Two diagenetic stages of zeolitic alteration were recognized in a study of a thin bed of rhyolitic ash that was deposited in Eocene Lake Gosiute (Laney Member of the Green River Formation). The ash bed can be traced for 30 km along strike and represents a single volcanic event. The bed was not buried deeply (<100°C), and originally it was compositionally homogeneous. Initially, the bed altered to clino-ptilolite, heulandite, an intermediate phase between these two zeolites, and mordenite. These early reactions involved the hydration and solution of glass by saline, alkaline solutions and the subsequent precipitation of zeolites. The variation in zeolite mineralogy is due to differences in interstitial fluid chemistry that resulted from either fluctuations in lake-water chemistry or the proximity of spring discharge. These reactions, exclusive of the addition of H2O, involved only minor amounts of mass transfer over very small distances. Later, after burial, the early-formed zeolites reacted with upward moving sodium carbonate brines that were produced by dewatering of underlying evaporite deposits. The sodium carbonate brines, in equilibrium with trona and nahcolite, elevated the activity of Na+ and produced analcime. These later dehydration reactions involved significant mass transfer.

Glauconite has been synthesized at low temperature by precipitation of Fe-hydroxides from Si-, Fe-, Al-, and K-containing solutions under reducing conditions. The compositions favorable for the synthesis at 20°C and pH 8.5 are 1 ppm Fe, 0.15 ppm Al, 13 ppm Si02, 1000 ppm KC1, and 1000 ppm dithionite. The K-content of the solutions must be sufficiently high to fix K in the precipitate.

Under special early diagenetic conditions glauconite is formed in marine sediments, probably at the interface between reducing and oxidizing zones in the muddy sediments. The silica content of pore waters seems to control the formation of glauconite or chamosite rather than depth or temperatures of the bottom waters.

Well-crystallized laumontite has been found for the first time precipitating naturally at the earth's surface at temperatures of 89° to 43°C as a component of gray to white coatings and efflorescences on exterior surface and as precipitates on interior fractures of stones and blocks lining Hot Springs Creek immediately downstream from Sespe Hot Springs, Ventura County, California. X-ray powder diffraction, scanning electron microscope (SEM), and electron microprobe analyses show thenardite to be the dominant phase in the exterior coatings, in association with minor microcrystalline (<50 μm) laumontite and gypsum. Macrocrystalline (>1 mm) laumontite is the dominant phase in interior fracture coatings and is associated with quartz, potassium feldspar, and gypsum. Trace amounts of smectite(?), halite, a mercury sulfide, an iron sulfide, an iron-bearing mineral (possibly an oxide or carbonate), and a copper mineral are also present. Zeolites other than laumontite have not been seen, and carbonate minerals are either entirely or nearly absent. SEM textures indicate nonreactive intergrowths of laumontite, quartz, potassium feldspar, and gypsum. Unbroken laumontite crystals are generally euhedral or have skeletal growth characteristics and exhibit sharp, fresh, non-corroded faces, edges, and corners.

The water issuing from the hottest and largest spring is 89°C, has a pH of 7.74, 1200 mg/liter total dissolved solids, and contains Na+, Cl−, SO42-, and H4SiO4 as the dominant dissolved species. Computations indicate that the water is supersaturated with respect to laumontite, quartz, chlorite, and prehnite and is slightly undersaturated with respect to calcite and noncrystalline silica. Water-dominated water-rock interaction is indicated by isotopic analyses. The δO18 composition expectable on the basis of the −81‰ δD composition is −11.38‰ instead of the −9.5‰ actually found (all referred to SMOW). The water chemistry suggests that the subsurface water source may have a temperature of 125°–135°C. This temperature range, together with the regionally low geothermal gradient, implies that the source is probably 3550 to 3900 m beneath the springs in fractured and permeable Mesozoic and older plutonites and gneisses.

The discovery of laumontite crystallizing at atmospheric pressure and 43°C (or lower) provides important insight into the processes responsible for burial diagenetic laumontite and a valuable perspective on the zeolite metamorphic facies.

Black shale is a dark-colored mudrock containing organic matter that may have generated hydrocarbons in the subsurface or that may yield hydrocarbons by pyrolysis. Many black shale units are enriched in metals severalfold above expected amounts in ordinary shale. Some black shale units have served as host rocks for syngenetic metal deposits.

Black shales have formed throughout the Earth's history and in all parts of the world. This suggests that geologic processes and not geologic settings are the controlling factors in the accumulation of black shale. Geologic processes are those of deposition by which the raw materials of black shale are accumulated and those of diagenesis in response to increasing depth of burial.

