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Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh (< 0.18 mm) sediments and in boulder coatings from a stream in Lincoln County, Georgia (U.S.A.). The stream drains an area containing a CuZnPb-sulfide deposit (Magruder Mine). The boulder coatings contain mainly Mn-oxides and organics, with minor hydrous Fe-oxides. In the sediment, the chemically active phases are mainly hydrous Fe-oxides and organics, probably because Mn is leaching out of the sediments and precipitating on the exposed surfaces of boulders. In the boulder coatings, competition among Fe- and Mn-oxides and organics for Cu, Zn and Pb follows the order: Cu, organics > Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Chemical Geology

Microbial methane in the shallow Paleozoic sediments and glacial deposits of Illinois, U.S.A.

Methane formed by the microbial decomposition of buried organic matter is virtually ubiquitous in the groundwaters of Illinois. Chemical and carbon isotopic compositions are reported for gas samples collected from over 200 private and municipal water wells and from 39 small gas wells completed in glacial deposits (drift-gas wells). Carbon and hydrogen isotopic data for methane, carbon dioxide and water show that these gases were formed by the carbon dioxide reduction pathway, the same mechanism which has been previously shown to be responsible for microbial methane formation in the marine environment. The isotopic composition of methane in these samples can be closely correlated with the chemical composition of the gas and with water chemistry. The data are interpreted as indicating that isotopically very light methane is found in waters where the residence time of groundwater in the methanogenesis zone was very short relative to the methane production rate. ?? 1988.

Chemical Geology

Evidence of the impacting body of the Ries crater - the discovery of Fe-Cr-Ni veinlets below the crater bottom

Fe-Cr-Ni particles and veinlets have been discovered in the top 15 m of the compressed zone with abundant shatter cones below the bottom of the Ries crater. The metallic particles are less than a few microns across. They occur in various minerals along healed intergranular and locally in intragranular microfractures in quartz diorite, amphibolite and chloritized granite of the basement crystalline rocks. The particles consist of major Fe, Cr, and Ni with minor Si and Ca. Origin due to contamination is absolutely ruled out. We believe that these Fe-Cr-Ni particles are probably condensed from the vaporized impacting body which produced the Ries crater. These particles were injected with high velocity into microfractures near the top of the compressed zone, implanted in and across various minerals before these microfractures were resealed. The presence of Si and Ca as well as the fact that the Cr content is nearly twice that of Ni, led us to conclude that the Ries impacting body is very likely not an iron meteorite but a stony meteorite.

Earth and Planetary Science Letters

Use of stable sulphur isotopes to monitor directly the behaviour of sulphur in coal during thermal desulphurization

A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 °C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 °C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur.

Illinois, Indiana, Kentucky

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO 2 . All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO x at pH 7) while the γ-MnO 2 showed the least (0.3 moles silver/ mole MnO x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.

Geochimica et Cosmochimica Acta

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density.

Geochimica et Cosmochimica Acta

A precise 232Th-208Pb chronology of fine-grained monazite: Age of the Bayan Obo REE-Fe-Nb ore deposit, China

We have obtained precise Th-Pb internal isochron ages on monazite and bastnaesite for the world's largest known rare earth elements (REE)-Fe-Nb ore deposit, the Bayan Obo of Inner Mongolia, China. The monazite samples, collected from the carbonate-hosted ore zone, contain extremely small amounts of uranium (less than 10 ppm) but up to 0.7% ThO 2 . Previous estimates of the age of mineralization ranged from 1.8 to 0.255 Ga. Magnetic fractions of monazite and bastnaesite samples (<60-μm size) showed large ranges in 232 Th 204 Pb "> 232 Th 204 Pb values (900–400,000) and provided precise Th-Pb internal isochron ages for paragenetic monazite mineralization ranging from 555 to 398 Ma within a few percent error (0.8% for two samples). These results are the first indication that REE mineralization within the giant Bayan Obo ore deposit occurred over a long period of time. The initial lead isotopic compositions (low 206 Pb 204 Pb "> 206 Pb 204 Pb and high 208 Pb 204 Pb) "> 208 Pb 204 Pb) and large negative ϵ Nd values for Bayan Obo ore minerals indicate that the main source(s) for the ores was the lower crust which was depleted in uranium, but enriched in thorium and light rare earth elements for a long period of time. Zircon from a quartz monzonite, located 50 km south of the ore complex and thought to be related to Caledonian subduction, gave an age of 451 Ma, within the range of monazite ages. Textural relations together with the mineral ages favor an epigenetic rather than a syngenetic origin for the orebodies. REE mineralization started around 555 Ma (disseminated monazite in the West, the Main, and south of the East Orebody), but the main mineralization (banded ores) was related to the Caledonian subduction event ca. 474-400 Ma.

