Genesis of monazite and Y zoning in garnet from the Black Hills, South Dakota

The paragenesis of monazite in metapelitic rocks from the contact aureole of the Harney Peak Granite, Black Hills, South Dakota, was investigated using zoning patterns of monazite and garnet, electron microprobe dating of monazite, bulk-rock compositions, and major phase mineral equilibria. The area is characterized by low-pressure and high-temperature metamorphism with metamorphic zones ranging from garnet to sillimanite zones. Garnet porphyroblasts containing euhedral Y annuli are observed from the garnet to sillimanite zones. Although major phase mineral equilibria predict resorption of garnet at the staurolite isograd and regrowth at the andalusite isograd, textural and mass balance analyses suggest that the formation of the Y annuli is not related to the resorption-and-regrowth of garnet having formed instead during garnet growth in the garnet zone. Monazite grains in Black Hills pelites were divided into two generations on the basis of zoning patterns of Y and U: monazite 1 with low-Y and -U and monazite 2 with high-Y and -U. Monazite 1 occurs in the garnet zone and persists into the sillimanite zone as cores shielded by monazite 2 which starts to form in the andalusite zone. Pelites containing garnet porphyroblasts with Y annuli and monazite 1 with patchy Th zoning are more calcic than those with garnet with no Y annuli and monazite with concentric Th zoning. Monazite 1 is attributed to breakdown of allanite in the garnet zone, additionally giving rise to the Y annuli observed in garnet. Monazite 2 grows in the andalusite zone, probably at the expense of garnet and monazite 1 in the andalusite and sillimanite zones. The ages of the two different generations of monazite are within the precision of chemical dating of electron microprobe. The electron microprobe ages of all monazites from the Black Hills show a single ca. 1713 Ma population, close to the intrusion age of the Harney Peak Granite (1715 Ma). This study demonstrates that Y zoning in garnet and monazite are critical to the interpretation of monazite petrogenesis and therefore monazite ages.     

东海超高压榴辉岩中绿帘石、褐帘石、磷灰石和钍石集合体的电子探针成分和化学定年研究

中国大陆超深钻(CCSD)主孔从100米到3000米切穿含柯石英榴辉岩,为系统研究大陆深俯冲过程中含稀土元素副矿物提供了机会。本文报道了该钻孔榴辉岩存在发现的绿帘石、褐帘石、磷灰石和钍石复合颗粒。它们以同心环带结构为特征,从边部向中心依次为绿帘石、褐帘石和磷灰石;钍石既可包裹再磷灰石中,也可见于褐帘石中。电子探针分析显示,褐帘石不仅含有较高的轻稀土元素(LREE2O3=23．36wt％),而且可含有2．6wt％ThO2。根据绿帘石和褐帘石的电子探针高分辨U、Th、Pb成分计算得到绿帘石边部的形成年龄为738±88Ma,该年龄与大别-苏鲁地体榴辉岩的元古代源岩的年龄相当,因此,绿帘石可能为残留相。相反,褐帘石的年龄为220±41Ma,与大别-苏鲁超高压变质年龄相近。因此,褐帘石与磷灰石和钍石一起应该为超高压变质事件的产物。根据绿帘石、褐帘石及其共生的磷灰石和钍石的结构、成分特征和化学定年结果,我们推测绿帘石与可能已完全消耗的独居石很可能为变质副矿物组合的先驱矿物。独居石-绿帘石复合颗粒在榴辉岩相高压／超高压变质过程中反应形成磷灰石+钍石+褐帘石组合。     

Thermochemistry of monazite-(La) and dissakisite-(La): implications for monazite and allanite stability in metapelites

