The smectite-to-illite conversion during shale diagenesis has recently been used to constrain the estimate of a basin's thermal history. We have systematically investigated the kinetics for the conversion of a Na-saturated montmorillonite (SWy-1) to a mixed-layer smectite/illite as a function of KCl concentration (from 0.1 to 3 moles/liter) over a temperature range of 250° to 325°C at 500 bars in cold-seal pressure vessels using gold capsules. The results show that the conversion rate can be described by a simple empirical rate equation

-dS/dt = A · exp(-Ea/RT) · [K+] · S2

where S = fraction of smectite layers in the I/S, t = time in seconds, A = frequency factor = 8.08 × 10-4 sec-1, exp = exponential function, Ea = activation Energy = 28 kcal/mole, R = gas constant, 1.987 cal/deg-mole, T = temperature (degree Kelvin), [K+] = K+ concentration in molarity (M) in the fluid.

The results also show that Ca2+ in solutions barely affects the illitization rate, whereas Mg2+ significantly retards the rate. The retardation, however, is not as severe as previously reported. Na+ ion can significantly retard the rate only if the concentration is high.

We found that by assuming a range 0.0026-0.0052 moles/liter (100-200 ppm) of K+, concentrations similar to the value typically reported in oil field brines, the present kinetic model can reasonably predict the extent of the smectite-to-illite conversion for a number of basins from various depths and age. This narrow range of potassium concentrations, therefore, is used to model the smectite-to-illite conversion in shale when the actual chemical information of pore fluid is not available.

The kinetic equation has been tested using field data from a large variety of geologic settings worldwide (i.e., the Gulf of Mexico, Vienna Basin, Salton Trough Geothermal Area, East Taiwan Basin, Huasna Basin, etc). The results show that the equation reasonably predicts the extent of the reaction within our knowledge of the variables involved, such as burial history, thermal gradients, and potassium concentration.

Since the initial studies of chlorite polytypes, it has been suggested that the stability of the various polytypes may be a function of the temperature at which the mineral formed; however, few studies have been performed in which polytypes of chlorite in a specific suite of samples have been determined and correlated with temperature. A review of the reported occurrences of type I chlorite indicates that other factors, including grain size of the host rock, may be at least as important as temperature in controlling the stability of these polytypes. Results of systematic studies in areas of diagenesis and very low-grade metamorphism suggest that type-II chlorite is stable at temperatures well below 200°C and that it can form as the initial chlorite phase without passing through any intermediate polytypic stages. The conditions under which type-I polytypes occur are somewhat restricted, and cognizance of those restrictions will help to direct future studies of chlorite polytype transformations. These studies should focus on the structural details of polytype transformations; on the relationship of polytype stability to pressure, composition and kinetics; and on experimental calibration of the transformations.

Chlorite minerals, found in a great variety of rocks and geological environments, display a wide range of chemical compositions and a variety of polytypes, which reflect the physicochemical conditions under which they formed. Of particular importance for studies dealing with ore deposit genesis, metamorphism, hydrothermal alteration or diagenesis is the paleotemperature of chlorite crystallization. However, in order to understand the relationship between chlorite composition and formation temperature and hence use chlorite as a geothermometer, one must determine how other parameters influence chlorite composition. These parameters may include fO2 and pH of the solution and Fe/(Fe + Mg) and bulk mineral composition of the host rock.

Four approaches to chlorite geothermometry, one structural and three compositional, have been proposed in the past: 1) a polytype method based on the (largely qualitative) observation that structural changes in chlorite may be partly temperature-dependent (Hayes, 1970); 2) an empirical calibration between the tetrahedral aluminum occupancy in chlorites and measured temperature in geothermal systems (Cathelineau, 1988), which has subsequently been modified by several workers; 3) a six-component chlorite solid solution model based upon equilibrium between chlorite and an aqueous solution, which uses thermodynamic properties calibrated with data from geothermal and hydrothermal systems (Walshe, 1986); and 4) a theoretical method based on the intersection of chlorite-carbonate reactions and the CO2-H2O miscibility surface in temperature-XCO2 space, which requires that the composition of a coexisting carbonate phase (dolomite, ankerite, Fe-calcite or siderite) be known or estimated (Hutcheon, 1990). These four approaches are reviewed and the different calculation methods for the compositional geothermometers are applied to a selection of chlorite analyses from the literature. Results of this comparative exercise indicate that no single chlorite geothermometer performs satisfactorily over the whole range of natural conditions (different temperatures, coexisting assemblages, Fe/(Fe + Mg), fO2, etc.). Therefore, chlorite geothermometry should be used with caution and only in combination with alternative methods of estimating paleotemperatures.

