金红石Zr温度计在苏鲁-大别榴辉岩研究中的应用：问题讨论

金红石Zr含量温度计在苏鲁-大别超高压榴辉岩中的应用普遍得出了比峰期变质温度明显偏低的温度值。通过对比国内外的研究,并结合岩相学的分析,认为除了超高压可能使金红石对Zr的容纳度降低外,较强的退变质和流体作用下的扩散丢失是造成金红石Zr含量降低的主要原因。同一样品不同金红石颗粒之间Zr含量和温度的显著差别说明金红石与共存锆石和石英之间的Zr配分平衡已受到退变质作用的破坏且未能达到再平衡,金红石Zr含量温度代表的是每个颗粒受不同程度退变质和扩散影响后的某个缓冲状态,其平均温度的地质意义很难界定。只有将金红石的赋存状态、岩相学分析等研究与数据本身的均匀性分析结合起来进行综合判断,才有可能对金红石Zr温度计给出合理解释。     

金红石和榍石Zr温度计在新疆西南天山榴辉岩中的应用

应用LA-ICP-MS方法对新疆西南天山高压-超高压变质带中的榴辉岩及其高压脉体中的金红石和榍石进行了Zr含量的检测和Zr温度计的计算。榴辉岩中位于石榴石幔部且与绿辉石共生的金红石包体Zr含量都集中于10~20μg/g;而基质金红石的Zr含量为30~50μg/g,高于包体金红石。榍石均为金红石退变质的产物,且各样品间的榍石Zr含量较均一,都集中在3~5μg/g之间。脉体金红石Zr含量则与榴辉岩中基质金红石的Zr含量相当甚至偏高一些,为30~60μg/g。金红石和榍石的Zr温度计研究也表明,榴辉岩石榴石中的金红石包体生长于压力峰期阶段,温压条件为480~540℃、2.7~3.0 GPa;基质金红石随温度增加达到退变质再平衡,记录了温度峰期的条件,约530~590℃、2.4~2.7 GPa;榴辉岩中高压脉体中的金红石则生长于退变质榴辉岩相阶段,金红石Zr温度计给出结果为540~580℃、1.5~2.1 GPa,记录了近等温降压的过程;榴辉岩中的榍石在1.0 GPa左右达到平衡,榍石Zr温度计给出的温度为540~560℃,记录了进一步的近等温降压的过程。根据以上4个阶段的分析结果,得出一个较完整的顺时针p-T轨迹,且与相平衡模拟所限定的p-T轨迹相一致。金红石的Zr含量可以作为压力的指示,表明压力校正在金红石Zr温度计中起到了重要作用。在对金红石和榍石Zr温度计进行应用时,要结合细致的岩相学观察,综合考虑压力、活度、扩散速率、退变质作用和流体影响等方面的因素,才能得到比较精确的温压估算结果和pT轨迹。     

俄罗斯白海地区太古代榴辉岩的金红石Zr温度计应用及其地质意义

金红石Zr温度计在研究高级变质岩的热演化过程中可以发挥重要的作用。而电子探针显微分析技术得益于其较小的分析束斑(直径1~2μm)和适中的轰击能量,通过合理的实验条件设定和仪器参数设置,是对薄片中金红石Zr含量进行原位分析的理想实验手段。本文中,我们对俄罗斯白海地区的太古代榴辉岩-退变榴辉岩中的金红石Zr含量进行了电子探针原位分析,并进行了金红石Zr温度计计算。结果表明,其中石榴子石包裹体类型(产状1)金红石的Zr含量比较稳定,主要集中在400×10~(-6)~500×10~(-6)范围,个别金红石颗粒中的Zr含量可以达到1000×10~(-6);而基质后成合晶中(产状2)金红石的Zr含量的波动范围则相对更广一些(200×10~(-6)~1000×10~(-6)),这可能与后期退变过程中的Zr重置和/或扩散有关。总体上,不同产状金红石的Zr温度计计算结果都给出了两个主要的温度区间:T1=700~750℃和T2=800~850℃。结合前人对白海榴辉岩变质温压条件的研究以及金红石Zr体系封闭温度的控制,我们认为金红石Zr温度计的计算结果区间T1更有可能代表的是榴辉岩的退变冷却温度,而温度区间T2则反映的是榴辉岩在抬升过程中受到高温麻粒岩相变质作用阶段的温度峰期条件。     

