Fine-grained biotite crystals within primary actinolite from a quartz monzonite body of the Bingham Canyon porphyry copper deposit, Utah, consist of 1M, 5M1, and 1Md polytype structures. HRTEM images directly show the stacking sequences of ordered biotite polytypes, stacking faults in ordered polytypes, and stacking sequences in disordered polytypes, if the stacking vectors for the 2:1 layers involve only 0° and ± 120° rotations. The most common type of stacking fault in the 1M biotite is a layer with −120° rotation, followed by a layer with +120° rotation, which corresponds to one unit cell of the 2M1 polytype inserted in the 1M structure. Disordered (or semi-random) biotite is composed primarily of thin domains of the 1M and 2M1 polytypes, with stacking faults. The structure of a new 5-layer (5M1) polytype has been determined from SAED and HRTEM results. The stacking sequence of the polytype is [02022].

A model of structural oscillation among 1M, 2M1, and 3T structural states is proposed to interpret nonperiodic stacking sequences in biotite crystals formed during non-equilibrium crystallization. The model also provides qualitative insights into the structure of complex long-period polytypes and may help to explain intergrowths of ordered and disordered polytypes that form during crystallization far from the equilibrium state.

Along the inner Coastal Plain, kaolinite-metahalloysite-rich, neritic muds of Cretaceous-Eocene age have undergone intense postdepositional alteration in the recharge area of the regional groundwater system. Weathering processes have had the following profound effects on the original sediments: 1) strong compositional and textural modification of both clay and non-clay minerals; 2) whitening of the originally darker sediments by partial removal of organic matter, Fe and Mn; and 3) recrystallization of kaolinite and metahalloysite, most conspicuous where there are coarse stacks and vermiforms. Where the combination of initial sediment composition and alteration intensity was most favorable, these changes have produced important deposits of commercial quality, which now sustain the world's largest kaolin production district. The earliest change was partial sequestration of iron as sulfide and concurrent destruction of some organic matter, mediated by sulfate-reducing bacteria. Subsequent weathering resulted in gradual leaching of alkalies, alkaline earths, iron and silica, and attendant nucleation and growth of minerals compatible with the compositional changes. The existence of several closely spaced erosional unconformities, separated by neritic sediments, is proof that weathering conditions commonly changed at a given site, in response to changes in thickness or lithology of the overlying rocks. Dsyoxic → ← oxic reversals modified both the rate and kind of alteration. (“Dysoxic” refers to molecular oxygen concentration too low to be toxic to anaerobes or cause abiotic oxidation; less extreme than “anoxic”.) Kaolins were produced partly by slower dysoxic weathering in saturated groundwater zones but mainly by more rapid oxic weathering in unsaturated zones, where bauxites also locally formed. Gradual transformation of some sediments to kaolin rarely began and ended in the same epoch. At several places most of the kaolinization (see “Definitions”) took place during Recent time, tens of millions of years after deposition of the sediments. Since the kaolins resulted from postdepositional alteration rather than sedimentary processes, they are better referred to as “Coastal Plain” rather than “sedimentary” kaolins.

The clay mineralogy of tuffs from Yucca Mountain, Nevada, the potential site of the nation's first high-level radioactive waste repository, has been studied in order to understand the alteration history of the rocks and to predict potential future alterations. Bulk-rock samples and clay-mineral separates from three drill holes at Yucca Mountain (USW G-1, USW G-2, and USW GU-3/G-3) were studied using X-ray powder diffraction, and supporting temperature information was obtained using fluid inclusion data from calcite. Twelve K/Ar dates were obtained on illite/smectite (I/S) separated from the tuffs from the two northernmost drill holes, USW G-1 and G-2. The predominant clay minerals in the Yucca Mountain tuffs are interstratified I/S, with minor amounts of chlorite and interstratified chlorite/smectite. The I/S reactions observed as a function of depth are similar to those observed for pelitic rocks; I/S transforms from R = 0 interstratifications through R = 1 and R ≥ 3 interstratifications to illite in USW G-2 and to R ≥ 3 I/S in USW G-1. The R = 0 I/S clays in USW GU-3/G-3 have not significantly transformed. K/Ar dates for the I/S samples average 10.4 my. These data suggest that the rocks at depth in the northern portion of Yucca Mountain were altered 10.0-11 my ago, soon after creation of the Timber Mountain caldera to the north. Both I/S geothermometry and fluid inclusion data suggest that the rocks at depth in USW G-2 were subjected to postdepositional temperatures of at least 275°C, those in USW G-1 reached 200°C, and rocks from USW GU-3/G-3 probably did not exceed 100°C. These data suggest that no significant hydrothermal alteration has occurred since Timber Mountain time, ~ 10.7 my ago.