Depositional processes involve a range of relationships among such factors as organic productivity, clastic sedimentation rate, and the intensity of oxidation by which organic matter is destroyed. If enough organic material is present to exhaust the oxygen in the environment, black shale results.

Diagenetic processes involve chemical reactions controlled by the nature of the components and by the pressure and temperature regimens that continuing burial imposes. For a thickness of a few meters beneath the surface, sulfate is reduced and sulfide minerals may be deposited. Fermentation reactions in the next several hundred meters result in biogenic methane, followed successively at greater depths by decarboxylation reactions and thermal maturation that form additional hydrocarbons. Suites of newly formed minerals are characteristic for each of the zones of diagenesis.

The Tertiary silicic volcanic rocks in the Silent Canyon Caldera beneath Pahute Mesa, of the Department of Energy's Nevada Test Site have been divided into three vertical mineralogical zones that vary in thickness and transgress stratigraphic boundaries. Zonal contacts are generally sharp. Zone 1, the uppermost zone, includes unaltered or incipiently altered rhyolitic glass. Zone 2 is characterized by a predominance of clinoptilolite and subordinate amounts of smectite, cristobalite, and mordenite. Zone 3 is a complex mineral assemblage that includes analcime, quartz, calcite, authigenic K-feldspar and albite, kaolinite, chlorite, and mixed-layer illite/smectite. The mixed-layer clay shows an increase in ordering and a decrease in expandability with depth.

Shortly after deposition and after shallow burial, hydration of relatively impermeable, highly porous vitric rocks resulted in the rapid formation of the Zone 2 assemblage (except mordenite). This stage of alteration resulted in a net porosity loss and negligible mass transfer. Continued burial and rise in temperature led to a dehydration stage in which the Zone 2 assemblage was replaced by the Zone 3 minerals. The dehydration stage resulted in a porosity increase and an increase in permeability of several orders of magnitude. This process, like the earlier reactions, also conserved mass. Precipitation of mordenite followed the formation of this zonal configuration. The diagenetic zones below Pahute Mesa were caused by: (1) changing pore-water chemistry in an essentially closed hydrologic system; (2) disequilibrium or kinetic precipitation of metastable phases; and (3) a higher thermal gradient than that now present.

Mixed-layer illite/smectite (I/S) clays in lower Eocene sediments of the Texas Gulf Coast decrease in expandability with depth as found in previous studies of clay diagenesis, but at the same depth the 1/S clays from sand laminae tend to be more expandable than clays from adjacent shales. The I/S clays with greater expandability from sands collapse to phases with very low expandabilities after saturation with K. This non-ideal smectite behavior indicates that many of the expandable layers in I/S clays from sand laminae possess an illite-level negative layer charge on the structure. The Greene-Kelley Li-saturation test of the I/S clays also reveals that a considerable portion of the increased layer charge deficiency is created by tetrahedral substitution. The illitization of individual smectite layers in an I/S clay is envisioned to be a two step process instead of the single step rapid transformation implied in many earlier studies. The first rate-limiting step is the creation of sufficiently large negative layer charge in the lattice, primarily by AI for Si substitution in the tetrahedral sheet. The second rate-limiting step is the supply of K to the high-charged expandable layers. The abundance of high-charged expandable layers in I/S clays from sand laminae suggests that the K supply is influenced more by competing ions in the interstitial waters than by the absolute activity of K.

Varieties of kaolin, a rock, may be classified geologically, mineralogically, crystallographically, genetically, texturally, morphologically, by industrial use, and in other ways which are desired. In this paper, the first-order of classification used is geological, i.e., transported and residual, after which other categories are used as subdivisions.

Scan electron micrographs, SEM, of the textures of kaolin show that distinctive textures characterize the several categories of classification. Varieties in texture of kaolin include similarities to those typical of sedimentary, igneous and metamorphic rocks. Because word descriptions of the textures are inadequate in comparison to pictures of them, the reader is referred to the micrographs.

SEM's illustrate differences between kaolins which were transported, formed, or deposited from solution, a colloidal phase, or as orthodox clastic particles. The parent source of kaolin deposited, or “grown,” from solution may be difficult to ascertain. It is suggested that the total role of solution work in kaolin petrology can be more important than has ordinarily been credited.

