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D. D. Eberl

Publications and source records attributed to D. D. Eberl.

At least 19 recordsLinked to original sources

Chemistry of illite/smectite and end-member illite

Chemical data from three different series of diagenetic illite/smectites (I/S), analyzed statistically by two regresion techniques, indicate that the content of fixed-K per illite layer is not constant, but ranges from ∼0.55 per O 10 (OH) 2 for illite layers in randomly interstratified I/S (R=0; > 50% smectite layers) to ∼1.0 per O 10 (OH) 2 for illite layers formed in ordered I/S (R>0; <50% smectite layers). By extrapolation of the experimental data, the following chemical characteristics were obtained for end-member illite derived from the alteration of smectite in bentonite: average fixed-K per illite layer = 0.75 per O 10 (OH) 2 ; total charge = about −0.8; cation-exchange capacity = 15 meq/100 g; surface area (EGME) = 150 m 2 /g.

Clays and Clay Minerals↗

Three zones for illite formation during burial diagenesis and metamorphism

Reinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K + . In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. The progressive loss of radiogenic argon in the deepest zone yielded a constant apparent age for the clays with depth, an effect previously attributed to “punctuated diagenesis.” The above hypothesis for illite formation emphasizes the need to establish the zone (i.e., the reaction mechanism) from which shales were derived before making detailed geologic interpretations based on illite mineralogy.

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↗

Measurement of fundamental illite particle thicknesses by X-ray diffraction using PVP-10 intercalation

The thicknesses of fundamental illite particles that compose mixed-layer illite-smectite (I-S) crystals can be measured by X-ray diffraction (XRD) peak broadening techniques (Bertaut-Warren-Averbach [BWA] method and integral peak-width method) if the effects of swelling and XRD background noise are eliminated from XRD patterns of the clays. Swelling is eliminated by intercalating Na-saturated I-S with polyvinylpyrrolidone having a molecular weight of 10,000 (PVP-10). Background is minimized by using polished metallic silicon wafers cut perpendicular to (100) as a substrate for XRD specimens, and by using a single-crystal monochromator. XRD measurements of PVP-intercalated diagenetic, hydrothermal and low-grade metamorphic I-S indicate that there are at least 2 types of crystallite thickness distribution shapes for illite fundamental particles, lognormal and asymptotic; that measurements of mean fundamental illite particle thicknesses made by various techniques (Bertant-Warren-Averbach, integral peak width, fixed cation content, and transmission electron microscopy [TEM]) give comparable results; and that strain (small differences in layer thicknesses) generally has a Gaussian distribution in the log-normal-type illites, but is often absent in the asymptotic-type illites.

Clays and Clay Minerals↗

Determination of layer-charge characteristics of smectites

A new method for calculation of layer charge and charge distribution of smectites is proposed. The method is based on comparisons between X-ray diffraction (XRD) patterns of K-saturated, ethylene glycol-solvated, oriented samples and calculated XRD patterns for three-component, mixed-layer systems. For the calculated patterns it is assumed that the measured patterns can be modeled as random interstratifications of fully expanding 17.1 Å layers, partially expanding 13.5 Å layers and non-expanding 9.98 Å layers. The technique was tested using 29 well characterized smectites. According to their XRD patterns, smectites were classified as group 1 (low-charge smectites) and group 2 (high-charge smectites). The boundary between the two groups is at a layer charge of −0.46 equivalents per half unit-cell. Low-charge smectites are dominated by 17.1 Å layers, whereas high-charge smectites contain only 20% fully expandable layers on average. Smectite properties and industrial applications may be dictated by the proportion of 17.1 Å layers present. Non-expanding layers may control the behavior of smectites during weathering, facilitating the formation of illite layers after subsequent cycles of wetting and drying. The precision of the method is better than 3.5% at a layer charge of −0.50; therefore the method should be useful for basic research and for industrial purposes.

Clays and Clay Minerals↗

Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m 2 , which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO 2 , Fe 2 O 3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al 2 O 3 , amorphous Al(OH) 3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m 2 /g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Clays and Clay Minerals↗

Beyond the Kubler index

The value of peak width at half-height for the illite 001 XRD reflection is known as the Kubler index or the illite ‘crystallinity’ index. This measurement, which has been related to the degree of metamorphism of very low-grade, pelitic rocks, is a function of at least two crystal-chemical factors: (1) illite X-ray scattering domain size; and (2) illite structural distortions (especially swelling). Reynolds' NEWMOD computer program is used to construct a grid with which these two contributions to illite peak width can be determined independently from measurements of the 001 peak width at half-height and the Środoń intensity ratio. This method yields more information about changes undergone by illite during metamorphism than application of the Kubler index method alone.