Estimates of the temperature of formation of illite/smectites yield probable stability limits for several minerals at Yucca Mountain. Clinoptilolite apparently became unstable at about 100°C, mordenite was not a major phase above 130°C, and analcime transformed to albite above 175°-200°C. It appears that cristobalite transformed to quartz at 90°-100°C in USW G-2 but must have reacted at considerably lower temperatures (and for longer times) in USW GU-3/G-3. The reactions with increasing depth appear coupled, and clinoptilolite and cristobalite disappear approximately simultaneously, supporting aqueous silica activity as a controlling variable in the clinoptilolite-to-analcime reaction. The reaction of clinoptilolite to analcime also coincides with the appearance of calcite, chlorite, and interstratified chlorite/smectite. Although the hydrothermal fluids may have been a source for some cations, breakdown of clinoptilolite (and mordenite) probably provided the source of some of the Ca for calcite, Mg for chlorite, K for the I/S found deeper in the section, and Na for analcime and albite.

Using the rocks in USW G-1, G-2, and GU/G-3 as natural analogs to repository-induced thermal alteration suggests that the bulk of the clinoptilolite- and mordenite-bearing rocks in Yucca Mountain will not react to less sorptive phases such as analcime over the required lifetime of the potential repository. The zeolites in zeolite interval I, directly underlying the proposed repository horizon, may transform at the predicted repository temperatures. However, the reaction of clinoptilolite to analcime in interval I may require the transformation of all of the abundant opal-CT and glass to quartz, an unlikely scenario considering the unsaturated nature of these rocks and the predicted temperatures of <100°C.

A synergistic mechanism for the retention of organic and inorganic pollutants in clays is discussed in this paper. The mechanism of adsorption of cis- or trans- 1,2-dichloroethylene vapor (CDE or TDE, respectively) by hydrated smectite clay (hectorite) exchanged with Pb2+, Hg2+, Cd2+, Ca2+, Ag+, or Na+ has been investigated by simultaneously measuring chlorohydrocarbon uptake and water desorption isotherm and by recording the infrared (IR) spectrum of the adsorbed phase. Hydrated hectorite saturated with divalent cations adsorbs about 55% more CDE or 35% more TDE than those saturated with monovalent cations. The quantity of chlorohydrocarbon adsorbed is also a function of the hydration of the clay interlayer space. When dehydrated, hectorite does not adsorb CDE or TDE. Upon long outgassing at room temperature or even at 100°C, the characteristic IR bands of clays with adsorbed chlorohydrocarbon, although much weakened, are still observable. The ratio of the amount of water desorbed to the amount of chlorohydrocarbon adsorbed varied from about 0.22 to 0.34. A shift of the center of gravity of the hydration water OH stretching frequency towards a higher wavenumber and of the asymmetric CC1 stretching vibration toward a lower frequency suggest that the formation of hydrogen bonds between CDE or TDE and water is the driving force for adsorption and that the cation-dipole interaction does not play a major role.

The rapid phase quantification method using X-ray diffraction (XRD) with a position-sensitive detector (PSD), outlined by Cressey and Schofield (1996), has been extended to facilitate mineral phase quantification of clay-bearing samples. In addition, correction factors for differences in matrix absorption effects have been calculated and applied. The method now enables mudrock mineralogy to be quantified rapidly and efficiently. Using this approach overcomes many of the problems hitherto associated with the quantitative analysis of clay minerals, in particular the effects of preferred orientation of crystallites and variable sample-area irradiation, that make the task of quantification extremely difficult by conventional Bragg-Brentano scanning diffractometry.