低温高压榴辉岩锆石Ti温度计的有效性

为了探讨锆石的Ti温度计对于低温高压（超高压）榴辉岩的适用性,利用前人版本的温度计对北祁连和西天山4个典型低温高压（超高压）榴辉岩中的锆石进行了温度计算.结合其他地区高压/超高压榴辉岩锆石文献数据,发现对于低温变质锆石,Ti温度计得到的结果普遍高于其他温度计算方法,最高可达到58%.虽然温度是控制锆石中Ti含量的主要因素,但是其他因素（例如压力、SiO₂和TiO₂的活度,锆石中的晶格缺陷、其他微量元素替代、锆石的不平衡生长和变质流体活动）也会影响锆石Ti温度计的计算结果.研究认为,在锆石重结晶和再生长过程中,流体活动可能是造成锆石Ti温度计计算结果偏高的主要原因.      

柴北缘超高压变质带的冷却历史：来自副片麻岩中锆石、金红石的U-Pb年代学和温度信息

本文运用LA-ICP-MS和SIMS对柴北缘超高压变质带中东端沙柳河剖面中的副片麻岩进行了锆石和金红石U-Pb年代和微量元素分析。锆石边部的变质时代为425±6Ma,所对应的锆石Ti含量温度计计算出的温度为689±14℃。金红石U-Pb定年给出的年龄为414.0±6.3Ma,代表了副片麻岩在折返过程中冷却到金红石U-Pb封闭温度约570℃的时代。而金红石Zr含量温度计给出同锆石边部较一致的温度685±9℃,代表了峰期变质时代的温度条件。根据锆石的变质时代和变质温度以及金红石的冷却年龄和封闭温度所限定的T-t轨迹,可以得出此副片麻岩在折返过程中的冷却速率约为11℃/Myr。     

南阿尔金巴什瓦克高压/超高温麻粒岩中金红石Zr温度计及其地质意义

文中对南阿尔金高压-超高压变质带巴什瓦克地区的高压麻粒岩中的金红石进行了电子探针和薄片原位LA ICP MS微量元素分析。数据结果显示,运用电子探针和薄片原位LA ICP MS两种实验方法测得巴什瓦克高压麻粒岩中的金红石Zr含量在误差范围内基本一致。对比研究表明,经过压力校正的Thomkins等(2007)的金红石Zr含量温度计算公式更适合本区高压麻粒岩温度的计算,而采用Zack等(2004)和Watson等(2006)的公式计算的温度分别比前人通过传统温度计获得的温度结果偏高和偏低。按照Thomkins等(2007)的金红石Zr含量温度计算公式,以压力为2 GPa计算获得,巴什瓦克地区新鲜高压麻粒岩样品中金红石Zr含量温度为890~962 ℃,被解释为代表了高压麻粒岩峰期的变质温度;而以压力为1 GPa计算得出,退变高压麻粒岩样品中金红石Zr含量温度为764~822 ℃,代表了晚期中温麻粒岩相退变质阶段的变质温度。以上结果进一步证实南阿尔金高压-超高压变质带巴什瓦克地区的高压麻粒岩经历了峰期超高温/高压麻粒岩相变质作用和晚期中温麻粒岩相退变质作用的叠加。     

