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At least 991 records · Page 55Linked to original sources

Acoustic tag retention rate varies between juvenile green and hawksbill sea turtles

Background Biotelemetry has become a key tool for studying marine animals in the last decade, and a wide range of electronic tags are now available for answering a range of research questions. However, comparatively, less attention has been given to attachment methods for these tags and the implications of tag retention on study design, especially when designing a comparative study looking at multiple species. Here, we reported our findings on acoustic tag retention rates for juveniles of two species of marine turtle: the green sea turtle (Chelonia mydas) and the hawksbill sea turtle (Eretmochelys imbricata). We captured both species twice annually (spring and fall) from 2012 through 2017, as part of a capture–mark–recapture study at Buck Island Reef National Monument, St. Croix, U.S. Virgin Islands. We assessed tag retention rates using physical recaptures of turtles previously outfitted with an acoustic tag. Results We deployed 72 acoustic tags on 60 juvenile greens and 37 acoustic tags on 29 hawksbills. We estimated the half-life for tags on greens to be 150 days (95% CI 117–188 days), whereas the half-life for tags on hawksbills was 1077 days (95% CI 870–2118 days), a marked difference. We observed that tag attachment holes, drilled into the posterior marginal scutes, migrated laterally towards the outer edge of the marginals in both species. Green turtles tended to exhibit tear-outs, as their attachment holes wore and/or tags grew near the edge of their scutes, whereas hawksbills tended to maintain the structure of these holes and did not exhibit these tear-outs. Conclusions We conclude that hawksbills can be tagged with long-battery-life acoustic tags for long-term studies of habitat use and movement patterns, whereas greens are likely to shed their tags in the 1st year, making long-term studies difficult. This study is the first clear evidence that tagging protocols should vary between species of hard-shelled turtles. Furthermore, shed tags on the seafloor continue to be detected by acoustic receivers, creating a challenge in data filtering before analysis. We encourage future research into an efficient method for filtering these data points prior to analysis.

Animal Biotelemetry↗

Linking bathythermal habitat selection to management of a migratory freshwater fish

Background For migratory fishes, habitat selection in dimensions of temperature and depth may be jointly used to define the bathythermal niche. Seasonal and long-term changes in the availability of bathythermal habitat can cause behavioral responses that have consequences for managing interjurisdictional fisheries that target migratory fishes. Management of such fisheries typically relies on standardized surveys to provide knowledge of stock status, yet changes in fish behavior may complicate interpretation of survey results. For example, changes in bathythermal habitat selection could uncouple fish availability from surveys designed to intercept migrating fish in predefined bathythermal habitats. Methods We applied electronic tagging methods to Lake Erie walleye ( Sander vitreus ) to address spatial management and stock assessment questions regarding bathythermal habitat. Specifically, we sought to determine if bathythermal habitat use varied in relation to body size, season, and time of day, with a particular focus on how these may influence availability to fisheries-independent surveys conducted during September-November. Results As predicted, bathythermal habitat distribution fluctuated substantially throughout the year, was most limited during spawning months, and most expansive during fall migration. During the summer stratified months, walleye primarily selected epilimnetic habitats, despite the prevailing notion that colder hypolimnetic waters would be preferred during this time. Conclusions While our results did not support a previous hypothesis that smaller fish were more available to assessment survey gears, our results did support previous assertions that walleye were more active and available to suspended gill nets during late crepuscular periods in fall. Considering uncertainties in water quality and long-term warming trends, our case study could improve decisions regarding spatial management of this species in the context of independent water quality management objectives.

Detroit River, Lake Erie, Lake St. Clair↗

A comprehensive system of automatic computation in magnetic and gravity interpretation

In the interpretation of magnetic and gravity anomalies, downward continuation of fields and calculation of first and second vertical derivatives of fields have been recognized as effective means for bringing into focus the latent diagnostic features of the data. A comprehensive system has been devised for the calculation of any or all of these derived fields on modern electronic digital computing equipment. The integral for analytic continuation above the plane is used with a Lagrange extrapolation polynomial to derive a general determinantal expression from which the field at depth and the various derivatives on the surface and at depth can be obtained. It is shown that the general formula includes as special cases some of the formulas appearing in the literature. The process involves a "once for all depths" summing of grid values on a system of concentric circles about each point followed by application of the appropriate one or more of the 19 sets of coefficients derived for the purpose. Theoretical and observed multilevel data are used to illustrate the processes and to discuss the errors. The coefficients can be used for less extensive computations on a desk calculator.

