R. J. Merriman

REPORT OF THE ASSOCIATION INTERNATIONALE POUR L’ÉTUDE DES ARGILES (AIPEA) NOMENCLATURE COMMITTEE FOR 2001: ORDER, DISORDER AND CRYSTALLINITY IN PHYLLOSILICATES AND THE USE OF THE “CRYSTALLINITY INDEX”

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllo-silicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, e.g. ‘Hinckley index’ or ‘Kubler index’, or in honor of a researcher who investigated the importance of the parameter extensively, e.g. ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra ( i.e. limited order) with each group displaced or rotated ( e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, in serpentine, …

A transmission electron microscope study of white mica crystallite size distribution in a mudstone to slate transitional sequence, North Wales, UK

High-resolution transmission electron microscopy (HRTEM) measurements of the thickness of white mica crystallites were made on three pelite samples that represented a prograde transition from diagenetic mudstone though anchizonal slate to epizonal slate. Crystallite thickness, measured normal to (001), increases as grade increases, whereas the XRD measured 10 Å peak-profile, the Kubler index, decreases. The mode of the TEM-measured size population can be correlated with the effective crystallite size N(001) determined by XRD. The results indicate that the Kubler index of white mica crystallinity measures changes in the crystallite size population that result from prograde increases in the size of coherent X-ray scattering domains. These changes conform to the Scherrer relationship between XRD peak broadening and small crystallite size. Lattice ‘strain’ broadening is relatively unimportant, and is confined to white mica populations in the diagenetic mudstone. Rapid increases in crystallite size occur in the anchizone, coincident with cleavage development. Changes in the distribution of crystallite thickness with advancing grade and cleavage development are characteristic of grain-growth by Ostwald ripening. The Kubler index rapidly loses sensitivity as an indicator of metapelitic grade within the epizone.

Transmission and analytical electron microscopic study of mixed-layer illite/smectite formed as an apparent replacement product of diagenetic illite

Ordered illite/smectite (I/S) and illite in a pelitic rock from a prograde metamorphic sequence in North Wales were observed by transmission electron microscopy. The dominant phyllosilicate noted was diagenetic-metamorphic illite, occurring as subparallel packets of layers, each about a few hundred Ångstroms thick. It exhibited two-layer polytypism (presumably 2M1) and numerous strain features and had a composition of (K1.21Na0.12)(Al3.36Fe0.31Mg0.33)(Si6.28Al1.72)O20(OH)4.I/S occurred as thick packets of wavy layers having 10-Å subperiodicity and sharp differences in contrast in successive lattice fringes. All stages in a replacement series were noted, from one or two layers of smectite within illite, through thin packets of I/S, to thick packets that contained inherited deformation textures of diagenetic-metamorphic illite. Deformed illite was replaced by I/S more commonly than was undeformed illite. The I/S replacing undeformed original illite had significantly greater order, primarily of R1 type (ISISIS…), than that replacing deformed illite. R> 1 I/S occurred as small crystallites and contained relatively less smectite than the ordered I/S, Single smectite layers were spaced within several illite layers, forming curved packets of layers. IISIIS… (R2) and IIISIIIS… (R3) ordering were present locally, as was discrete smectite. Analytical electron microscopic analyses indicated that the I/S, (K0.46Na0.43)(Al3.75Fe0.06Mg0.19)(Si6.26Al1.74)O20(OH)4, was rectorite-like in composition and had smaller (Mg + Fe) contents and greater Al/Si ratios than the coexisting illite, which was also anomalous in terms of general crystal-chemical relationships between coexisting illite and I/S in burial diagenesis environments. The I/S appears to have formed by replacement of diagenetic-metamorphic illite, presumably at very low temperatures under hydrous conditions via dissolution and crystallization.

Report of the Association Internationale pour l’Etude des Argiles (AIPEA) Nomenclature Committee for 2001: Order, disorder and crystallinity in phyllosilicates and the use of the ‘Crystallinity Index’

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions, or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, as in ‘Hinckley index’ or ‘Kubler index’, or in honour of a researcher who investigated the importance of the parameter extensively, as in ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra (i.e. limited order) with each group displaced or rotated (e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, …

40AR/ 39AR ILLITE DATING OF LATE CALEDONIAN (ACADIAN) METAMORPHISM AND COOLING OF K-BENTONITES AND SLATES FROM THE WELSH BASIN, U.K.