金红石微量元素电子探针分析

金红石电子探针微量元素分析一般以人工合成的氧化物来作为监测标样,尚较缺乏对金红石标样进行系统地测试分析。本文运用CAMECA SXFive电子探针对金红石标样R10进行微量元素分析,根据金红石中主要微量元素在地质学中的应用,本次共分析了Al、Si、Ti、Fe、Cr、Zr、V、Nb、Ta等9个元素,Ti、Si元素作为本次分析的监测元素。本文通过调整加速电压和电流、背景和峰值测试时长以及干扰谱峰处理等来提高微量元素分析精度和准确度。分析结果显示,其中,Zr(780±29×10~(-6))(1SD,n=25)、Nb(2799±66×10~(-6))、V(1276±33×10~(-6))、Fe(4309±34×10~(-6))、Cr(718±31×10~(-6))的分析结果与二次离子质谱(SIMS)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)的推荐值在误差范围内一致。大部分元素数据波动范围在10%以内,V、Fe元素的数据波动范围仅在5%以内。V、Nb和Fe测试精度比前人电子探针分析结果有较大提高。金红石Zr测试误差传递给金红石Zr温度计给出的温度误差一般22℃。本文还对金红石Zr温度计应用、提高Ta元素分析精度和准确度、金红石Fe~(3+)分析等问题进行了探讨。     

金红石中锆含量温度计及其微量元素地球化学特征

Zack et al.(2004a)、Watson et al.(2006)以及Tomkins et al.(2007)(在2GPa条件下)的金红石中锆含量温度计计算结果显示,徐淮地区中生代侵入杂岩所含榴辉岩类包体所经历的榴辉岩相变质的温度范围分别为776～1099℃(平均898℃)、663～923℃(平均750℃)和714～981℃(平均804℃),这些温度结果可能并非榴辉岩相峰期变质温度;其角闪岩相退变质作用过程中保存的温度范围分别为555～777℃(平均697℃)、541～663℃(平均6170C)和588～714℃(平均667℃),这些结果不能代表角闪岩相退变质再平衡后的温度,而只能代表角闪岩相退变质作用过程中某-阶段的温度.微量元素地球化学特征研究表明,榴辉岩类包体所含金红石中的某些微量元素(如Nb、Ta、Cr、Fe、V等)含量与其原岩有继承和对应关系,其原岩主要为镁铁质岩石;榴辉岩类包体与其寄主岩石中部分高价态/高场强元素(HFSE)呈相互消长的关系.榴辉岩的形成与扬子地块和华北地块之间的俯冲,碰撞作用有关.     

曲阳金红石矿地质特征

曲阳金红石矿含矿带长约4km，出露宽度约1km，总体呈东西向展布。矿床受层位控制，赋存于下元古界东焦群豆村组二段含金红石赤铁绢云母石英片岩和赤铁白（绢）云母石英片岩中，共圈定矿体8个，矿体长500m-1700m，平均厚度1m-2m，TiO2平均品位1％～4．02％，矿体产状与围岩一致。矿床形成于古元古代山间盆地相沉积一变质建造中，经历了多次变形变质作用，变质程度达低绿片岩相，为沉积变质矿床。矿床特点与内蒙古羊蹄子山钛矿床相似。目前矿床控制规模为中型，有望成为大型。     

石英和锆石Ti温度计在地学中的应用及其Ti含量的微区分析技术进展

石英和锆石Ti温度计在地球科学研究领域具有广泛的应用,本文系统回顾了石英和锆石Ti温度(压力)计发展史,并综述了其在地学中的典型应用实例。当前主要有3个石英Ti温度计和2个锆石Ti温度计计算公式,这些公式的使用范围和适用的地质情况已有统一的认识。石英和锆石Ti温度计应用的前提是Ti含量的准确测定。本文综述了现有Ti元素含量微区分析技术(电子探针、离子探针和激光剥蚀电感耦合等离子体质谱),重点讨论了激光剥蚀电感耦合等离子质谱在石英和锆石Ti分析的技术难点,包括不可控的剥蚀行为、多原子离子团干扰、缺乏基体匹配的标准物质等。最后展望了该技术未来发展趋势,特别是采用飞秒激光、高灵敏度/高分辨SF-ICP-MS、三重四级杆ICP-MS等仪器,有望实现低含量(< 5.0×10^-6) Ti的准确测定,这为石英和锆石Ti温度计的广泛应用提供有力保障。

     

