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Paleomagnetism and the compositions of highly-oxidised iron-titanium oxides in basalts

As a preliminary step towards determination of the source of the natural remanence in highly-oxidised basalt lava flows, electron probe microanalysis has been carried out on the two main phases in each of two types of highly-oxidised iron-titanium oxide. The discovery of the source of NRM in these basalts is important because the correlations obtained recently by several workers between high oxidation and reversed polarity in basalts appear to support the possibility of self-reversal, even though some of the rocks studied give independent indications that the reversed magnetizations are due to field reversal. In one type of grain analysed the probe data are consistent with a titanohematite phase and a pseudobrookite phase. This agrees with previous petrographic data. In the other type of grain the probe data are consistent with one phase of titanohematite but contradict petrographic data by showing that the other phase cannot be titanomagnetite. It is concluded that significant contributions to the NRM could possibly arise from the titanohematite (whose magnetic properties in basalts are little known) or the unindentified phase (unless subsequent work rules this phase out), but not in the pseudobrookite phase. However, the NRM may not lie in the analysed grains at all; and other workers are at present investigating this possibility.

Physics of the Earth and Planetary Interiors↗

Comparison of geoelectrical/tectonic models for suture zones in the western U.S.A. and eastern Europe: are black shales a possible source of high conductivities?

Large-scale geoelectrical anomalies have been mapped with geomagnetic depth sounding (GDS) and magnetotelluric (MT) surveys in the Carpathian Mountains region. These anomalies are associated with the zone of closure between stable Europe and a complex of microplates in front of the converging African plate. The zone of closure, or suture zone, is largely occupied by an extensive deformed flysch belt. The models derived to fit the observed geoelectrical data are useful in the study of other suture zones, and Carpathian structures have been compared with areas currently being studied in the western Cordillera of the U.S.A. Models derived for a smaller-scale suture zone mapped in western Washington State have features that are similar to the Carpathian models. The geoelectrical models for both the Carpathian and Washington anomalies require dipping conductive slabs of 1-5 ?? m material that extends to depths > 20 km. In both instances there is evidence that these materials may merge with lower crustal-mantle conductors along the down-dip margins of the slab. The main conductive units are interpreted to be sedimentary rocks that have been partially subducted due to collisional processes. Heat flow is low in both regions and it is difficult to explain fully the deep conduction mechanisms; however, evidence suggests that the conduction at depth may include electronic conduction in sulfide mineral or carbon films as well as ionic conduction in fluids or partial melt. ?? 1989.

Physics of the Earth and Planetary Interiors↗

A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates

A valence-specific analytical method for determining V 3+ in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V 3+ /V tot ratio, followed by determination of V 3+ in the presence of V 4+ . The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100° in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V 3+ -thiocyanate complex in aqueous-acetone medium. Fe 3+ is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mössbauer spectroscopy.

Talanta↗

Zooplankton production and manipulation in striped bass rearing ponds

Zooplankton production and survival of striped bass fry ( Morone saxatilis ) were examined in ponds treated either with organic fertilizer (in 1980) or with a combination of organic and liquid inorganic fertilizers and inoculated with Daphnia pulex (in 1981). In 1980, there were significant differences in water quality variables and chlorophyll α levels among treatments in three series of three ponds fertilized only with different amounts of ground hay. Production of crustacean zooplankton was low, and rotifer populations increased as the number of crustaceans was reduced by predation. Electron transport system (ETS) activity was low in all treatments. Survival of striped bass differed greatly within and between treatments, ranging from 1 to 64% and averaging 17%. In 1981, water quality variation was less among treatments in four series of three ponds inoculated with Daphnia and fertilized either with chicken litter-chicken manure in combination with liquid ammonium nitrate and phosphoric acid, or with ground hay. Rotifer species were less abundant and numbers of crustacean zooplankton, total protein, and ETS activity were higher than in 1980. Survival of striped bass in 1981 ranged from 1 to 96% and averaged 45% in the ponds fertilized and inoculated with Daphnia . Numbers of striped bass fingerlings produced per hectare and percent survival were significantly greater in 1981 (manure-fertilized ponds) than in 1980 (hay-fertilized ponds). Combinations of organic and liquid inorganic fertilizers and zooplankton inoculation are suggested to develop and maintain the zooplankton forage base in striped bass rearing ponds. Management effort (including the amounts and timing of organic and liquid inorganic fertilizers) should be shifted to maximize crustacean zooplankton foods during the period 2 weeks before and 2 weeks after the fish are stocked.