Low-temperature chlorites formed in diagenetic to low-grade metamorphic environments generally have greater Si contents and larger numbers of octahedral vacancies, and smaller Fe+Mg contents than higher-grade metamorphic chlorites. The compositional variations are characterized approximately by four end-member components: Al-free trioctahedral chlorite, chamosite, corundophilite, and sudoite. The solid solution is considered to be a random mix of cations and vacancies in the octahedral sites. Using the compositions of chlorites from Niger, Rouez, and Saint Martin diagenetic-hydrothermal series, a new, more convenient geothermometer, applicable to low-T chlorites is proposed and comparison made with geothermometers proposed previously. The chlorites studied contain appreciable amounts of Fe(III) (>14% of the total Fe), determined by Mössbauer spectroscopy. The calculations under which all Fe was regarded as ferrous gave considerable overestimates for the formation temperature, irrespective of the geothermometer used. This problem was reduced by taking into account the presence of Fe(III) in the octahedral sites. The geothermometer from this study gave more reasonable estimates than the geothermometers proposed by Walshe (1986) and Vidal et al. (2001), particularly in the case of the Niger chlorites which crystallized in the lowest-temperature conditions. The ordered-site substitution model of solid solution developed by Vidal et al. (2001) predicted satisfactorily the formation temperature of the Rouez chlorites and of some of the Saint Martin chlorites, suggesting that the chlorite compositions are controlled by the exchange at low-T conditions while they are controlled by Tschermak exchange at higher temperatures. The decreasing number of vacancies with temperature are poorer in Fe-rich than in Fe-poor chlorites. Furthermore, the ordered-site occupation of cations and vacancies in trioctahedral chlorite occurs concomitantly with the compositional changes ruled by increasing temperature conditions.

The Little Michiru complex is a composite intrusion of pyroxenite and pyroxene syenite which is located at the boundary between amphibolite and granulite facies gneisses in the Shire rift valley. Pyroxene and feldspar chemistry shows that the intrusion consolidated from two magmatic fractions, one a pyroxenite cumulate that equilibrated at 870–1000 °C, the other a partly anatectic pyroxene syenite magma which metasomatized the surrounding gneisses during granulite-facies metamorphism and equilibrated at a temperature of 730–830 °C at 7 kbar.

Orthopyroxene and clinopyroxene, with biotite, are widespread in the high-level Cheviot granite, while amphibole is rare. The pyroxene compositions are very close to (Mg,Fe)2Si2O6 and Ca(Mg,Fe)Si2O6. Biotite compositions, with low Si and Al, are characteristic of biotites coexisting with pyroxenes. Geothermometric estimates based on oxide and pyroxene compositions show that present mineral compositions result from post-consolidation equilibration.

In the central granulite belt of Sri Lanka, garnet-pyroxene granulites of granitic and gabbro-noritic composition are the most abundant rock types. The micro-structures and mineral chemistry data prove complete attainment of textural and large-scale chemical equilibrium during and following a phase of extreme penetrative deformation at conditions of the granulite facies (800–850 °C, 5 to 9 kbar). On a local scale, especially along the intergranular system, continued cation exchange decoupling from the early ceasing net-transfer reactions destroyed the near-peak metamorphic equilibrium. The extreme compositional variation of the coexisting ferro-magnesian phases (Fe/(Fe + Mg): gar 0.98−0.65, opx 0.92−0.40, cpx 0.88−0.28) and the near-isothermal conditions of equilibration throughout the studied area enabled examination of the effects of non-ideal mixing in garnet and pyroxenes on the equilibrium constants of reactions used in geothermobarometry, and tests on the quality of commonly applied thermometers/barometers and the validity of activity models adopted in the calibrations. The Sri Lankan data set reveals more or less pronounced compositional dependences for all of the tested gar-opx/gar-cpx Fe-Mg exchange thermometers and the opx + plg ⇌ gar + qtz barometers. Evidently the recommended solution models do not adequately describe the mixing properties of the involved ferro-magnesium mineral phases (garnet, orthopyroxene and clinopyroxene).