Metamorphic P–T conditions and thermal structure of Chinese Continental Scientific Drilling main hole eclogites: Fe–Mg partitioning thermometer vs. Zr-in-rutile thermometer

Core rocks recovered from the main hole (5158 m deep) of the Chinese Continental Scientific Drilling (CCSD‐MH) project, southern Sulu UHP terrane, east‐central China, consist of eclogites, various gneisses and minor metaperidotite cumulates; this lithological section underwent subduction‐zone UHP metamorphism. Coesite‐bearing eclogites are mainly present between the depths of 100–2000 m, but below 2000 m, mafic eclogites are rare. Selected elements (Zr, Nb, Cr, Fe, Si, Mg, Al & Ti) in rutile from 39 eclogite cores from 100 to 2774 m, and major elements of minerals from representative eclogites were analysed by electron microprobe. Zirconium and Nb concentrations of rutile cluster ～100–400 and 200–700 ppm respectively. However, Zr and Nb contents in rutile from strongly retrograded eclogites show larger variations than those of fresh or less retrograded eclogites, implying that somehow fluid infiltration affected rutile chemistry during retrograde metamorphism. Zr contents in rutile inclusions in garnet and omphacite are slightly lower than those of the matrix rutile, suggesting that the rutile inclusions formed before or close to the peak temperature. The P–T conditions of the CCSD‐MH eclogites were estimated by both Fe–Mg exchange and Zr‐in‐rutile thermometers, as well as by the Grt–Cpx–Phn–Ky geothermobarometer. The maximum temperature range of 700–811 °C calculated at 40 kbar using the Zr‐in‐rutile thermometer is comparable with temperature estimates by the Fe–Mg exchange thermometer. The temperature estimates of eclogites in a ～3000 m thick section define a continuous gradient, and do not show a distinct temperature gap, suggesting that the rocks from 100 to 3000 m depth might belong to a single, large‐scale UHP slab. These data combined with P–T calculations for CCSD‐MH peridotites yield a low geotherm (～5 °C km^?1) for the Triassic subduction zone between the Sino‐Korean and Yangtze cratons; it lies ～30–35 mW m^?2 conductive model geotherm.     

New thermodynamic models and revised calibrations for the Ti-in-zircon and Zr-in-rutile thermometers

The models recognize that ZrSiO₄, ZrTiO₄, and TiSiO₄, but not ZrO₂ or TiO₂, are independently variable phase components in zircon. Accordingly, the equilibrium controlling the Zr content of rutile coexisting with zircon is ZrSiO₄ = ZrO₂ (in rutile) + SiO₂. The equilibrium controlling the Ti content of zircon is either ZrSiO₄ + TiO₂ = ZrTiO₄ + SiO₂ or TiO₂ + SiO₂ = TiSiO₄, depending whether Ti substitutes for Si or Zr. The Zr content of rutile thus depends on the activity of SiO₂ as well as T, and the Ti content of zircon depends on and as well as T. New and published experimental data confirm the predicted increase in the Zr content of rutile with decreasing and unequivocally demonstrate that the Ti content of zircon increases with decreasing . The substitution of Ti in zircon therefore is primarily for Si. Assuming a constant effect of P, unit and that and are proportional to ppm Zr in rutile and ppm Ti in zircon, [log(ppm Zr-in-rutile) + log] = A₁ + B₁/T(K) and [log(ppm Ti-in-zircon) + log − log] = A₂ + B₂/T, where the A and B are constants. The constants were derived from published and new data from experiments with buffered by either quartz or zircon + zirconia, from experiments with defined by the Zr content of rutile, and from well-characterized natural samples. Results are A₁ = 7.420 ± 0.105; B₁ = −4,530 ± 111; A₂ = 5.711 ± 0.072; B₂ = −4,800 ± 86 with activity referenced to α-quartz and rutile at P and T of interest. The zircon thermometer may now be applied to rocks without quartz and/or rutile, and the rutile thermometer applied to rocks without quartz, provided that and are estimated. Maximum uncertainties introduced to zircon and rutile thermometry by unconstrained and can be quantitatively assessed and are ≈60 to 70°C at 750°C. A preliminary assessment of the dependence of the two thermometers on P predicts that an uncertainty of ±1 GPa introduces an additional uncertainty at 750°C of ≈50°C for the Ti-in-zircon thermometer and of ≈70 to 80°C for the Zr-in-rutile thermometer.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

