应用二次离子质谱定量分析矿物中的稀土元素

利用下列技术对独居石和辉石样品中稀土元素(REE)进行了定量分析:(a)样品分离二次离子质谱法(SISIMS);(b)仪器中子活化分析(INAA):(c)电子探针显微分析(EPMA,仅独居石样品,(d)常规的能量渗滤法(CEFSIMS)的SIMS(仅独居石样品)。矿物晶粒中REE的含量范围从独居石的高含量(wt％)到辉石的ppm级。用CEF和SI两技术的SIMS分析同其它分析的结果非常一致,这表明可以把SIMS应用于矿物中的REE分析。辉石晶粒的分析表明:使用样品分离的SIMS,其检测限在ppm到近于ppm范围。     

含稀土磷矿稀土元素赋存特性

采用化学分析、X射线衍射分析和MLA矿物自动检测技术等手段,对湖北地区伴生稀土磷矿选矿精矿进行元素赋存特性研究,分析了该矿物的化学成分、矿物组成、稀土元素的赋存状态等理化特征。结果表明,稀土元素Ce、Nd、Sm主要赋存在独居石中,Gd、La全部赋存在独居石中,Dy则全部赋存在磷灰石矿物中,Pr全部赋存在磷灰石和独居石的复合矿物中,Y主要赋存在易解石中。独居石是含有稀土元素最多的矿物。磷灰石与稀土矿物相互交生,独居石主要呈稀疏星散浸染状充填于黑云母、萤石和赤铁矿等脉石矿物的粒间、边缘及孔洞中,多数粒度过于细小而与脉石构成极为复杂的镶嵌关系。     

计算机差谱技术在矿物红外光谱研究中的应用

在矿物红外光谱研究中运用差谱技术可消除其它矿物相谱带的覆盖,鉴定混合相中微量矿物成分,并得到单矿物谱图。 本文通过两个实例,介绍计算机差谱技术的特点、操作要点。云南腾冲热泉地区的粘土样品,用Perkin-Elmer983型红外分光光度计和3600数据站配合,应用视屏差减程序(Screen Diffe-rence)剥离掉主要组成矿物玉髓的红外光谱后,清晰显示出微量矿物明矾石的单矿物谱。西藏羊应乡热泉地区的岩心经处理后得到的粘粒,用计算机差谱技术进行多次剥离,得到一系列差减光谱,经确定,其矿物相为高岭石、蒙脱石、伊利石、石英、钠长石和微斜长石。     

离子探针质谱分析技术

1、离子探针的特点和功能:(1)检测灵敏度高,能测量包括氢在内的元素周期表上全部元素。绝对灵敏度为10~(-15)～10~(19),能检测相对含量为10~(-6)～10~(-9)原子浓度的微量杂质。因此它可以作金属超纯分析,半导体微量杂质测量和矿物微量元素分析。(2) 微区表面薄膜分析。它的横向(X—Y)分辨率为1～2μm,能在1～6nm厚的表面薄膜上检测样品表面杂质含量和分布,可以观测晶体界面结构信息和矿物离子显微图像。(3) 深度分析。其深度Z方向上分辨本领为5～10nm,可以提供包括轻元素在内的三维空间分析图像,可研究矿物元素氧化过程和离子扩散。(4) 同位素分析。同位素比值测量精度0.1％,在测定陨石,月岩和地球样品的微量元素和同位素组或以及地质年代学研究方面都能发挥作用。(5)绝缘体样品分析。要在试样表面上先镀一层碳膜(或金属膜),或者利用低能量电子喷射样品表面,或用负离子轰击样品来解决绝缘非导电体样品分析过程中在其表面积累电荷,以及由此产生的电位变化现象。(6)样品需要量少。消耗样品量仅1ng左右,且制备方法简单     

