Cathodoluminescence imaging and titanium thermometry in metamorphic quartz

Cathodoluminescence (CL) of quartz from metamorphic rocks representing a range of conditions from the garnet grade to the migmatite grade reveals a variety of textures, that is, a function of metamorphic grade and deformation history. Ti concentrations, determined by electron microprobe and ion microprobe, generally correlate with CL intensity (blue wavelengths), and application of the Ti‐in‐quartz thermometer (TitaniQ) reflects the temperature of quartz growth or recrystallization, and, in some settings, modification by diffusion. Quartz from garnet grade samples is not visibly zoned, records temperatures of 425–475 °C, and is interpreted to have recrystallized during fabric formation. Quartz grains from staurolite grade samples are zoned in CL with markedly darker cores and brighter rims, some of which are interpreted to have been produced by the dominant staurolite‐producing reaction, whereas others are interpreted as having formed by diffusion of Ti into quartz rims. Quartz from the matrix of kyanite and sillimanite grade samples are generally unzoned, although locally displays slightly brighter rims (higher Ti); quartz inclusions within garnet and staurolite have distinctly brighter rims, which are interpreted as having been produced by diffusive exchange with the host mineral. Quartz from migmatite grade samples displays highly variable CL intensity, which is dependent on the location of the grain. Matrix grains in melanosomes are largely unzoned or rarely zoned with darker cores. Leucosome quartz is strongly zoned with bright cores and dark rims and is interpreted as having formed during crystallization of the melt. Locally within the leucosome is observed oscillatory‐zoned quartz, which is interpreted as a subsolidus recrystallization to achieve strain relaxation. Quartz inclusions within garnet or plagioclase crystals often show bright domains separated by zones of dark CL. These enigmatic textures possibly reflect local melting fluxed by fluid inclusions. Temperatures calculated from the Ti–in–quartz thermometer are a function of the metamorphic grade of the sample, the textural setting of the quartz, the reaction history and the deformation history of the rock. The TitaniQ temperatures can be used to constrain the conditions at which various metamorphic processes have occurred.     

固溶体矿物的性质对计算河南西峡红柱石矿形成条件的影响

自然界的大多数造岩矿的是由两种或多种组分混合而成的固溶体。因此，在矿物，岩石和矿床等地质体的平衡热力学研究中不可避免地要涉及固溶体矿物热力学地为的问题。河南省西峡县杨乃沟红柱石矿泥质片岩中仅出现红柱石而没有蓝晶石和夕线石，红柱石矿物包裹体测温结果为420－600℃。通过矿物共生平衡p-t曲线所计算出的片岩形成温度和压力条件也应位于上述岩石学和岩相学等特征所限定的范围内。以此为基础，通过构筑矿物共生p-t平衡曲线的方法，对片岩中若干固溶体矿物理想性／非理想性问题进行了研究。其中斜长石必须以非理想固溶体处理，而石榴子石，黑云母和白云母视作理想固溶体的计算结果同片岩的岩石学和岩相学等特征相一致。     

Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ¹³C and δ¹⁸O values in calcite and heterogeneous single crystal δ¹³C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ¹³C and δ¹⁸O values in marbles by infiltration of low δ¹³C–δ¹⁸O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO₂‐rich fluid, and that the infiltration had occurred under high temperature and low f_O2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ¹³C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.     

Interpreting zirconium‐in‐rutile thermometric results

At first sight, experimental results and observations on rocks suggest that the Zr content in rutile, where equilibrated with quartz and zircon, should be a useful thermometer for metamorphic rocks. However, diffusion data for Zr in rutile imply that thermometry should not, for plausible rates of cooling, give the high temperatures commonly observed in high‐grade metamorphic rocks. It is suggested here that such observations can be accounted for by high‐T diffusive closure of Si in rutile, causing the interior of rutile grains to become insensitive to the thermometer equilibrium well above the temperature of Zr diffusive closure. Paired with comparatively slow grain boundary diffusion and problematic zircon nucleation, this allows for cases of Zr retention in rutile through temperatures where Zr is still diffusively mobile within rutile grains. Other observations that may be accounted for in this context are large inter‐grain ranges of rutile Zr contents uncorrelated with rutile grain size, and flat Zr profiles across individual rutile grains, counter to what would be expected from diffusive closure. A consequence is that it is unlikely that Zr‐in‐rutile thermometry will be useful for estimating rock cooling rates.     