Geophysics↗

Discrimination of hydrothermal altered and unaltered rocks in visible and near infrared multispectral images

Mineralogical differences between altered rocks and most unaltered rocks in south-central Nevada cause visible and near-infrared (0.45 to 2.4 mu m) spectral-reflectance differences which can be used to discriminate these broad categories of rocks in multispectral images. The most important mineralogical differences are the increased abundance of goethite, hematite, and jarosite, and the presence of alunite, montmorillonite, and kaolinite in the altered rocks. Analysis of reflectance spectra recorded in the field showed that the altered rock spectra are characterized by broad absorption bands in the 0.45-0.50 mu m and 0.85-0.95 mu m regions which are due to electronic processes in the iron ions, and a band near 2.2 mu m which is due to vibrational processes in the OH ions. These features are absent or weak in most of the unaltered rock spectra. Therefore, the shapes of the 0.45-2.4 mu m spectra for these altered and unaltered rocks are conspicuously different. However, because of the wavelength positions and widths of the Landsat Multispectral Scanner (MSS) bands, these spectral differences are not apparent in individual or color-infrared composite MSS images.The technique developed to enhance these subtle spectral differences combines rationing of the MSS bands and contrast stretching. The stretched ratio values are used to produce black-and-white images which depict materials according to spectral reflectance; ratioing minimizes the influence of topography and overall albedo on the grouping of spectrally similar materials. Color compositing of two or more stretched ratio images to form color-ratio composites provides additional enhancement. The most effective color-ratio composite for discriminating between the altered and unaltered areas, as well as among many of the unaltered rocks in south-central Nevada, was prepared using the following diazo color and stretched ratio image combinations: blue for MSS 4/5, yellow for MSS 5/6, and magenta for MSS 6/7. Altered areas appear green and brown in this combination.Field evaluation of this color-ratio composite shows that excluding alluvial areas, approximately 80 percent of the green and brown color patterns are related to hydrothermal alteration. The remaining 20 percent consists mainly of pink hematitic crystallized tuff, a result of vapor-phase crystallization, and of tan and red ferruginous shale and siltstone. Discrimination of this unaltered tuff from the altered rocks may be possible in the 2.2 mu m region because this absorption band is absent in the tuff spectra. However, because the shale and siltstone are mineralogically and spectrally similar to the altered rocks, there appears to be little prospect of distinguishing these rocks from altered rocks in visible and near-infrared multispectral images.

Nevada↗

Controls on pore types and pore-size distribution in the Upper Triassic Yanchang Formation, Ordos Basin, China: Implications for pore-evolution models of lacustrine mudrocks

Our main objectives are to (1) learn if pore-evolution models developed from marine mudrocks can be directly applied to lacustrine mudrocks, (2) investigate what controls the different pore types and sizes of Chang 7 organic matter (OM)-rich argillaceous mudstones of the Upper Triassic Yanchang Formation, and (3) describe the texture, fabric, mineralogy, and thermal maturity variation in the Chang 7 mudstones. Lacustrine mudstones from nine cored wells along a depositional dip in the southeastern Ordos Basin, China, were investigated. Helium porosimetry, nitrogen adsorption, and field-emission scanning electron microscopy of Ar-ion milled samples were applied. Measured average total porosity of samples from a proximal to distal transect ( ϕ = 5.0 % "> ϕ = 5.0 % ) is higher than those from the two adjacent cored wells ( ϕ = 2.3 % "> ϕ = 2.3 % ). This difference in porosity partly caused by differences in the clay mineral content implies that in the fluvial-deltaic-lacustrine depositional environment, reservoir quality can vary significantly in a short distance. Owing to the uneven distribution of the sample set from proximal to distal area, we mainly evaluate variations in the proximal setting. Results from nitrogen-gas adsorption experiments show that there are four distinct patterns of pore-size distribution within the Chang 7 member of the Yanchang Formation with no particular correlation with mineralogical composition and thermal maturity. The pore network within Chang 7 mudstones is dominated by OM-hosted pores, with a lesser abundance of interparticle and intraparticle pores. The size distribution of mineral-hosted pores within these mudstones is found to be closely related to the rock texture (sorting and grain size) and fabric. Mudstones with well-sorted grains and a higher percentage of coarser grains have more abundant mineral pores. The sizes of OM-hosted pores in these compaction-dominated lacustrine mudstones were one to two orders of magnitude smaller than those in the marine mudstones that display abundant early cementation.

