The Maungaparerua halloysite deposit is located on the North Island of New Zealand some 210 km north of Auckland. The halloysite deposit was formed by hydrothermal alteration of rhyolite flow rocks. Superimposed on the hydrothermally altered halloysite is deep intensive surficial weathering resulting from the humid climate on the extreme tip of the North Island. The deposit has been drilled and the cores have been analyzed mineralogically and chemically. Drilling has shown that the deposit is circular or ovate and covers about 350 acres. The altered rocks contain about 50% quartz and fine amorphous silica and 50% of a mix of halloysite, kaolinite, and allophane with a small amount of plagioclase feldspar in the coarse fraction. The upper 8–30m, with an average of 15m, of the halloysite alteration deposit consists of relatively soft clay. Below this soft clay, which is the result of intense surficial weathering, the clay becomes hard and dense. The halloysite and kaolin from this deposit are mined and beneficiated using wet process techniques of dispersion, centrifugation, leaching, dewatering, and drying. The products are used as filler in paper, paint, and plastics and as a ceramic raw material for producing whiteware and fine china. This deposit is unique in that it contains a very high proportion of halloysite in the clay fraction. The detailed geology, mineralogy, geochemistry, and the physical properties of the clay will be discussed.

Previous applications of the method of known additions for quantitative X-ray fluorescent analysis have assumed a linear relationship between peak intensity and concentration of the element being analyzed. This assumption is true for soils or sediments containing small amounts of the element in question. In this paper, an equation is derived which takes into account both absorption and enhancement and thus is applicable to samples containing high concentrations of the element. The equation was tested by analyzing an artificial soil sample containing 60% kaolinite and 40% hematite, i.e. the sample contained 28% by weight iron. The fluorescent analysis utilizing the equation derived here resulted in an iron content of 27%. In addition, nine soils from Hawaii were analyzed by this method and the results of these analyses compared with analyses by atomic absorption. The agreement between the two methods is good. It is concluded that the method and equations proposed here provides a reliable measurement of elements in a soil sample which contains high concentrations of the elements in question.

The sedimentary rocks of the Taconic Cow Head klippe contain three clay-mineral suites of progressively younger stratigraphic occurrence. An illite—14A chlorite suite is the oldest, occurring in the Middle Cambrian to early Lower Ordovician part of the 310-m Cow Head Breccia. These earliest clays were transported from the stable craton and shelf, slowly accumulating during 70 x 106 yr on the continental slope in limestone breccia, green and gray shale, and argillaceous limestone. The illite and 14A chlorite are judged to be largely detrital. An illite-expandable chlorite suite is in early to late Lower Ordovician limestone breccia, green and gray shale, and argillaceous limestone of the Cow Head Breccia. A corrensite-illite-smectite suite of late Lower to Middle Ordovician age occurs in the Cow Head Breccia and throughout the overlying 200-m ‘Red Shale’ and the more than 400-m ‘Green Sandstone’ flysch sequence of volcanogenic sandstone and gray shale. Beginning in the early Lower Ordovician, increasing amounts of Mg2+-rich volcanic detritus were rapidly transported westward from a developing volcanic island arc in central Newfoundland. During burial metamorphism, volcanic materials and their alteration products reacted to form the illite-smectite with 5–10% expandable layers plus corrensite or expandable chlorite found in the younger two clay-mineral suites.

A method for the determination of the cations of Na, K, Mg and Ca adsorbed on clay minerals mixed with CaCO3 and MgCO3 is described. An ethanolic solution of LiCl-CsCl is used to displace the exchangeable cations. Blank determinations performed using either a second ethanolic leach or a second LiCl-CsCl leach, are used to correct for carbonate dissolution. Details of the methods development are given.

The method has been tested using mixtures of homoionic forms (Na, K, Mg, Ca) of smectite and kaolinite with either CaCO3 or MgCO3. The smectite and kaolinite were found to have total CECs (with standard deviations) of 765 (4.4) and 39.8 (0.52) mequiv kg−1, respectively. The amount of cation exchanged was found to vary directly with the proportion of clay mineral in the mixture; regression coefficients consistently greater than 0.997 were obtained.