Clay Minerals↗

Synthesis of illite-smectite from smectite at Earth surface temperatures and high pH

It is well known that illite-smectite can form from smectite at elevated temperatures in natural and experimental systems. However, the conversion of smectite to illite-smectite is also found in some natural systems that have never been heated. The present experiments show that illite layers can form from smectite by chemical reaction at 35° and 60°C at high solution pH. The rate of this reaction is accelerated by wetting and drying.

Clay Minerals↗

Varying sediment sources (Hudson Strait, Cumberland Sound, Baffin Bay) to the NW Labrador Sea slope between and during Heinrich events 0 to 4

Core HU97048-007PC was recovered from the continental Labrador Sea slope at a water depth of 945 m, 250 km seaward from the mouth of Cumberland Sound, and 400 km north of Hudson Strait. Cumberland Sound is a structural trough partly floored by Cretaceous mudstones and Paleozoic carbonates. The record extends from ∼10 to 58 ka. On-board logging revealed a complex series of lithofacies, including buff-colored detrital carbonate-rich sediments [Heinrich (H)-events] frequently bracketed by black facies. We investigate the provenance of these facies using quantitative X-ray diffraction on drill-core samples from Paleozoic and Cretaceous bedrock from the SE Baffin Island Shelf, and on the < 2-mm sediment fraction in a transect of five cores from Cumberland Sound to the NW Labrador Sea. A sediment unmixing program was used to discriminate between sediment sources, which included dolomite-rich sediments from Baffin Bay, calcite-rich sediments from Hudson Strait and discrete sources from Cumberland Sound. Results indicated that the bulk of the sediment was derived from Cumberland Sound, but Baffin Bay contributed to sediments coeval with H-0 (Younger Dryas), whereas Hudson Strait was the source during H-events 1–4. Contributions from the Cretaceous outcrops within Cumberland Sound bracket H-events, thus both leading and lagging Hudson Strait-sourced H-events.

Hudson Strait;Cumberland Sound;Baffin Bay↗

Determination of sediment provenance by unmixing the mineralogy of source-area sediments: The "SedUnMix" program

Along the margins of areas such as Greenland and Baffin Bay, sediment composition reflects a complex mixture of sources associated with the transport of sediment in sea ice, icebergs, melt-water and turbidite plumes. Similar situations arise in many contexts associated with sediment transport and with the mixing of sediments from different source areas. The question is: can contributions from discrete sediment (bedrock) sources be distinguished in a mixed sediment by using mineralogy, and, if so, how accurately? To solve this problem, four end-member source sediments were mixed in various proportions to form eleven artificial mixtures. Two of the end-member sediments are felsic, and the other two have more mafic compositions. End member and mixed sediment mineralogies were measured for the < 2 mm sediment fractions by quantitative X-ray diffraction (qXRD). The proportions of source sediments in the mixtures then were calculated using an Excel macro program named SedUnMix, and the results were evaluated to determine the robustness of the algorithm. The program permits the unmixing of up to six end members, each of which can be represented by up to 5 alternative compositions, so as to better simulate variability within each source region. The results indicate that we can track the relative percentages of the four end members in the mixtures. We recommend, prior to applying the technique to down-core or to other provenance problems, that a suite of known, artificial mixtures of sediments from probable source areas be prepared, scanned, analyzed for quantitative mineralogy, and then analyzed by SedUnMix to check the sensitivity of the method for each specific unmixing problem.

Baffin Bay↗

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate‐reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu‐2, mixed‐layer illite‐smectite RAr‐1 and ISCz‐1, and illite IMt‐1) were exposed to D. vulgaris in a non‐growth medium with and without anthraquinone‐2,6‐disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X‐ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals.

Geobiology↗

Anatomy of a metabentonite: Nucleation and growth of illite crystals and their coalescence into mixed-layer illite/smectite

The illite layer content of mixed-layer illite/smectite (I/S) in a 2.5 m thick, zoned, metabentonite bed from Montana decreases regularly from the edges to the center of the bed. Traditional X-ray diffraction (XRD) pattern modeling using Markovian statistics indicated that this zonation results from a mixing in different proportions of smectite-rich R0 I/S and illite-rich R1 I/S, with each phase having a relatively constant illite layer content. However, a new method for modeling XRD patterns of I/S indicates that R0 and R1 I/S in these samples are not separate phases (in the mineralogical sense of the word), but that the samples are composed of illite crystals that have continuous distributions of crystal thicknesses, and of 1 nm thick smectite crystals. The shapes of these distributions indicate that the crystals were formed by simultaneous nucleation and growth. XRD patterns for R0 and R1 I/S arise by interparticle diffraction from a random stacking of the crystals, with swelling interlayers formed at interfaces between crystals from water or glycol that is sorbed on crystal surfaces. It is the thickness distributions of smectite and illite crystals (also termed fundamental particles, or Nadeau particles), rather than XRD patterns for mixed-layer I/S, that are the more reliable indicators of geologic history, because such distributions are composed of well-defined crystals that are not affected by differences in surface sorption and particle arrangements, and because their thickness distribution shapes conform to the predictions of crystal growth theory, which describes their genesis.