超高压榴辉岩中磷灰石的针状出溶物及其成因

金河桥榴辉岩是一含柯石英的超高压榴辉岩,其中的磷灰石中发现有针状出溶物,这些针状矿物长轴方向平行于磷灰石的c轴。根据电子探针分析结果,出溶物可能是以下三种矿物：独居石、黄铜矿和硅钍石(?)。它们的主要组成元素REE、S和Th等可以呈类质同象形式存在于磷灰石中,在超高压的条件下,由于温度相对较低,趋向于从寄主矿物中分离出来。矿物在高压下的这种“自净”行为可能是固态条件下矿物之间微量元素重新分配的一种方式,这种行为可能对地球不同层圈的化学组成演化有特别意义。     

X射线衍射和电子探针技术在矿物药雄黄鉴定及质量评价中的应用

雄黄是我国常用的矿物类中药,由于晶体空间结构不同,可分为α雄黄(AsS)和β雄黄(As4S4)。雄黄受氧化作用会产生剧毒物质砒霜(As2O3),其中β雄黄因空间结构关系更易被氧化,因此对矿物药雄黄的成分鉴定和质量评价具有重要的意义。常用的分析雄黄中砷及其他元素的方法(原子吸收光谱法、电感耦合等离子体质谱法、高效液相色谱-质谱法等)是通过测定总砷、价态砷和其他相关元素实现对雄黄的鉴别和有害成分的检测,分析过程复杂,试剂消耗大,需对样品进行破坏,而且不能直接对矿物结构进行判定。本文采用薄片鉴定、X射线衍射和电子探针对来自代表性生产地贵州思南和湖南石门的6种药用雄黄样品进行鉴别和质量评价。首先通过薄片鉴定初步确定雄黄样品的主要成分及伴生矿物,进一步利用X射线粉晶衍射和电子探针技术对雄黄的主要成分、伴生矿物进行半定量分析,再利用电子探针研究雄黄中As、S、O等元素的赋存状态,在这些技术综合鉴定的基础上,对收集的雄黄进行质量评价。分析结果显示:产自贵州思南的1号矿药由石英(82.8%)、方解石(9.5%)和白云石(7.7%)组成,2号矿药由α雄黄(64.7%)和石英(35.3%)组成;产自湖南石门的6号矿药由β雄黄(86.5%)和电气石(13.5%)组成,3号和4号矿药由α雄黄单矿物组成,5号矿药由β雄黄单矿物组成,3号、4号和5号三个样品中As含量大于70%,符合药典规定;电子探针分析样品中均未检测到砒霜,总体上表明湖南产的雄黄品质较高。研究表明,X射线粉晶衍射法利用了衍射图谱与晶体结构的一一对应性,找到不同矿物药样品的专属特性,而对于多组分矿物药样品,只要混合组分恒定,其衍射图谱就相对稳定,具有指纹特征;电子探针利用As、O等元素的赋存状态,可以有效地对雄黄的质量进行评价。X射线衍射和电子探针技术的结合用于鉴定雄黄矿物药是一种极为有效、可行的办法,与传统方法相比更为快速、经济。     

基于大罗兰圆(R=140mm)大分光晶体的SPI独居石标样化学成分精准测定

独居石是常见的稀土矿物之一,常出现在各类岩石中,是重要的成因指示矿物和定年矿物,因此准确测定独居石化学成分不仅具有重要的地质成因意义,同时也为后续的电子探针定年、原位同位素等分析工作提供可靠的参数。电子探针分析方法具有原位无损和高空间分辨率（~ 1 μm）的优势,该研究以SPI公司独居石标样为分析对象,在精细全元素波谱扫描工作基础上,对其化学成分的电子探针测试条件：加速电压、束流和测量时间的设定、分光晶体、分析线系、检测限、干扰系数,标样的选择等多个参数进行了系统研究和讨论,确定最佳测试条件参数,并获得和各元素含量推荐值基本一致的成分数据。文章建立了日本电子JEOL JXA-8530F Plus电子探针下独居石化学成分的最佳分析条件,实现了大罗兰圆大分光晶体（R=140 mm）对微量元素的精准测定,同时各元素含量相对标准偏差均低于20%（范围为0.05%～17.75%）,满足了后续实际样品的化学成分和CHIME定年的整合分析测试精度的要求。     

