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.

Clay mineralogy (including illite crystallinity) was studied in Pennsylvanian synorogenic sediments (Atoka Formation) in the subsurface of the Arkoma Basin and the adjacent Ouachita thrust belt. Vitrinite reflectance values range from ≥0.8% at the surface up to as high as 4.7% Ro at the base of the Atoka Formation. The mineralogy of the <2 µm fraction of the mudrocks is fairly monotonous and composed of illite (<10% interstratified smectite), Fe-chlorite, kaolinite, quartz, and traces of feldspars. Kaolinite is common at shallow levels and “disappears” in most wells at a thermal maturity of 1.9–2.1% Ro, suggesting its possible use as an independent paleothermal indicator in this basin. Illite crystallinity (IC) values are fairly high (0.3–0.5° 2θ) and show little variation throughout the entire maturity range. In addition, no relation was observed between vitrinite reflectance and illite crystallinity, indicating that IC is not a useful paleothermal indicator in these rocks. Illite is almost exclusively of the 2M1 polytype, suggesting a predominantly detrital origin. Incipient metamorphic and low-grade metamorphic mudrocks in the Ouachita thrust belt to the east of the Arkoma Basin are regarded as the source rocks for the clays of the Atoka Formation. Rapid transportation and deposition by turbidity currents probably played a key role in protecting these unweathered micas from pervasive alteration in the terrestrial environment.

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.

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.

Clay mineralogy and its palaeoclimatic interpretation of the early-Eocene (∼53.3–49.70 Ma) sediments at Lulehe, Qaidam basin, northwest China, were investigated using optical microscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). The interval of ∼53.3–49.70 Ma, including the early-Eocene climate optimum (EECO) with isotopic events, was the transition period of “greenhouse” to “icehouse”. Climate changes during the episode were documented in the sediments and were expressed by the proportion of clay species and clay indices, as well as by the proportion of non-clay minerals, gypsum, halite and calcite. Our results suggest that a warm and humid climate prevailed over the period ∼53.3–52.90 Ma, followed by a warm and seasonally dry and humid climate in the period ∼52.90–51.0 Ma and a subsequently warm and humid climate in the period ∼51.0–49.70 Ma. Three warmer and more humid intervals were observed at 52.7, 51.0 and 50.5 Ma based on clay indices. The climate evolution in the Qaidam Basin during the period derived from the clay mineralogical study is in good agreement with the early Eocene global climate change, and the warm and seasonally dry and humid episode in the early Eocene in Qaidam basin is a regional response to the global early-Eocene climate optimum.

The main reason for the initial determinations of illite crystallinity (IC) was to support the exploration for liquid and gaseous hydrocarbons. The application in 1960 of the Weaver Sharpness Ratio to core materials of a borehole from eastern France indicated that it was not a reliable tool for identifying well-crystallized illite. This ratio was later replaced by the Full Width at Half-Maximum (FWHM), the value of which decreases regularly and consistently towards greenschist facies. The use of FWHM allowed a precise definition of the anchimetamorphic zone between the upper diagenesis and the epimetamorphism. Afterwards, analysis of weak-tointermediate diagenetic sequences showed that illite crystallinity decreases together with the amount of swelling interlayers in mixed-layer clay minerals. Technological improvements, such as computing and modelling of X-ray diffraction patterns, increased the analytical precision relative to measurements of the plain FWHM. Consequently, illite crystallinity went back to its initial use, namely detection of the transitions between diagenesis, anchi- and epi-metamorphism in smectitefree lithologies, where it can be used as a stratigraphic and mineralogic marker of alteration stages.

Clay mineral evolution in diagenetic and very low-grade metamorphic sedimentary rocks from the Maláguide Complex was studied using the following parameters: illite and chlorite crystallinity, b cell dimension of illite, chemistry of chlorite, and the occurrence and distribution of the following phyllosilicates: I-S mixed-layer minerals, kaolin polytypes, chlorite-bearing mixedlayer minerals (tosudite and mica-chlorite interstratifications), vermiculite-like minerals, paragonite and biotite. The distribution of IC values permits the subdivision of the study area into three zones: diagenetic, anchizone and epizone. On the contrary, the distribution of CC values cannot be used in the study of the metamorphic zonation. The mineralogy and b dimension of illite indicate that the Maláguide samples display a low to low-medium pressure metamorphism, also characterized by steep temperature gradients.

