The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

Conditions and timing of high-pressure Variscan metamorphism in the South Carpathians, Romania

High-pressure (HP) metamorphic rocks, including garnet peridotite, eclogite, HP granulite, and HP amphibolite, are important constituents of several tectonostratigraphic units in the pre-Alpine nappe stack of the Getic–Supragetic (GS) basement in the South Carpathians. A Variscan age for HP metamorphism is firmly established by Sm–Nd mineral–whole-rock isochrons for garnet amphibolite, 358±10 Ma, two samples of eclogite, 341±8 and 344±7 Ma, and garnet peridotite, 316±4 Ma.

A prograde history for many HP metamorphic rocks is documented by the presence of lower pressure mineral inclusions and compositional zoning in garnet. Application of commonly accepted thermobarometers to eclogite (grt+cpx±ky±phn±pg±zo) yields a range in “peak” pressures and temperatures of 10.8–22.3 kbar and 545–745 °C, depending on tectonostratigraphic unit and locality. Zoisite equilibria indicate that activity of H₂O in some samples was substantially reduced, ca. 0.1–0.4. HP granulite (grt+cpx+hb+pl) and HP amphibolite (grt+hbl+pl) may have formed by retrogression of eclogites during high-temperature decompression. Two types of garnet peridotite have been recognized, one forming from spinel peridotite at ca. 1150–1300 °C, 25.8–29.0 kbar, and another from plagioclase peridotite at 560 °C, 16.1 kbar.

The Variscan evolution of the pre-Mesozoic basement in the South Carpathians is similar to that in other segments of the European Variscides, including widespread HP metamorphism, in which P–T–t characteristics are specific to individual tectonostratigraphic units, the presence of diverse types of garnet peridotite, diachronous subduction and accretion, nappe assembly in pre-Westphalian time due to collision of Laurussia, Gondwana, and amalgamated terranes, and finally, rapid exhumation, cooling, and deposition of eroded debris in Westphalian to Permian sedimentary basins.     

P–T–X evolution in garnet pyroxenites from Tin Begane (Central Hoggar, Algeria)

Garnet pyroxenite from high pressure granulite facies occurs with different mineral assemblages which involve garnet, clinopyroxene, orthopyroxene, plagioclase, amphibole and quartz with spinel developing as symplectite with orthopyroxene and plagioclase in large cracks. Three successive parageneses have been identified. The primary assemblage is characterised by the presence of quartz. The second assemblage involves orthopyroxene–plagioclase–hornblende symplectite, and the third assemblage is characterised by the development of spinel in symplectites with orthopyroxene and plagioclase. Using THERMOCALC (V2.7), a quantitative pseudosection in the system CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O has been calculated. The assemblage involving quartz developed at high pressure, while the assemblage involving spinel developed at lower pressure. The peak of metamorphism in Tin Begane was calculated at 860 °C and 13.5 kb with a_H2O=0.2. These conditions are followed by a decrease of pressure down to 4.8 kb.     

Garnet-ilmenite-perovskite transitions in the system Mg4Si4O12-Mg3Al2Si3O12 at high pressures and high temperatures: phase equilibria, calorimetry and implications for mantle structure

Phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ were examined at pressures of 19-27 GPa and relatively low temperatures of 800-1000 °C using a multianvil apparatus to clarify phase transitions of pyroxene-garnet assemblages in the mantle. Both of glass and crystalline starting materials were used for the experiments. At 1000 °C, garnet solid solution (s.s.) transforms to aluminous ilmenite s.s. at 20-26 GPa which is stable in the whole compositional range in the system. In Mg₄Si₄O₁₂-rich composition, ilmenite s.s. transforms to a single-phase aluminous perovskite s.s., while Mg₃Al₂Si₃O₁₂-rich ilmenite s.s. dissociates into perovskite s.s. and corundum s.s. These newly determined phase relations at 1000 °C supersede preliminary phase relations determined at about 900 °C in the previous study. The phase relations at 1000 °C are quite different from those reported previously at 1600 °C where garnet s.s. transforms directly to perovskite s.s. and ilmenite is stable only very close to Mg₄Si₄O₁₂. The stability field of Mg₃Al₂Si₃O₁₂ ilmenite was determined at 800-1000 °C and 25-27 GPa by reversed phase boundaries. In ilmenite s.s., the a-axis slightly increases but the c-axis and molar volume decrease substantially with increasing Al₂O₃ content. Enthalpies of ilmenite s.s. were measured by differential drop-solution calorimetry method using a high-temperature calorimeter. The excess enthalpy of mixing of ilmenite s.s. was almost zero within the errors. The measured enthalpies of garnet-ilmenite and ilmenite-perovskite transitions at 298 K were 105.2±10.4 and 168.6±8.2 kJ/mol, respectively, for Mg₄Si₄O₁₂, and 150.2±15.9 and 98.7±27.3 kJ/mol, respectively, for Mg₃Al₂Si₃O₁₂. Thermodynamic calculations using these data give rise to phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ at 1000 and 1600 °C that are generally consistent with those determined experimentally, and confirm that the single-phase field of ilmenite expands from Mg₄Si₄O₁₂ to Mg₃Al₂Si₃O₁₂ with decreasing temperature. The earlier mentioned phase relations in the simplified system as well as those in the Mg₂SiO₄-Fe₂SiO₄ system are applied to estimate mineral proportions in pyrolite as a function of depth along two different geotherms: one is a horizontally-averaged temperature distribution in a normal mantle, and the other being 600 °C lower than the former as a possible representative geotherm in subducting slabs. Based on the previously described estimated mineral proportions versus depth along the two geotherms, density and compressional and shear wave velocities are calculated as functions of depth, using available mineral physics data. Along a normal mantle geotherm, jumps of density and velocities at about 660 km corresponding to the post-spinel transition are followed by steep gradients due to the garnet-perovskite transition between 660 and 710 km. In contrast, along a low-temperature geotherm, the first steep gradients of density and velocities are due to the garnet-ilmenite transition between 610 and 690 km. This is followed by abrupt jumps at about 690 km for the post-spinel transition, and steep gradients between 700 and 740 km that correspond to the ilmenite-perovskite transition. In the latter profile along the low-temperature geotherm, density and velocity increases for garnet-ilmenite and ilmenite-perovskite transitions are similar in magnitude to those for the post-spinel transition. The likely presence of ilmenite in cooler regions of subducting slabs is suggested by the fact that the calculated velocity profiles along the low-temperature geotherm are compatible with recent seismic observations indicating three discontinuities or steep velocity gradients at around 600-750 km depth in the regions of subducting slabs.     

大陆科学钻探CCSD-PP3钻孔超镁铁岩岩石学和矿物学特征及其意义

PP3超镁铁岩在钻孔中出露厚度达480米,包括纯橄岩、石榴橄榄岩和闪石化金云母橄榄岩等岩石类型。岩石主要组成矿物橄榄石、铬尖晶石、石榴子石、单斜辉石和斜方辉石等。橄榄石为镁橄榄石(Fo在88.7-93.1之间),SiO2含量在38.8wt.%-42.4wt.%;石榴子石为钙饱和的镁铝榴石(Py65.945Alm18.095Uv7.518Gr4.695And3.605Sp0.142),MgO含量在16.77wt.%-20.04wt.%,CaO含量在5.4到6.4wt.%之间,Cr2O3含量在0.3到3.3wt.%,FeO含量在2.48wt.%-11.78wt.%,TiO2含量小于0.04wt.%,代表早期矿物组合;两类斜方辉石的成分都为顽火辉石(OpxⅠ:En91.86Fs7.80Wo0.34,OpxⅡ:En91.83Fs7.91Wo0.21Ac0.06)。斜方辉石Mg#(Mg/(Mg Fe)×100)在91.7-92.5间,Cr2O3含量低于0.32wt.%,CaO含量在0.102-0.199wt.%间,Al2O3含量为0.32-1.06wt.%,均值在0.72wt.%;单斜辉石可分为早期透辉石(Wo45.98En47.89Fs2.73Ac3.39)和晚期顽透辉石(Wo27.61En68.78Fs2.27Ac1.34)两种。铬尖晶石的Cr#(Cr/(Cr Mg)×100)从51到89变化,TiO2和MnO2含量分别低于0.26wt%和0.46wt%。橄榄石、铬尖晶石和单斜辉石等矿物组合表现为3-4期次的特点。     

