Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.     

鄂东南地区鸡笼山矽卡岩金矿床的矽卡岩矿物学特征及其意义

鸡笼山金矿是长江中下游鄂东南地区典型的矽卡岩金矿床,其矽卡岩矿物学特征研究较少。围岩为三叠纪大冶组灰岩和白云质灰岩,决定了该矿床发育丰富的矽卡岩矿物组合,主要包括石榴石、透辉石、硅灰石、绿帘石、金云母等。本文详细研究了不同阶段矽卡岩的矿物学特征,并对其进行了电子探针分析（EMPA）。结果表明石榴石属于钙铝-钙铁系列,辉石为透辉石,以钙铁榴石-透辉石共生的富金矽卡岩组合是在较高氧逸度和较低酸度条件下形成的,具有铜金矿的成矿专属性。伴随着流体的演化,矽卡岩与矿体在时空和成因上都具有密切的联系。结合矿区内发育有斑岩型矿体,暗示鸡笼山金矿床可能具有统一的斑岩-矽卡岩型成矿系统,深部具有很大的找矿潜力。     

辽宁瓦房店金伯利岩中石榴石特征及种类鉴定

辽宁瓦房店金刚石矿区金伯利岩中的石榴石一直被当作镁铝榴石。为了确定矿区颜色复杂的石榴石种类,本文对矿区的石榴石进行了系统的采样分析,测定了112件石榴石样品的晶胞参数、50件样品的微区化学成分和40件样品的红外光谱。利用石榴石晶胞参数、红外光谱、化学成分和化学分子式方法对矿区石榴石进行分类,结果显示:晶胞参数分类法误差大,容易得出错误结论;红外图谱分类法准确度不高,只能作为参考方法;化学成分分类法太过笼统,达不到详细划分石榴石种类的目的;化学分子式分类法可把矿区的石榴石详细划分6个矿种:镁钙铁-铝铬铁榴石、镁铁钙-铝铬铁榴石、镁钙铁-铝铬榴石、镁钙-铝铬铁镁榴石、镁铁钙-铝铬榴石、镁铁钙-铝铁铬榴石,每种石榴石都充分反映了A、B离子的种类及占位特征,是4种分类方法中最为科学的方法。研究认为瓦房店金刚石矿区金伯利岩中石榴石A端元成分以Mg²⁺离子占位为主;B端元成分以Al³⁺离子占位为主。由于阳离子替代普遍,A、B端元成分复杂,瓦房店金伯利岩中不存在单纯意义上的镁铝榴石。     

Rare earth element fractionation in magmatic Ca-rich garnets

Igneous garnets have the potential to strongly fractionate rare earth elements (REE). Yet informations on partition coefficients are very scant, and criteria for distinguishing between hydrothermal and magmatic garnets are ambiguous. To fill this gap, we present trace element and isotopic data for two types of Ca-rich garnets from phonolites (Mt. Somma-Vesuvius). Both Ca-garnet populations are different in their style and dynamics of fractionation: one population is progressively strongly depleted in HREE from core to rim, reflecting REE fractionation in the host phonolite via earlier-crystallized garnets. Such examples for extreme changes in HREE in garnets are only known for hydrothermal grandites by REE-bearing fluids. The second garnet population is homogeneous and formed in a closed system. Near-flat patterns between Sm and Lu confirm experimental data indicating lower D(Sm)/D(Lu) for Ca-rich garnets than for e.g. pyrope-rich garnets. It follows: D ^Grt/PhMelt for La = 0.5, Sm = 48 and Yb = 110.     

