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Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation ("expandable chlorite") and/or have excess A1 w relative to A1TM, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and "expandable chlorite", which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high AlVl/A1TM and low FeVl/(Fe+ Mg) vl ratios of "chlorites" are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200-500 A. thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low AlIV/SiIV and low FeVI/(Fe + Mg) vI, while chlorite has high AlIV/Si~V and high FeW/(Fe + Mg) vl. This implies that the trioctahedral smectite-like component of corrensite has significantly lower AlIV/Si TM and FeVl/(Fe + Mg) w. The ratios of FeVI/(Fe + Mg) vt and AllV/Si TM thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of" chlorites" in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-Offprint requests to: Yen-Hong Shau layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.

Abstract--Diagenetic clay minerals usually occur as heterogeneous assemblages of submicroscopic layers consisting of different structure types such as illite, smectite and chlorite, with variable composition within a given structure type, and with highly variable concentrations of imperfections. The dimensions of mixed-layering, the semi-coherent to coherent nature of the structures across the layering, and compositional heterogeneity occur at a scale well below that of an individual thermodynamic phase. These relations imply that most clays are not distinct minerals or phases, and that assemblages of clays in shales and mudstones are incompatible with the phase rule. Such relations are better evaluated in terms of the formation of metastable materials with each small unit having unique chemical properties, rather than as a small number of stable homogeneous phases. Consequently, treatment of most clay minerals in terms of equilibrium stability with either a thermodynamic or experimental approach is subject to error.Chemical reactions involving most clay minerals are best understood with kinetic models. These involve a great variety of parameters such as time, fluid/rock ratio, deformation history, nature of starting materials and transformation mechanisms, as well as the variables, such as temperature, pressure and composition, that are commonly used to define equilibrium. Solubility experiments on the stabilities of clay minerals are unlikely to attain equilibrium at low temperatures. Moreover, the activity of soluble species may be controlled by surface equilibria, or by absorbed or exchangeable cations. Interpretations of available experiments on the solubility of illite vs. other mineral assemblages are in violation of Schreinemakers' rules and indicate lack of equilibrium.Predictable sequences of clay minerals as a function of temperature are best understood through the Ostwald step rule, in which clay mineral assemblages undergo reactions in response to kinetic factors that represent reaction progress rather than an approach to equilibrium. Currently used clay mineral thermometers (illite crystallinity, smectite/illite reaction, chlorite composition) are not based on equilibrium reactions. Such systems are not accurate thermometers and therefore have questionable utility.

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 K D 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.

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