昌化田黄的矿物学特征及其与田黄的区别

对昌化田黄和田黄进行了红外光谱（IR）、X射线粉末衍射（XRD）、扫描电子显微镜（SEM）和激光剥蚀等离子质谱（LA-ICP-MS）测试,以获得两者的矿物学和地球化学特征,并对比研究它们之间的差别.研究表明,昌化田黄主要由地开石或者高岭石组成,而田黄主要由地开石、珍珠陶石或者伊利石组成.田黄和昌化田黄样品中均可含有少量的硫磷铝锶矿.有的昌化田黄中存在微量明矾石,其石皮中含有微量石英.昌化田黄中的地开石晶体颗粒为自形半自形结构,集合体呈书本状叠置排列;田黄中的地开石大多为他形结构,晶体颗粒在三维空间无序堆叠.田黄中P,V,Cr,Ga和Sr元素的质量分数低于昌化田黄,而Rb元素的质量分数明显高于昌化田黄.V-Rb,Cr-Rb,Ga-Rb元素投点图可区分昌化田黄和田黄品种.另外,昌化田黄石皮中Mg,Cr,Fe和Sn元素的质量分数高于其石肉.昌化田黄和田黄皆为轻稀土富集,重稀土亏损.昌化田黄比田黄的REE富集程度高.当所测主要矿物组成为非地开石,如珍珠陶石或者伊利石时,可能为田黄;如为高岭石时,可能为昌化田黄.当所测主要矿物组成为地开石时,两者皆有可能.矿物组成测试结合微量元素的质量分数和微形貌特征可对田黄和昌化田黄进行产地鉴别.     

阴离子交换色谱分离和测定微量单矿物方铅矿和闪锌矿中铜、铅、锌、银、铋、镉、锰、钴和镍等元素

微量单矿物方铅矿和闪锌矿中主体元素和痕量元素的多项分析,作者根据金属元素在阴离子交换树脂上与在盐酸、氢溴酸、硝酸、硫酸溶液之间的行为差别,试验了用阴离子交换色谱分离的条件,选用不同浓度的盐酸溶液洗提铜、钴、镍、锰、铅和银;氢溴酸溶液洗提锌;硝酸溶液洗提镉;最后用硫酸溶液洗提铋。本文所拟定的分析流程简便,试用于微量单矿物方铅矿和闪锌矿中九个元素的测定,效果较好。 实验部分 一、主要试剂     

定量确定中国大陆科学钻探工程主孔榴辉岩磷灰石中出溶体的组成:扫描电镜能谱分析(EDS)的应用

在不同类型变质岩和超基性岩的造岩矿物(如橄榄石、石榴子石、绿辉石等)中都发现了大小不一的固态出溶体。对大小仅为几个微米的出溶体,利用常规方法,电子探针、拉曼光谱等很难定量地确定它们的化学组分,严重地限制了对这些出溶体的地球化学动力学意义的认识。在最近的一系列研究中,发现榴辉岩中磷灰石含大量的出溶体,这些出溶体是平行于磷灰石C轴出溶的含铁、铜、铅等元素的硫化物。采用扫描电镜能谱分析(EDS)的点分析和线扫描技术,确定出溶体的主要组成元素,然后通过扣除磷灰石对所分析出溶域的贡献,能较准确地确定这些出溶体的化学组分,主要为FeS和FeS2。这些实验结果表明,利用扫描电镜的能谱分析(EDS)技术,通过点分析和线扫描,能够较精确地测量与母矿物之间化学成分差异较大的出溶体的化学组成。本文所提出的处理方法也适用于电子探针。     

