Illite crystallinity and fluid inclusion techniques are used to understand the thermal histories of rocks on either side of the disconformity between the Lower and Upper Paleozoic strata in South Korea. Illite crystallinity studies show that the metamorphic grade of the upper strata of the Lower Paleozoic Joseon Supergroup, platform carbonates with subordinate siliciclastics, belongs to the epizone and that of the lowermost strata of the Upper Paleozoic Pyeongan Supergroup, paralic to nonmarine clastics, belongs to the anchizone. The maximum mode of homogenization temperature for fluid inclusion of the uppermost strata of the Joseon Supergroup is 260 to 270 °C and that of the lowermost strata of the Pyeongan Supergroup is 240 to 250 °C. These data reveal a difference in thermal histories of strata below and above the unconformity, suggesting that, in contrast to the previous supposition of a period of non-deposition, at least a 1-km thick section of sediment was removed by erosion during development of the unconformity. Burial and heat flux from a proposed hot spot are suggested as the dominant factors causing differences in a metamorphic grade for the Joseon Supergroup before the deposition of the Upper Paleozoic strata.

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.

Two orientations of white micas with subordinate chlorite have been observed in a fine-grained (50 Å to 2 μm) matrix of a Silurian lower anchizonal mudrock from central Wales: one parallel to bedding and one parallel to cleavage that is approximately 30°-50° to bedding. Bedding-parallel micas consist of small (50-200 Å thick) deformed packets (1Md polytype) and larger (100 Å-2 μm) strain-free grains (2M1 polytype). All strained micas and some strain-free grains have compositions varying from Mu86Pg14 to Mu58Pg42, intermediate to muscovite and paragonite, and falling within the Mu-Pg solvus. Individual packets of layers are chemically homogeneous and some of them give only one set of 00l reflections (d ≈ 19.6 Å). Micas with such intermediate compositions are metastable. Some packets of coarse, strain-free micas have compositions of approximately Mu93Pg7 or Mu11Pg89. Split pairs of 00l reflections with d-values of 20 Å and 19.6 Å, and 20 Å and 19.2 Å, respectively, were observed in some SAED patterns, suggesting coexistence of muscovite and intermediate Na/K mica (∼Mu60Pg40), and of discrete muscovite and paragonite, consistent with the splitting of the basal reflections of micas as observed in bulk-rock XRD patterns. Cleavage-parallel micas (2M1 and 3T polytypes) occur as strain-free large grains (200 Å to 2 μm) of discrete muscovite (Mu100Pg0) and paragonite (Mu6Pg94), often with subhedral to euhedral cross-sections.

The data suggest that bedding-parallel metastable micas with disordered interlayer K and Na were initially derived from alteration of smectite during burial diagenesis. They subsequently underwent dissolution, with crystallization of more evolved bedding-parallel micas during deep burial. Discrete grains of stable muscovite and paragonite then crystallized in the cleavage orientation through tectonic stress-induced dissolution of bedding-parallel matrix micas. Combined XRD and TEM/AEM data further show that the so-called 6:4 ordered mixed-layer paragonite/muscovite actually corresponds to cation-disordered, homogeneous mica of intermediate composition.

Thermal maturity of the Lower Cretaceous Sindong and Hayang groups in the Gyeongsang Basin, Korea, was investigated using the Kübler illite “crystallinity” index (KI) which is based on the numerical expression of the 10-Å peak width after calibration to the Crystallinity Index Standard scale. The metamorphic grade of the Sindong and Hayang groups ranges from late diagenetic zone to high anchizone. Depth of burial was not a major factor controlling KI variation in the basin because Hayang mudrocks have higher thermal maturity than the underlying Sindong mudrocks. Short-lived heating by the emplacement of the Upper Cretaceous plutonic rocks is responsible for the higher thermal maturity in the Hayang mudrocks. A linear NNE-SSW trending belt is drawn by connecting the lowest KI values, and it seems to reflect a hidden fault trace beneath the Hayang Group. Emplacement of Upper Cretaceous plutonic rocks and introduction of hydrothermal fluids along the inferred fault may have been the main cause of the lowering of KI values along this belt. This inferred fault is interpreted to represent the buried eastern boundary of the Nagdong Trough, which was the main depositional site for the Sindong Group in the western part of the Gyeongsang Basin. Deposition of the Hayang Group occurred in the enlarged basin when the basin extended eastward. This study provides an example that KI values can be used in the reconstruction of an early history of basin evolution.