Aquaculture↗

Effect of subatmospheric pressure on the performance of an automated packed-column nitrogen desorption system

A portable vacuum degasser was developed to satisfy seasonal hatchery pretreatment needs. Dissolved-gas pressures in water exiting a packed column were regulated automatically with a unique feedback control loop incorporating a gasometer, pressure transducer, electronic (PID) controller and an electrically actuated pump discharge valve. The flow capacity of the system was 160 l/min with a total power requirement of 0·81 kW. Following controller tuning, field tests demonstrated the ability of the feedback loop to set appropriate column vacuum levels quickly in response to varying inlet dissolved-gas pressures or changes in selected controller set points. The degasser's ability to reduce dissolved nitrogen (DN) and increase dissolved oxygen (DO) concentrations was also assessed at four or five pure-oxygen feed rates under each of four column vacuum levels (−4·5, −9·0, −14·6 and −20·0 cm Hg). Performance was then compared with that predicted with a multicomponent gas transfer model. Relative error of model projections averaged just 7·7% for DO and 2·3% for DN (n = 19). Effluent DN ranged between 60·6 and 96·4% of saturation concentrations at 8·8°C with the influent DN at 135% of saturation. The high DN desorption rates achieved allow side-stream pretreatment with blending.

Aquacultural Engineering↗

Variation of organic sulfur in macerals of selected Illinois Basin coals

An electron microbeam technique was used to determine the distribution of organic sulfur in the main macerals of five Illinois Basin coals. On average, sporinites are the highest, inertinites the lowest, and vitrinites intermediate in organic sulfur for each coal. The observed differences are likely due to varying affinities of the different pre-maceral materials for sulfur and/or local variation in the production of H 2 S primarily during the peat stage. Investigation of molecular structures of individual macerals in relation to the findings of this study may delineate the relative abundance of organic sulfur in various organic compounds and thus lead to the development of efficient desulfurization processes.

Organic Geochemistry↗

Differentiation of volcanic ash-fall and water-borne detrital layers in the Eocene Senakin coal bed, Tanjung Formation, Indonesia

The Sangsang deposit of the Eocene Senakin coal bed, Tanjung Formation, southeastern Kalimantan, Indonesia, contains 11 layers, which are thin (<5 cm) and high in ash (> 70%). These layers are characterized by their pelitic macroscopic texture. Examination of eight of the layers by scanning-electron microscopy, energy-dispersive X-ray, and X-ray diffraction analyses show that they are composed primarily of fairly well-crystallized kaolinite, much of which is vermicular. Accessory minerals include abundant Ti oxide, rare-earth element-rich Ca and A1 phosphates, quartz that luminescences in the blue color range, and euhedral to subhedral pyroxene, hornblende, zircon, and sanidine. Although this mineral suite is suggestive of volcanic ash-fall material, only the four pelitic layers in the middle of the bed are thought to be solely derived from volcanic ash-falls on the basis of diagnostic minerals, replaced glass shards, and lithostratigraphic relationships observed in core and outcrop. The three uppermost pelitic layers contain octahedral chromites, some quartz grains that luminesce in teh orange color range, and some quartz grains that contain two-phase fluid inclusions. These layers are interpreted to be derived from a combination of volcanic ash-fall material and hydrologic transport of volcaniclastic sediment. In contrast, the lowermost pelitic layer, which contains large, rounded FeMg-rich chromites, is thought to have been dominantly deposited by water. The source of the volcanic ash-fall material may have been middle Tertiary volcanism related to plate tectonic activity between Kalimantan and Sulawesi. The volcanic ash was deposited in sufficient amounts to be preserved as layers within the coal only in the northern portions of the Senakin region: the southern coal beds in the region do not contain pelitic layers.

southeastern Kalimantan↗

SEM-EDX and isotope characterization of the organic sulfur in macerals and chars in Illinois Basin coals

Two samples of the Herrin (Illinois No. 6) Coal and one sample of the Colchester (Illinois No. 2) Coal from the Illinois Basin were studied to evaluate the spatial distribution of organic sulfur within macerals occurring next to pyrite grains, both in the raw coal and their chars. The chars were produced by pyrolysing the coal at 250–550°C in a nitrogen atmosphere. Representative splits of the coals and their chars were mounted in epoxy and polished for optical microscopy and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX). Determinations of organic sulfur concentrations were made at 996 locations within macerals, mostly vitrinite, around 115 grains of pyrite and at 50 locations around 5 pores in chars. The pyrite considered here is restricted to the disseminated type within macerals. On the average, the organic sulfur content increased near pyrite grains after the coals were charred at 550°C, indicating that some of the pyritic sulfur released during charring was retained within the organic matrix rather than being emitted to the atmosphere. One of the coal samples and its chars were isotopically characterized by chemically separating the pyritic and organic sulfur fractions, followed by analyzing the isotopes of the sulfur forms with a Nuclide 6–60 ratio mass spectrometer. The sulfur isotope (δ 34 S) data confirmed the movement of pyritic sulfur into the macerals after charring to 550°C. About 18% of the organic sulfur that remained in the 550°C char had originally been pyritic sulfur in the untreated coal.

