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.     

拉萨地块东南缘晚白垩世高温变质作用及其地质意义:来自石英出溶金红石的证据和锆石U-Pb定年

文中对拉萨地块东南缘林芝杂岩中的含榴斜长角闪岩进行了详细的岩相学研究和锆石U-Pb定年。岩相学观察表明,含榴斜长角闪岩经历了峰期麻粒岩相变质和角闪岩相退变质作用。峰期麻粒岩相矿物组合为石榴子石+高Ti角闪石+紫苏辉石+斜长石+石英+金红石,其中的石榴子石、石英和角闪石中含有大量金红石出溶体,说明这些矿物的初始成分具有高Ti含量。角闪岩相退变质矿物组合为低Ti角闪石+斜长石+斜黝帘石+石英+金红石。利用Ti在石英中的含量(TitaniQ)温度计计算得到峰期麻粒岩相变质温度为803～924℃,后期角闪岩相退变质温度为555～732℃。样品中的锆石具有明显的核边结构,核部为典型岩浆型锆石,具有高的Th/U值,强烈富集HREE,明显的正Ce异常和负Eu异常,206Pb/238U年龄为(89.3±0.6)Ma,代表含榴斜长角闪岩原岩结晶年龄。锆石边部呈无环带结构,同核部相比,具有低的Th/U值,低的M-HREE和弱的Eu负异常,为变质峰期生长的锆石,206Pb/238U年龄为(81.1±0.8)Ma,代表麻粒岩相峰期变质年龄。我们认为约81Ma高温麻粒岩相变质作用可能与洋中脊俯冲造成的板片窗导致的软流圈上涌有关。     

Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti,Al, Li,Fe, Mn,Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP‐MS, electron probe microanalysis (EPMA) and solution ICP‐MS to determine the concentration of twenty‐four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium‐in‐quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA‐ICP‐MS laboratories, three EPMA laboratories and one solution‐ICP‐MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g^?1), Al (154 ± 15 μg g^?1), Li (30 ± 2 μg g^?1), Fe (2.2 ± 0.3 μg g^?1), Mn (0.34 ± 0.04 μg g^?1), Ge (1.7 ± 0.2 μg g^?1) and Ga (0.020 ± 0.002 μg g^?1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.     

Using microstructures and TitaniQ thermobarometry of quartz sheared around garnet porphyroclasts to evaluate microstructural evolution and constrain an Alpine Fault Zone geotherm

Interpretations of deformation processes within ductile shear zones are often based on the characterisation of microstructures preserved in exhumed rocks. However, exhumed microstructures provide only a snapshot of the closing stages of deformation and we need ways of understanding how microstructures change through time and at what rate this occurs. To address this problem, we study optical microstructures and electron backscatter diffraction (EBSD) data from samples of quartz layers deflected around garnet porphyroclasts (which generate local stress and strain rate perturbations) during mylonitic deformation in the Alpine Fault Zone of New Zealand.During shearing around rigid garnet porphyroclasts, quartz undergoes grain size reduction in response to locally increased stresses, while c-axes reveal increasing components of rhomb <a> and prism <a> slip, reflecting a local increase in shear strain and strain rate. TitaniQ thermobarometry and quartz microstructures suggest a rather narrow range of recorded quartz deformation temperatures around 450–500 °C, which we propose reflects the cessation of grain boundary migration driven deformation. Given that temperatures well above the brittle–ductile transition for quartz (∼350 °C) are preserved, we anticipate that rapid cooling and exhumation must have occurred from the 500 °C isotherm. Ultimately, we propose a modified geotherm for the central Alpine Fault Zone hanging wall, which raises the 500 °C isotherm to 11 km depth, near the brittle–ductile transition. Our updated Alpine Fault Zone geotherm implies a hotter and weaker middle to lower crust than previously proposed.     

Application of the titanium-in-quartz thermometer to pelitic migmatites from the Adirondack Highlands, New York

The 'TitaniQ' (Ti-in-quartz) solubility thermometer was applied to migmatitic metapelites from the southern and western Adirondack Highlands, New York, to examine the effect of granulite facies metamorphism on the distribution of Ti in quartz. Both cathodoluminescence imaging and quantitative traverses revealed that individual grains of Adirondack quartz are highly zoned with respect to Ti, and that core-to-rim decreases of Ti are common. Large ranges in calculated temperature were observed within each sample. One sample, not considered to be saturated with respect to TiO₂, gave maximum temperatures more than 100 °C lower than previously estimated peak temperatures. Rutile-saturated southern and western Adirondack samples yielded peak estimates of ≥803 ± 11 °C and ∼860–870 °C, respectively, which are similar to previous estimates from major phase thermometry. Minimum Ti-in-quartz matrix temperatures from rutile-saturated samples are 630 °C, which is interpreted as the closure temperature for Ti diffusion in quartz in these samples. This study demonstrates that Ti-in-quartz thermometry can yield details of rock evolution if the textural setting and reaction history of the quartz is clear, and can yield near-peak metamorphic temperatures in some cases, if care is taken to test for post-peak diffusional resetting.     

A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.