Other tests with smectite-CaCO3 mixtures in sea-waters of various salinity vindicated the use of the method with heteroionic forms of smectite. These tests also suggest that the phenomenon of fixation observed in most other studies of clay minerals in estuarine conditions might be redundant. It is contended that there is an urgent need for this suggestion to be tested.

Scan electron micrographs (SEMs), are shown of three representative types of Georgia kaolin: ‘soft’, Cretaceous-age clay; ‘hard’, fine-grained clay; and ‘flint kaolin’.

Sparta Granite and a thick deposit of its overlying saprolite are taken to serve as examples of probable source rock for Georgia kaolin. SEMs are presented to show sequential argillation of this fresh granite through a transition zone to the saprolite. The saprolite contains abundant books of kaolinite similar to those occurring in Cretaceous kaolin, accompanied by some elongates, whereas in the transition zone elongates are predominant. A morphologic type of fibrous, elongate 1:1 clay mineral, hitherto not illustrated, is shown from kaolinizing Sparta Granite, and from Pre-Cambrian saprolitic gneiss 25 km south of Athens, GA.

Whereas kaolin elongates originated in contact with feldspar in the Sparta transition zone, well-formed books of kaolinite are shown to have been formed in contact with feldspar in the saprolite from a Missouri granite. The arkose above the granite in the Missouri occurrence has altered to loosely packed books of kaolinite. The interpretation is made that book-type kaolinite, where it occurs in large deposits of saprolite or kaolin, was formed under geochemical conditions of relative chemical stability between kaolinite and feldspar, as might prevail in a geological ‘weathering crust’. It is interpreted that elongate kaolin morphology may be formed under conditions of limited or lesser geochemical stability.

SEMs show that the established book-morphology of Sparta saprolite is disarranged during secondary Holocene surface weathering and pedogenic processing.

SEMs show that books of kaolinite, although individually fragile, may be protected from destruction or delamination during artificial blunging and transport when moved within naturally coalesced pellets. Possibly original books of weathered kaolinite might similarly survive natural stream transport during sedimentational processes.

Some ‘flint kaolin’ contains molds of sponge spicules coated with low-cristobalite.

The optical spectra of Cu2+ and Ni2+ on Camp Berteau montmorillonite after lyophilization and evacuation at room temperature are characteristic for the presence of Cu(H2O)42+ and Ni(H2O)62+ in the interlamellar space. The most probable ligand field parameters for Cu(H2O)2+4 are Dqxy = 1310 cm−1, Ds = 1807 cm−1 and Dt = 664cm−1. The covalent character of the Cu2+-OH2 bond is not negligible as indicated by the orbital reduction factors k∣∣2 = 0.66 and k⊥2 = 0.76. This is also the case for Ni(H2O)62+ which is characterized by a ligand field strength, Dq = 850 cm−1 and an electronic repulsion parameter B = 920 cm−1. After desorption in vacuum the optical spectra of Cu2+ were poorly resolved, while Ni2+ was present partially as (Ol)3Ni2+, partially as (Ol)3Ni-OH2 where Ol means an oxygen of the hexagonal rings in the tetrahedral layers.

Previous studies by Electron Spin Resonance (ESR) have established the substitution of Fe3+ and Mg2+ in the kaolinite structure. It is shown that Fe2+ can substitute in kaolinite and stabilize defects which are detectable by ESR in a manner identical to Mg2+. The development of methods of preparing a synthetic kaolinite doped with Fe2+ is described in detail. It is shown that the main ESR signals, which occur at g = 2.0 in natural kaolinites and which previously have been interpreted in terms of iron and magnesium, can be attributed to iron alone.