Organic Geochemistry↗

Factors affecting the geochemistry of a thick, subbituminous coal bed in the Powder River Basin: Volcanic, detrital, and peat-forming processes

The inorganic geochemistry and mineralogy of three cores from the Anderson-Dietz 1 coal bed, a 15.2-m-thick subbituminous coal bed in the Tongue River Member (Paleocene) of the Fort Union Formation, were examined (1) to determine if the cores could be correlated by geochemical composition alone over a total distance of 2 km and (2) to identify the major factors that influenced the geochemistry of the coal bed. Chemical data (46 elements on a coal-ash basis) for 81 coal samples and 4 carbonaceous rock samples, with most samples representing a 0.6-m-thick (2-ft) interval of core, were grouped into compositional clusters by means of cluster analysis. Seven major clusters were produced; two of these clusters can be used to correlate the coal bed throughout the study area. Data from scanning electron and optical microscope analyses indicate that several factors influenced the geochemistry of the Anderson-Dietz 1 coal bed. The majority of mineral grains in the coal bed are interpreted to be detrital (water borne); evidence includes the presence of rounded to subrounded quartz grains having two-phase, aqueous fluid inclusions characteristic of hydrothermal or low-to-moderate grade metamorphic quartz. These quartz grains are found throughout the coal bed but are most abundant in samples from the midpart of the bed, which was influenced by detrital input associated with the deposition of the clastic rocks that form the split between the Anderson and Dietz 1 coal beds 900 m to the east of the study area. In addition to the detrital minerals mentioned above, volcanic ash that was fluvially transported to the sites of peat deposition or possibly deposited as air-fall volcanic ash also affected the geochemistry of the coal bed. For example, crandallite(?), a mineral reported to form as an alteration product of volcanic ash, is found in seven samples from the coal bed. The presence of quartz grains containing silicate-melt inclusions in eight samples from the coal bed.provides further support for a volcanic ash component. Other factors that probably affected the geochemistry of the coal bed include (1) detrital input associated with the deposition of the roof rocks of the coal bed, (2) peat-forming processes and plant material, and (3) epigenetic ground-water flow.

Montana, Wyoming↗

Origin and significance of high nickel and chromium concentrations in pliocene lignite of the Kosovo Basin, Serbia

Trace element data from 59 Pliocene lignite cores from the lignite field in the Kosovo Basin, southern Serbia, show localized enrichment of Ni and Cr (33-304 ppm and 8-176 ppm, respectively, whole-coal basis). Concentrations of both elements decrease from the western and southern boundaries of the lignite field. Low-temperature ash and polished coal pellets of selected bench and whole-coal samples were analyzed by X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray analyses. These analyses show that most of the Ni and Cr are incorporated in detrital and, to a lesser degree, in authigenic minerals. The Ni- and Cr-bearing detrital minerals include oxides, chromites, serpentine-group minerals and rare mixed-layer clays. Possible authigenic minerals include Ni-Fe sulfates and sulfides. Analyses of three lignite samples by a supercritical fluid extraction technique indicate that some (1-11%) of the Ni is organically bound. Ni- and Cr-bearing oxides, mixed-layer clays, chromites and serpentine-group minerals were also identified in weathered and fresh samples of laterite developed on serpentinized Paleozoic peridotite at the nearby Glavica and C??ikatovo Ni mines. These mines are located along the western and northwestern rim, respectively, of the Kosovo Basin, where Ni contents are highest. The detrital Ni- and Cr-bearing minerals identified in lignite samples from the western part of the Kosovo Basin may have been transported into the paleoswamp by rivers that drained the two Paleocene laterites. Some Ni may have been transported directly into the paleoswamp in solution or, alternatively, Ni may have been leached from detrital minerals by acidic peat water and adsorbed onto organic matter and included into authigenic mineral phases. No minable source of Ni and Cr is known in the southern part of the lignite field; however, the mineral and chemical data from the lignite and associated rocks suggest that such a source area may exist.

International Journal of Coal Geology↗

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↗

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HCl HF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C "> HC ratios, X-ray diffraction (XRD), 13 C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C "> HC ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp 2 -hybridized and 20% is sp 3 -hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300°C shows that the materials examined have not previously been subjected to temperatures as high as 300°C.