Chlorite and illite are commonly associated with ubiquitous secondary K-rich feldspar in the rocks located immediately above and below the Precambrian-Paleozoic unconformity in southwestern Ontario, and elsewhere in the mid-continent of North America. This alteration assemblage is attributed to long-distance migration of hot brines driven westward by orogenic processes originating along the eastern seaboard of North America. The δD and δ18O values of chlorite and illite, plus K-Ar dates for secondary K-rich feldspar and illite, were used to determine the nature, origin, and timing of the fluids that altered Precambrian granites and their overlying rocks in southwestern Ontario. The δ18O values of the chlorite-forming fluids are best explained by initial hot brines (≥50°C) evolved mostly from seawater. Secondary K-rich feldspar formation followed shortly thereafter, as the fluids cooled and perhaps mixed with meteoric water. Regional migration of the brines was induced by Taconic orogenic events to the east. The hydrogen and oxygen isotopic compositions for the secondary illite of the early to mid-Carboniferous indicate its crystallization from local meteoric water at low temperatures (40–55°C). Infiltration of local meteoric water into the Paleozoic and uppermost altered Precambrian rocks occurred during uplift, erosion, and subaerial exposure of local arches in southern Ontario. The local basement reactivation and associated secondary illite formation in this portion of the North American hinterland was likely a distal expression of east-coast Acadian and Alleghanian orogenic activity.

The influence of tartaric acid and pH on chemical composition, morphology, surface area, and porosity of short-range ordered Al precipitation products was studied. Samples were prepared (1) at pH 8.0 and at the tartaric acid/Al molar ratios (R) ranging from 0 to 0.25 and (2) at R = 0.1 and in the pH range of 4.7 to 10.0. In Al precipitation products formed at pH 8.0, the organic C content increased from 8 g/kg (R = 0.01) to 93 g/kg (R = 0.25), whereas the Al content decreased from 363 g/kg (R = 0.01) to 271 g/kg (R = 0.25). The specific surface of the materials was particularly high (>400 m2/g) when samples were prepared at R < 0.1, but drastically decreased when samples were prepared at R > 0.1 (e.g., 78.6 m2/g at R = 0.25). When the C content was relatively high (>45 g/kg), aggregation between the particles was promoted, and the specific surface, thus, decreased. Electron optical observations showed that such samples were strongly aggregated. In the materials prepared at R = 0.1, but at different initial pH values, the C content decreased from 90 g/kg (pH = 4.7) to 25 g/kg (pH = 10.0). As a consequence, the lower the initial pH, the lower was the specific surface of the Al precipitation products. Tartaric acid plays an important role in both Pertubation of crystallization of Al hydroxides and promotion of aggregation of the reaction products. The two processes counteract in influencing the specific surface and pore volume of Al hydroxides.

Heating treatments greatly affected the specific surface and porosity of Al precipitation products. The specific surface and porosity of the samples generally increased by increasing the temperature up to 400°C and then decreased. Small amounts of C still remained after heating some samples for 12 hr at 600°C.

Nontronite and microbes were detected in the surface layers of deep-sea sediments from Iheya Basin, Okinawa Trough, Japan. Nontronite, an Fe-rich smectite mineral, was embedded in acidic polysaccharides that were exuded by microbial cells and electron microscopy showed that the nontronite layers were apparently oriented in the polysaccharide materials. We propose that the formation of nontronite was induced by the accumulation of Si and Fe ions from the ambient seawater and that extracellular polymeric substances (EPS) served as a template for layer-silicate synthesis. Experimental evidence for this hypothesis was obtained by mixing a solution of polysaccharides (dextrin and pectin) with ferrosiliceous groundwater. After stirring the mixture in a sealed vessel for two days, and centrifuging, Fe-rich layer silicates were identified within the precipitate of both the dextrin and pectin aggregates, whereas rod-shaped or spheroidal Si-bearing iron hydroxides were found in the external solution. Microbial polysaccharides would appear to have affected layer-silicate formation.

An indirect Fourier transformation applied to small-angle X-ray scattering data has been used to determine the thickness and surface properties of two common clay minerals. For an illite system, the particle density distribution function (PDDF) generated by the analysis gave a correct description of particle geometry, and the calculated electron density profile was in accordance with the theoretical electron density distribution for this mineral. This approach provides the opportunity to determine the thickness of fundamental particles of illite while avoiding the difficulties encountered in other methods. Both the PDDF and the electron density profile accurately predict the thickness of Na-montmorillonite layers, and the results suggest that an electron inhomogeneity exists at the interface of this mineral.

57Fe Mössbauer spectra of two synthetic samples of ferrihydrite, recorded at 4.2 K in applied fields of up to 9 T, have been analysed by a mean-field model. The samples exhibit two and six X-ray diffraction peaks. It is shown that only one ferric ion site is present in the mineral, and that in this site the ions are octahedrally coordinated. The spectra show the presence of different magnetic states: ferrimagnetism in two-line ferrihydrite, and antiferromagnetism in six-line ferrihydrite. The ferrimagnetism in two-line ferrihydrite is analysed in terms of random fluctuations arising from the small numbers of ferric ions per particle, and it is shown that the different magnetic states may arise purely as a result of these fluctuations.

