Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

富宁洞哈钛铁矿

印支期暗色、致密块状辉绿岩中含较高的含铁矿物,地磁异常较高,为矿源层。辉绿岩与灰岩接触形成矽卡岩带为有利的含矿带。矿体沿大断裂或次级断层形成的通道侵入穹窿状构造中,于二叠系砂岩、板岩隔层的下部形成工业钛铁矿体。     

Indicator mineralogy of kimberlite boulders from eskers in the Kirkland Lake and Lake Timiskaming areas, Ontario, Canada

Sixteen kimberlite boulders were collected from three sites on the Munro and Misema River Eskers in the Kirkland Lake kimberlite field and one site on the Sharp Lake esker in the Lake Timiskaming kimberlite field. The boulders were processed for heavy-mineral concentrates from which grains of Mg-ilmenite, chromite, garnet, clinopyroxene and olivine were picked, counted and analyzed by electron microprobe. Based on relative abundances and composition of these mineral phases, the boulders could be assigned to six mineralogically different groups, five for the Kirkland Lake area and one for the Lake Timiskaming area. Their indicator mineral composition and abundances are compared to existing data for known kimberlites in both the Kirkland Lake and Lake Timiskaming areas. Six boulders from the Munro Esker form a compositionally homogeneous group (I) in which the Mg-ilmenite population is very similar to that of the A1 kimberlite, located 7–12 km N (up-ice), directly adjacent to the Munro esker in the Kirkland Lake kimberlite field. U–Pb perovskite ages of three of the group I boulders overlap with that of the A1 kimberlite. Three other boulders recovered from the same localities in the Munro Esker also show some broad similarities in Mg-ilmenite composition and age to the A1 kimberlite. However, they are sufficiently different in mineral abundances and composition from each other and from the A1 kimberlite to assign them to different groups (II–IV). Their sources could be different phases of the same kimberlite or—more likely—three different, hitherto unknown kimberlites up-ice of the sample localities along the Munro Esker in the Kirkland Lake kimberlite field. A single boulder from the Misema River esker, Kirkland Lake, has mineral compositions that do not match any of the known kimberlites from the Kirkland Lake field. This suggests another unknown kimberlite exists in the area up-ice of the Larder Lake pit along the Misema River esker. Six boulders from the Sharp Lake esker, within the Lake Timiskaming field, form a homogeneous group with distinct mineral compositions unmatched by any of the known kimberlites in the Lake Timiskaming field. U–Pb perovskite age determinations on two of these boulders support this notion. These boulders are likely derived from an unknown kimberlite source up-ice from the Seed kimberlite, 4 km NW of the Sharp Lake pit, since indicator minerals with identical compositions to those of the Sharp Lake boulders have been found in till samples collected down-ice from Seed. Based on abundance and composition of indicator minerals, most importantly Mg-ilmenite, and supported by U–Pb age dating of perovskite, we conclude that the sources of 10 of the 16 boulders must be several hitherto unknown kimberlite bodies in the Kirkland Lake and Lake Timiskaming kimberlite fields.     

华南花岗岩类中铁钛副矿物组合与氧逸度关系

华南花岗岩中存在两类矿物组合:(1)铁透闪石 钛铁矿 榍石 磁铁矿 石英;(2)钛铁矿 方解石 石英 磁铁矿 榍石。可通过以下关系分别计算上述两组矿物组合的岩浆氧逸度。组合(1)为: logfo_2=-24940.31/T 9.25 243.43(P-10~5Pa)/T 0.86logfH_2O-0.86logα铁透闪石组合(2)为: logfo_2=-3673.68/T-37.73 590.53(P-10~5Pa)/T 6logfco_2岩浆作用过程的氧逸度(fo_2)是控制磁铁矿、钛铁矿、榍石等铁、钛副矿物形成和稳定的重要因素。     

Ilmenite composition in the Tellnes Fe–Ti deposit,SW Norway: fractional crystallization,postcumulus evolution and ilmenite–zircon relation