华南云开高州紫苏花岗岩及其两类石榴石的成因：岩石学和锆石U-Pb年代学证据

云开地块早古生代的构造背景至今仍存有争论。对云炉-龙修一带出露的含石榴石紫苏花岗岩进行研究可为该区构造-变质演化提供重要制约。详细的岩相学研究表明紫苏花岗岩中存在两种成因的石榴石(石榴石Ⅰ和石榴石Ⅱ),并识别出该岩石保留了三阶段演化的矿物组合(M_1-M_3)。峰期前矿物组合(M_1)由紫苏辉石变斑晶中的包裹体矿物石榴石+黑云母+斜长石+钛铁矿+石英组成。峰期变质-深熔矿物组合(M_2)由基质中平衡共生的斑晶矿物石榴石Ⅰ+紫苏辉石+黑云母+石英+斜长石+钛铁矿构成。退变质矿物组合(M_3)以紫苏辉石和黑云母以及钛铁矿边部降温生成石榴石Ⅱ+石英冠状体("红眼圈")和黑云母+石英后成合晶为特征。传统地质温压计、平均温压法及在NCKFMASHTO模式体系下的相平衡模拟结果表明,紫苏花岗岩峰期前矿物组合形成条件为720℃/70kbar(M1),峰期变质-深熔结晶条件为835～810℃/65～58kbar(M_2),退变质条件为740℃/56kbar(M_3)。岩相观察和P-T计算结果表明紫苏花岗岩的形成可能反映了一条顺时针的P-T轨迹,且以峰期前略微减压并伴随明显的升温和峰期后具有近等压冷却(IBC)过程为特征。LA-ICP-MS锆石U-Pb年代学结果显示锆石核部加权平均年龄为～431Ma,锆石边部加权平均年龄为～243Ma。我们认为峰期深熔作用和岩浆结晶石榴石Ⅰ的形成可能发生于早古生代(加里东期),而晚期退变质作用和变质重结晶石榴石Ⅱ的形成可能发生在早中生代(印支期)。本研究也表明云开地区含石榴石紫苏花岗岩的形成与早古生代扬子和华夏陆块碰撞后抬升过程有紧密联系,并遭受了早中生代印支期构造热事件的明显叠加。     

Garnet Sm–Nd data from the Saualpe and the Koralpe (Eastern Alps, Austria): chronological and P–T constraints on the thermal and tectonic history

Garnets from recrystallized, staurolite- and kyanite-bearing mica schists from the central Saualpe basement, representing the host rocks of the type-locality eclogites, give concordant Sm–Nd garnet–whole-rock isochron ages between 88.5±1.7 and 90.9±0.7 Ma. The millimetre-sized, mostly inclusion-free grains show fairly homogeneous element profiles with pyrope contents of 25–27%. Narrow rims with an increase in Fe and Mn and a decrease in Mg document minor local re-equilibration during cooling. According to phengite geothermobarometry, peak metamorphic conditions at 90 Ma were close to 20  kbar and 680  °C and similar to those recorded by the eclogites. The garnet rims record about 575  °C/7  kbar for the final stages of metamorphism. A phengitic garnet–mica schist, sampled at the immediate contact with the Gertrusk eclogite, gave a garnet–whole-rock Sm–Nd age of 94.0±2.7 Ma.
Garnet porphyroclasts separated from a pegmatite–mylonite of the Koralpe plattengneiss near Stainz are unzoned and show spessartine contents of 15%. Composition and Sm–Nd ages of close to 260 Ma point to a magmatic origin for these garnets.
The garnet data from the Saualpe document an intense Alpine metamorphism for this part of the Austroalpine basement. The mica schists recrystallized during decompression and rapid exhumation, at the final stages of and immediately following a high- P event. The Koralpe data show that high Alpine temperatures did not reopen the Sm–Nd isotope system, implying a closure temperature in excess of c . 600  °C for this isotopic system in garnet.     

The evolution of lithospheric mantle beneath the Kalahari Craton and its margins

The compositional structure and thermal state of the subcontinental lithospheric mantle (SCLM) beneath the Kalahari Craton and the surrounding mobile belts have been mapped in space and time using >3400 garnet xenocrysts from >50 kimberlites intruded over the period 520–80 Ma. The trace-element patterns of many garnets reflect the metasomatic refertilisation of originally highly depleted harzburgites and lherzolites, and much of the lateral and vertical heterogeneity observed in the SCLM within the craton is the product of such metasomatism. The most depleted, and possibly least modified, SCLM was sampled beneath the Limpopo Belt by early Paleozoic kimberlites; the SCLM beneath other parts of the craton may represent similar material modified by metasomatism during Phanerozoic time. In the SW part of the craton, the SCLM sampled by “Group 2” kimberlites (>110 Ma) is thicker, cooler and less metasomatised than that sampled by “Group 1” kimberlites (mostly ≤95 Ma) in the same area. Therefore, the extensively studied xenolith suite from the Group 1 kimberlites probably is not representative of primary Archean SCLM compositions. The relatively fertile SCLM beneath the mobile belts surrounding the craton is interpreted as largely Archean SCLM, metasomatised and mixed with younger material during Paleoproterozoic to Mesoproterozoic rifting and compression. This implies that at least some of the observed secular evolution in SCLM composition worldwide may reflect the reworking of Archean SCLM. There are strong correlations between mantle composition and the lateral variations in seismic velocity shown by detailed tomographic studies. Areas of relatively low Vp within the craton largely reflect the progressive refertilisation of the Archean root during episodes of intraplate magmatism, including the Bushveld (2 Ga) and Karroo (ca. 180 Ma) events; areas of high Vp map out the distribution of relatively less metasomatised Archean SCLM. The relatively low Vp of the SCLM beneath the mobile belts around the craton is consistent with its fertile composition. The seismic data may be used to map the lateral extent of different types of SCLM, taking into account the small lateral variations in the geotherm identified using the techniques described here.     