The evolution of texture, structure and chemical composition of chloritic clays in coeval pairs of metabasites and metapelites of a prograde sequence from the Bükk Mountains has been investigated using electron microscopy techniques. Samples are from the Bükkium (innermost Western Carpathians, Hungary) that underwent Alpine metamorphism, ranging from late diagenesis to epizone for pelites and from prehnite-pumpellyite to greenschist facies for the metabasites.

Although bulk-rock compositions, textures and primary minerals are different, chlorite evolved at similar rates in coeval metabasites and metasediments, but along different paths. The principal similarities in the prograde sequence are a decrease in the percentage of interstratified material in both dioctahedral and trioctahedral phyllosilicates and increase in thicknesses of chlorite and illite crystallites. The principal difference is in the type of interstratification in chlorite, with berthierine in metapelites, and smectite (saponite) in metabasites, although smectitic mixed layers also occur in the former. The evolution of trioctahedral phyllosilicates is marked by a decrease in the number of mineral species with increasing grade, chlorite, sensu stricto, being the only trioctahedral mineral at higher grades. This is consistent with the trend in reaction progress where both metastable systems (metabasites and metapelites) tend toward the same end-member, thermodynamically stable chlorite, as well as texture (crystal size), and where all intermediate states are metastable, and determined by the Ostwald step rule.

The distribution and crystal-chemical characteristics of chlorite, corrensite, and mica in samples from a stratigraphic profile in the Cameros basin are controlled by changes in the sedimentary facies. The lacustrine marls and limestones from the base and the top of the profile contain quartz + calcite + illite ± dolomite ± chlorite ± albite ± paragonite ± Na, K-rich mica. Chlorite is rich in Mg, with Fe/(Fe + Mg) ratios ranging between 0.18–0.37. A formation mechanism involving reaction between Mg-rich carbonate and dioctahedral phyllosilicates is proposed for these Mg-rich chlorites, on the basis of the mutually exclusive relationship found between Mg-rich chlorite and dolomite, together with the relative increase in the proportion of calcite in samples containing chlorite.

The mudrocks from the middle part of the profile are composed of quartz + albite + illite + corrensite (with a mean coefficient of variability of 0.60%) ± chlorite. Corrensite and chlorite are richer in Fe2+ than those from the base or top of the profile, with mean Fe/(Fe + Mg) ratios of 0.51 and 0.56, respectively. Textural and compositional features suggest a formation mechanism for the corrensite, chlorite, and chlorite-mica crystals through replacement of detrital igneous biotite. Whether or not corrensite occurs with chlorite appears to be related to redox conditions. The presence of corrensite alone is apparently favored by oxidizing conditions, whereas the occurrence of corrensite + chlorite is related to more reducing conditions. Corrensite shows higher Si and Na + K + Ca contents, and slightly lower Fe/(Fe + Mg) ratios than chlorite. The presence of corrensite and the lack of random chlorite-smectite interlayering is discussed in terms of the fluid/rock ratio; the occurrence is related to the hydrothermal character of metamorphism in the Cameros basin.