Ordos basin↗

A new laboratory approach to shale analysis using NMR relaxometry

Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T 1 and T 2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T 1 -T 2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T 2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T 1 and T 2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T 1 -T 2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T 1 and T 2 measurements were used to improve assessment of the solid organic phases, specifically kerogen, thermally degraded kerogen, and char. Integrated peak areas from the LF-NMR results representative of kerogen and bitumen were found to be well correlated with S1 and S2 parameters from Rock-Eval programmed pyrolysis. This study demonstrates that LFNMR relaxometry can provide a wide range of information on shales and other reservoir rocks that goes well beyond porosity and pore-fluid analysis.

Conference Paper↗

TREMOR: A wireless MEMS accelerograph for dense arrays

The ability of a strong-motion network to resolve wavefields can be described on three axes: frequency, amplitude, and space. While the need for spatial resolution is apparent, for practical reasons that axis is often neglected. TREMOR is a MEMS-based accelerograph using wireless Internet to minimize lifecycle cost. TREMOR instruments can economically augment traditional ones, residing between them to improve spatial resolution. The TREMOR instrument described here has dynamic range of 96 dB between ??2 g, or 102 dB between ??4 g. It is linear to ???1% of full scale (FS), with a response function effectively shaped electronically. We developed an economical, very low noise, accurate (???1%FS) temperature compensation method. Displacement is easily recovered to 10-cm accuracy at full bandwidth, and better with care. We deployed prototype instruments in Oakland, California, beginning in 1998, with 13 now at mean spacing of ???3 km - one of the most densely instrumented urban centers in the United States. This array is among the quickest in returning (PGA, PGV, Sa) vectors to ShakeMap, ???75 to 100 s. Some 13 events have been recorded. A ShakeMap and an example of spatial variability are shown. Extensive tests of the prototypes for a commercial instrument are described here and in a companion paper. ?? 2005, Earthquake Engineering Research Institute.

Earthquake Spectra↗

Geomicrobial interactions with arsenic and antimony

Although arsenic and antimony are generally toxic to life, some microorganisms exist that can metabolize certain forms of these elements. Some can use arsenite or stibnite as potential or sole energy sources, whereas others can use aresenate and antimonite (as was discovered only recently) as terminal electron acceptors. Still other microbes can metabolize arsenic and antimony compounds to detoxify them. These reactions are important from a geomicrobial standpoint because they indicate that a number of microbes contribute to arsenic and antimony mobilization or immobilization in the environment and play a role in arsenic and antimony cycles. Recent reviews include five on prokaryotes and arsenic metabolism, a review with an arsenic perspective on biomining, and a series on environmental antimony, including one about antimony and its interaction with microbiota.

Book chapter↗

Estimating pore and cement volumes in thin section

Point count estimates of pore, grain and cement volumes from thin sections are inaccurate, often by more than 100 percent, even though they may be surprisingly precise (reproducibility + or - 3 percent). Errors are produced by: 1) inclusion of submicroscopic pore space within solid volume and 2) edge effects caused by grain curvature within a 30-micron thick thin section. Submicroscopic porosity may be measured by various physical tests or may be visually estimated from scanning electron micrographs. Edge error takes the form of an envelope around grains and increases with decreasing grain size and sorting, increasing grain irregularity and tighter grain packing. Cements are greatly involved in edge error because of their position at grain peripheries and their generally small grain size. Edge error is minimized by methods which reduce the thickness of the sample viewed during point counting. Methods which effectively reduce thickness include use of ultra-thin thin sections or acetate peels, point counting in reflected light, or carefully focusing and counting on the upper surface of the thin section.