The most prominent authigenic reaction in Holocene tuffaceous sediments at Teels Marsh, Nevada, is the hydration of rhyolitic glass by interstitial brines and the subsequent formation of phillipsite. This reaction has the form: rhyolitic glass + H2O → hydrous alkali alumninosilicate gel → phillipsite. Phillipsite is the most abundant authigenic phase in the tuffaceous sediments (>95%), analcime is the next most abundant phase, and clinoptilolite occurs as a trace mineral in the <2-mm fraction. Analcime forms by the reaction of phillipsite and Na+. Gaylussite and searlesite also are common authigenic phases at Teels Marsh. The concentration of silica in the interstitial brines is controlled by one or more of the authigenic reactions at less than 100 ppm. A stoichiometric equation for the reaction of phillipsite to analcime at Teels Marsh is:

$$0.43N{a + }\, + {K_{0.43}}N{a_{0.57}}AlS{i_{3.1}}{O_{8.2}}\, \cdot \,3.2{H_2}O\, \to \,NaAlS{i_2}{O_6}\, \cdot \,{H_2}O\, + \,1.1{H_4}Si{O_4}\, + \,0.43{K + }.$$

Sodium and potassium activities of brines associated with both phillipsite and analcime were used to estimate the equilibrium constant for this reaction as 3.04 × 10−5. The ΔG0 value for the reaction is +6.2 kcal/mole at 25°C and 1 atm pressure. The estimated ΔG0 value of phillipsite, using this reaction, is −1072.8 kcal/mole at 25°C and 1 atm.

Microprobe analyses of optically homogeneous detrital biotites from sandstones of the Visingsö Group and the Dala Sandstone, Sweden, revealed a consistently low K content (generally <0.75 atom/formula unit) and variable amounts of Fe, Mg, Al, and Si. Electron probe profiles of some biotite grains indicated two major types of interstratification, one consisting of mainly illite layers and the other apparently consisting of chlorite layers. The layer thicknesses commonly ranged between 0.5 and 3 μm. Microprobe analyses of some thick (∼5 μm) illitic layers indicated a phengitic composition, wherein the mica was relatively rich in octahederal Fe and Mg. The chloritic layers appeared to be Fe-Mg-rich and generally had octahederal totals of <6 atom/formula unit. Variations in the chemical composition of the biotite and some of the illite and chlorite were probably due to an uneven distribution of small amounts of the interstratified phases. The illite and chlorite layers were apparently formed by pseudomorphic replacement of detrital biotites, i.e., gradual replacement of one biotite layer by one layer(s) of illite and/ or chlorite during diagenesis.

The conversion of smectite to illite by way of a mixed-layer illite/smectite (I/S) series was found to be the major depth-related reaction in clay-mineral assemblages from two cored sedimentary sequences in the Rocky Mountains. The I/S reaction occurred in both interbedded sandstone and shale of Upper Cretaceous and lower Tertiary age in the Green River basin, Wyoming, and in chalk and chalky shale of the Upper Cretaceous Niobrara Formation, Denver basin, Colorado. As the proportion of illite layers in I/S increased with depth in these rocks, the amount of I/S in the clay fraction decreased, and the amount of discrete illite increased. Scanning electron microscopy revealed that the morphologies of highly expansible, randomly interstratified I/S clay (samples from shallow cores) exhibited no distinctive intergrowth or overgrowth textures. In deeply buried rocks containing highly illitic, ordered I/S and abundant discrete illite, however, fibers or laths of illite were formed on earlier I/S substrates. Less commonly, I/S of low expandability shows morphological features of both smectite and illite whereby rigid laths of illite appear to have formed diagenetically from the wall surfaces of I/S honeycombs. This combined morphology suggests some dissolution and reprecipitation (or some reorganization) of materials from the I/S substrate as the substrate was transformed into a more illitic mixed-layer clay.

These data suggest that some I/S clay was destroyed by the selective cannibalization of smectite layers in I/S to provide the components needed to make a more illitic I/S. Moreover, discrete illite and other minerals apparently were formed during the reaction. Also, coarser mineral phases, such as potassium feldspar and detrital micas, may not have been required to supply the chemical components in the reaction. The observations provide an explanation for late diagenetic I/S reactions that occurred in restricted or relatively closed geochemical systems, as in early cemented rocks having extremely low permeability and little or no potassium feldspar.