Major and trace element XRF and in situ LA-ICP-MS analyses of ilmenite in the Tellnes ilmenite deposit, Rogaland Anorthosite Province, SW Norway, constrains a two stage fractional crystallization model of a ferrodioritic Fe-Ti-P rich melt. Stage 1 is characterized by ilmenite-plagioclase cumulates, partly stored in the lower part of the ore body (Lower Central Zone, LCZ), and stage 2 by ilmenite-plagioclase-orthopyroxene-olivine cumulates (Upper Central Zone, UCZ). The concentration of V and Cr in ilmenite, corrected for the trapped liquid effect, (1) defines the cotectic proportion of ilmenite to be 17.5 wt% during stage 1, and (2) implies an increase of D _V^Ilm during stage 2, most likely related to a shift in fO₂. The proportion of 17.5 wt% is lower than the modal proportion of ilmenite (ca. 50 wt%) in the ore body, implying accumulation of ilmenite and flotation of plagioclase. The fraction of residual liquid left after crystallization of Tellnes cumulates is estimated at 0.6 and the flotation of plagioclase at 26 wt% of the initial melt mass. The increasing content of intercumulus magnetite with stratigraphic height, from 0 to ca. 3 wt%, results from differentiation of the trapped liquid towards magnetite saturation. The MgO content of ilmenite (1.4–4.4 wt%) is much lower than the expected cumulus composition. It shows extensive postcumulus re-equilibration with trapped liquid and ferromagnesian silicates, correlated with distance to the host anorthosite. The Zr content of ilmenite, provided by in situ analyses, is low (<114 ppm) and uncorrelated with stratigraphy or Cr content. The data demonstrate that zircon coronas observed around ilmenite formed by subsolidus exsolution of ZrO₂ from ilmenite. The U-Pb zircon age of 920 ± 3 Ma probably records this exsolution process. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

中国还原性斑岩矿床研究进展及判别标志

世界上大多数斑岩矿床的成矿流体为氧化流体(CO_2 CH_4)。然而,Rowins(2000)提出一些斑岩Cu-Au矿床的成矿流体为富含CH_4的还原流体,矿床缺乏磁铁矿、赤铁矿和硬石膏等表征高氧逸度的矿物,而发育大量的磁黄铁矿,矿床规模小,矿床形成与含钛铁矿的还原性的Ⅰ型花岗岩类有关,并将其称之为还原性斑岩Cu-Au矿床。我国学者研究发现,中国不但发育还原性斑岩铜矿床,还发育还原性斑岩-矽卡岩铜矿床和还原性斑岩钼矿床,我们建议将这三种矿床统称为还原性斑岩矿床。本文基于课题组近十年来的研究工作,并结合前人的研究成果,综合分析了中国发育的大中型还原性斑岩矿床的典型实例,在此基础上,重点阐明中国大型还原性斑岩矿床的特点、流体中CH_4来源及其有关的成矿作用、容矿围岩特点、成矿岩浆氧化还原状态及其成因、矿床形成的构造背景等。与Rowins(2000)提出的还原性斑岩铜矿床规模小的特点不同,中国发育的一些还原性斑岩矿床规模大;我们研究还识别出该类矿床发育独特的热液矿物和矿石矿物,比如,还原性斑岩铜矿发育热液钛铁矿,矿石矿物以黄铜矿为主,罕见斑铜矿、辉铜矿等矿物;还原性斑岩钼矿床出现热液钛铁矿,矿石矿物以辉钼矿为主,罕见黑钨矿和锡石等矿物;还原性斑岩-矽卡岩铜矿床的矽卡岩期发育钙铝榴石、钙铁辉石等还原性矽卡岩矿物和大量的磁黄铁矿,热液期以发育黄铜矿而非斑铜矿和辉铜矿等矿石矿物为特征。因此,还原性斑岩矿床除了Rowins(2000)提出的发育富CH_4还原流体和磁黄铁矿等识别标志之外,还可辅以独特的脉石矿物(如钛铁矿、钙铝榴石、钙铁辉石等)和简单的矿石矿物(如黄铜矿、辉钼矿等)这两个标志进行识别。中国还原性斑岩矿床含矿岩体的围岩中普遍发育还原性岩石(如含碳质沉积岩或火山沉积岩、含亚铁的火山岩或火山沉积岩等);对于成矿流体中CH_4、C_2H_6等还原性气体的来源,多数学者认为CH_4、C_2H_6等还原性气体主要源于还原性围岩,部分源于岩浆。关于还原性斑岩矿床的成矿岩体是否为含钛铁矿的、还原性的花岗岩类,目前研究较少且存在争议,多数学者认为成矿原始岩浆为氧化性岩浆,但其氧逸度偏低,少数学者认为成矿岩浆始终为还原岩浆。还原性斑岩矿床与经典的斑岩矿床的成矿构造背景类似,二者没有明显区别。还原性斑岩矿床显示的还原性热液蚀变和成矿特点均与成矿流体富含CH_4还原气体密切相关,因此,富含CH_4还原流体是还原性斑岩矿床形成的关键。     