The structural significance of micas with Na-K intermediate composition, and their chemical and structural evolution at increasing metamorphic grade have been investigated in Triassic rocks from the transition between the Maláguide and Alpujárride complexes (Internal zones of the Betic Cordillera, Spain). Micas were studied by X-ray diffraction (XRD) and by scanning and transmission electron microscopy (SEM/TEM). Three samples, belonging to the late diagenesis and to the low and medium anchizone, were selected for this study. Na-bearing mica appears as submicroscopic packets intergrown in parallel with K-mica, becoming more compositionally uniform with increasing grade. The diagenetic sample contains illite, minor paragonite, and two main populations of intermediate Na-K micas, with average compositions Ms60Prg40 and Ms35Prg65, respectively, where Ms represents muscovite and Prg, paragonite. The lattice-fringe images of mica packets with intermediate compositions suggest the presence of random mixed-layered paragonite-muscovite. Under low anchizonal conditions the amount of discrete paragonite increases and the Na-K intermediate mica has a mean composition of Ms40Prg60. The TEM images suggest that the packets with intermediate composition are solid solutions of paragonite and illite. Micas with Na-K intermediate composition are lacking in the sample with the highest metamorphic grade. In this sample, paragonite and muscovite coexist with mica, with composition intermediate between paragonite and margarite. The lattice-fringe images of these Na-Ca-bearing packets suggest that they consist of irregularly shaped domains enriched either in Na or in Ca.

Our data indicate that Na+K-bearing micas have several origins: detrital stacks of K- and Na-bearing micas coexist with authigenic phases, formed from dickite in the diagenetic, coarse-grained samples, and perhaps from smectite-bearing mixed-layers or detrital illite, in the fine-grained rocks. The changes observed at increasing metamorphic grade can be related to the influence of the lithology, the metamorphic grade, and the different geological settings. Intermediate Na-Ca mica appears to have grown from paragonite, with calcite as the source of Ca.

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.

Illite is a distinctive clay mineral formed by K alteration within hydrothermal alteration zones in porphyry Cu deposits. Based on differences in spatial distribution, Kübler index, number of swelling layers, and polytype, two kinds of illite are recognized within the Dexing porphyry Cu deposit, East China. One is a hydrothermal mineral within hydrothermally-altered granodiorite porphyry and altered tuffaceous phyllite near the contact zone with the granodiorite porphyry cupola. The hydrothermal illite is formed by illitization of plagioclase and/or micas during hydrothermal fluid-rock interaction. The considerable variation of their higher Kübler indices (0.17–1.41°Δ2θ) with swelling layer is affected by fluid/rock ratio or fluid flux. The other type of illite is a product of low-grade metamorphism within tuffaceous phyllite away from the porphyry cupola (>2 km), and has a lower Kübler index (0.06–0.13°Δ2θ), a 2M1 polytype, and no swelling layers. We suggest that, within the mineralized alteration zone, the lower the Kübler index, the stronger the degree of alteration, and the higher the copper grade. This is caused by a higher fluid/rock ratio in the middle-upper portions of the contact zone.

A set of 99 samples covering the whole range of low- and very low-grade metamorphic conditions has been used to compare Kübler index (KI) values measured on the illite 10 Å reflection (KI10 Å) with those obtained from the 5 Å reflection (KI5 Å). Evaluation of peak widths have been carried out both graphically on the recorded peak profiles from chart-strip X-ray diffraction (XRD) patterns and with the WINFIT computer program (Krumm, 1996) on fitted and decomposed profiles. All the measurements were performed both on air-dried and glycolated preparations. The data collected show that in the rock samples where illite is associated with significant amounts of I-S interstratified minerals, and/or K/Na intermediate micas, paragonite and other interfering phases, full width at half-maximum (FWHM) measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts give more reliable KI values than those obtained from the 10 Å peak. This is because of the easier and more complete de-summation of the illite second reflection from the contributions of all the interfering phases. In each sample population in which the rocks have the same metamorphic grade, KI5 Å values from fitted and decomposed profiles show much lower scattering in comparison with KI10 Å values and appear consistent with the values measured in lithologies without interfering phases.

The relationship between KI10 Å and KI5 Å appears very close to a 1:1 linear relationship; nevertheless, the conversion from KI5 Å to KI10 Å through the appropriate equation (KI10 Å = KI5 Å × 0.965 + 0.023°2θ) is recommended in order to avoid a small, but systematic, error.