Journal of Sedimentary Petrology↗

Reservoir properties of submarine- fan facies: Great Valley sequence, California

Submarine-fan sandstones of the Great Valley sequence west of the Sacramento Valley, California, have low porosities and permeabilities (64 samples averaged 10.1% porosity and 0.87 millidarcies permeability). However, petrography and scanning electron microscope studies indicate that most sands in almost all submarine fan environments are originally porous and permeable. Thin turbidite sandstones deposited in areas dominated by shale in outer-fan, basin-plain, and overbank environments are cemented mainly by calcite; shale dewatering is inferred to contribute to rapid cementation early in the burial process. Sands deposited in inner- and middle-fan channels within interchannel and fan-fringe environments that contain only thin shale beds have small percentages of intergranular matrix or cement. The original porosity is substantially reduced mechanically at shallow depths and by pressure solution at deeper levels. Permeability decreases systematically with increasing age of the rocks, presumably as a result of increasing burial depths. Computer-run stepwise regression analyses show that the porosity is inversely related to the percentage of calcite cement. Such parameters as the contents of quartz, feldspar, and unstable rock fragments have no correlative effect on either porosity or permeability. The results reported here indicate original porosity and permeability can be high in deep-water submarine fans and that fan environments dominated by sand (with high sand/shale ratios) are more likely to retain higher porosity and permeability to greater depths than sand interbedded with thick shale sequences.

Journal of Sedimentary Petrology↗

Dolomitization in a mixing zone of near-seawater composition, Late Pleistocene, northeastern Yucatan Peninsula

Patches of dolomite occur in cores of reefal limestone from the shallow subsurface on the northeastern coast of the Yucatan Peninsula. This limestone accumulated during an interglacial high stand of sea level about 200,000 years ago. Dolomitization was preceded by freshwater diagenesis, including precipitation of sparry calcite cement, stabilization of Mg-calcitic skeletal fragments, and partial dissolution of aragonitic components. This suggests a predolomitization lowering of sea level with the consequent freshening of pore water. The subsequent precipitation of dolomite indicates a return to high sea level with the consequent increase in Mg/Ca ratio of pore water. Dolomitization took place during a brief high stand of sea level, either shortly after deposition about 200,000 yr BP, or, more likely, about 125,000 yr BP. Dolomite occurs both as microcrystalline replacement dolomite and as cement. The cement is part of the following diagenetic sequence: 1) limpid euhedral-subhedral calcian dolomite crystals, 2) zoned dolomite crystals with zones formed by variations of the calcium/magnesium ratio in dolomite, 3) layers of alternating calcian dolomite and magnesian calcite or calcite, and 4) calcite. This sequence represents the progressive freshening of ground water during the initial stage of a fall in sea level. Average cation composition of the limpid dolomite cement is Ca 57 Mg 43 (electron microprobe analysis). Zoned cement crystals are composed of Ca (sub 57-59) Mg (sub 43-41) layers and Ca 62 Mg 38 layers. Most of the higher-calcium dolomite layers are dissolved, forming hollow-zone crystals. In cement with alternating dolomite and calcite zones, the calcite is Ca (sub 99-97) Mg (sub 1-3) (low-Mg calcite) and Ca (sub 96-93) Mg (sub 4-7) (Mg calcite). The dolomite and Mg calcite zones are partially to totally leached. delta 18 O compositions of Yucatecan dolomite and of modern ground water suggest dolomite precipitation from mixed water ranging from about 75% seawater, 25% freshwater to nearly all seawater. (Isotope analyses are for the most stable calcian dolomites; more soluble, calcium-rich dolomite presumably is analyzed with calcite and thought to be isotopically lighter than the less soluble dolomite.) In the cement sequence, the most stable dolomite is followed by more soluble dolomite as ground water becomes less saline. Isotope analyses, together with position of dolomite in the cement sequence, suggest the most stable calcian dolomite (including limpid dolomite) precipitated from mixed water with large proportions of seawater, and the less stable, more calcian dolomite precipitated from fresher mixed water.

