The Ti content of biotite can serve as a geothermometer for graphitic, peraluminous metapelites that contain ilmenite or rutile and have equilibrated at roughly 4–6 kbar. The relationship between Ti-content, temperature, and Mg/(Mg + Fe) value was calibrated empirically using an extensive natural biotite data set (529 samples) from western Maine and south-central Massachusetts in combination with the petrogenetic grid of Spear et al. (1999). The calculated Ti-saturation surface is curved such that for a given Mg/(Mg + Fe) value, Ti concentration increases as a function of temperature in a nonlinear fashion, and for a given temperature Ti concentrations decrease with an increase in Mg/(Mg + Fe). The fit to the Ti-saturation surface can be reformulated as the geothermometric expression: T = {[ln(Ti) − a − c ( X Mg)3]/ b }0.333, in which T is temperature in degrees Celsius, Ti is the number of atoms per formula unit (apfu) normalized on the basis of 22 O atoms, X Mg is Mg/(Mg + Fe), a = −2.3594, b = 4.6482 × 10−9 and c = −1.7283. The calibration range for this expression is X Mg = 0.275–1.000, Ti = 0.04–0.60 apfu, and T = 480–800 °C. Precision of the Ti-in-biotite geothermometer is estimated to be ±24 °C at the lower temperature range and improves to ±12 °C at higher temperatures. Application of the Ti-in-biotite geothermometer to ilmenite- or rutile-bearing, graphitic, peraluminous metapelites equilibrated at 3–6 kbar is generally consistent with independent temperature determinations, but with some deviations that represent local reequilibration. Consequently, the Ti systematics in biotite can also serve as the basis of a very sensitive indicator of chemical equilibrium, or lack thereof. Application of the geothermometer to metapelites not containing the requisite mineral assemblages can lead to minor-to-significant errors in estimated temperatures.

Biotite Ti-substitution mechanisms are controlled by several factors. Based on the biotite calibration data set, magnesian biotites ( X Mg > 0.65) incorporate Ti in accordance with the exchange vector TiAl2R−1Si−2, where R is the sum of the divalent cations Mg + Fe + Mn. This substitution mechanism is primarily a response to misfit of the octahedral and tetrahedral layers in magnesian biotites. Intermediate biotites ( X Mg <0.65), particularly at higher temperatures, exhibit enhanced Ti concentrations, most consistent with the Ti-deprotonation TiO2R−1(OH) −2 exchange vector. Dominance of Ti-deprotonation substitution is largely a function of reduction of H2O activity at higher metamorphic grades. Supplementary biotite data from metaluminous amphibolites and mafic granulites, metamorphosed isothermally with variable H2O activities, reveal that low-Al biotite incorporates significantly higher concentrations of Ti relative to peraluminous biotite as a result of a combination of the exchange vectors TiO2R−1(OH) −2 and RSiAl−2 substituting in roughly an 8:1 ratio.

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The Ti-saturation surface for low-to-medium pressure metapelitic biotites: Implications for geothermometry and Ti-substitution mechanisms

A combined microstructural, X-ray texture goniometry and transmission electron microscopy study has been undertaken to document rare examples of c direction of slip in naturally deformed quartz. The presence of optically visible basal (0001) subgrain boundaries and strong concentrations of c axes parallel to the inferred shearing direction (close to the stretching lineation) are considered characteristic of c slip. Dominant c slip appears to be limited to high-temperature (>650 °C) and possibly hydrous conditions. The possibility of plastic softening associated with the relatively easy glide on this system is discussed.

Dominant c slip in naturally deformed quartz: Implications for dramatic plastic softening at high temperature

Water-Saturated and -Undersaturated Melting of Metaluminous and Peraluminous Crustal Compositions at 10 kb: Evidence for the Origin of Silicic Magmas in the Taupo Volcanic Zone, New Zealand, and Other Occurrences

Precambrian granulites of the Aldan shield in southern Yakutia, USSR, form a massif of 200,000 km2 bounded by younger fold-belts to the south, west and east. The massif consists of several blocks that reflect a primary heterogeneity of composition and differences in structural and thermodynamic evolution of different parts of the area. According to structural and petrological data the massif can be divided into two megablocks: eastern Aldan and western Aldan. They are separated by a narrow meridional fold-belt. Structural evolution of this central zone was determined by the geodynamics of the mega-blocks and was completed in the late Archaean. Towards the south, this central zone is ‘transformed’into the relatively small Sutam block adjoining the Stanovoy fold-belt that bounds the Aldan shield on the south. The Sutam block is separated from the other structural units of the Aldan shield by a system of north trending grabens filled by post-Archaean sediments.