The robustness of the Zr-in-rutile and Ti-in-zircon thermometers during high-temperature metamorphism (Ivrea-Verbano Zone, northern Italy)

This study investigates the behaviour of the Zr-in-rutile and Ti-in-zircon thermometers in granulite facies metapelites from the Ivrea-Verbano Zone lower crustal section. U–Pb ages of zircon constrain the timing of regional amphibolite–granulite facies metamorphism to 316 ± 3 Ma and record zircon recrystallisation and resetting of U–Pb ages at 276 ± 4 Ma and 258 ± 3 Ma. Zr-in-rutile thermometry records peak contact metamorphic temperatures related to intrusion of mafic magmatic rocks and gives peak temperatures between 900–930 °C and 1,000–1,020 °C that are consistent with the geological settings of the samples. Ti-in-zircon temperatures of 700–800 °C and 810–870 °C record growth or re-equilibration of zircon after cooling from peak temperatures. Ti-in-quartz thermometry for one sample records both peak and retrograde temperatures. Some rutiles in all samples record resetting of Zr-in-rutile temperatures at ~750–800 °C. Electron microprobe profiles across individual rutiles demonstrate that Zr expulsion occurred by recrystallisation rather than by diffusive exchange. Exsolution of small needles of baddelyite or zircon from rutile is an important method of Zr redistribution, but results in no net Zr loss from the grain. The demonstration that Zr-in-rutile thermometry can robustly record peak temperatures that are not recorded by any other thermometer emphasises the relevance of this technique to investigating the evolution of high-grade metamorphic terranes, such as those that characterise the lower crust.     

变质岩中金红石研究进展及存在问题

随着原位微区分析技术的发展,金红石作为常见的副矿物,受到越来越多的关注.结合目前地学研究的热点科学问题,文中总结了金红石在变质岩石学中研究进展及存在的问题:(1)金红石在变质岩中的产状及形成过程;(2)金红石Zr含量温度计的进展及在低级、中级及高级变质岩中的应用;(3)金红石微量元素在弧岩浆过程和俯冲带变质作用的行为;...     

On the role of subducting oceanic plateaus in the development of shallow flat subduction

Oceanic plateaus, aseismic ridges or seamount chains all have a thickened crust and their subduction has been proposed as a possible mechanism to explain the occurrence of flat subduction and related absence of arc magmatism below Peru, Central Chile and at the Nankai Trough (Japan). Their extra compositional buoyancy could prohibit the slab from sinking into the mantle. With a numerical thermochemical convection model, we simulated the subduction of an oceanic lithosphere that contains an oceanic crustal plateau of 18-km thickness. With a systematic variation, we examined the required physical parameters to obtain shallow flat subduction. Metastability of the basaltic crust in the eclogite stability field is of crucial importance for the slab to remain buoyant throughout the subduction process. In a 44-Ma-old subducting plate, basalt must be able to survive a temperature of 600–700 °C to keep the plate buoyant sufficiently long to cause a flat-slab segment. We found that the maximum yield stress in the slab must be limited to about 600 MPa to allow for the necessary bending to the horizontal. Young slabs show flat subduction for larger parameter ranges than old slabs, since they are less gravitationally unstable and show less resistance against bending. Hydrous weakening of the mantle wedge area and lowermost continent are required to allow for the necessary deformation of a change in subduction style from steep to flat. The maximum flat slab extent is about 300 km, which is sufficient to explain the observed shallow flat subduction near the Nankai Trough (Japan). However, additional mechanisms, such as active overthrusting by an overriding continental plate, need to be invoked to explain the flat-slab segments up to 500 km long below Peru and Central Chile.