Thermochemical properties have been either measured or estimated for synthetic monazite, LaPO₄, and dissakisite, CaLaMgAl₂(SiO₄)₃OH, the Mg-equivalent of allanite. A dissakisite formation enthalpy of ?6,976.5 ± 10.0 kJ mol^?1 was derived from high-temperature drop-solution measurements in lead borate at 975 K. A third-law entropy value of 104.9 ± 1.6 J mol^?1 K^?1 was retrieved from low-temperature heat capacity (C _p) measured on synthetic LaPO₄ with an adiabatic calorimeter in the 30–300 K range. The C _p values of lanthanum phases were measured in the 143–723 K range by differential scanning calorimetry. In this study, La(OH)₃ appeared as suitable for drop solution in lead borate and represents an attractive alternative to La₂O₃. Pseudo-sections were calculated with the THERIAK-DOMINO software using the thermochemical data retrieved here for a simplified metapelitic composition (La = ∑REE + Y) and considering monazite and Fe-free epidotes along the dissakisite-clinozoïsite join, as the only REE-bearing minerals. Calculation shows a stability window for dissakisite-clinozoïsite epidotes (T between 250 and 550°C and P between 1 and 16 kbar), included in a wide monazite field. The P–T extension of this stability window depends on the bulk-rock Ca-content. Assuming that synthetic LaPO₄ and dissakisite-(La) are good analogues of natural monazite and allanite, these results are consistent with the REE-mineralogy sequence observed in metapelites, where (1) monazite is found to be stable below 250°C, (2) around 250–450°C, depending on the pressure, allanite forms at the expense of monazite and (3) towards amphibolite conditions, monazite reappears at the expense of allanite.     

New insights into mineralogy and geochemistry of allanite-bearing Mediterranean coastal sands from Northern Greece

Allanite-bearing black coastal sands of Kavala (N. Greece) were studied using a combination of single-crystal XRD, EMPA, μ-XRF, bulk ICP-MS, LA-ICP-MS, μ-XANES and γ-ray spectrometry. The sands are rich in REE (ΣREE + Y: 4010 to 10,810 mg/kg), Th (236–1205 mg/kg) and other critical metals such as Nb, Ta and Co. The main REE- and Th-hosts are allanite and titanite. The allanite unit cell parameters were calculated whereas its formula was found to be (REE_0.470Ca_1.499Th_0.031) (Ti_0.031Fe⁺³_1.089Al_1.880) (Si_2.906Al_0.094O₁₂) (OH). The μ-XANES spectra showed that LREE are present in trivalent oxidation state. Analyses of the non-magnetic sand fractions showed higher LREE (12,470 mg/kg) due to accumulation of allanite. The materials showed elevated radioactivity ranging from 885 ± 13 to 3467 ± 20 Bq/kg. The obtained results provide new insights on the provenance of the sands, the abundance of REE, Th, and other immobile elements, and offer new clues for potential exploration and exploitation.     

LA-ICP-MS褐帘石的U-Th-Pb定年——以广东新丰稀土花岗岩为例

褐帘石是一种常见的副矿物,是控制岩石中LREE、Th、U和Sr等微量元素的重要载体。由于Th、U可以在褐帘石中以类质同象形式进入并富集于其晶格,因而褐帘石是一种良好的年代学工具。但是,由于褐帘石中含有不同含量的普通铅,分析结果中的普通铅扣除成为难题,这就使得近年来褐帘石U-Th-Pb定年的应用受到很大的限制。本文利用通过激光熔样-电感耦合等离子质谱（LA-ICP-MS）原位分析技术,对广东新丰稀土花岗岩中褐帘石单颗粒矿物原位分析,运用232Th/206Pbc—208Pb/206Pbc等时线方法,再根据等时线年龄利用铅同位素演化两阶段模型扣除普通铅的方式,对建立单颗粒褐帘石的U-Th-Pb激光定年方法进行了探讨。运用该方法对广东新丰稀土花岗岩中褐帘石单颗粒矿物进行分析得出的年龄约为160Ma,与早期通过岩浆锆石U-Pb定年法得出的年龄之前研究159Ma~165Ma十分相似。褐帘石中微量元素、δEu、Th/U比值和普通铅含量显示其特征的岩浆成因褐帘石。褐帘石定年这一在国内首次使用尚未开展的定年方法具有简单、方便、准确的特点,对于确定含此矿物的岩体年龄,尤其是成成矿花岗岩的岩体形成时年代限制将发挥重大作用,具有非常良好和广泛的应用前景。     

Petrology of two granite types from the Tribeč Mountains,Western Carpathians: An example of allanite (+ magnetite) versus monazite dichotomy

Two granitoid series have been distinguished in the Tribeč Mountains (Western Carpathians) on the basis of the contrasting petrological behaviour of their accessory minerals. The allanite–magnetite-bearing (AM) tonalite–granodiorite–granite series typically contains dark magmatic enclaves and is produced from oxidizing, more hydrous (about 5.2 wt.% water) melts that were emplaced at depths equivalent to 350 ± 100 MPa. The monazite-bearing (M) tonalite–granodiorite–granite series contains only metamorphic xenoliths and comes from reduced and drier (about 2.3 wt.% water) melts that were probably emplaced at a shallower depth. The inferred magma properties probably reflect source rock effects. The mineralogical discrimination scheme between the AM and M series corresponds broadly to I- and S-type subdivision and may be useful not only for the granitoid bodies in the Western Carpathians but also for the whole Variscan orogenic belt.     

