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DISTRIBUTION OF TRACE ELEMENTS IN COAL MINERALS OF SELECTED EASTERN UNITED STATES COALS.

The association of 34 elements with minerals found in coal was determined by a combination of analytical techniques on size and density fractions of low-temperature ash (LTA). Instrumental neutron activation analysis was used to determine the concentrations of the elements, and X-ray diffraction analysis, scanning electron microscopy, and scanning transmission electron microscopy were used to identify the minerals present in the LTA. The distribution of elemental and mineral concentrations in different size fractions was also determined. Between 35 and 60 weight percent of the LTA was composed of particles smaller than 2 mu m.

Conference Paper

Elemental X-ray mapping of agglutinated foraminifer tests: A non- destructive technique for determining compositional characteristics.

The composition of agglutinated foraminiferal tests vary remarkably in response to local substrate characteristics, physiochemical properties of the water column and species- dependant selectivity of test components. We have employed a technique that combines a scanning electron microscope with an energy dispersive X-ray spectrometer system to identify major and minor elemental constituents of agglutinated foraminiferal walls. As a sample is bombarded with a beam of high energy electrons, X-rays are generated that are characteristic of the elements present. As a result, X- ray density maps can be produced for each of several elements present in the tests of agglutinated foraminifers.

Micropaleontology

PROTON MICROPROBE ANALYSIS OF TRACE-ELEMENT VARIATIONS IN VITRINITES IN THE SAME AND DIFFERENT COAL BEDS.

The PIXE (proton-induced X-ray emission) microprobe can be used for nondestructive, in-situ analyses of areas as small as those analyzed by the electron microprobe, and has a sensitivity of detection as much as two orders of magnitude better than the electron microprobe. Preliminary studies demonstrated that PIXE provides a capability for quantitative determination of elemental concentrations in individual coal maceral grains with a detection limit of 1-10 ppm for most elements analyzed. Encouraged by the earlier results, we carried out the analyses reported below to examine trace element variations laterally (over a km range) as well as vertically (cm to m) in the I and J coal beds in the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in central Utah, and to compare the data with the data from two samples of eastern coals of Pennsylvanian age.

Scanning Micros

Enzyme leaching of surficial geochemical samples for detecting hydromorphic trace-element anomalies associated with precious-metal mineralized bedrock buried beneath glacial overburden in northern Minnesota

One objective of the International Falls and Roseau, Minnesota, CUSMAP projects was to develop a means of conducting regional-scale geochemical surveys in areas where bedrock is buried beneath complex glacially derived overburden. Partial analysis of B-horizon soils offered hope for detecting subtle hydromorphic trace-element dispersion patterns. An enzyme-based partial leach selectively removes metals from oxide coatings on the surfaces of soil materials without attacking their matrix. Most trace-element concentrations in the resulting solutions are in the part-per-trillion to low part-per-billion range, necessitating determinations by inductively coupled plasma/mass spectrometry. The resulting data show greater contrasts for many trace elements than with other techniques tested. Spatially, many trace metal anomalies are locally discontinuous, but anomalous trends within larger areas are apparent. In many instances, the source for an anomaly seems to be either basal till or bedrock. Ground water flow is probably the most important mechanism for transporting metals toward the surface, although ionic diffusion, electrochemical gradients, and capillary action may play a role in anomaly dispersal. Sample sites near the Rainy Lake-Seine River fault zone, a regional shear zone, often have anomalous concentrations of a variety of metals, commonly including Zn and/or one or more metals which substitute for Zn in sphalerite (Cd, Ge, Ga, and Sn). Shifts in background concentrations of Bi, Sb, and As show a trend across the area indicating a possible regional zoning of lode-Au mineralization. Soil anomalies of Ag, Co, and Tl parallel basement structures, suggesting areas that may have potential for Cobalt/Thunder Baytype silver viens. An area around Baudette, Minnesota, which is underlain by quartz-chlorite-carbonate-altered shear zones, is anomalous in Ag, As, Bi, Co, Mo, Te, Tl, and W. Anomalies of Ag, As, Bi, Te, and W tend to follow the fault zones, suggesting potential for lode-Au deposits. Soil anomalies of Co, Mo, and Tl appear to follow northwest-striking structures that cross the shear zones, suggesting that Thunder Bay-type mineralization may have overprinted earlier mineralization along the shear zones.

Conference Paper

Geochemistry of the 1989-1990 eruption of redoubt volcano: Part I. Whole-rock major- and trace-element chemistry

The 1989-1990 eruption of Redoubt Volcano produced medium-K calc-alkaline andesite and dacite of limited compositional range (58.2-63.4% SiO2) and entrained quenched andesitic inclusions (55% SiO2) which bear chemical similarities to the rest of the ejecta. The earliest (December 15) magmas are pumiceous, often compositionally banded, and the majority is relatively mafic (< 59% SiO2). The most silicic magmas of the eruption are the late December to early January domes (up to 63.4% SiO2). Subsequent magmas formed domes and rare pumices which converge on 60% SiO2. Chemical variations among ejecta comprise tight, linear, two-component arrays for all elements for which the analytical uncertainty is much less than the compositional range. The two-component arrays are interpreted as mixing arrays between unrelated magmas because several of the arrays are at steep angles to the normal liquid line of descent. Additionally, the felsic endmember cannot be easily related to the mafic endmember by normal high-temperature igneous processes (e.g., the silicic endmember has higher Zr yet lower Hf than the mafic endmember). Also relative enrichments of highly incompatible elements are dramatically different across the arrays. The mixing event must have preceded eruption by a significant, yet unspecified amount of time because groundmass glass compositions are homogeneous for all post-December samples (Swanson et al., 1994-this volume), in spite of the whole-rock chemical diversity. This implies time for additional crystallization after the mixing event. Swanson et al. (1994-this volume) discuss evidence for a potentially different mixing event recorded only in December 15 magmas. Cognate cumulate xenoliths composed of pl+cpx+opx+hb+mt+melt were recovered from January and April deposits. These blocks differ from local batholithic country rock in their low concentrations of incompatible elements (e.g., Rb < 5 ppm vs 20-90 ppm, Ba < 150 ppm vs 300-2000 ppm) and low SiO2 (< 50 wt.% vs > 60 wt.%). They have Mg, Cr, Ni, Sc, and V contents higher than the andesites, but lower than Redoubt basalts and basaltic andesites. Thus, they may be crystallization products of andesites, but do not represent the cumulate residue of basalt fractionation. The xenoliths were probably derived from a shallow or intermediate crustal chamber. ?? 1994.