Almost four decades of study of Desmoinesian strata of Middle Pennsylvanian age in south-central Iowa and north-central Missouri have provided the stratigraphic control required to test the variation of clay mineralogy vertically and laterally within various paralic clay and shale facies. Local and regional variations in clay mineralogy within Desmoinesian strata are generally predictable and are in agreement with current knowledge of deltaic deposition. A principal environmental variation within a deltaic system is the change from normal marine salinities in deltaic marine environments to brackish- and fresh-water conditions in the marshy delta plains, in upper interdistributary bays, and within flanking interdeltaic embayments. Changes from marine to nonmarine facies coincide with a decrease in illite, and an increase in kaolin, mixed-layer clays, and in the percentage of expansible layers in the mixed-layer clay. The principal clay detritus entering the area was illite, which underwent various degrees of alteration in different aqueous and subaerial environments within deltaic and interdeltaic areas. Clay-mineral composition alone does not provide unique environmental answers. The distribution of clay-mineral suites within these systems, however, both supports the deltaic-interdeltaic depositional model and can be understood within the context of this framework.

The effect of heat treatment on surface area, pore volume, pore size distribution, physical and chemical structure up to 700°C have been studied on samples of naturally occurring chrysotile minerals from California and Quebec. Techniques used included thermogravimetric analysis, low-temperature nitrogen adsorption, electron microscopy, X-ray powder and electron diffraction. The materials behaved similarly on heating to 100°C showing a 0.5% weight loss attributable to desorption of physisorbed water. At 500°C, Quebec samples retained the chrysotile crystal structure while Californian samples were X-ray amorphous. Forsterite was formed by dehydration of both chrysotiles at 700°C; the greater stability of the Quebec samples to this process is explained by the presence of brucite as an impurity which enters into stray solid-solid interactions with the chrysotile.

Scan electron micrographs are shown of the textures of flint clays, tonsteins, kaolin associated with combustion-metamorphism, sedimentary kaolin, and dickite from the Sydney Basin of Australia. The textures of the flint clays and tonsteins indicate those clays were derived largely from volcanic products. The clay samples were collected at stops on the Kaolin Excursion No. 4 of the August, 1976, International Geological Congress.

In like manner, kaolin samples were collected in Japan from stops made on the field excursions of the Seventh Conference of the Committee on Correlation of Age and Genesis of Kaolin which met in Tokyo, September, 1976. SEMs illustrate representative kaolins of Japan, including Gaerome and Kibushi types of kaolin, Roseki (‘wax stone’) pyrophyllite and dickite, hydrothermal kaolin at Itaya, and flint clay at Iwate. Varied morphologies of halloysite, including spherical halloysite, from the Yamaka open-pit at Naegi are micrographed.

Word descriptions of the textures are frustratingly inadequate in comparison to what may be seen at a glance in the micrographs—hence, the abstract becomes in reality a rapid view of the SEMs.

The adsorption of nitroxide spin probes on smectites solvated in liquids of greatly different polarity was studied using electron spin resonance (ESR) spectroscopy. Adsorbed probes demonstrate various degrees of restricted rotational motion and alignment at the silicate surfaces, depending upon the properties of the solvating liquid. The results are interpreted in terms of direct surface—molecule interaction modified by solvent competition effects. A fraction of the probe molecules is immobilized in many of the solvated clays because of small spacings between platelets. The data indicate lowered reactivity of surface-adsorbed molecules, especially in the case of hydrated smectites.

Various kaolinites, a dickite and halloysites have been treated by DMSO in presence of D2O and subsequently washed by D2O. This procedure allowed to record OD stretching bands which are due specifically to the intercalated fraction and, for the washed samples, to the fraction of the solid which has been intercalated and has subsequently collapsed.

No structural difference is found between the intercalated materials prepared from the various minerals. Washing usually restores the starting mineral; however, for a non-tubular halloysite, DMSO intercalation and subsequent washing gave a product similar to kaolinite.

The hydrolysis of aluminum-tri-(sec-butoxide), ASB, in ionic and nonionic media is shown to be a useful method for the synthesis of aluminum minerals. Infrared and X-ray analysis were used to identify the reaction products. Pseudoboehmite is formed at low water to aluminum ratios. At higher water content, transformation of pseudoboehmite occurs with bayerite as the final phase. Dawsonite-type minerals are produced when ASB is hydrolyzed in the presence of sodium, potassium, or ammonium bicarbonate. Infrared evidence suggests that the carbonate group is more perturbed than indicated by the proposed crystal structure. A compound with a structure like the pyoaurite-sjögrenite group was obtained when ASB reacted with a lithium carbonate solution. The infrared spectrum indicates the possible existence of bicarbonate and carbonate ions between the brucite-like layers.