The continuous conversion of smectite to illite in samples from the Shinzan hydrothermal alteration area of Japan has been examined by X-ray powder diffraction (XRD) and transmission (TEM) and analytical transmission electron microscopy (AEM). TEM shows that randomly interstratified illite/ smectite (I/S) containing 100-50% expandable layers exhibits a flakey shape, whereas regularly and partially ordered interstratified I/S having 50-0% expandable layers exhibits a lath-like habit. An early- formed lath of regularly interstratified I/S is typically <35 Å in thickness and 300–500 Å in width; these dimensions gradually increase with decreasing percentage of expandable layers. XRD shows that the lathshaped I/S has a 1M polytype mica structure. AEM shows that the interlayer K content of flakey I/S increases monotonously with decreasing percentage of expandable layers in the range 100-50% expandable layers, whereas the interlayer K content of lath-shaped I/S increases along a different trend from that for the flakey I/S in the range 50-0% expandable layers. These observations suggest that randomly interstratified I/S is fundamentally smectite that is undergoing K-fixation and dissolution and that regularly and partially ordered interstratified I/S are immature illite which is still growing. Consequently, they suggest a mechanism for the hydrothermal smectite-to-illite conversion that is based on the K-fixation in and dissolution of smectite and the precipitation and growth of thin illite particles. Furthermore, these data suggest that the kinetics of smectite dissolution and illite growth are the most important factors controlling the smectite-to-illite conversion.

Samples of cuttings from the Borchard A-2 well, Imperial Valley, California, were collected over a measured borehole temperature interval 135° to 275°C. The <0.5-µm (e.s.d.) fraction was separated using high-gradient magnetic separation (HGMS) to create a nonmagnetic fraction rich in illite and a magnetic fraction rich in chlorite. Chlorite was less easily separated from illite in lower temperature samples (<200°C), presumably due to the presence of polymineralic grains of chlorite and illite. Grains in higher temperature samples were more nearly monomineralic and more easily separated.

The chlorite is the IIb polytype. The thickness of coherent scattering domains of chlorite increased until 220°C and then remained constant. The amount of 7-Å interstratified material increased downhole until 195°C and then decreased. Over the same temperature interval, the illite polytypes varied systematically from 1Md (135° to 175°C) to 1M + 2M1 (230° to 275°C) and coherent scattering domains in the mineral became thicker to about 200°C and then remained constant in thickness. The percentage of illite in mixed-layer illite/smectite (I/S) increased from 40% at 135°C to 100% at temperature >205°C; ordering in the I/S changes from R0 to R1 between 135° and 155°C, and from R1 to R ≥ 3 at temperatures >155°C.

The concurrent structural changes in chlorite and illite indicate a general improvement in the overall structural order of the clay minerals with increasing temperature. Differences between chlorite and illite suggest that the minerals may have reacted differently to changing conditions or that they may have formed by different mechanisms. The exclusive occurrence of IIb chlorite at temperatures as low as 135°C extends the limit of IIb chlorite stability to temperatures lower than previous estimates.

Oxygen isotope ratios of <0.1-μm smectite in bottom sediments of the Mississippi River and the Gulf of Mexico near the mouth of the river have been determined to investigate diagenesis of land-derived clay minerals during sedimentation in the sea. No difference was detected in δ18O (SMOW) between the river and the Gulf samples indicating that no smectite alteration or addition of neoformed smectite to the river samples took place during sedimentation. Thus, authigenic minerals in the river sediments cannot make up more than a few tenths of a percent of the bulk sediments.

Similar results were obtained from 3 × 106-yr b.p. sediments buried to 80 to 600 m at Deep Sea Drilling Project site 323, Bellingshausen Abyssal Plain. No significant change with depth was noted in the δ18O of the <0.3-μm size fraction, mostly smectite, of these land-derived sediments. On the basis of the δ18O of the deepest sample, the maximum amount of authigenic minerals in the land-derived sediments during burial in the sea cannot be more than one or two percent of the bulk sediments. Hence, the alteration at seafloor temperatures of 25-45% of the <0.1-μm size clays in 3 × 106 yr b.p. sediments reported in a previous study is not substantiated. The data demonstrate that land-derived smectite is stable in the sea, and that oxygen isotopes can be used to investigate the modes and the temperatures of formation of authigenic smectites in marine sediments that are younger than 25 × 106 yr and that formed below 25°C.