The correlation between IC data and distribution of other significant minerals has permitted the establishment of a zonation within the chlorite zone, which is confirmed by the appearance of some index minerals, such as paragonite, biotite, chloritoid and andalusite.

The Puncoviscana Formation, largely cropping out in NW Argentina, is mainly composed of a pelite-greywacke turbidite sequence affected by incipient regional metamorphism and polyphase deformation. Metapelites, composed mainly of quartz, albite, dioctahedral mica and chlorite, were sampled in the Lules-Puncoviscana and Choromoro belts. Lattice-fringe images, selected area electron diffraction and analytical electron microscopy analyses, coupled with previous data from white mica crystallinity index, indicate a state of reaction progress for Puncoviscana slates consistent with medium anchizone- to epizone-grade metamorphism. The 2M polytype prevails in dioctahedral micas, coexisting in a few cases with the 1Md polytype as a consequence of lack of equilibrium. The 2Mpolytype coexists with 3T in two slates and long-range four-layer and ten-layer stacking sequences were identified in another sample. Samples with 3T and long-range stacking sequences present b values characteristic of intermediate–high pressure metamorphism and ordered chlorites (1L, 2L, 3L and 7L) prevail.

Based on the Si contents of dioctahedral micas and considering peak temperatures of ∼350 –400ºC, pressures from 5 kbar and 5 –7 kbar were derived for metapelites from the Lules- Puncoviscana and Choromoro belts, respectively. These values agree with facies series derived from the b values. Micas with a wide range of phengitic substitution, as evidenced by Fe + Mg and Si contents, coexist. These variations could not arise from the disturbing effect of detrital white K-mica because TEM evidence indicates that they are absent or represent <10% of the mica population. Thus, compositional variations suggest that dioctahedral micas of individual slates crystallized at different pressure conditions in response to the P-T path of the metamorphism. Moreover, in several biotite-free slates the illite crystallinity (IC) values lead to an underestimation of the metamorphic grade attained in these rocks.

The coexistence of IC corresponding to anchizone and the occurrence of biotite in some slates and felsic metavolcanic rocks intercalated in the Puncoviscana metasediments are interpreted to be the result of a metamorphic path including a relatively high-pressure/ low-temperature (HP/LT) event, followed by a lower-pressure overprint possibly at higher temperatures than the HP/LTevent. Small micas formed during the high-pressure stage would prevail in the <2 mm fraction, producing anchizone IC.

The relationship between illite crystallinity (IC) and finite strain as well as lattice strain and crystallite size of illite is examined in a series of 27 deformed breccia samples from the inverted limb of the Morcles nappe. The IC is determined independently for limestone components and a red/green clay-silt matrix. The finite strain varies widely (D= 0.8–2.5). The IC values vary from diagenetic to epizonal, but no correlation with finite strain could be established. The spread of IC values is explained by heterogeneities within the protolith which have not been homogenized/ obliterated by the anchizonal to epizonal metamorphic overprint. While limestone pebbles display IC values in agreement with the regional metamorphic conditions, the clay-silt matrix has anomalously high IC values, even after deconvolution of the 10 Å peak to correct for the presence of paragonite/muscovite. No correlation could be established between finite strain, lattice strain and/or crystallite size of illite.