Hydrotalcite-like compounds [MgI − xAlx(OH)2]x+ [A2−x/2, mH2O]x−, where A2− is SO42− or CrO42− and x ≇ 0.25, were prepared by a coprecipitation method and their physico-chemical properties were studied by X-ray diffraction, thermal analysis, i.r. absorption spectra and acidity-basicity measurement.

The compounds including SO42− and CrO42− were analogous to an orthorhombic hydrotalcite and the lattice constants, a0 and c0 were 3.05 and 25.97 Å, and 3.05 and 26.48 Å, respectively. The crystallite size and strain in the 003 direction were 127 Å and 4.77 × 10−2 for the SO42− system or 83 Å and 6.60 × 10−2 for the CrO42− system, indicating a largely distorted microcrystallite. Two endothermic peaks observed at 240 and 455°C for the SO42− system and at 230 and 460°C for the CrO42− system are ascribed to the eliminations of interlayer water (mH2O) and structural water, respectively. The compound including SO42− formed MgO by calcination at 500°C and MgSO4 and MgAl2O4 by calcination at 800°C while the compound including CrO42− formed MgO at 400°C and MgAl2 − xCrxO4 at 800° I.r. study of the SO42− compound indicated that the bonding of SO42− was a bridge type. The highest acid and base strengths of the SO42− compound were H0 ≤ 1.5 and H− ≥ 12.2, the acidity and basicity being 0.3 and 0.1 mmol/g, respectively.

A series of chloro-alkylammonium montmorillonites was produced by cation exchange from Na+-montmorillonite. Gas chromatographic data were obtained for light hydrocarbons and certain oxides of nitrogen. Surface area and X-ray powder diffraction studies were made on each organo-clay, making possible differentiation between possible chromatographic pathways. Adsorption of the gas molecules on the silicate sheet was determined to be the dominant chromatographic pathway for all gases studied.

New and published experimental data on hydrothermally treated (2-kbar water pressure, 300–400°C natural clay minerals is used to construct phase diagrams in composition and pressure-temperature space which define the phase relations of mixed layering solid solution in dioctahedral (illite-montmorillonite) and trioctahedral expanding chlorite and corrensite-like minerals. Three major relations are established:

1. (1) The R3+, i.e. Al13+ and/or Fe3+, content of the assemblage will control whether or not an expanding chlorite or corrensite phase will appear. These minerals are R3+-rich in composition as well as R2+ (Mg and Fe2+)-rich.

2. (2) Temperature-pressure variables control the type and composition of the mixed layered illite-montmorillonite mineral which is stable with aluminous phases. A sequence of different types of mixed layered ordering can be established which might be correlated with diagenetic or epimetamorphic grade.

3. (3) The presence of ‘metamorphic’ trioctahedral phyllosilicate phases, i.e. those due to the effects of earliest metamorphism, is correlated with the P-T-X variables. These phases include 7 Å chlorite (iron-rich), 14 Å chlorite and the expanding chlorite and corrensite-like minerals.

It is not possible to give absolute temperatures for the different reactions implied by the phase diagram due to the slow rate of crystallization in the experiments. However, the general sequence of assemblages and the phase relations proposed should correspond to those which are encountered in nature when pressure and temperature vary.

A study was undertaken to investigate the adsorption of hemin, protoporphyrin and hematoporphyrin by kaolinite and a Ca-montmorillonite in aqueous solutions buffered at pH 4 and 9.

Although experimental restrictions at pH 4 prevented the complete characterization of the adsorption isotherms, kaolinite did exhibit a saturation of exchange sites by the cationic porphyrins. Both kaolinite and montmorillonite displayed a similar saturation of sites by the porphyrins in their anionic forms at pH 9. The major differences in the adsorption isotherms are attributed to differences in the exchange capacities of the clays.

Adsorption of the porphyrins at pH 9 was inhibited largely by phosphate treatment of the clays; this effect is interpreted as blockage of the anion exchange sites by irreversibly-bound phosphate.