Yucatan Peninsula↗

Fabric and its relation to sedimentologic and physical properties of near-surface sediment, Shelikof Strait and Alsek prodelta, Alaska

To investigate the possible relation between the fabric (microstructural arrangement of particles) of a fine-grained sedimentary deposit and the depositional and environmental processes of that deposit, the fabric of sediment samples from the sea floor of two different depositional settings, Shelikof Strait and the Alsek prodelta, Alaska, were studied by using scanning electron microscopy (SEM). Sediment of both areas is texturally similar, consisting of a muddy sand that grades to a mud with increasing water depth. Mineralogically, both areas are characterized by a clay-size fraction dominated by illite, chlorite, and rock flour. The dominant fabric of undisturbed sediment from both study areas consists of a sand- and coarse-silt-size agranular fraction surrounded by an open matrix of clay- and fine-silt-size platelets arranged in a combination of randomly oriented flocs and many single grain contacts. The similarity of the fabric of sediment from the two study areas suggests that the fabric is not controlled by the different depositional settings but rather by the dominant clay mineralogy and sediment texture. The most noticeable alteration of the original fabric of Shelikof Strait and Alsek prodelta sediment occurs as a result of high levels of consolidation and the shearing process.

Journal of Sedimentary Petrology↗

Mineralogy and petrology of the Cretaceous- Tertiary boundary clay bed and adjacent clay-rich rocks, Raton Basin, New Mexico and Colorado.

The Cretaceous-Tertiary (K-T) boundary is preserved in a sequence of coal-bearing, fluvial rocks in the lower part of the Raton Formation (Late Cretaceous and Paleocene) at several sites in the east-central part of the Raton Basin. The K-T boundary occurs at the top of a kaolinitic claystone layer, commonly referred to as the "boundary clay layer," in an interval of coal and carbonaceous shale. The boundary is defined by the disappearance of certain fossil-pollen taxa. The boundary clay layer also contains shocked quartz grains and abundance anomalies of iridium, chromium, and other elements. Each of these characteristics support the hypothesis of an asteroid impact at the end of the Cretaceous. Small goyazite spheres were also found in the boundary clay bed; however, their origin is uncertain. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thin-section petrography have shown that the boundary clay bed exhibits unique mineralogic and petrologic characteristics not possessed by other clay-rich beds in coal-bearing rocks of the Raton Basin. The boundary clay bed is composed primarily of well-crystallized kaolinite but also contains subordinate, randomly interstratified, mixed-layer illite/smectite, both of which appear to have been formed by the alteration of vitreous material in a coal-swamp environment. The bulk mineralogy of the boundary clay bed is similar to that of other kaolinite-rich clay beds (tonsteins) that altered in coal swamps from airfall volcanic ash. The alteration process and diagenetic products of the host material in the boundary clay bed, however, differed from those of the tonsteins, resulting in a unique petrographic fabric. The boundary clay bed is characterized by an overall imbricate fabric that may reflect an original vitreous material that included shards, bubbles, and spheres. The original fallout material of the boundary clay bed first altered to "cabbage-like" microspherules, indicating a halloysite or allophane precursor, and then to well-crystallized kaolinite; the well-crystallized kaolinite is the diagenetic stable phase for these rocks at their maximum burial conditions. In comparison, the vitreous components of the tonsteins were altered directly to coarse vermicular and platey kaolinite. Alteration of the original fallout material in the boundary bed was probably rapid, leading to hydrated, disordered, fine-grained clay minerals that formed into curled spherical or tubular shapes. The factors that produced these unique fabrics in the boundary clay bed existed at all K-T sites in the Raton Basin and were much different from those that formed the coarse platey and vermicular fabrics of ordinary tonsteins. The distinctive character of the boundary clay may be due to the unique nature and chemistry of the fallout material and (or) physical or chemical conditions existing shortly after its deposition.

Journal of Sedimentary Petrology↗

Surface area of vermiculite with nitrogen and carbon dioxide as adsorbates

Surface-area studies were made on several homoionic vermiculites with both nitrogen and carbon dioxide as adsorbates. These studies show that only very slight penetration occurs between individual vermiculite platelets. This is in contrast to an earlier investigation of montmorillonite where it was found that the degree of penetration between layers is quite high, particularly for carbon dioxide, and is governed by the size and charge of the interlayer cation. The inability of these adsorbates to penetrate substantially between vermiculite platelets is due primarily to this mineral's high surface-charge density. The extent of penetration of nitrogen and carbon dioxide at the edges of vermiculite platelets, though slight, is influenced by the coordinated water retained within the sample at a given degassing temperature. Forces between layers are weakened with increasing water content, which permits slightly greater penetration by adsorbate gases. Thus, the surface area of vermiculite, as determined by gas adsorption, is larger than the calculated external surface area based upon particle size and shape considerations. In addition, "extra" surface is provided by the lifting and scrolling of terminal platelets. These morphological features are shown in scanning electron micrographs of a naturally occuring vermiculite.