The vacuum-encapsulation laser 40Ar39Ar technique allows extremely small (10−6 g) samples of fine-grained materials such as diagenetic clays to be dated. Here we show that the method can be extended to higher-grade clay minerals. The integration of transmission electron microscopic (TEM) characterization with 40Ar39Ar dating of vacuum encapsulated samples permits the resolution of the timing of metamorphic growth/cooling from the time of diagenesis. We have applied this technique to well characterized Lower Paleozoic slates and K-bentonites from the Welsh Basin, which span the transition from anchizonal to epizonal grade, which had been previously studied using RbSr and SmNd dating. TEM observations of epizonal K-bentonites and slate showed that illite in these samples is of 2M1 polytype, of muscovite-like composition, and oriented parallel to cleavage, suggesting that they are of metamorphic origin. Total gas ages (equivalent to conventional KAr ages) for encapsulated epizonal K-bentonites and slate (340–408 Ma) are considerably variable. The Ar retention ages (calculated from 39Ar and 40Ar atoms retained in the sample after irradiation) are more consistent (383–411 Ma). The 39Ar recoil losses are minor for illites from whole rock samples of epizonal K-bentonites but very significant for clay separates of epizonal slate. Plateaus in age spectra were observed in epizonal K-bentonites and slate. The plateau ages (414–421 Ma) and retention ages (383–411 Ma) can be correlated with the onset of Acadian metamorphism and culmination of uplift and inversion of the Welsh Basin, respectively. These ages are significantly younger than the ∼ 450 Ma ages previously reported for diagenetic clays using the same method, suggesting that diagenetic history has been lost in these epizonal K-bentonites and slate. TEM observations of anchizonal slates showed that there are two modes of illite. The first mode is similar to that observed in epizonal samples, suggesting a metamorphic origin. The second mode consists of the 1Md polytype, has typical diagenetic illite composition, and is oriented parallel to bedding, suggesting a diagenetic origin. Total gas ages for encapsulated anchizonal slates vary considerably (361–422 Ma). The retention ages are more consistent (413–432 Ma) than the total gas ages. The 39Ar recoil losses are more significant than those for epizonal K-bentonites and slate. Plateaus in age spectra are generally not observed. However, the consistent retention ages for the anchizonal slates correspond to the plateau ages for the epizonal samples, and are inferred to represent the onset of Acadian metamorphism. These data, when combined with our previously published results for diagenetic shales, suggest that thermal conditions near the boundary of anchizonal and epizonal grades are necessary to completely reset Ar systems in shales and slates.

Clay minerals and sedimentary basin history

Clay minerals in the mud and soil that coat the Earths surface are part of a clay cycle that breaks down and creates rock in the crust. Clays generated by surface weathering and shallow diagenetic processes are transformed into mature clay mineral assemblages in the mudrocks found in sedimentary basins. During metamorphism, the release of alkali elements and boron from clay minerals generates magmas that are subsequently weathered and recycled, representing the magma-to-mud pathway of the clay cycle. Volcanogenic clay represents an important but hitherto underestimated proportion of recycled clay. Within sedimentary basins, immature clays are transformed to mature and supermature clay assemblages by a series of reactions that generally obey the Ostwald Step Rule. Bedding-parallel microfabric generated by these reactions produce significant changes in the physical properties of deeply buried mudrocks. Clay minerals react to form equilibrium assemblages in 1 × 104 years in some hydrothermal systems, but immature clays may survive for up to 2 × 109 years in mid-continental rift basins. Clay mineral assemblages and the b cell dimension of K-white mica can be used to infer the geotectonic settings of sedimentary basins.