Crystallographic properties of illite and chemical properties of organic matter in various mudstones ranging in age from Archean to Miocene were investigated. The breadth of the (001) X-ray powder diffraction peak of illite correlates significantly with the ratio of aliphatic to condensed-aromatic components and the degree of condensation of aromatic rings of the polar (“humic”) fraction of extract-able bituminous organic matter. The broader the diffraction peak, the less highly condensed and aromatic (i.e. less highly humified) is the organic matter associated with the illite. Breadth of illite diffraction peak and degree of humification of polar organic matter vary in a complex and apparently systematic way through geologic time. All of the three different suites of mudstones investigated (“calcareous,” “non-calcareous,” and “glacial” mudstones) gave similar patterns of secular variation. In addition, the ratio of diffraction intensities for the (002) and (001) reflections (I002/I001) of illite in calcareous mudstones and limestones showed a strong negative correlation with geologic age, indicating that the illites in the older rocks are enriched in magnesium with respect to aluminum.

The correlation between crystal structure of illite and degree of humification of its associated organic matter could, by itself, be interpreted as an effect of post-depositional maturation processes, whereby “crystallinity” and degree of humification both increased as functions of heat and pressure. However, the patterns of secular variation suggest that the observed variations are primary, or were pre-determined by primary characteristics of the sample materials. The possibility that the original structure and composition of the organic matter influenced post-depositional changes in the crystallographic properties of sedimentary clay minerals, or post-depositional genesis of clay, would seem to merit consideration. The demonstrated relationship between crystallographic properties of illite and the nature of the “humic” matter constitutes evidence that most of the extractable organic matter is truly indigenous to the rock in which it occurs. The results also imply that molecular structure of extractable organic matter can be used in place of the breadth of the (001) diffraction peak of illite as an index of incipient metamorphism within a single formation or stratigraphic sequence, provided the primary characteristics of the organic matter are nearly the same in all samples. This method would have the advantage of being applicable to all sediments, not just those containing illite (specifically, aluminum-rich illite).

The secular variation of the I002/I001 ratio of illite in calcareous sediments is provisionally ascribed to diagenetic processes whereby magnesium is abstracted from pore water and groundwater and is gradually assimilated into the crystal structure.

While studying the retention of additives used in tertiary recovery of petroleum (waterflooding) on minerals present in a rock reservoir, an investigation has been undertaken into the adsorption mechanism of Polyacrylamides on to clays. The adsorption of amides and Polyacrylamides takes place exclusively on the external surfaces of the clay particles. The organic molecules are protonated on the surface and adsorbed by ionic forces. There is a linear relationship between the adsorption ratio and the polarizing power of the exchangeable cations of the clay mineral. The adsorption isotherms and the thermal analyses reveal the existence of two adsorption mechanisms: (i) a strong, irreversible adsorption, which corresponds to the formation of a monolayer of chemisorbed molecules, (ii) a more important adsorption of molecules retained by hydrogen bonding, which can be eliminated by heating at low temperature. The retention ratio in the irreversible process, which is practically identical both for acetamide and Polyacrylamide, is low (3 mg/g). It depends on the external cation exchange capacity (CEC) of the mineral and increases with the surface area. The Polyacrylamide adsorption depends on the physico-chemical characteristics of the macromolecule, more particularly on the CONH2/COO−ratio, which determines the extent of the carbon chain, and the molecular weight. The accessibility of the organic macromolecule to the clay particle is controlled by the preceding factors. The quantity of Polyacrylamide irreversibly adsorbed by clay minerals is important in the context of the use of the polymer on a petroleum field. It may be reduced to a minimum by working at low concentrations with a weakly hydrolyzed Polyacrylamide solution.

Mössbauer spectra of 15 smectites were investigated. In these samples, ferric iron occupies both M(1) and M(2) octahedral sites, the distribution being partly determined by the relative covalency of the bonds formed.

The quadrupole splittings are linearly related to b−3. They show that Fe3+ octahedra are much more distorted in montmorillonite and beidellite than in nontronite and volkonskoite and that M(1) sites are more prone to change than M(2). Ferrous iron occurs in relatively undistorted octahedra in some otherwise distorted octahedral sheets and vice versa.