Authigenic chlorites and illites coexisting in clastic reservoir sandstones have been studied by energy dispersive X-ray spectroscopy (EDS) in the transmission electron microscope (TEM). All 16 samples studied are drill or sidewall cores from sandstones of relatively uniform age situated offshore Norway with burial depths ranging between 2400 m and 5000 m and representing temperatures between 90°C and 180°C. Chlorites and illites with authigenic equilibrium type texture and morphology were analyzed by EDS. Tetrahedral Al and octahedral Fe+Mg in chlorite increases with burial at the expense of Si and vacant octahedral positions in the chlorite structure. Illites show a clear increase in K. These factors indicate that a continuous chemical modification of these minerals takes place in the diagenetic interval studied through continuous dissolution and precipitation reactions.

Laboratory-hydrolyzed and commercial OH-Al solutions were characterized using kinetics of Al-ferron color development, kinetics of structural OH neutralization with H+, 27Al NMR spectroscopy, and sulfate precipitation. The results showed that the Al13 complexes having the Keggin structure were dominant only in fresh, laboratory-hydrolyzed OH-Al solutions of OH/Al molar ratio = 1.8 and above. These species gradually converted to other polynuclear forms that reacted with ferron slowly, were not detectable by 27Al NMR spectroscopy, and yielded different basic Al sulfates following Na2SO4 addition. These more stable complexes can best be interpreted to have a Al(OH)3-fragment structure. In the three commercial aluminum chlorohydrate (ACH) solutions studied, Al13 complexes accounted for a small portion of the total Al present. More than 80% of the Al was present as species that were not detectable with NMR spectroscopy and resembled the slow-reacting complexes in aged, laboratory-hydrolyzed OH-Al solutions. Small portions of the slow-reacting complexes appeared to be submicron particulates that acted as nuclei for gibbsite formation or aggregates of Al13 complexes that dispersed to Al13 upon dilution. Polyaluminum chloride (PA) solution resembled the moderately aged laboratory-hydrolyzed OH-Al solutions.

The chemical composition of hydrothermal chlorite was determined by means of more than 200 electron microprobe analyses (EMPA) in almost all of the 70 chlorite-bearing samples taken from 5 boreholes in a study of the active geothermal system of Los Humeros, Mexico. Bulk rock composition of 6 different volcanic lithologies, as well as available in situ temperatures and chemical compositions of chlorite, were analyzed by principal component analysis (PCA) in order to test the dependence of chlorite composition on physicochemical parameters. The results show that chlorite minerals display a wide range of chemical compositions in this hydrothermal system that reflect the particular conditions of crystallization episodes: The Na + K + 2Ca values are low (from 0 to 0.6) and they show no correlation patterns with octahedral vacancies (¤) in chlorite, indicating that compositional variations are not due to the intergrowth of smectite and/or illite. The octahedral occupancy of most chlorite is relatively high (from 11.3 to 11.95), especially that from a high-temperature range, as is the case of metamorphic chlorite. The octahedral occupancy seems not to be related to other chemical variables of chlorite from the G3, G4 and G5 lithologic units, suggesting that the lack of complete occupancy is not dependent on “contamination” by other silicates (such as quartz). Cationic substitution in tetrahedral sites in chlorite is small and via a Tschermak exchange (MgVISiIV ↔ AlVIAlIV). To preserve a charge balance in the structure, an octahedral substitution of R2+ by Al3+ accompanies the Tschermak exchange. The chemical composition of hydrothermal chlorite is very similar to that of metamorphic chlorite but slightly different from equivalent phases found in diagenetic environments. In hydrothermal chlorite the SiVI, AlVI and ¤ decrease, whereas the AlIV and Fe2+ contents increase with the degree of alteration and depth, the same way as in chlorite formed in diagenetic high-temperature environments. The ferrous iron content, in general, increases with depth and temperature; however, whole-rock chemistry affects the iron distribution in chlorite of Los Humeros. Changes in the oxygen fugacity of fluids at depth also affect the iron distribution in chlorite, XFe = Fe/(Fe + Mg), which ranges from 0.30 to 0.38 in oxidizing conditions and from 0.39 to 0.60 in reducing conditions. Finally, the chemical composition of chlorite in Los Humeros appears to change with temperature, but the correlations of ¤ and AlIV with temperature are more variable than in another nearby active geothermal system located in Los Azufres, Mexico. This implies that geothermometers based on chlorite composition and empirically calibrated in some geothermal systems cannot be generalized and it is necessary to consider other physicochemical variables.