Interaction of rhyolite melts with monazite,xenotime, and zircon surfaces

The interfacial contact region between a rhyolite melt and the accessory minerals monazite, xenotime, and zircon is investigated using molecular dynamics simulations. On all surfaces, major structural rearrangement extends about 1 nm into the melt from the interface. As evidenced by the structural perturbations in the ion distribution profiles, the affinity of the melt for the surface increases in going from monazite to xenotime to zircon. Alkali ions are enriched in the melt in contact with an inert wall, as well as at the mineral surfaces. Melt in contact with zircon has a particularly strong level of aluminum enrichment. In xenotime, the enrichment of aluminum is less than that in zircon, but still notable. In monazite, the aluminum enrichment in the contact layer is much less. It is expected that the relative surface energies of these accessory minerals will be a strong function of the aluminum content of the melt and that nucleation of zircon, in particular, would be easier for melts with higher aluminum concentration. The crystal growth rate for zircon is expected to be slower at a higher aluminum concentration because of the effectiveness of aluminum in solvating the zircon surface. The variable interfacial concentration profiles across the series of accessory minerals will likely affect the kinetics of trace element incorporation, as the trace elements must compete with the major elements for surface sites on the growing accessory minerals.     

应用能谱-扫描电镜和X射线衍射技术研究原煤伴生矿物中稀土和放射性元素赋存形式

研究原煤中稀土及放射性元素的赋存形式,对原煤是集中还是分散利用、燃煤过程中粉煤灰的排放截留、从原煤或粉煤灰中提取稀土及放射性元素等方面都具有指导意义。由前人研究可知不同矿区原煤中稀土及放射性元素的赋存形式有差异。本文研究了山西省霍西煤田两个矿区175个煤样中稀土及放射性元素的赋存形式,应用背散射电子图像(BSEI)定位分析区域,应用BSEI、能谱-扫描电镜法(EDX-SEM)中的面分析(EDS-mapping)和粉晶X射线衍射法确定了主要伴生矿物,应用BSEI和EDX-SEM中的点分析(EDS-point)确定了微量伴生矿物。在煤样中发现了铈镧钕钇镝钪六种稀土元素及一种放射性元素钍,其中铈、镧和钕主要以磷酸盐形式伴生于高岭石类矿物中,部分伴生在含氧化铝或氧化硅较多的矿物中,少量存在于碳中;钇、镝以磷酸盐或氧化物形式独立存在于碳中;在部分锆石、独居石中分别发现了钪和钍。研究表明,该矿区煤样中稀土元素主要以细粒自生矿物的形式伴生在其他矿物中,少数以独立矿物的形式存在于碳中,放射性元素钍伴生在独居石中。     

北京十三陵地区前寒武纪岩石中稀土矿物的发现及对同位素测年的意义

华北中、新元古代地层的年龄数据很混乱(表1),本文建议将北京十三陵地区新发现的稀土矿物用SHRIMP方法测年,有助于问题的解决。北京十三陵地区保存了新太古代五台群和新—中元古代较完整的地层,电子耦合等离子体分析(即原子收光谱分析)(ICP)的定量分析数据表明,在这些地层中,岩石中所含钾和稀土元素含量都比北美页岩(NASC)、欧洲页岩(ES)和澳大利亚后太古宙页岩(PAAS)高出很多,经电子扫描+能谱仪+波谱仪(SEM+EDS+WDS)分析证明,在岩石中包含独居石(碎屑的和自生-成岩的)和磷钇矿(自生-成岩的),并首次发现钍石-独居石环带状混合矿物(变质的)以及显微脉状稀土硅酸盐矿物(地下流体形成的)等稀土矿物。利用激光拉曼光谱鉴定发现稀土矿物的分布状态包括:1在太古宙五台群的片麻岩中,云母、石英和长石之间有非自形晶独居石,而且在石英单晶里还有独居石的自形晶包裹体;并发现独居石和钍石-独居石环带状混合矿物,这些稀土矿物都是变质成因的;2在新太古代五台群片麻岩的准平原化风化面上,沉积的元古宙常沟组的底砾岩中发现了碎屑的独居石,这些独居石的同位素年龄对于元古宇的底界定年意义重大;3在常州沟组下部压扁-透镜状层理的粉砂岩中,普遍发现碎屑锆石的外缘生长出自生-成岩磷钇矿,磷钇矿的同位素定年对于常州沟组的地层年代有代表性意义;4串岭沟组的粉砂岩中发现了无形晶状自生-成岩独居石和磷钇矿,并且较多出现在显微缝合线内外,可作为SHRIMP测年的对象;5大红峪组粉砂岩中除了发现碎屑独居石外还发现脉状硅-铝稀土矿物,可能与后元古宙热液活动有关。事实上这些自生-成岩的稀土矿物的形成,都是源自太古宙富含稀土元素的变质岩石,其形成机理也与地下流体活动有关。笔者认为北京十三陵以及至华北地区,前寒武系富稀土元素形成的自生-成岩的稀土矿物,有助于用SHRIMP方法对前寒武纪地层的同位素测年研究。     