This paper examines the effects of shear stress on the structural parameters that define the ‘crystallinity’ of graphite. The results show that highly crystalline graphite samples ground for up to 120 min do not undergo detectable changes in the three-dimensional arrangement of carbon layers but crystallite sizes (Lc and La) decrease consistently with increasing grinding time. Grinding also involves particle-size diminution that results in lower temperatures for the beginning of combustion and exothermic maxima in the differential thermal analysis curves. These changes in the structural and thermal characteristics of graphite upon grinding must be taken into account when such data are used for geothermometric estimations.

Tectonic shear stress also induces reduction of the particle size and the Lc and La values of highly crystalline graphite. Thus, the temperature of formation of graphite according to structural as well as thermal data is underestimated by up to 100°C in samples that underwent the most intense shear stress. Therefore, application of graphite geothermometry to fluid-deposited veins where graphite is the only mineral found should take into consideration the effect of tectonic shearing, or the estimated temperatures must be considered as minimum temperatures of formation only.

A genetic linkage between W, (Cu, Mo)-mineralization and chlorite minerals, and the discrimination of different mineralization events in the magmatic-hydrothermal system of Borralha, northern Portugal, is discussed on the basis of textural relationships, crystal chemistry and stable isotopic data obtained from chlorite. Chlorite minerals were identified in assemblages with quartz, feldspars, tungstates and sulfides. X-ray diffraction studies of selected chlorite minerals shows a trioctahedral structural type. Electron probe micro-analyses identified four different compositions and associations: (1) Fe,Mn-chlorite with scheelite I; (2) Fe-chlorite with wolframite + scheelite II ± sulfide; (3) Fe,Mg-chlorite with molybdenite + bismuthinite; and (4) Mg,Fe-chlorite with chalcopyrite. The composition of Fe-chlorite (Al3.01Fe3+0.25Fe2+7.95Mn0.26Mg0.19)11.66(Si5.44Al2.56)8O20(OH)8 corresponds to daphnite and Fe,Mn-chlorite (Al2.69Fe3+0.02 Fe2+7.54Mn1.08Mg0.62)11.89(Si5.31Al2.68)4O20(OH)8 to a mixed composition between daphnite and amesite. The Fe,Mg-chlorite (Al2.89Fe3+0.24Fe2+6.42Mn0.21Mg2.08)11.84 (Si5.31Al2.79)8F0.31O20(OH)8 corresponds to ripidolite and Mg,Fe-chlorite (Al2.63Fe3+0.37Fe2+1.72Mn0.01Mg6.40Ca0.26)11.39(Si6.02Al1.98)8O20(OH)8 to pychnochlorite.

Chlorite geothermometry estimates a temperature for Fe,Mn-chlorite (scheelite I) from 400°C to 500°C, for Fe-chlorite (Mn-rich wolframite + scheelite II ± sulfide) from 250 to 350°C, for Fe,Mg-chlorite (Mo-mineralization) from 200°C to 250°C and for Mg,Fe-chlorite at ~150°C. Oxygen isotopes (V-SMOW) yielded values of +3.8 (1σ) (Fe-chlorite), +6.91 (1σ) (Fe,Mn-chlorite) and +1.5 (1σ) (Fe,Mg-chlorite). The calculated δ18OF of Fe- and Fe,Mg-chlorite is ~+3.75 (1σ) and +1.45 (1σ) for the mineralizing fluid, whereas for Fe,Mn-chlorite it is +8.17 (1σ). The δ18O data obtained from quartz in W- and Mo-mineralization yielded values of +12.6 and +11.4 (1σ), whereas for adularia δ18O is about +10 (1σ). These estimates allow us to conclude that the Fe,Mn-chlorite crystallized from a magmatic-hydrothermal fluid, whereas the Fe- and Fe,Mg-chlorite quartz and adularia resulted from a mixed contribution between meteoric and magmatic-hydrothermal fluid.

A compilation of Fe3+-bearing chlorite analyses is used: (1) to investigate the Alfree di-trioctahedral (AFDT) substitution 2Fe3+ +□= 3(Mg,Fe2+) in chlorite; and (2) to estimate the composition of a ferri-sudoite end-member (Si3Al)[(Fe2+,Mg)2□Al]O10(OH)8 within the chlorite solid-solution domain. According to our observations, up to two Fe3+ cations might be allocated in the M2-M3 chlorite sites by the substitution AFDT, which does not involve Al. These unexpected observations were made possible by the development of μXANES techniques allowing in situ measurements of XFe3+ (Fe3+/(Fe2+ + Fe3+)) in heterogeneous chlorite. Although further studies are required to confirm the crystallographic position of Fe3+ and refine its ionic/ magnetic behaviour in chlorite, this development creates opportunities for developing new geothermometers.