In the range from late diagenesis to middle anchizone, where several phases may give diffraction effects interfering with illite peaks, the proposed procedure (i.e. FWHM measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts) seems to allow better estimates of the metamorphic grade than those obtained through traditional KI measurements.

The [MnO|SiO2,Al2O3,FeO,MgO] balanced ratio (i.e. the isometric log-ratio of the MnO concentration relative to the concentration of SiO2, Al2O3, FeO and MgO) of chlorite and of whole-rock composition is an effective discriminant between Mesozoic stratigraphic formations in the Magallanes Basin (Chile). The MnO content in chlorite is only controlled by the host rock chemistry and is dependent on the geological environment. The MnO content in chlorite remains unchanged at low-grade metamorphic conditions. Single-grain chlorite analysis (n = 1042, electron microprobe) and whole-rock analysis (n = 40, X-ray fluorescence) were used to discriminate stratigraphic formations and to decipher differences in the depositional environment in the Magallanes Basin. The samples are from one Upper Jurassic and three Cretaceous sedimentary units that were affected either by low-grade regional metamorphism or by Miocene contact metamorphism. The highest [MnO|SiO2,Al2O3,FeO,MgO] values are recorded in the upper Zapata Formation. The Punta Barrosa, Cerro Toro and Tobífera Formations show slightly lower [MnO|SiO2,Al2O3,FeO,MgO] values. Elevated [MnO|SiO2,Al2O3,FeO,MgO] values at the transition between Zapata and Punta Barrosa Formations record an oxygenated shallow marine environment that can be linked to the closure of the Rocas Verdes Basin and the onset of fold-and-thrust belt formation. Decreasing [MnO|SiO2,Al2O3,FeO,MgO] values from the Punta Barrosa towards the Cerro Toro Formation indicate gradually increasing water depths during the Upper Cretaceous that correlate well with the global sea level.

The clay mineral assemblages of the Tithonian and Berriasian sediments (Tera and Oncala Groups) in the eastern part of the Cameros basin are investigated at seven localities. The lowest-grade assemblage, located on the southern border of the basin, contains calcite + quartz + hematite + kaolinite + mixed-layer illite-smectite (R = 1, 65 85% illite layers) + discrete illite (IC = 0.5 0.65Δ°2θ). Systematic increases in the illite and chlorite crystallinities suggest increasing metamorphic grade from the northwest part of the basin to the southeast. This trend does not follow the pattern previously described for the overlying late Berriasian–early Aptian sediments (Urbión and Enciso Groups), which exhibit a higher metamorphic grade. This may result from local variations in sedimentary facies, as well as the circulation of hot migratory fluids. Tertiary compression occurring long after the main metamorphic event is considered to be responsible for the enhanced illite and chlorite crystallinities measured in the SE extreme of the basin.

Triassic sequences from 'intermediate units' between the Alpujárride and the Malâguide complexes (Betic Cordilleras, Spain) of the westernmost part of the Cordilleras (Casares area) occur as four superimposed tectonic units; the uppermost unit shows lithological characteristics similar to those of the Malâguide complex, changing progressively at increasing depth, towards lithologies typical of the Alpujárride complex. The units studied, with a maximum thickness of ~400 m, record important variations in metamorphic pressures, according to the b parameter of white micas: from low-pressure metamorphism (in the unper unit) to high-pressure faciès series (in the deepest one). The mean b values range from 8.988 Å in the uppermost unit (Crestellina) to 9.042 Å in the lowermost one (Jubrique). The lowest metamorphic grade is represented by mineral assemblages consisting of phengite + intermediate Na-K white mica ± Fe-chlorite ± sudoite ± pyrophyllite, which record temperatures of ~300°C and pressures of 1.5—3 kbar. At increasing tectonic depth, intermediate Na-K mica and pyrophyllite disappear and the metamorphic assemblages consist of phengite ± paragonite ± margarite + Mg-chlorite ± sudoite, which record minimum pressures of ~7 kbar and temperatures in the order of 400—450°C. These mineral assemblages provide evidence of the passage from collisional to extensional geotectonic settings. The units showing different metamorphic patterns were juxtaposed tectonically, after the development of metamorphic mineral assemblages.