CHIME dating of monazite, xenotime, zircon and polycrase: Protocol, pitfalls and chemical criterion of possibly discordant age data

This paper outlines the CHIME (chemical Th–U-total Pb isochron method) dating method, which is based on precise electron microprobe analyses of Th, U and Pb in Th- and U-bearing accessory minerals such as monazite, xenotime, zircon and polycrase. The age-mapping technique that is applicable to young monazite and zircon is also described. CHIME dating consists of analyzing multiple spots within homogeneous age domains that show sufficient compositional variation, and then these data are used to construct a “pseudo-isochron” from which an age can be obtained via regression. This method, when coupled with discrimination of possibly concordant age data by chemical criteria such as the (Ca + Si)/(Th + U + Pb + S) ratio for monazite and Ca and S contents for zircon, has the potential advantage of significant precision, and the ability to work with minerals that have a significant initial common Pb component. This technique can identify two or more homogeneous domains that are separated by age gaps smaller than the error on individual spot age analysis. Many features that are insignificant in major element analysis can have major impact in the acquisition of trace element data. Critical factors include the roles of collimator slit, detector gas, background estimation, accelerating voltage, probe current, X-ray interferences and count rate in affecting the accuracy, and a way to apply the Th and U interference correction without pure Th- and U-oxides or synthesized pure ThSiO₄. The age-mapping procedure for young monazite and zircon includes acquiring PbMα (or PbMβ) intensity of individual pixels with multiple spectrometers, correcting background with background maps computed from a measured background intensity by the intensity relationships determined in advance of the measurement, calibrating of intensity with standards and calculating of ages from the Th, U and Pb concentrations. This technique provides age maps that show differences in age domains on the order of 20 Ma with in monazite as young as 100 Ma. The effect of sample damage by irradiation of intense and prolonged probe measurement is also described.     

Equilibration and disequilibration between monazite and garnet: indication from phase‐composition and quantitative texture analysis

The integration of information which can be gained from accessory [i.e. age (t)] and rock‐forming minerals [i.e. temperature (T) and pressure (P)] requires a more profound understanding of the equilibration kinetics during metamorphic processes. This paper presents an approach comparing conventional P–T estimate from equilibrated assemblages of rock‐forming minerals with temperature data derived from yttrium‐garnet‐monazite (YGM) and yttrium‐garnet‐xenotime (YGX) geothermometry. Such a comparison provides an initial indication on differences between equilibration of major and trace elements. Regarding this purpose, two migmatites, two polycyclic and one monocyclic gneiss from the Central Alps (Switzerland, northern Italy) were investigated. While the polycyclic samples exhibit trace‐element equilibration between monazite and garnet grains assigned to the same metamorphic event, there are relics of monazite and garnet obviously surviving independent of their textural position. These observations suggest that surface processes dominate transport processes during equilibration of those samples. The monocyclic gneiss, on the contrary, displays rare isolated monazite with equilibration of all elements, despite comparably large transport distances. With a nearly linear crystal‐size distribution of the garnet grain population, growth kinetics, related to the major elements, were likely surface‐controlled in this sample. In contrast to these completely equilibrated examples, the migmatites indicate disequilibrium between garnet and monazite with a change in REE patterns on garnet transects. The cause for this disequilibrium may be related to a potential disequilibrium initiated by a changing bulk chemistry during melt segregation. While migmatite environments are expected to support high transport rates (i.e. high temperatures and melt presence), the evolution of equilibration in migmatites is additionaly related to change in chemistry. As a key finding, surface‐controlled equilibration kinetics seem to dominate transport‐controlled processes in the investigated samples. This may be decisive information towards the understanding of age data derived from monazite.     