Montana↗

Arsenic in sediments, groundwater, and streamwater of a glauconitic Coastal Plain terrain, New Jersey, USA-Chemical " fingerprints" for geogenic and anthropogenic sources

Glauconite-bearing deposits are found worldwide, but As levels have been determined for relatively few. The As content of glauconites in sediments of the Inner Coastal Plain of New Jersey can exceed 100 mg/kg, and total As concentrations (up to 5.95 μg/L) found historically and recently in streamwaters exceed the State standard. In a major watershed of the Inner Coastal Plain, chemical “fingerprints” were developed for streambed sediments and groundwater to identify contributions of As to the watershed from geologic and anthropogenic sources. The fingerprint for streambed sediments, which included Be, Cr, Fe and V, indicated that As was predominantly of geologic origin. High concentrations of dissolved organic C, nutrients (and Cl − ) in shallow groundwater indicated anthropogenic inputs that provided an environment where microbial activity released As from minerals to groundwater discharging to the stream. Particulates in streamwater during high flow constituted most of the As load; the chemical patterns for these particulates resembled the geologic fingerprint of the streambed sediments. The As/Cr ratio of these suspended particles likely indicates they derived not only from runoff, but from groundwater inputs, because As contributed by groundwater is sequestered on streambed sediments. Agricultural inputs of As were not clearly identified, although chemical characteristics of some sediments indicated vehicle-related inputs of metals. Sediment sampling during dry and wet years showed that, under differing hydrologic conditions, local anthropogenic fingerprints could be obscured but the geologic fingerprint, indicating glauconitic sediments as an As source, was robust.

New Jersey↗

Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri

Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H 2 /CO 2 , methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H 2 /CO 2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7–13% with H 2 /CO 2 as substrate, depending on nontronite concentration (5–10 g/L). The extent was higher when methanol was used as a substrate, reaching 25–33%. Methanogenesis was inhibited by Fe(III) reduction in the H 2 /CO 2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.

Geochimica et Cosmochimica Acta↗

Surface (sea floor) and near-surface (box cores) sediment mineralogy in Baffin Bay as a key to sediment provenance and ice sheet variations

To better understand the glacial history of the ice sheets surrounding Baffin Bay and to provide information on sediment pathways, samples from 82 seafloor grabs and core tops, and from seven box cores were subjected to quantitative X-ray diffraction weight percent (wt.%) analysis of the <2 mm sediment fraction. The samples were collected between 67°N and 78°N, in water depths of 155 to 2375 m and were retrieved on cruises between A.D. 1964 and 2009. Grain size, magnetic characteristics, and colour reflectance data were also obtained on many of the samples. Twenty-one non-clay and 10 clay mineral species were identified; the average wt.% of the non-clay minerals was 70% and was dominated by quartz, various feldspars, and dolomite, whereas the dominant clay minerals were 1 M illite, biotite, and chlorite. Cluster analysis on principal component scores identified three main mineral groups, which also had strong associations with grain size and sediment magnetic properties. Box cores from the deep central basin (>2000 m) all show an abrupt drop in calcite wt.% (post-5 cal ka BP?) following a major peak in detrital carbonate (mainly dolomite). This dolomite-rich detrital carbonate (DC) event in JR175BC06 is possibly coeval with the Younger Dryas cold event. Four possible glacial-sourced end members were employed in a compositional unmixing algorithm to gain insight into down core changes in sediment provenance at the deep central basin. Estimates of the rates of sediment accumulation in the central basin are only in the range of 2 to 4 cm/cal ka, surprisingly low given the glaciated nature of the surrounding land.

Canadian Journal of Earth Sciences↗

Comparison of transport and attachment behaviors of Cryptosporidium parvum oocysts and oocyst-sized microspheres being advected through three minerologically different granular porous media