An unusual vanadium chlorite precipitated during the formation of a vanadium-uranium ore deposit in the Henry Basin, southeastern Utah. The ore deposit formed by reduction and precipitation of U and V in the presence of organic matter at the interface between a stagnant brine and overlying, circulating meteoric water. Some samples of the vanadium chlorite (heated before analysis) contain ≥ 10% V2O5. In fresh samples, most of the vanadium is in the trivalent oxidation state. X-ray powder diffraction data suggest that Fe and V are concentrated preferentially in the interlayer hydroxide sheets of the chlorite. A d(060) value of 1.52 Å indicates that the chlorite probably has a dioctahedral structure which is distended by the presence of octahedral Fe and V. The vanadium ore zone is flanked by peripheral zones containing perfectly ordered chlorite/smectite. This chlorite/smectite contains much less V than the pure chlorite. This chlorite may have formed by the progressive precipitation of vanadium-rich interlayer hydroxide sheets in the mixed-layer chlorite/smectite in the most reducing portion of the ore zone. The pure chlorite is a IIb polytype, which, for nonvanadiferous analogs, is ordinarily found in high-temperature environments; however, no evidence exists to show that these rocks have ever been exposed to elevated temperatures. In fact, the presence of unreacted smectite in a potassium-rich setting and the low vitrinite reflectance of coalified plant debris indicate a low-temperature history for these sediments.

Clay and zeolite mineral assemblages were determined for five deep wells in volcano-clastic sediments (Japan) and for one well in mudstones (California). The clay mineral suites in these wells showed a gradual change with depth of illite/smectite (I/S) composition, which increases in smectite content in the upper portion towards a fully expandable mineral (2–3-km depth) and then decreases in smectite content with depth (2–5 km). The temperature of transformation or recrystallization to a fully expandable smectite mineral is about 60°–70°C in non-zeolite bearing rocks and 70°–90°C in zeolite-bearing rocks, with no apparent dependence on time. Comparison is made between the I/S smectite content in the lower part of the wells (i.e., below the occurrence of the fully expandable mineral) and the zeolite mineral zone boundaries. The 60% smectite composition was found at 108°–118°C maximum burial temperatures. The zeolite II/III zone boundary, i.e., the onset of the analcime zone, occurs between 85° and 95°C and may be slightly time-related in the span of 1–15 Ma. The clay and zeolite minerals can be used as temperature indicators in the range of the Neogene age.

X-Ray powder diffraction and thin section analyses indicate that marginal lacustrine mudstones of the Green River Formation in the south-central Uinta basin, Utah, contain abundant analcime. The analcime has a low Si/Al ratio (<2.31) and occurs as very fine grained disseminated crystals and, to a lesser extent, as coarser-grained pore-filling cement. Analcime-rich mudstones and associated sandstones, siltstones, and carbonates lack volcanic detritus and zeolites other than analcime, thus making it difficult to support the concept that the analcime formed from precursor zeolites derived from volcanic glass altered in saline, alkaline-lake water. Abundant dolomite, syneresis cracks, and the absence of freshwater pelecypods and gastropods suggest that the lake (Lake Uinta) was moderately saline and alkaline. The restricted illite-illite/smectite clay mineral suite in the analcime-rich mudstones suggests that detrital clays significantly altered in a moderately saline and alkaline environment, thereby providing a source of Si and Al for the formation of analcime.

Red mudstones contain twice as much analcime as green mudstones (14 vs. 7 wt. %). Green mudstones have a day mineral suite consisting of illite (44 wt. %), mixed-layer illite/smectite (35 wt. %), smectite (12 wt. %), and minor kaolinite (4 wt. %) and chlorite (5 wt. %), whereas red mudstones have a more restricted day mineral suite consisting ofillite (68 wt. %) and mixed-layer illite/smectite (26 wt. %) with very minor smectite, chlorite, and kaolinite. Periodic minor fluctuations in lake level probably exposed large areas of shallow lacustrine-interdistributary green mud. Evaporative pumping on the exposed mudflats concentrated the moderately saline and alkaline-lake water, thereby producing Na-rich brines that enhanced the formation of analcime by accelerating the alteration of detrital clays and, perhaps, other minerals. Oxidation of iron from altered iron-bearing minerals stained the analcime-rich mud red with iron hydroxide or oxide (perhaps hematite). The overall reaction from green to red mud (mudstones) was probably: detrital phyllosilicates + Na-brine + iron-bearing minerals + oxygen → analcime + iron hydroxide or iron oxide.