苏鲁超高压变质带含褐帘石正、副片麻岩中变质锆石的地球化学性质及其SHRIMP U-Pb定年

含褐帘石正、副片麻岩是苏鲁地体重要的超高压变质岩石。矿物包体激光拉曼鉴定、阴极发光图像分析、锆石微区LA-ICP-MS成分测试及SHRIMP U-Pb定年结果表明,含褐帘石正、副片麻岩中的锆石具有明显的三层结构,即弱发光效应的继承性(碎屑或岩浆结晶)锆石的核、强发光效应的含柯石英变质增生幔部和弱发光效应的退变边。继承性岩浆结晶锆石核部记录了新元古代(>810Ma)的原岩形成年龄,含柯石英锆石微区记录了241～223Ma的超高压变质年龄(正、副片麻岩的加权平均年龄分别为230±7Ma和229±7Ma),锆石的退变边记录了217～200Ma的角闪岩相退变质年龄(正、副片麻岩的加权平均年龄分别为211±3Ma和210±2Ma),由此限定苏鲁地体构造抬升速率为5.3km/Myr,表明苏鲁超高压岩石经历了一个相对快速抬升的变质演化过程。与苏鲁-大别其它超高压岩石变质增生锆石对比,含褐帘石正、副片麻岩中的超高压变质增生锆石微区具有十分独特的地球化学性质,主要表现为重稀土元素(HREE)明显富集,U含量明显偏低(10～29×10~(-6)),而Th/U比值则明显偏高(0.45～0.92)。HREE的明显富集与寄主岩石普遍存在超高压矿物褐帘石(富集轻稀土元素)有关,而低U含量和高Th/U比值的特点则表明超高压峰期变质阶段处在高氧逸度(f_o_2)的体系环境。     

褐帘石的谱学特征

本文研究了6个来自不同产状、不同地区的含褐帘石样品,包括4个伟晶岩(M1663来自内蒙集宁益元兴、M7673来自内蒙集宁察汗营地区、M4960来自美国Amherst County Virginia地区、M4976来自挪威Liksviken地区)、2个矽卡岩(M1697产自河北地区、M1679产自湖南郴县地区)。通过对这6个不同产状褐帘石的电子探针主量、稀土和微量元素分析及拉曼、红外光谱学的研究来揭示褐帘石晶体化学特征。结果表明,褐帘石成分均匀,晶体内发育微裂隙,局部有脉体充填,但不同产状的褐帘石样品在主量元素如Fe O、Ca O、Al_2O_3以及REE如Ce_2O_3、Nd_2O_3、La_2O_3的含量具有明显的差别。其系统的光谱学数据表明褐帘石晶体的特征峰强度和峰位的偏移均与其组分有关,并分析指派了部分光谱峰位的归属,揭示了褐帘石中特殊谱峰位置的迁移与其元素含量、晶体结构之间的关系。拉曼光谱揭示了褐帘石单晶有20组拉曼活性谱峰(ν1～ν20),其中ν2～ν4、ν5～ν8、ν16～ν19谱峰的迁移与A位上的Ca与稀土元素之间置换作用有关;ν10～ν12谱峰是O-Si-O弯曲振动引起,其拉曼谱峰的偏移可能与Si含量有关;ν13～ν14谱峰的迁移则可能是多种元素变化共同作用的结果。褐帘石单晶红外光谱展示了13组红外活性谱峰(a-m),h-k谱峰的偏移与在M1或M3位上Fe~(3+)和Al相互替代而导致的; b-g谱峰的偏移是与硅氧四面体中Si-O非对称伸缩振动有关; OH(l-m)双峰的出现可能与M1、M3位上Fe~(3+)的含量有关。研究结果表明伟晶岩类岩石中褐帘石晶体结构中Fe~(3+)与Al~(3+)间的置换作用强于矽卡岩类岩石中的褐帘石;而矽卡岩类岩石中褐帘石晶体结构中在A位上稀土元素与Ca置换作用则大于伟晶岩类岩石中的褐帘石。