换了层间域中的Ca2+,K+和Na+等,而且置换了位于八面体位的Mn2+ 和少量 Al3+,并较大量的进入硅氧四面体的六边形孔洞、甚至有可能置换极少量的四面体位的Al3+和Fe3+等。此外,根据X射线衍 射分析可知,在0.2 mol/L硫酸铬溶液中充分交换吸附后的蒙脱石存在两层水型和单层水型两种含铬蒙脱石,其水合阳离子 分别为[Cr(H2O)6]3+和[Cr(H2O)3O3]3+,当吸附量增大至一定程度后水合铬离子借助TOT结构片的硅氧四面体的底氧形成配位多 面体。     

Adsorption Behavior of Hexavalent Chromium in Vadose Zone

Adsorption behavior of Cr (VI) in vadose zone, which is silty clay and clayey soil, was studied through kinetics experiments, isothermal adsorption experiments under various conditions, including different ph, temperature and organic contents. The results from kinetics experiments showed that the sorption progress of Cr (VI) has clear features in different stages, and adsorption equilibrium showed at 30 min, the adsorption rate of silty clay and clayey soil were 60%. The isothermal adsorption curve of Cr (VI) fitted closely with Freundlich equation model. When pH is 3-5 a plateau were seen, thereafter with increase in pH the adsorption rate of Cr (VI) dropped sharply and the minimum achieved at pH 10, the adsorption rate were only 35%. Adsorption rate of Cr (VI) increased gradually with the increase of temperature, the temperature of vadose zone is 14.7 ℃, according to the experimental results, the adsorption rate of Cr (VI) is about 40%. The use of organics represents an important contribution to the sorption of Cr (VI), sorption rate up to 100% when 30% of organic content. These studies will provide basis for manager to minimize the impacts, and provide basic data for pollution prevention and remediation of vadose zone.     

地下水中铬的分离技术及其应用

提出了一种将地下水中的铬与其他基本离子分离的技术,用于固体离子源热电离质谱计(TIMS)测定铬同位素比值.利用铬的氧化态以阴离子形式存在的特点,采用阴离子交换色层分离法将Cr5 与干扰阳离子分离;利用铬的还原态以阳离子形式存在的特点,将Cr3 与硫酸根等干扰阴离子分离.该方法可以成功地应用于地下水中铬同位素信息的测定,在地下水铬污染研究中有着广阔的应用前景.