Volcanogenic clays in Jurassic and Cretaceous strata of England and the North Sea basin

Abstract The nature and origin of authigenic clay minerals and silicate cements in the Jurassic and Cretaceous sediments of England and the North Sea are discussed in relation to penecontemporaneous volcanism in and around the North Sea Basin. Evidence, including new REE data, suggests that the authigenic clay minerals represent the argillization of volcanic ash under varying diagenetic conditions, and that volcanic ash is a likely source for at least the early silicate cements in many sandstones. The nature and origin of smectite-rich, glauconite-rich, berthierine-rich and kaolin-rich volcanogenic clay mineral deposits are discussed. Two patterns of volcanogenic clay minerals facies are described. Pattern A is related to ash argillization in the non-marine and marine environments. Pattern B is developed by the argillization of ash concentrated in the sand and silt facies belts in the seas bordering ash-covered islands and massifs. It is associated with regression/ transgression cycles which may be related to thermal doming and associated volcanism, including the submarine release of hydrothermal fluids rich in Fe. The apparent paucity of volcanogenic clay deposits in the Jurasssic and Early Cretaceous sediments of the North Sea is discussed.

The diagenetic to low-grade metamorphic evolution of matrix white micas in the system muscovite-paragonite in a mudrock from central Wales, United Kingdom

Two orientations of white micas with subordinate chlorite have been observed in a fine-grained (50 Å to 2μm) 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.

Precise dating of low-temperature deformation: Strain-fringe analysis by 40Ar-39Ar laser microprobe

Pyritized graptolites from the Welsh Basin (United Kingdom) slate belt acted as rigid bodies during cleavage formation, and epizonal white micas formed within the resulting. strain shadows, orthogonal to the principal stress orientation. Although the quantities of mica are small, they are a pure synkinematic mineral and have been dated by Ar-40-Ar-39 infrared laser microprobe as a means to dating cleavage. Four samples of strain-fringe mica from different hand samples yielded ages ranging from 394.4 +/- 3.1 to 397.8 +/- 1.8 Ma (2sigma), with a mean age of 396.1 +/- 1.4 Ma (2sigma). By focusing on minerals that are unequivocally synkinematic, this technique provides a novel solution to the problems of isotopically dating slaty cleavage. Previous studies have predominantly relied on dating whole-rock slate samples or separated illite grains by Ar-40-Ar-39 techniques; problems encountered included (1) separating the effects of isotopic contamination by detrital phases, (2) Ar-39 loss during the irradiation of illite mineral separates, and (3) thermally induced Ar-40 loss in nature from fine-grained minerals. By circumventing these problems, this new method provides the first unequivocal and high-precision age data for Acadian deformation in the well-characterized Welsh Basin slate belt. With such precision, the method may afford geologists the opportunity to track tectonic fronts across orogens and assess the rates of accretion processes in areas that are peripheral to sites of continent-continent collision.

The influence of strain, lithology and stratigraphical depth on white mica (illite) crystallinity in mudrocks from the vicinity of the Corris slate belt, Wales; implications for the timing of metamorphism in the Welsh Basin

Low and very low grade metamorphism in a mudrock-dominated succession, ranging from Upper Cambrian to Wenlock, is characterized by the white mica (illite) crystallinity technique. Kubler indices indicate that grade ranges from late diagenetic to low epizonal. The prograde reaction most easily observed by XRD study is the progressive ordering of K/Na micas; diagnostic 2M 1 polytypic reflections become recognizable at 0.4 Δ 2θ and strengthen as grade advances. Grade generally correlates with thickness of overburden in the > 9 km thick succession. However, strain exercises additionally a profound influence on grade, and the distribution of strain was related to decollement resulting from inhomogeneities and ductility contrasts within the succession. Strain energy is seen as an additional and important variable in the development of white mica crystallinity in slates. The distribution of metamorphic grade implies that the Lower Palaeozoic succession was augmented by several kilometres of Lower Devonian (Old Red Sandstone) strata at the metamorphic culmination. The culmination was syntectonic and represents an Acadian rather than an early diastathermal event. Subsequent dextral movement on the Bala Fault displaced the regional isocryst pattern by c. 4 km. Retrogressive smectite appears to be localized to the vicinity of the Bala Fault and is probably of Variscan age.