Witwatersrand goldfields↗

Test system for exposing fish to resuspended, contaminated sediment

We describe a new test system for exposing fish to resuspended sediments and associated contaminants. Test sediments were resuspended by revolving test chambers on rotating shafts driven by an electric motor. The timing, speed, and duration of test-chamber revolution were controlled by a rheostat and electronic timer. Each chamber held 45 litres of water and accommodated about 49 g of test fish. The system described had three water baths, each holding six test chambers. We illustrate the performance of this system with results from a 28-day test in which juvenile bluegills Lepomis macrochirus were exposed to resuspended, riverine sediments differing in texture and cadmium content. The test had one sediment-free control and five sediment treatments, with three replicates (chambers) per treatment and 25 fish per replicate. Two-thirds (30 litres) of the test water and sediment in each chamber was renewed weekly. The mean concentration of total suspended solids (TSS) did not vary among treatments; the grand-mean TSS in the five sediment treatments was 975 mg litre −1 , similar to the target TSS of 1000 mg litre −1 . At the end of the test, an average of 50% of the introduced cadmium was associated with the suspended sediment compartment, whereas the filtered (0.45 μm) water contained 0.4% and bluegills 1.8% of the cadmium.

Environmental Pollution↗

Regional and local networks of horizontal control, Cerro Prieto geothermal area

The Cerro Prieto geothermal area in the Mexicali Valley 30 km southeast of Mexicali, Baja California, is probably deforming due to (1) the extraction of large volumes of steam and hot water, and (2) active tectonism. Two networks of precise horizontal control were established in Mexicali Valley by the U.S. Geological Survey in 1977 - 1978 to measure both types of movement as they occur. These networks consisted of (1) a regional trilateration net brought into the mountain ranges west of the geothermal area from survey stations on an existing U.S. Geological Survey crustal-strain network north of the international border, and (2) a local net tied to stations in the regional net and encompassing the area of present and planned geothermal production. Survey lines in this net were selected to span areas of probable ground-surface movements in and around the geothermal area. Electronic distance measuring (EDM) instruments, operating with a modulated laser beam, were used to measure the distances between stations in both networks. The regional net was run using a highly precise long-range EDM instrument, helicopters for transportation of men and equipment to inaccessible stations on mountain peaks, and a fixed wing airplane flying along the line of sight. Precision of measurements with this complex long-range system approached 0-2 ppm of line length. The local net was measured with a medium-range EDM instrument requiring minimal ancillary equipment. Precision of measurements with this less complex system approached 3 ppm for the shorter line lengths. The detection and analysis of ground-surface movements resulting from tectonic strains or induced by geothermal fluid withdrawal is dependent on subsequent resurveys of these networks. ?? 1979.

Geothermics↗

Physio-chemical and morphological characteristics of avian encephalomyelitis virus

Avian encephalomyelitis virus (AEV) was purified from infected chick embryos by a gradient centrifugation in cesium chloride. The virus had a buoyant density of 1.31 to 1.32 g/ml and a sedimentation coefficient of 148 S. The purified AEV was resistant to treatments with chloroform, acid pH or trypsin. The presence of Mg++ stabilized the virus against heat inactivation (56&deg;C, 1 h). Electron microscopic study showed the virus to be 24 to 32 nm in diameter. The surface structure of the purified virus was not easily discernable. Nevertheless, with uranyl acetate-stained particles, Markham's rotation technique revealed that AEV has five-fold symmetry with 32 or 42 capsomers. Exact classification of AEV awaits characterization of the viral nucleic acid.

Veterinary Microbiology↗

Surface chemical effects on colloid stability and transport through natural porous media

Surface chemical effects on colloidal stability and transport through porous media were investigated using laboratory column techniques. Approximately 100 nm diameter, spherical, iron oxide particles were synthesized as the mobile colloidal phase. The column packing material was retrieved from a sand and gravel aquifer on Cape Cod, MA. Previous studies have indicated enhanced stability and transport of iron oxide particles due to specific adsorption of some inorganic anions on the iron oxide surface. This phenomenon was further evaluated with an anionic surfactant, sodium dodecyl sulfate. Surfactants constitute a significant mass of the contaminant loading at the Cape Cod site and their presence may contribute to colloidal transport as a significant transport mechanism at the site. Other studies at the site have previously demonstrated the occurrence of this transport mechanism for iron phosphate particles. Photon correlation spectroscopy, micro-electrophoretic mobility, and scanning electron microscopy were used to evaluate particle stability, mobility and size. Adsorption of negatively charged organic and inorganic species onto the surface of the iron oxide particles was shown to significantly enhance particle stability and transport through alterations of the electrokinetic properties of the particle surface. Particle breakthrough generally occurred simultaneously with tritiated water, a conservative tracer. The extent of particle breakthrough was primarily dependent upon colloidal stability and surface charge.

Massachusetts↗

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Journal of Photochemistry and Photobiology A: Chem↗

Direct chemical analysis of uv laser ablation products of organic polymers by using selective ion monitoring mode in gas chromatography/mass-spectrometry

Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the iaser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in anatyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.

Journal of the American Society for Mass Spectrome↗