Bayan Obo, Kuanggou Fault

Trace elemental analysis of bituminuos coals using the Heidelberg proton microprobe

Trace elements in coal can occur as components of either the organic constituents (macerals) or the inorganic constituents (minerals). Studies of the concentrations and distribution of the trace elements are vital to understanding the geochemical millieu in which the coal was formed and in evaluating the attempts to recover rare but technologically valuable metals. In addition, information on the trace element concentrations is important in predicting the environmental impact of burning particular coals, as many countries move toward greater utilization of coal reserves for energy production. Traditionally, the optical and the electron microscopes and more recently the electron microprobe have been used in studying the components of coal. The proton-induced X-ray emission (PIXE) microprobe offers a new complementary approach with an order of magnitude or more better minimum detection limit. We present the first measurements with a PIXE microprobe of the trace element concentrations of bituminous coal samples. Elemental analyses of the coal macerals-vitrinite, exinite, and inertinite-are discussed for three coal samples from the Eastern U.S.A., three samples from the Western U.S.A., and one sample from the Peoples Republic of China. ?? 1981.

Nuclear Instruments and Methods

Matrix effects on the determination of manganese in geological materials by atomic-absorption spectrophotometry under different flame conditions

Suppression caused by five of the seven matrix elements studied (Si, Al, Fe, Ca and Mg) was observed in the atomic-absorption determination of manganese in geological materials, when synthetic solutions and the recommended oxidizing air—acetylene flame were used. The magnitude of the suppression effects depends on (1) the kind and concentration of the interfering elements, (2) the type of acid medium, and (3) the concentration of manganese to be determined. All interferences noted are removed or alleviated by using a reducing nitrous oxide—acetylene flame. The atomic-absorption method using this flame can be applied to the determination of total and extractable manganese in a wide range of geological materials without interferences. Analyses of six U.S. Geological Survey rock standards for manganese gave results in agreement with the reported values.

Talanta

Determination of total tin in geological materials by electrothermal atomic-absorption spectrophotometry using a tungsten-impregnated graphite furnace

An electrothermal atomic-absorption spectrophotometric method is described for the determination of total tin in geological materials, with use of a tungsten-impregnated graphite furnace. The sample is decomposed by fusion with lithium metaborate and the melt is dissolved in 10% hydrochloric acid. Tin is then extracted into trioctylphosphine oxide-methyl isobutyl ketone prior to atomization. Impregnation of the furnace with a sodium tungstate solution increases the sensitivity of the determination and improves the precision of the results. The limits of determination are 0.5–20 ppm of tin in the sample. Higher tin values can be determined by dilution of the extract. Replicate analyses of eighteen geological reference samples with diverse matrices gave relative standard deviations ranging from 2.0 to 10.8% with an average of 4.6%. Average tin values for reference samples were in general agreement with, but more precise than, those reported by others. Apparent recoveries of tin added to various samples ranged from 95 to 111% with an average of 102%.

Talanta

Determination of gold, indium, tellurium and thallium in the same sample digest of geological materials by atomic-absorption spectroscopy and two-step solvent extraction

A rock, soil, or stream-sediment sample is decomposed with hydrofluoric acid, aqua regia , and hydrobromic acid-bromine solution. Gold, thallium, indium and tellurium are separated and concentrated from the sample digest by a two-step MIBK extraction at two concentrations of hydrobromic add. Gold and thallium are first extracted from 0.1 M hydrobromic acid medium, then indium and tellurium are extracted from 3 M hydrobromic acid in the presence of ascorbic acid to eliminate iron interference. The elements are then determined by flame atomic-absorption spectrophotometry. The two-step solvent extraction can also be used in conjunction with electrothermal atomic-absorption methods to lower the detection limits for all four metals in geological materials.

Talanta

Removal of iron interferences by solvent extraction for geochemical analysis by atomic-absorption spectrophotometry

Iron is a common interferent in the determination of many elements in geochemical samples. Two approaches for its removal have been taken. The first involves removal of iron by extraction with methyl isobutyl ketone (MIBK) from hydrochloric acid medium, leaving the analytes in the aqueous phase. The second consists of reduction of iron(III) to iron(II) by ascorbic acid to minimize its extraction into MIBK, so that the analytes may be isolated by extraction. Elements of interest can then be determined using the aqueous solution or the organic extract, as appropriate. Operating factors such as the concentration of hydrochloric acid, amounts of iron present, number of extractions, the presence or absence of a salting-out agent, and the optimum ratio of ascorbic acid to iron have been determined. These factors have general applications in geochemical analysis by atomic-absorption spectrophotometry.