An unusually complete sequence of pelitic rocks ranging from diagenetic to greenschist-facies metamorphic grades occurs in southern Sierra Espun˜a, Spain. Prograde and retrograde reactions have been studied by X-ray diffraction and electron microscopy (SEM, TEM and AEM). The prograde reaction series, with reactions facilitated by tectonic stress, includes: (1) R4 interstratified illite-smectite in the diagenetic Malaguide Complex that preserves the variable orientation of original smectite packets, and has 1Md polytypism; (2) chemically heterogeneous illite and Na-K dioctahedral white micas that progressively evolve toward chemical and textural equilibrium in the anchizonal Intermediate Units; and (3) thick, defect-free packets of phengite, paragonite and clinochlore which have a typical metamorphic texture, in the Alpujarride Complex. Two superimposed retrograde episodes produced: (a) sudoite at near-peak metamorphic conditions and (b) dioctahedral smectite during low-temperature retrograde diagenesis.

The degree of metamorphism affecting the Devonian-Carboniferous rocks of the Palaeozoic Cinco Villas massif has been studied by (a) petrographic techniques, (b) illite crystallinity, and (c) degree of graphitization of the carbonaceous material. Some mineralogical differences have been found between the Devonian and Carboniferous rocks; paragonite and mixed-layer paragonite/muscovite, typical of anchimetamorphic areas, appear in the Devonian but are not found in the Carboniferous rocks. These are characterized by the local appearance of chloritoid, garnet, amphibole, epidote, andalusite and biotite, and the generalized presence of muscovite/chlorite. Illite crystallinity shows a metamorphic zonation (anchizone epizone) towards the granitic Aya massif, and a concentric pattern around the intrusive body.

The optical analysis shows that the first effects of the regional metamorphism began before the D2 deformation, reaching its paroxysm during this phase and continuing afterwards. The degree of graphitization evolves progressively with metamorphism, and this fact is reflected in an exponential relationship between d(002) and crystallinity Lc(002). The similarity in the degree of graphitization between homologous materials within and outside the Aya aureole suggests a similar kinetic factor for both the thermal and regional metamorphisms, or a similar duration time. This fact, as well as the distribution and relationship between the deformation and recrystallization of the minerals, suggests a syn-plutonic regional metamorphism developed at low pressures, in accordance with the value of the b0 parameter for the white micas, and probably a maximum temperature of about 500°C.

A horizon containing graphite in the Early Silurian slates of the Eastern Central System, Central Spain, has been studied. The carbonaceous slates contain quartz, muscovite, graphitized organic matter, plagioclase, pyrite and apatite; and the slates above the graphite horizon contain quartz, phengite, plagioclase and chlorite. The origin of the graphite is related to a period of very slow accumulation rate, anoxic seafloors deep-water upwellings and plankton blooms. The chlorite and graphite are mutually exclusive and by' using the chlori te AlIV content and the graphite Co parameter, the conditions of metamorphism were calculated to be 300 ± 20°C and 1.5-2 kbar.

Analysis of pelites with detrital white-micas in the Clew Bay–Galway Bay segment of the Irish Caledonides indicates that b0 data from whole-rock and < 2 μm fractions generally show differences smaller than the errors of the method, irrespective of (001) illite crystallinity values, probably due to metamorphic recrystallization. Intermediate pressure metamorphism of the Ordovician–Silurian Clew Bay Group indicates slow subduction, allowing partial thermal re-equilibration before exhumation. In contrast, the Croagh Patrick Group Laurentian shelf-sediments underwent high-pressure alteration, suggesting rapid subduction/exhumation, synchronous with strike-slip faulting. The Murrisk Group, which underwent high-intermediate pressure metamorphism in an Ordovician back-arc, forms a separate terrane to the Croagh Patrick Group to the north and also to the Ordovician Lough Nafooey and Tourmakeady groups and Rosroe Formation in the south, in which low-intermediate pressure alteration occurred. These, together with the Silurian North Galway Group, may have undergone heating due to movement over or deposition on the hot Gowlaun Detachment as the Connemara Dalradian was exhumed. The South Connemara Group also underwent a high-pressure alteration, consistent with its inferred subduction environment. Evidence of contact alteration, due to known or inferred buried late- to post-Caledonian granitoid plutons, has been found in the Clew Bay, Louisburg–Clare Island, Croagh Patrick, Murrisk and South Connemara groups. These show evidence of lower-pressure alteration than the surrounding country-rocks.

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.