苏鲁超高压榴辉岩的石榴石生长成分环带及变质作用P—T轨迹

在南苏鲁东海地区，部分超高压榴辉岩中的变斑晶石榴石具有复杂的生长成分环带和多期矿物包体组合，它们记录了超高压变质岩的多阶段变质演化过程，即绿帘角闪岩相进变质、柯石英榴辉岩相峰期变质、石英榴辉岩相和角闪岩相退变质作用。运用相关的地质温、压计，使用代表最高变质温度的变斑晶石榴石慢部（具最低的Fe／Mg比值）和与其平衡的绿辉石包体成分，获得了〉900℃和4．1～4．5GPa的超高压变质务件。联合其他变质阶段的温、压条件，一个顺时针的变质作用P—T轨迹得以建立。它的特征是进变质与退变质路径近于平行，早期退变质作用为降温、降压过程．榴辉岩石榴石生长成分环带的保存说明超高压变质岩在峰期变质阶段有非常短暂的停留时间，并以很快的折返速率抬升到地壳浅部，超高压变质岩折返过程中的明显降温是石榴石生长环带得以保存的另一个有利条件，     

Coesite inclusions and prograde compositional zonation of garnet in whiteschist of the HP-UHPM Kokchetav massif, Kazakhstan: a record of progressive UHP metamorphism

Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan.

Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and P_H20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field.

Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free.

Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H₂O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid.

During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H₂O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

Metamorphic discontinuities in orogenic belts: example of the garnet–biotite–albite zone in the Otago Schist, New Zealand

A regional petrographic reconnaissance of psammitic and pelitic rocks in the Otago Schist, New Zealand, has revealed the presence of garnet (“grossalspite” with typical rim composition almandine₄₁, spessartine₂₅, grossular₃₃, pyrope₁) and biotite in 37 new samples, more than doubling the previously known number. A new garnet–biotite–albite zone can now be defined in the greenschist facies Otago Schist that is distinct from the better-known biotite, garnet and oligoclase zones in the along-strike Alpine Schist. The garnet–biotite–albite zone is in part metamorphically discontinuous with adjacent schists and does not support models of simple, continuous, progressive Jurassic regional metamorphism in Otago. The structurally higher (lower grade) boundary of the zone coincides in at least three places with previously mapped regional shear zones. The structurally lower (expected higher grade) boundary of the zone appears to be obliterated by a chlorite zone overprint which can be spatially related to Alpine Schist recrystallisation of ?Cretaceous age. The Otago situation serves as an example of the subtle metamorphic discontinuities that probably pervade many orogenic belts.     

石榴石Lu-Hf、原位独居石U-Pb定年对多期变形的时代制约——以北祁连托勒牧场为例

多期变质变形事件的精确年代限定是造山构造年代学研究的热点问题之一。本文尝试运用面理弯切轴测量技术,结合石榴石Lu-Hf和原位独居石U-Pb定年,厘定北祁连托勒牧场地区石榴石和斜长石斑晶记录的两期构造变形事件:石榴石斑晶生长记录的早期构造变形事件年代为512.3±2.7Ma;斜长石斑晶生长记录的晚期构造变形事件年代不早于481.0±2.3Ma,并推断该期构造变形水平挤压主应力方向为北东-南西。斜长石斑晶内未发现独居石,用于年代学测试的独居石颗粒均位于斜长石斑晶外基质中。显微构造分析认为,独居石生长不早于斜长石斑晶。481.0±2.3Ma的独居石U-Pb年龄,应为斜长石斑晶所记录构造变形的时代下限。结合前人锆石U-Pb定年和Hf同位素研究结果分析认为,获得的512.3±2.7Ma石榴石-全岩Lu-Hf等时线年龄,代表了祁连洋俯冲过程中石榴石的生长时间,后期变质变形作用未对石榴石的Lu-Hf同位素体系产生明显影响。结合显微构造分析,石榴石Lu-Hf定年可为早期构造变形提供有效年代学制约。