In order to gain more information about the fate of Cryptosporidium parvum oocysts in tropical volcanic soils, the transport and attachment behaviors of oocysts and oocyst-sized polystyrene microspheres were studied in the presence of two soils. These soils were chosen because of their differing chemical and physical properties, i.e., an organic-rich (43–46% by mass) volcanic ash-derived soil from the island of Hawaii, and a red, iron (22–29% by mass), aluminum (29–45% by mass), and clay-rich (68–76% by mass) volcanic soil from the island of Oahu. A third agricultural soil, an organic- (13% by mass) and quartz-rich (40% by mass) soil from Illinois, was included for reference. In 10-cm long flow-through columns, oocysts and microspheres advecting through the red volcanic soil were almost completely (98% and 99%) immobilized. The modest breakthrough resulted from preferential flow-path structure inadvertently created by soil-particle aggregation during the re-wetting process. Although a high (99%) removal of oocysts and microsphere within the volcanic ash soil occurred initially, further examination revealed that transport was merely retarded because of highly reversible interactions with grain surfaces. Judging from the slope of the substantive and protracted tail of the breakthrough curve for the 1.8-μm microspheres, almost all (>99%) predictably would be recovered within ∼4000 pore volumes. This suggests that once contaminated, the volcanic ash soil could serve as a reservoir for subsequent contamination of groundwater, at least for pathogens of similar size or smaller. Because of the highly reversible nature of organic colloid immobilization in this soil type, C. parvum could contaminate surface water should overland flow during heavy precipitation events pick up near-surface grains to which they are attached. Surprisingly, oocyst and microsphere attachment to the reference soil from Illinois appeared to be at least as sensitive to changes in pH as was observed for the red, metal-oxide rich soil from Oahu. In contrast, colloidal attachment in the organic-rich, volcanic ash soil was relatively insensitive to changes in pH in spite of the high iron content. Given the fundamental differences in transport behavior of oocyst-sized colloids within the two volcanic soils of similar origin, agricultural practices modified to lessen C. parvum contamination of ground or surface water would necessitate taking the individual soil properties into account.

Water Research↗

Continental-scale patterns in soil geochemistry and mineralogy: results from two transects across the United States and Canada

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada (GSC) initiated a pilot study that involved collection of more than 1500 soil samples from 221 sites along two continental transects across Canada and the United States. The pilot study was designed to test and refine protocols for a soil geochemical survey of North America. The two transects crossed a wide array of soil parent materials, soil ages, climatic conditions, landforms, land covers and land uses. Sample sites were selected randomly at approximately 40-km intervals from a population defined as all soils of the continent. At each site, soils representing 0 to 5 cm depth, and the O, A, and C horizons, if present, were collected and analyzed for their near-total content of over 40 major and trace elements. Soils from 0–5 cm depth were also collected for analysis of organic compounds. Results from the transects confirm that soil samples collected at a 40-km spacing reveal coherent, continental- to subcontinental-scale geochemical and mineralogical patterns that can be correlated to aspects of underlying soil parent material, soil age and climate influence. The geochemical data also demonstrate that at the continental-scale the dominance of any of these major factors that control soil geochemistry can change across the landscape. Along both transects, soil mineralogy and geochemistry change abruptly with changes in soil parent materials. However, the chemical influence of a soil’s parent material can be obscured by changing climatic conditions. For the transects, increasing precipitation from west to east and increasing temperature from north to south affect both soil mineralogy and geochemistry because of climate effects on soil weathering and leaching, and plant productivity. Regional anomalous metal concentrations can be linked to natural variations in soil parent materials, such as high Ni and Cr in soils developed on ultramafic rocks in California or high P in soils formed on weathered Ordovician limestones in central Kentucky. On local scales, anomalous metal concentrations recognized in soil profiles, such as high P in soils from animal confinement sites, are consistent with local anthropogenic disturbances. At a larger scale, the distribution of Hg across the west to east transect demonstrates that it can be difficult to distinguish between natural or anthropogenic contributions and that many factors can contribute to an element’s spatial distribution. Only three samples in a subset of seventy-three 0–5 cm depth soil samples from the north to south transect had organochlorine pesticides values above the method detection limit, apparently related to historic usage of the pesticides DDT and dieldrin.

Applied Geochemistry↗

Mineralogy of soils from two continental-scale transects across the United States and Canada and its relation to soil geochemistry and climate

Quantitative mineralogy correlates with major-, minor- and trace-element chemistry for 387 samples of A-horizon and deeper soils collected from east-west and north-south transects across the USA and Canada, where the deeper soils were collected beneath the A-horizon samples. Concentrations of the major elements correlate with specific mineral phases. Minor- and trace-element concentrations correlate with the same phases as the major elements with which they share similar geochemical behavior. Concentrations of quartz and feldspar correlate with precipitation trends east of the Rocky Mountains, and are independent of the underlying rock type and age, indicating that the weathering of soils in this region may have reached a steady-state mineralogy. Other trends in mineralogy relate to physiographic province. The combination of quantitative mineralogy and chemical analysis yields a much richer portrait of soils than can be gained from chemistry alone, because the origins of chemical trends and the chemical availability of specific elements are related to mineralogy.

Applied Geochemistry↗