The Aldan shield is composed of Archaean high-grade granulites, while the Stanovoy fold-belt, to the south, consists of highly foliated Proterozoic rocks metamorphosed under relatively lower-grade conditions. However, relics of the granulites are mapped within the fold-belt. They contain high-grade assemblages (e.g. Opx + Sil + Qz, Sap + Qz, Opx + Gr + Sil, etc.). One of the relics, the Tokskii block, which is only slightly touched by diaphthoresis, is located in the southeastern part of the Stanovoy fold-belt. Metamorphic conditions of the Tokskii block are compared with those of the Sutam block and a similar evolution of the units is revealed.



Mineral assemblages and mineral compositions do not vary within each unit, but they change in a north-south direction. The Opx + Sil + Qz assemblage has been found only in Sutam and Tok, but not in eastern Aldan and western Aldan. The Sap + Qz assemblage has been found in the Tokskii block but has not yet been found in the Sutam block. The pyrope content in garnets, from metapelites of both blocks, is significantly higher than that from the Aldan (eastern and western blocks) rocks to the north. The most important assemblages from different units of the Aldan shield have been studied using the electron microprobe in order to unravel the metamorphic evolution of the granulites and thus to deduce the thermodynamic regime of this evolution. A geodynamic model for the Aldan shield is discussed in terms of Archaean island arc development.

Precambrian granulites of the Aldan shield, eastern Siberia, USSR

Summary Information on pressure (P) and temperature (T) is a fundamental aspect of research on metamorphic terrains. Unfortunately, many workers employ thermobarometers that are not experimentally calibrated, are insensitive or too sensitive to P-T changes, depend on a priori assumptions of water pressure (such as most petrogenetic grids), or are rapidly reset on cooling. Many systems are based on inaccurate thermodynamic data, involve solids with inadequately characterized structural states, neglect effects of thermal expansion and compressibility, or require long extrapolations in P-T-X space. For instance, application of the widely used garnet-clinopyroxene KD thermometer may require extrapolation to temperatures where current thermodynamic models of pyroxenes and garnets remain uncertain. Current versions of the Mg/Fe exchange thermometer for biotite-garnet involve substantial compositional extrapolations for many applications and the biotite is easily reset while cooling from higher T. The most widely employed barometer is based on dilution of the reaction grossular + kyanite + quartz = anorthite, but failure to correct molar volumes for P-T-X may yield systematic errors of 1–2 kbar for barometry of crustal metamorphites. Application of this barometer to rocks equilibrated at T < 600–650°C is presently unwarranted in view of unknown a-X relations of garnets and plagioclases at these T. However, by careful selections, thermobarometry may be accurate to ±50°C and ±1 kbar in many metamorphic terrains if a variety of different equilibria can be applied. Well-calibrated barometers that are useful for T τ 600–650°C rely on continuous reactions based on equilibria such as almandine + rutile = ilmenite + sillimanite + quartz, garnet + quartz = ferrosilite + plagioclase, garnet + rutile = ilmenite + anorthite + quartz, and almandine + sillimanite = hercynite + quartz. An extensive survey of the recent literature on thermobarometry of individual metamorphic facies reveals the range of P-T encountered in each facies. Temperature estimates are in good agreement with the inferences of Turner (1968). Barometry reveals that the blueschist, amphibolite and granulite facies give way to the eclogite facies over the pressure range of 12–16 kbar.

The current status of thermobarometry in metamorphic rocks

The crystal structure of a metamorphic biotite from Au Sable Forks, New York (northeast Adirondacks) has been refined to an unweighted R value of 4.2Vo. The Au Sable biotite is a 2M, mica with space group symmetry C2/c. Although the biotite equilibrated near and cooled slowly from Z: 7fi)ot5OoC, octahedral and tetrahedral cations are apparently disordered. There are few, if any, octahedral and interlayer cation site deficiencies. Average bond lengths are Ml-O 2.106, M2-O 2.086, Tl-O 1.657,T2-O 1.661, inner K-O 3.046, ourer K-O 3.289A. The tetrahedral rotation angle (a) is 5.3o. The Au Sable biotite structure is nearly identical to theigreous 2M, biotite of similar composition refned by Takeda and Ross (le7s). The Au Sable biotite coexists with magnetite (usp ,r), ilmenite (Hmr), perthite (orur), and plagioclase (Anrr). This assemblage fxes f 000"C), Io,(10-t12y, and /;r,o (lG-103) for metamorphic pressure of 7tl kbar. Metamorphism of orthogneisses in the Au Sable area of the Adirondacks took place under quite dry (p""o ( p*ua) conditions.

S. R. Bohlen

Papers

Crystal chemistry of a metamorphic Biotite and its significance in water barometry

Crystal chemistry of a metamorphic biotite and its significance in water barometry from Au Sable Forks, New York