岩浆包裹体化学成分研究

岩浆包裹体化学成分研究难度较大,为了获得可信的数据,应当注意:1.非演化型岩浆包裹体的化学成分可以代表其初始成分。演化型岩浆包裹体应先均一、淬火后再行测定。2.均一演化型岩浆包裹体应严格遵守加热规则,否则过热作用会使包裹体壁部分熔化,造成淬火后所测包裹体成分与其真正的初始成分并不相当。3.实测资料证明,“边界层效应”对于岩浆包裹体化学成分影响微不足道。4.岩浆包裹体的化学成分只能代表其主矿物结晶时周围岩浆的成分,即仅相当于岩浆液相线上的一个点。5。把显微冷热台测温、激光喇曼探针和电子探针分析技术结合使用,对查明单个包裹体中挥发组分的性状和浓度具有很大的潜力和前途。     

Characteristics of shallow geothermal fields in major cities of Tibet Autonomous Region

Based on the project titled “Investigation and evaluation of shallow geothermal energy in major cities of Tibet Autonomous Region”, the distribution characteristics and occurrence conditions of shallow geothermal fields in these cities were introduced in this paper. To this end, relevant data in Lhasa, Shigatse and Nyingchi Cities through vertical thermometry was a focus, so as to analyze groundwater temperature and the distribution law of strata with constant temperature. Then through comprehensive comparisons and analysis of the relationship between groundwater temperature and climate, differences in this aspect of Nagqu City were taken as a typical case to clarify formation of geothermal field and corresponding influence on groundwater temperature, furthermore providing basic data for rational development and utilization of shallow geothermal energy in Tibet Autonomous Region.     

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

Stable isotope constraints on the Al2SiO5'triple-point' rocks from the Proterozoic Priest pluton contact aureole, New Mexico, USA

The Priest pluton contact aureole in the Manzano Mountains, central New Mexico preserves evidence for upper amphibolite contact metamorphism and localized retrograde hydrothermal alteration associated with intrusion of the 1.42 Ga Priest pluton. Quartz–garnet and quartz–sillimanite oxygen isotope fractionations in pelitic schist document an increase in the temperatures of metamorphism from 540 °C, at a distance of 1 km from the pluton, to 690 °C at the contact with the pluton. Comparison of calculated temperature estimates with one‐dimensional thermal modelling suggests that background temperatures between 300 and 350 °C existed at the time of intrusion of the Priest pluton. Fibrolite is found within 300 m of the Priest pluton in pelitic and aluminous schist metamorphosed at temperatures >580 °C. Coexisting fibrolite and garnet in pelitic schist are in oxygen isotope equilibrium, suggesting these minerals were stable reaction products during peak metamorphism. The fibrolite‐in isograd is coincident with the staurolite‐out isograd in pelitic schist, and K‐feldspar is not observed with the first occurrence of fibrolite. This suggests that the breakdown of staurolite and not the second sillimanite reaction controls fibrolite growth in staurolite‐bearing pelitic schist. Muscovite‐rich aluminous schist locally preserves the Al₂SiO₅ polymorph triple‐point assemblage – kyanite, andalusite and fibrolite. Andalusite and fibrolite, but not kyanite, are in isotopic equilibrium in the aluminous schist. Co‐nucleation of fibrolite and andalusite at 580 °C in the presence of muscovite and absence of K‐feldspar suggests that univariant growth of andalusite and fibrolite occurred. Kyanite growth occurred during an earlier regional metamorphic event at a temperature nearly 80 °C lower than andalusite and fibrolite growth. Quartz–muscovite fractionations in hydrothermally altered pelitic schist and quartzite are small or negative, suggesting that late isotopic exchange between externally derived fluids and muscovite, but not quartz, occurred after peak contact metamorphism and that hydrothermal alteration in pelitic schist and quartzite occurred below the closure temperature of oxygen self diffusion in quartz (<500 °C).     

Sub-micron scale distributions of trace elements in zircon

Sub-micron scale zoning of Ti concentrations and correlations between concentrations of Ti and other trace elements (P, Ce, and Y) and cathodoluminescent (CL) banding is observed in natural zircons. Ion images were made using the Caltech Microanalysis Center’s CAMECA NanoSIMS 50L with an O⁻ primary beam focused to ~300 nm on the sample surface. The high spatial resolution of this technique allows for interrogation of chemical variations at or below the scale of CL banding in natural zircons. Images produced in this manner display two types of correlations among Ti, P, Ce, and Y (which appears to be a proxy for CL intensity): strong (correlation coefficients >0.8) and subtle (correlation coefficients ~0.15–0.4). Strongly correlated images, which display Ti variations of ca. a factor of 3 between adjacent CL bands and overall elevated trace element concentrations in CL-dark bands, were found within an oscillatory-zoned, trace element enriched sector of a CL sector-zoned zircon. Three possible causes for such correlations include: temperature-dependent equilibrium partitioning, trace element partitioning limited by diffusion in the host melt and surface-controlled, non-equilibrium growth. Comparison of our data with the expected results of these processes suggests that: (1) Ti partitioning in zircon is dependent upon non-equilibrium effects in addition to temperature and/or (2) the incorporation of elements that co-vary with Ti in zircon (e.g., Y, P and Ce) is also temperature-dependent. Sub-micron scale, high-Ti regions are also found within Proterozoic Adirondack and >4 Ga Jack Hills zircons as well as trace element enrichments (including Ti) along cracks within Jack Hills zircons.