东喜马拉雅构造结泥质高压麻粒岩的锆石和独居石定年与地质意义

东喜马拉雅构造结的南迦巴瓦杂岩含有广泛分布的高压麻粒岩,但由于以前获得了许多不同的年龄,对这些麻粒岩的变质与深熔时代、持续时间和成因存在不同认识。本文对泥质高压麻粒岩（蓝晶石榴黑云片岩）中的锆石和独居石进行了系统的内部结构、U-（Th）-Pb定年和微量元素分析,以求揭示这些岩石是否具有相同的演化过程。所研究的6个蓝晶石榴黑云片岩由石榴石、蓝晶石、黑云母、石英、钾长石、斜长石、夕线石、白云母、石墨和副矿物金红石、钛铁矿、锆石和独居石组成,峰期矿物组合是石榴石+蓝晶石+斜长石+钾长石+黑云母+石英+金红石。6个样品中的锆石均由继承碎屑核+变质（深熔）幔+变质（深熔）边组成。其中3个样品中的锆石幔和边较宽,均可进行原位定年,幔部给出了类似的较老年龄范围（39.6~31.6Ma、40.8~32.0Ma和38.1~31.3Ma）,而边部给出了类似的较年轻年龄范围（26.8~17.3Ma、28.3~18.6Ma和28.4~18.8Ma）。另外3个样品的锆石幔部较窄,不能进行分析,其边部给出了与前3个样品锆石边部类似的年轻年龄范围（22.0~17.0Ma、20.9~16.9Ma和22.2~16.6Ma）。一个片岩样品中的独居石给出了与其锆石幔部+边部年龄类似的较宽年龄范围（38.1~17.5Ma）,而另外3个样品中的独居石获得了与其锆石边部年龄相似的年轻年龄范围（26.0~18.8Ma、22.3~16.9Ma和26.4~19.4Ma）。随着年龄的减小,锆石和独居石的Th/U比值增大,Eu/Eu^*减小,独居石的HREE和Y含量减小。基于这些分析结果,笔者认为所研究的6个片岩记录了相同的、从~41Ma持续到~17Ma的进变质与深熔过程。但是,由于某些样品中的锆石和独居石在早期变质和深熔过程中形成的结晶域（锆石幔部）很窄,无法定年,导致不同的样品获得了不同的年龄范围。结合现有研究成果,笔者推测南迦巴瓦杂岩中的高压麻粒岩经历了相似的长期进变质与深熔过程。     

CHIME dating of monazite,xenotime, zircon and polycrase: Protocol,pitfalls and chemical criterion of possibly discordant age data

This paper outlines the CHIME (chemical Th–U-total Pb isochron method) dating method, which is based on precise electron microprobe analyses of Th, U and Pb in Th- and U-bearing accessory minerals such as monazite, xenotime, zircon and polycrase. The age-mapping technique that is applicable to young monazite and zircon is also described. CHIME dating consists of analyzing multiple spots within homogeneous age domains that show sufficient compositional variation, and then these data are used to construct a “pseudo-isochron” from which an age can be obtained via regression. This method, when coupled with discrimination of possibly concordant age data by chemical criteria such as the (Ca + Si)/(Th + U + Pb + S) ratio for monazite and Ca and S contents for zircon, has the potential advantage of significant precision, and the ability to work with minerals that have a significant initial common Pb component. This technique can identify two or more homogeneous domains that are separated by age gaps smaller than the error on individual spot age analysis. Many features that are insignificant in major element analysis can have major impact in the acquisition of trace element data. Critical factors include the roles of collimator slit, detector gas, background estimation, accelerating voltage, probe current, X-ray interferences and count rate in affecting the accuracy, and a way to apply the Th and U interference correction without pure Th- and U-oxides or synthesized pure ThSiO₄. The age-mapping procedure for young monazite and zircon includes acquiring PbMα (or PbMβ) intensity of individual pixels with multiple spectrometers, correcting background with background maps computed from a measured background intensity by the intensity relationships determined in advance of the measurement, calibrating of intensity with standards and calculating of ages from the Th, U and Pb concentrations. This technique provides age maps that show differences in age domains on the order of 20 Ma with in monazite as young as 100 Ma. The effect of sample damage by irradiation of intense and prolonged probe measurement is also described.     