The vitric matrix of pre-caldera acid tuff and tuff breccia of the Santorini volcano, Aegean Sea, Greece has been generally replaced by one or more of the following authigenic minerals: K-rich and (K,Ca)-rich clinoptilolite, mordenite, opal-CT, and clay minerals. Halite is also present in some samples. Initial compositional inhomogeneities between the dacitic blocks in tuff breccia and tuff seem to have controlled the type of K-rich heulandite-group zeolite that formed. Mordenite postdates the heulandite-group zeolites and opal-CT. Some mordenite has replaced the rims of glass shards. The alteration minerals are not related to vertical or lateral zonation, and the irregular distribution of their assemblages is attributed to variations in heat flow, ionic activity in interstitial waters, and permeability. The pyroclastic rocks were in a region of active heat flow during and after their emplacement. The formation of authigenic silicates may have led to the sealing of open spaces and fractures, imposing barriers to permeability and subdividing the original open system into smaller closed systems. As alteration progressed, some of the trapped water in each individual domain was consumed in hydration reactions. Salts could have been concentrated by such a process, and halite probably precipitated from solutions of appropriate composition in the individual closed systems.

Ash layers from Searles Lake, California, were sampled in core of drill hole KM-3, which penetrated 693 m of lacustrine sediment deposited in a playa-lake complex over the past 3.2 my. Lake water changed from moderately saline and slightly alkaline (pH ~7.5) to highly saline 2.04 my ago and to highly saline and alkaline (pH ~9.5) 1.28 my ago. As a result of brines flushing downward, the upper 291 m of sediment, spanning the past 1.28 my, contain highly saline, alkaline pore fluid. Silicic ash layers in contact with highly saline, alkaline pore fluid were first altered to phillipsite and meriinoite and then to K-feldspar and searlesite. The transformation of phillipsite and/or meriinoite to K-feldspar required more than 45,000 years and was largely completed in 140,000 years. Tephra layers in contact with moderately saline, slightly alkaline pore fluid vary from uncemented vitric ash containing minor smectite to bentonites in which glass is wholly altered to smectite, clinoptilolite, analcime, and opal. Layers with much fine tephra are more altered than the coarser, better-sorted layers. Alteration is attributed to hydrolysis in essentially a closed hydrologic system, in which the alteration of glass to smectite raised the pH, aSiO2, and (Na+ + K+)/H+ activity ratio to the level where clinoptilolite formed. Some diffusion and/ or fluid flow is, however, indicated by the loss of SiO2 during the alteration of ash layers to smectite and by anhydrite deposited during and after clinoptilolite in some tuffaceous sandstones.

Glauconites in early ankerite concretions, ferroan calcite-cemented sandstones, and uncemented sandstones in the first Wilcox sandstone of the Lockhart Crossing field, Livingston Parish, Louisiana, show a progressive substitution of Fe for octahedral Al with increasing diagenesis. An octahedral Fe content of 0.50 atoms was calculated from glauconite located in early ankeritic concretions. Octahedral Fe averaged 0.60 and 0.90 atoms in later ferroan calcite-cemented sandstone and uncemented sandstone, respectively. Corresponding octahedral Al averages were 1.16, 1.03, and 0.67, respectively. A systematic increase in average interlayer K from 0.49 to 0.54 to 0.61 was also observed, with apparent increases in diagenesis. All element determinations were made with an electron microprobe and recast on an anion equivalent basis to structural formulae based on the O10(OH)2 unit. The clay preserved in the early ankerite concretions was found to be an illite/smectite containing about 20% expandable layers, and the mineral in the glauconite pellets from uncemented areas of the sandstone, an ordered glauconite. “Minus cement” porosities of the sandstone indicate that glauconitization may have taken place at burial depths greater than 0.6 to 1.8 km, but the mechanism for the incorporation of Fe3+ in the glauconite at that depth is not apparent.

In Upper Cretaceous-Tertiary marine shales (Campos Formation) from the Campos basin, Brazil, mixed-layer illite/smectite (I/S) has remained randomly interstratified to depths of 3500 m and to temperatures as high as 100°C, in contrast to the typical pattern of shale diagenesis in, for example, the Gulf Coast area. X-ray powder diffraction analysis of the bulk shale and several size fractions from samples from one well in the Brazilian basin and from one in the Gulf Coast region were carried out to assess the factors that might have controlled the lack of illitization in the Campos Formation shales.

In samples from the Gulf Coast well, the clay minerals are I/S (montmorillonite-type), discrete illite, chlorite, and minor kaolinite. In contrast, the clay minerals in samples from the Campos basin well are kaolinite, clay-size biotite, and I/S (nontronite-type). Kaolinite is abundant in this well, and the variation of its abundance with depth seems to reflect variations in sea-level stands. The original composition of the I/S (nontronite-type) was probably the main factor controlling the lack of illitization in the shales of the Campos Formation.