Manganoan berthierine, sometimes only a few layers thick, is preserved interlayered with manganoan chlorite (chamosite) in small recrystallized patches in cherty metapelagites matamorphosed in the prehnite–pumpellyite facies at Meyers Pass, Torlesse Terrane, South Canterbury, New Zealand. The Mn occupies 11–12% of the octahedral sites, making this the most Mn–rich berthierine reported so far. The ratio (Fe+Mn)(Fe+Mn+Mg), 0.67–0.70, is at the lower end of those of previously reported occurrences, making these amongst the most Mg-rich berthierines known. Manganoan berthierine and interlayered manganoan chlorite also make up ~11–13% of the cryptocrystalline groundmass in which the berthierine is believed to have crystallized under early diagenetic conditions near a deep-ocean–sediment interface. The occurrence of berthierine in the recrystallized patches lends support to the possibility of a stability field at the temperature of prehnite-pumpellyite facies recrystallization in association with chlorite of similar but not identical composition.

A series of boreholes in Horton Quarry, northwest Yorkshire (Horton-in-Ribblesdale Inlier) penetrated mudstones and slates belonging to the Austwick Formation (Windermere Supergroup) overlying laminated mudstones of the Ingleton Group. Illite (IC) and chlorite (ChC) crystallinity measurements indicate a metamorphic inversion between the two groups of mudrocks. The Windermere Supergroup mudrocks are mostly in the high anchizone or epizone, whereas the Ingletonian samples are lower grade in terms of IC, and are mostly deep diagenetic zone or low anchizone. Hence younger strata at higher grades rest on older strata at lower grades, creating a metamorphic inversion. Ingletonian slates exposed at Pecca Falls on the River Twiss show epizonal and anchizonal IC values, and greywacke samples from Ingleton Quarry contain pumpellyite. This suggests that grade in the Ingletonian may increase to the NW from the Horton to Ingleton inliers. K-white mica b cell dimensions show further differences between the Ingleton Group and the Windermere Supergroup. The Ingletonian samples are characterized by low b cell values (8.989–9.035, mean 9.007 Å), whereas the Windermere Supergroup has higher values in the range 9.022–9.034, mean 9.027 Å. The Windermere Supergroup values are similar to those recorded from the Windermere Supergroup of the southern Lake District, and Lower Palaeozoic rocks from the Scottish Southern Uplands, and are consistent with metamorphism in a low heat flow, convergent geotectonic setting. The Ingletonian b cell values suggest metamorphism in a higher heat flow setting, most likely an extensional basin. The metamorphic inversion at Horton and differences in K-white mica b cell dimensions suggest that the Ingleton Group and Windermere Supergroup strata evolved in different geotectonic settings and record two separate metamorphic events. The discovery of the metamorphic inversion at Horton provides further evidence in favour of an Ordovician rather than Neoproterozoic depositional age for the controversial Ingleton Group.

Transition from diagenesis to metamorphism has been characterized in the central part of the Picos de Europa unit (Cantabrian Zone) by conodont colour alteration index (CAI), complemented with Kübler index (KI) data. This unit essentially comprises Carboniferous limestone. The study leads us to deduce two successive tectonothermal events. The first event generated a pattern with palaeotemperatures increasing towards the Pisuerga–Carrión unit, located south of the Picos de Europa unit. The present pattern is the result of an original dip to the north of the isothermal surfaces and the subsequent rising of the Picos de Europa unit along the frontal ramp of a deep Alpine thrust. This episode is interpreted as related to an extensional tectonic regime that occurred close to the Carboniferous–Permian boundary. The second event, which gave rise to thermal anomalies in the pattern of the first episode, was the result of hydrothermal processes in which fluid movement was facilitated by a dense network of fractures in the area close to the eastern section of the studied region. These processes gave rise to numerous mineralizations and have been related to a Permian extensional tectonic regime.