Talanta

Application of automated image analysis to coal petrography

The coal petrologist seeks to determine the petrographic characteristics of organic and inorganic coal constituents and their lateral and vertical variations within a single coal bed or different coal beds of a particular coal field. Definitive descriptions of coal characteristics and coal facies provide the basis for interpretation of depositional environments, diagenetic changes, and burial history and determination of the degree of coalification or metamorphism. Numerous coal core or columnar samples must be studied in detail in order to adequately describe and define coal microlithotypes, lithotypes, and lithologic facies and their variations. The large amount of petrographic information required can be obtained rapidly and quantitatively by use of an automated image-analysis system (AIAS). An AIAS can be used to generate quantitative megascopic and microscopic modal analyses for the lithologic units of an entire columnar section of a coal bed. In our scheme for megascopic analysis, distinctive bands 2 mm or more thick are first demarcated by visual inspection. These bands consist of either nearly pure microlithotypes or lithotypes such as vitrite/vitrain or fusite/fusain, or assemblages of microlithotypes. Megascopic analysis with the aid of the AIAS is next performed to determine volume percentages of vitrite, inertite, minerals, and microlithotype mixtures in bands 0.5 to 2 mm thick. The microlithotype mixtures are analyzed microscopically by use of the AIAS to determine their modal composition in terms of maceral and optically observable mineral components. Megascopic and microscopic data are combined to describe the coal unit quantitatively in terms of (V) for vitrite, (E) for liptite, (I) for inertite or fusite, (M) for mineral components other than iron sulfide, (S) for iron sulfide, and (VEIM) for the composition of the mixed phases (X i ) i = 1,2, etc. in terms of the maceral groups vitrinite V, exinite E, inertinite I, and optically observable mineral content M. The volume percentage of each component present is indicated by a subscript. For example, a lithologic unit was determined megascopically to have the composition (V) 13 (I) 1 (S) 1 (X 1 ) 83 (X 2 ) 2 . After microscopic analysis of the mixed phases, this composition was expressed as (V) 13 (I) 1 (S) 1 (V 63 E 19 I 14 M 4 ) 83 (V 67 E 11 I 13 M 9 ) 2 . Finally, these data were combined in a description of the bulk composition as V 67 E 16 I 13 M 3 S 1 . An AIAS can also analyze textural characteristics and can be used for quick and reliable determination of rank (reflectance). Our AIAS is completely software based and incorporates a television (TV) camera that has optimum response characteristics in the range of reflectance less than 5%, making it particularly suitable for coal studies. Analysis of the digitized signal from the TV camera is controlled by a microprocessor having a resolution of 64 gray levels between full illumination and dark current. The processed image is reconverted for display on a TV monitor screen, on which selection of phases or features to be analyzed is readily controlled and edited by the operator through use of a lightpen. We expect that automated image analysis, because it can rapidly provide a large amount of pertinent information, will play a major role in the advancement of coal petrography.

International Journal of Coal Geology

Recommended procedures and techniques for the petrographic description of bituminous coals

Modern coal petrology requires rapid and precise description of great numbers of coal core or bench samples in order to acquire the information required to understand and predict vertical and lateral variation of coal quality for correlation with coal-bed thickness, depositional environment, suitability for technological uses, etc. Procedures for coal description vary in accordance with the objectives of the description. To achieve our aim of acquiring the maximum amount of quantitative information within the shortest period of time, we have adopted a combined megascopic-microscopic procedure. Megascopic analysis is used to identify the distinctive lithologies present, and microscopic analysis is required only to describe representative examples of the mixed lithologies observed. This procedure greatly decreases the number of microscopic analyses needed for adequate description of a sample. For quantitative megascopic description of coal microlithotypes, microlithotype assemblages, and lithotypes, we use (V) for vitrite or vitrain, (E) for liptite, (I) for inertite or fusain, (M) for mineral layers or lenses other than iron sulfide, (S) for iron sulfide, and (X 1 ), (X 2 ), etc. for mixed lithologies. Microscopic description is expressed in terms of V representing the vitrinite maceral group, E the exinite group, I the inertinite group, and M mineral components. volume percentages are expressed as subscripts. Thus (V) 20 (V 80 E 10 I 5 M 5 ) 80 indicates a lithotype or assemblage of microlithotypes consisting of 20 vol. % vitrite and 80% of a mixed lithology having a modal maceral composition V 80 E 10 I 5 M 5 . This bulk composition can alternatively be recalculated and described as V 84 E 8 I 4 M 4 . To generate these quantitative data rapidly and accurately, we utilize an automated image analysis system (AIAS). Plots of VEIM data on easily constructed ternary diagrams provide readily comprehended illustrations of the range of modal composition of the lithologic units making up a given coal bed. The use of bulk-specific-gravity determinations is alo recommended for identification and characterization of the distinctive lithologic units. The availability of an AIAS also enhances the capability to acquire textural information. Ranges of size of maceral and mineral grains can be quickly and precisely determined by use of an AIAS. We assume that shape characteristics of coal particles can also be readily evaluated by automated image analysis, although this evaluation has not yet been attempted in our laboratory. Definitive data on the particulate mineral content of coal constitute another important segment of petrographic description. Characterization of mineral content may be accomplished by optical identification, electron microprobe analysis, X-ray diffraction, and scanning and transmission electron microscopy. Individual mineral grains in place in polished blocks or polished this sections, or separated from the coal matrix by sink-float methods are studied by analytical techniques appropriate to the conditions of sampling.