A model for garnet and plagioclase growth in pelitic schists: implications for thermobarometry and P-T path determinations

Numerical models of the progressive evolution of pelitic schists in the NCMnKFMASH system with the assemblage garnet + biotite + chlorite ± staurolite + plagioclase + muscovite + quartz + H₂O are presented with the goal of predicting compositional changes in garnet and plagioclase along different P-T paths. The numerical models support several conclusions that should prove useful for interpreting the P-T paths of natural parageneses: (i) Garnet may grow along P-T vectors ranging from heating with decompression to cooling with compression. P-T paths deduced from garnet zoning that are inconsistent with these growth vectors are self-contradictory. (ii) There is a systematic relation between garnet and plagioclase composition and growth such that for most P-T paths, garnet growth requires plagioclase consumption. Furthermore, mass balance in a closed system requires that as plagioclase is consumed the remaining plagioclase becomes increasingly albitic. Inclusions of plagioclase in the core of garnet should be more anorthitic than those near the rim and zoned matrix plagioclase should have rims that are more albitic than the cores. Complex plagioclase textures may arise from the local variability of growth and precipitation kinetics. (iii) A decrease of Fe/(Fe + Mg) in a garnet zoning profile is a reliable indicator of increasing temperature for the assemblage modelled. However, there is no single reliable ΔP monitor and inferences about ΔP can only be made by considering plagioclase and garnet together. (iv) Consumption of garnet during the production of staurolite removes material from the outer shell of a garnet and may make recovery of peak metamorphic compositions and P-T conditions impossible. Low ‘peak’temperatures typically recorded by staurolite-bearing assemblages may reflect this phenomenon. (v) Diffusional homogenization of garnet affects the computed P-T path and results in a clockwise rotation of the computed P-T vector relative to the true P-T path.     

Trace element and Sm–Nd 'age' zoning in garnets from peridotites of the Caledonian and Variscan Mountains and tectonic implications

ABSTRACT Ion probe traverses across garnets from peridotites of the Caledonides of Norway and the Variscides of Poland show zoning patterns for Y, V, Zr, Cr, Ti and the REE. The complexly zoned patterns of garnets from the Bystrzyca Górna peridotite, Poland, are interpreted in terms of a changing P–T history (isobaric cooling followed by decompression and cooling). Weak rimward gradients in REE concentrations in garnets from the Almklovdalen and Sandvika peridotites, Norway, may be relicts of the original growth history of the garnets, but the nearly flat Y, V, Zr, Cr and Ti profiles from the same garnets imply a later period of near-homogenization at uniform P–T. Crushed garnet separates from each body were separated into three or more fractions on the assumption that density and magnetic susceptibility vary with Fe/Mg ratio, and Fe/Mg ratios change from garnet core to rim. Sm-Nd garnet–clinopyroxene ‘ages’ were determined for each fraction to determine whether they are also zoned. Four garnet fractions from the Góry Sowie peridotite give nearly the same ages (397–412 Ma) that are believed to span the interval of garnet growth. Garnet fractions from the Norwegian peridotites define scattered ages (816–1350 Ma) that are suspect, but hint at a Sveconorwegian equilibration event. The data indicate the Variscan and Norwegian peridotites had different histories, despite superficial mineralogical and tectonic similarities. Norwegian garnet peridotites had a long pre-Caledonian history and were extracted from a relatively cold mantle whereas the Variscan garnet peridotites had a comparatively short pre- or Eo-Variscan history and were extracted from a hot mantle.     

Local structural heterogeneity,mixing behaviour and saturation effects in the grossular–spessartine solid solution

Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of W^H_spec = 14.4(7) kJ mol^–1 in H^mix = W^H_specX_GrX_Sp. W^H_spec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V², where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.