Electron microprobe analyses of 128 detrital rutile grains from two Jurassic sandstone samples (Hettangian and Bajocian–Bathonian in age) from hydrocarbon exploration wells on the Norwegian margin confirm that more than 85 % of the rutiles were derived from metapelitic rocks. Zr-in-rutile geothermometry confirms that about 83 % of the rutile was formed under high-grade metamorphism (>750 °C). Sixty-two rutile grains, including 60 of the identified high-temperature rutile population, were also analysed for U–Pb geochronology using SHRIMP. The 206Pb–238U rutile ages range from approximately 485–292 Ma, with a major cluster between 450 and 380 Ma. These data suggest that the detrital rutile was predominantly derived from a felsic source that experienced granulite-facies metamorphism about 450–380 Ma ago. This conclusion is consistent with derivation from high-grade Caledonian metasedimentary rocks, probably the Krummedal sequence in central East Greenland, as previously suggested by an earlier provenance study using conventional heavy mineral analysis, garnet geochemistry and detrital zircon age dating. The present study underscores the importance of rutile geochemistry and geochronology in quantitative single-mineral provenance analysis of clastic sedimentary rocks.

Blocks of medium-grained granodiorite to 4 m, and minor diabase, quartz diorite, granite, aplite and granophyre, are common in ejecta of the ∼6,900 yrBP calderaforming eruption of Mount Mazama. The blocks show degrees of melting from 0–50 vol%. Because very few have adhering juvenile magma, it is thought that the blocks are fragments of the Holocene magma chamber's walls. Primary crystallisation of granodiorite produced phenocrystic pl + hyp + aug + mt + il + ap + zc, followed by qz + hb + bt + alkali feldspar (af). Presence of fluid inclusions in all samples implies complete crystallisation before melting. Subsolidus exchange with meteoric hydrothermal fluids before melting is evident in δ18O values of −3·4+4·9‰ for quartz and plagioclase in partially melted granodiorites (fresh lavas from the region have δ18O values of +5·8−+7·0‰); δ18O values of unmelted granodiorites from preclimatic eruptive units suggest hydrothermal exchange began between ∼70 and 24 ka. Before eruption, the granitic rocks equilibrated at temperatures, estimated from Fe-Ti oxide compositions, of up to ∼1000°C for c. 102–104 years at a minimum pressure of 100-180 MPa. Heating caused progressive breakdown or dissolution of hb, af, bt, and qz, so that samples with the highest melt fractions have residual pl + qz and new or re-equilibrated af + hyp + aug + mt + il in high-silica rhyolitic glass (75-77% SiO2). Mineral compositions vary systematically with increasing temperature. Hornblende is absent in rocks with Fe-Ti oxide temperatures >870°C, and bt above 970°C. Oxygen isotope fractionation between qz, pl, and glass in partially fused granodiorite also is consistent with equilibration at T≥900°C (Δ18Oqz.pl = +0·7 ± 0·5‰). Element partitioning between glass and crystals reflects the large fraction of refractory pl, re-equilibration of af and isolation or incomplete dissolution of accessory phases. Ba and REE contents of analysed glass separates can be successfully modelled by observed degrees of partial melting of granodiorite, but Rb, Sr and Sc concentrations cannot. Several samples have veins of microlite-free glass 1–5 mm thick that are compositionally and physically continuous with intergranular melt and which apparently formed after the climactic eruption began. Whole-rock H2O content, microprobe glass analysis sums near 100% and evidence for high temperature suggest liquids in the hotter samples were nearly anhydrous. The occurrence of similar granodiorite blocks at all azimuths around the 8 × 10 km caldera implies derivation from one pluton. Compositional similarity between granodiorite and pre-Mazama rhyodacites suggests that the pluton may have crystallised as recently as 0·4 Ma; compositional data preclude crystallisation from the Holocene chamber. The history of crystallisation, hydrothermal alteration, and remelting of the granitic rocks may be characteristic of shallow igneous systems in which the balance between hydrothermal cooling and magmatic input changes repeatedly over intervals of 104-106 years.