PT conditions and trace element variations of picroilmenites and pyropes from placers and kimberlites in the Arkhangelsk region,NW Russia

Compositions of picroilmenite and pyrope concentrates from Carboniferous sandstones in the Arkhangelsk kimberlite province were analyzed by EPMA and LAM ICP MS in Analytic Center of V.S. Sobolev’s Institute of Geology and Mineralogy, SD RAS, Novosibirsk. The results from single grain thermobarometry (Ashchepkov et al., 2010, Ashchepkov et al., 2011, Ashchepkov et al., 2012) for garnet, spinel, ilmenite and clinopyroxene suggest heating of the base of the lithospheric mantle to 1400 °C (45 mw/m²) at 7.0–7.5 GPa and to 900 °C (35 mw/m²) at 3.5–5.5 GPa in an interval corresponding to a lens enriched in chromite and clinopyroxene. The pipes from the eastern fields reveal smoother mantle geotherms and lower temperature PT paths. Mantle columns beneath the kimberlites from northern (Verkhotinskoe field) and western pipes (Kepinskoe field) show heating from the lithosphere base to 5.0 GPa and stepped PT paths shown by chromites probably due to interaction with magmas which caused local Ti-enrichment near 3.0 and 5.5 GPa. The PT paths in the mantle columns beneath the alnöite pipes reveal higher temperature and relatively shallow PT conditions with two major clusters around 3.0 and 5.0 GPa. Trace element patterns for garnets vary from S-type typical of harzburgites to those with a hump in MREE (middle REE) typical for pyroxenites. Lherzolitic garnets with sinusoidal decrease of LREE show distinctive HFSE enrichment. Trace element ratios (Sm/Er)_n and (La/Yb)_n of garnets correlate positively with pressures estimates by single grain thermobarometry (Ashchepkov et al., 2010, Ashchepkov et al., 2011, Ashchepkov et al., 2012) but only poorly with Cr₂O₃ content. Enrichment in HFSE of all garnets is related to metasomatism that accompanied the picroilmenite-forming event.Ilmenites reveal two compositional trends. One corresponds to fractionation within conduits at the lower mantle (6.0–7.0 GPa) without contamination. A second trend at <6.0 GPa, formed due to assimilation fractional crystallization (AFC), is characterized by Fe and Cr increase with decreasing pressure. Similar trace element patterns of the various in HREE in ilmenites, possibly partly due to garnet assimilation from wall rock peridotites. The PT conditions and geochemistry for the minerals from the Carboniferous sediments are similar to those from the Lomonosovskoe deposit and Arkhangelskaya pipe (Lehtonen et al., 2009).     

Coastal Placer Deposits of Central Tamil Nadu, India

Placer mineral exploration has been undertaken along the beach of Central Tamil Nadu coast from Pondicherry to Vedaranyam. On the basis of the drainage network, geomorphology, and the coastal environment, the study area has been grouped into three sectors, North, Central, and South. Heavy mineral by Wt% shows a slightly higher abundance in the Northern sector, an enrichment of opaques in the Central sector from stations between Poompuhar and Karaikal, and a total depletion in the Southern sector. An abundance of heavies in the Northern sector is considered to be the result of a higher wave energy, and the cymatogenic downwarping of the basin during the present transgression. An enrichment of heavies in the Central sector from Poompuhar to Karaikal is attributable to the reworking of the beach ridges, which were submerged during the present transgression, and to the role of density sorting. A depletion of heavies in the Southern sector is accounted for by the absence of a terrigenous supply and the prevalence of wave shadow conditions throughout the year. The nature of the heavy mineral assemblage reflects the derivation of sediments principally from khondalites, granites, metamorphic rocks and paleo-sediments. Factor analysis also supplements the predominant role of a density factor in the segregation of heavy minerals in the study area. A five-stage model is proposed for the formation of placer deposits in the study region. The present study has disclosed rich concentrations of ilmenites in the central sector between Poompuhar and Karaikal that can be commercially exploited.     

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.     

Phase boundary between ilmenite and perovskite structures in MnGeO3 determined by in situ X-ray diffraction measurements

In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO₃ were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure in MgSiO₃.