To obtain Cu-kaolinites with a controlled range of chemical compositions, syntheses were performed by hydrothermally ageing gels with kaolinite stoichiometric compositions. Gels were prepared with sodium metasilicate and nitrates of octahedral cations. Temperature of synthesis was 250°C with a corresponding equilibrium water pressure of 38 bars.

Three samples with copper contents ranging from 0.1 to 7% and another one with the chemical composition of the Cu end-member were synthesized. While this fourth sample led to tenorite after the hydrothermal treatment, the three others crystallized well into kaolinite.

Up to almost 1% CuO was measured by TEM in some isolated ‘clean’ and hexagonal kaolinite particles. EPR and XPS spectroscopies were consistent with an octahedral position of Cu2+. In IR spectra, vAl-OH-Cu absorption bands were not observed, but vAl2OH bands appeared more and more blurred when Cu content of samples increased. Weak bands situated at 868 cm−1 and 840 cm−1 are tentatively attributed to δAlCuOH. By differential thermal analysis, a downward shift of 20°C in temperature of the endothermic peak from the less Cu-rich sample to the most Cu-rich one, argued for the existence of some Al-OH-Cu bonds, whose binding energies are presumed to be less than the Al-OH-Al ones.

In view of these results, Cu2+ appears incorporated in the octahedral sheet of kaolinite. Moreover, this incorporation is made without major perturbation of the kaolinite structure.

Silanol groups in protonated magadiite (H-magadiite) were characterized by 1H and 2H solid-state nuclear magnetic resonance (NMR). H-magadiite and deuterated (D) magadiite were synthesized by the treatment of Na-rich magadiite with 0.2 N HC1 and 0.2 N DC1, respectively. In the 1H NMR spectrum measured at room temperature, silanol groups of H-magadiite showed two signals at 3.75 and 5.70 ppm, indicating that two types of silanol groups were present. The ratio of silanol groups associated with strong hydrogen bonding (5.70 ppm) to those with weaker hydrogen bonding (3.75 ppm) was 2 to 1. The 2H NMR spectra of deuterated magadiite were measured in the temperature range from 150 to 440 K. In the spectra measured at temperatures below 294 K, silanol groups showed Pake doublet patterns. These patterns were composed of two components corresponding to the two types of silanol groups shown in the 1H NMR analysis. Both silanol groups produced wobbling motions with increasing temperature. Above 294 K, the profile of the Pake doublet pattern was transformed gradually to a near triangular pattern, indicating that the silanol groups underwent other motions also, such as a two-site jump.

Dante Cicchetti’s remarkable contributions to the field of developmental psychopathology include the advancement of key principles such as the interplay of typical and atypical development, multifinality and equifinality, the dynamic processes of resilience, and the integration of multiple levels of analysis into developmental theories. In this paper we assert that person-centered data analytic methods are particularly well-suited to advancing these tenets of developmental psychopathology. We illustrate their utility with a brief novel empirical study focused on underlying patterns of childhood neuroendocrine regulation and prospective links with emerging adult functioning. Results indicate that a childhood neuroendocrine profile marked by high diurnal cortisol paired with low diurnal DHEA was uniquely associated with more adaptive functioning in emerging adulthood. We discuss these findings, and person-centered methods more broadly, within the future of developmental psychopathology.

The mode of growth of authigenic, lath-shaped illitic particles has been investigated using field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). Two types of clay lath have been identified: overgrowths on platelets of illite or illite-smectite and discrete particles. Both are neoformed and show a slight increase in abundance with depth over the 70 m depth interval sampled. Interpretation of lattice fringe data is not unambiguous but indicates that the clay is either illite or illite-smectite with R1 structure. The formation of discrete particles of authigenic illite, or even R1 illite-smectite, is compatible with present burial depths and a regional geothermal gradient of approximately 40°C/km. This illite also differs from many previous reported occurrences of authigenic illite in mudrocks in that it appears to have formed, without being preceded by progressive illitization of illite-smectite.