International Journal of Coal Geology

Synchrotron radiation determination of elemental concentrations in coal

The variations with depth of the elemental concentrations in vitrinites in a series of vitrites have been determined using radiation from the Cornell high energy synchrotron source. All of the vitrites were selected from a single drill core sample of coal from the Emery coalfield, Utah. The results are compared with similar determinations using the Heidelberg proton microprobe. The advantages and disadvantages of the two techniques are discussed. Results are reported for S, Ca, Ti, Fe, Zn, Br, and Sr. For example, it is found that Fe increases from top to bottom of the coal bed in contrast to S, which decreases from top to bottom of the bed. Other features of the two data sets are also described. ?? 1984.

Nuclear Instruments and Methods in Physics Researc

Determination of the occurrence of gold in an unoxidized Carlin-type ore sample using synchrotron radiation

The occurrence of the so-called invisible gold in two unoxidized Carlin-type gold samples from Nevada has been determined using synchrotron X-ray fluorescence (SXRF) analysis at the National Synchrotron Light Source, Brookhaven National Laboratory. A bedded sample from the East ore zone of the Carlin deposit and a breccia sample from Horse Canyon were analyzed. Preliminary results show that gold is found only in the Horse Canyon breccia sample. Experimental details including other X-ray line and diffraction peak interferences, standards used, and minimum detection limits (MDLs) are discussed. Gold, with a MDL range of 0.8 to 3 ppm, was not detected in euhedral pyrite crystals except in the interior porous portion of one grain. Gold was detected in some parts of the matrix. The phase which contains gold has not yet been identified. The highest content of gold so far analyzed is about 40 ppm. There are interesting implications of these new findings. ?? 1987.

Nuclear Instruments and Methods in Physics Researc

The uses of synchrotron radiation sources for elemental and chemical microanalysis

Synchrotron radiation sources offer important features for the analysis of a material. Among these features is the ability to determine both the elemental composition of the material and the chemical state of its elements. For microscopic analysis synchrotron X-ray fluorescence (SXRF) microprobes now offer spatial resolutions of 10 ??m with minimum detection limits in the 1-10 ppm range depending on the nature of the sample and the synchrotron source used. This paper describes the properties of synchrotron radiation and their importance for elemental analysis, existing synchrotron facilities and those under construction that are optimum for SXRF microanalysis, and a number of applications including the high energy excitation of the K lines of heavy elements, microtomography, and XANES and EXAFS spectroscopies. ?? 1990.

Nuclear Instruments and Methods in Physics Researc

Rare earth element concentrations in geological and synthetic samples using synchrotron X-ray fluorescence analysis

The concentrations of rare earth elements (REEs) in specific mineral grains from the Bayan Obo ore deposit and synthetic high-silica glass samples have been measured by synchrotron X-ray fluorescence (SXRF) analysis using excitation of the REE K lines between 33 and 63 keV. Because SXRF, a nondestructive analytical technique, has much lower minimum detection limits (MDLs) for REEs, it is an important device that extends the in situ analytical capability of electron probe microanalysis (EPMA). The distribution of trace amounts of REEs in common rock-forming minerals, as well as in REE minerals and minerals having minor quantities of REEs, can be analyzed with SXRF. Synchrotron radiation from a bending magnet and a wiggler source at the National Synchrotron Light Source, Brookhaven National Laboratory, was used to excite the REEs. MDLs of 6 ppm (La) to 26 ppm (Lu) for 3600 s in 60-??m-thick standard samples were obtained with a 25-??m diameter wiggler beam. The MDLs for the light REEs were a factor of 10-20 lower than the MDLs obtained with a bending magnet beam. The SXRF REE concentrations in mineral grains greater than 25 ??m compared favorably with measurements using EPMA. Because EPMA offered REE MDLs as low as several hundred ppm, the comparison was limited to the abundant light REEs (La, Ce, Pr, Nd). For trace values of medium and heavy REEs, the SXRF concentrations were in good agreement with measurements using instrumental neutron activation analysis (INAA), a bulk analysis technique. ?? 1993.

Nuclear Instruments and Methods in Physics Researc