Clays and Clay Minerals↗

Mixed-layer kaolinite-montmorillonite from the Yucatan Peninsula, Mexico

Clay beds 1–2 m thick and interbedded with marine limestones probably of early Eocene age are composed of nearly pure mixed-layer kaolinite-montmorillonite. Particle size studies, electron micrographs, X-ray diffraction studies, chemical analyses, cation exchange experiments, DTA, and TGA indicate that clays from three different localities contain roughly equal proportions of randomly interlayered kaolinite and montmorillonite layers. The montmorillonite structural formulas average K 0·2 Na 0·2 Ca 0·2 Mg 0·2 (Al 2·5 Fe 1·0 3+ Mg 0·5 )(Al 0·75 Si 7.25 )O 20+ (OH) 4− , with a deficiency of structural (OH) in either the montmorillonite or kaolinite layers. Nonexchangeable K + indicates that a few layers are mica-like. Crystals are mostly round plates 1/10 to 1/20 µ across. The feature most diagnostic of the mixed-layer character is an X-ray reflection near 8 Å after heating at 300°C. The clays are inferred to have developed by weathering of volcanic ash and subsequent erosion and deposition in protected nearshore basins.

Clays and Clay Minerals↗

Interlamellar adsorption of carbon dioxide by smectites

The adsorption of CO 2 at low temperature (∼ −70°C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d 001 spacings of these clay films upon adsorption of CO 2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35° with respect to the i.r. beam. The CO 2 stretching vibration at 2350 cm −1 was used for the i.r. study. These observations conclusively show that CO 2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids—the limiting process proposed by other investigators. Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO 2 . Scanning electron photomicrographs of Li- and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO 2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs.

Clays and Clay Minerals↗

Phosphates in some Missouri refractory clays

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays. The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley”" clay). The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality. The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay. Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

Clays and Clay Minerals↗

XRD measurement of mean crystallite thickness of illite and illite/smectite: Reappraisal of the Kubler index and the Scherrer equation

The standard form of the Scherrer equation, which has been used to calculate the mean thickness of the coherent scattering domain (CSD) of illite crystals from X-ray diffraction (XRD) full width data at half maximum (FWHM) intensity, employs a constant, K sh , of 0.89. Use of this constant is unjustified, even if swelling has no effect on peak broadening, because this constant is valid only if all CSDs have a single thickness. For different thickness distributions, the Scherrer “constant” has very different values. Analysis of fundamental particle thickness data (transmission electron microscopy, TEM) for samples of authigenic illite and illite/smectite from diagenetically altered pyroclastics and filamentous illites from sandstones reveals a unique family of lognormal thickness distributions for these clays. Experimental relations between the distributions' lognormal parameters and mean thicknesses are established. These relations then are used to calculate the mean thickness of CSDs for illitic samples from XRD FWHM, or from integral XRD peak widths (integrated intensity/maximum intensity). For mixed-layer illite/smectite, the measured thickness of the CSD corresponds to the mean thickness of the mixed-layer crystal. Using this measurement, the mean thickness of the fundamental particles that compose the mixed-layer crystals can be calculated after XRD determination of percent smectitic interlayers. The effect of mixed layering (swelling) on XRD peak width for these samples is eliminated by using the 003 reflection for glycolated samples, and the 001, 002 or 003 reflection for dehydrated, K-saturated samples. If this technique is applied to the 001 reflection of air-dried samples (Kubler index measurement), mean CSD thicknesses are underestimated due to the mixed-layering effect. The technique was calibrated using NEW MOD©-simulated XRD profiles of illite, and then tested on well-characterized illite and illite/smectite samples. The XRD measurements are in good agreement with estimates of the mean thickness of fundamental particles obtained both from TEM measurements and from fixed cations content, up to a mean value of 20 layers. Correction for instrumental broadening under the conditions employed here is unnecessary for this range of thicknesses.

Clays and Clay Minerals↗