Capabilities and constraints of the Pb-Pb dating of metamorphogenic minerals using the step-leaching method

Based on particular examples, this paper considers the capabilities and constraints of the step-leaching Pb-Pb dating (PbSL) of metamorphogenic minerals. It was shown that stepwise leaching allows the separation of fractions enriched in uranogenic and thorogenic Pb isotopes, which can be used for the determination of mineral ages and the time of crystallization of coexisting equilibrium and, occasionally, disequilibrium monazites. The presence of monazite in a mineral is indicated by a high Th/U ratio similar to that of monazite. The main limitation of the method is related to the presence in minerals of both disequilibrium domains of the mineral matrix and disequilibrium monazite microinclusions. By the example of minerals studied, we discussed three scenarios for the development of the U-Th-Pb isotopic systems of metamorphogenic minerals.     

REE-Depleted Leucogranites, Black Hills, South Dakota: a Consequence of Disequilibrium Melting of Monazite-Bearing Schists

Two isotopically distinct but otherwise chemically similar leucogranitesuites in the Proterozoic Horney Peak Granite, Black Hills,South Dakota, have contrasting light rare earth element (LREE)concentrations. Most samples of a relatively ¹⁸O-depleted suitehave LREE- enriched, chondrite-normalized patterns, typicalof melts derived from metasedimentary protoliths, whereas allsamples of the regionally significant, relatively ¹⁸O-enrichedsuite have LREE-depleted patterns. The latter patterns are interpretedto have resulted from disequilibrium melting of schists. Monaziteand perhaps other accessory minerals remained armored by biotiteand garnet which did not partake in the muscovite dehydration-meltingreaction that produced LREE-depleted melts. The REE concentrationsin the LREE-depleted samples are below saturation levels formonazite at reasonable melting temperatures and melt water contents,whereas the REE concentrations in the LREE-enriched samplesyield 700–800C monazite saturation temperatures, reasonablefor biotite dehydration-melting reactions. LREE depletions,analogous to those in the LREE-depleted granites, are also foundin leucosomes of partially molten schists, thought to be theprotolith for the granite. In contrast, the melanosomes holdthe accessory minerals and bulk of the LREEs. KEY WORDS: accessory minerals; leucogranites; Black Hills; monazite; partial melting ^*Corresponding author at Department of Geological Sciences, University of Missouri. Telephone: 314-884-6463. Fax: 314-882-5458. e-mail: geolpin{at}showme.missouri.edu.     

Residence and redistribution of REE, Y, Zr, Th and U during granulite-facies metamorphism: behaviour of accessory and major phases in peraluminous granulites of central Spain

Accessory minerals are thought to play a key role in controlling the behaviour of certain trace elements such as REE, Y, Zr, Th and U during crustal melting processes under high-grade metamorphic conditions. Although this is probably the case at middle crustal levels, when a comparison is made with granulite-facies lower crustal levels, differences are seen in trace element behaviour between accessory minerals and some major phases. Such a comparison can be made in Central Spain where two granulite-facies terranes have equilibrated under slightly different metamorphic conditions and where lower crustal xenoliths are also found. Differences in texture and chemical composition between accessory phases found in leucosomes and leucogranites and those of melanosomes and protholiths indicate that most of the accessory minerals in melt-rich migmatites are newly crystallized. This implies that an important redistribution of trace elements occurs during the early stages of granulite-facies metamorphism. In addition, the textural position of the accessory minerals with respect to the major phases is crucial in the redistribution of trace elements when melting proceeds via biotite dehydration melting reactions. In granulitic xenoliths from lower crustal levels, the situation seems to be different, as major minerals show high concentration of certain trace elements, the distribution of which is thus controlled by reactions involving final consumption of Al-Ti-phlogopite. A marked redistribution of HREE–Y–Zr between garnet and xenotime (where present) and zircon, but also of LREE between feldspars (K-feldspar and plagioclase) and monazite, is suggested.