Journal of Volcanology and Geothermal Research

Paragenetic and minor- and trace-element studies of Mississippi Valley-type ore deposits of the Silesian-Cracow district, Poland

Paragenetic and minor- and trace-element studies were conducted on samples of epigenetic ore and gangue minerals collected from mines and drill core in the Silesian-Cracow (S-C) district of southern Poland. Four discrete mineral suites representing four mineralizing stages can be identified throughout the district. The earliest epigenetic minerals deposited during stage 1 consist of a late dolomite cement together with minor pyrite and marcasite. Stage 2 was the first ore-forming stage and included repetitive deposition of sphalerite and galena in a variety of morphologies. Stage 3 abruptly followed the first ore stage and deposited marcasite and pyrite with variable amounts of late sphalerite and galena. In the samples studied, minerals deposited during stage 3 are predominately marcasite-pyrite with minor sphalerite and galena in the Pomorzany and Olkusz mines, whereas, at the Trzebionka mine, stage 3 mineralization deposited mostly galena and sphalerite with little marcasite or pyrite. Stage 4 minerals include contains barite, followed by calcite, with very minor pyrite and a rare, late granular sphalerite. Compared to other major Mississippi Valley-type (MVT) districts of the world, the Silesian-Cracow district contains sphalerite with the second largest range in Ag concentrations and the largest range in Fe and Cd concentrations of any district. Unlike in other districts, very wide ranges in minor- and trace-element concentrations are also observed in paragenetically equivalent samples collected throughout the district. This wide range indicates that the minor- and trace-element content of the ore-forming environment was highly variable, both spatially and temporally, and suggests that the hydrologic system that the ore fluids traversed from their basinal source was very complex. Throughout the district, a significant increase in Tl, Ge, and As concentrations is accompanied by a lightening of sulfur isotopes between stage 2 and stage 3 minerals. This change appears to record a major district-scale hydrologic event that probably reflects the introduction of fluids with significantly different geochemistry than that of earlier ore-forming fluids.

Prace - Panstwowego Instytutu Geologicznego

Scale as a factor in designing sampling programs for determination of annual trace element fluxes

Concentration data of suspended sediment-associated trace elements are a requisite for estimation of annual chemical fluxes. Fluvial suspended sediment and associated trace elements display marked shortterm spatial and temporal variability, suggesting that determination of annual fluxes requires high frequency depth and width integrated sampling and subsequent chemical analyses. When time scales are shifted from hours or days to a year, short-term variability is less important. A 2 year study on the Arkansas River indicates that it may be possible, after detailed site characterization of mean/median sediment chemical data, to estimate annual fluxes of trace elements solely through monitoring of discharge and suspended sediment concentration.

Effects of scale on interpretation and management

Critical elements in sediment-hosted deposits (clastic-dominated Zn-Pb-Ag, Mississippi Valley-type Zn-Pb, sedimentary rock-hosted Stratiform Cu, and carbonate-hosted Polymetallic Deposits): A review: Chapter 12

Some sediment-hosted base metal deposits, specifically the clastic-dominated (CD) Zn-Pb deposits, carbonate-hosted Mississippi Valley-type (MVT) deposits, sedimentary-rock hosted stratiform copper deposits, and carbonate-hosted polymetallic (“Kipushi type”) deposits, are or have been important sources of critical elements including Co, Ga, Ge, and Re. The generally poor data concerning trace element concentrations in these types of sediment-hosted ores suggest that there may be economically important concentrations of critical elements yet to be recognized.

Book chapter

Distribution of major anions and trace elements in the unsaturated zone at Franklin Lake Playa, California, USA

The composition of surficial salts formed near dry and drying saline lakes are partly the product of processes active in the unsaturated zone between the ground surface and the water table. These processes were investigated by determining the abundance of water-extractable solutes in sediment from the ground surface to the water table (~2.8 m) beneath Franklin Lake playa, California. Accumulation of solutes in the sediment is attributed to evaporation of aqueous solutions transported upward from the water table through the capillary fringe to an evaporation font that is currently 20-30 cm below the ground surface. Salts in the sediment from 0 to 20 cm depth are depleted in chloride and enriched in carbonate relative to deeper samples. Chloride depletion is most likely a product of selective dissolution by vertical recharge. The entire unsaturated zone contains greater amounts of carbonate than expected for evaporation of ground water and is best explained by preferential dissolution of more soluble salts in recharging precipitation but may also reflect the assimilation of CO2 as carbonate minerals precipitate. Variations in the concentrations of arsenic, molybdenum, tungsten, and uranium in the water-soluble fraction of the sediment are complex and suggest unique geochemical controls on the abundance of each element. The distribution of these trace element abundances indicates the arsenic is the element most likely to accumulate in near-surface salts.

California

Conventional rare earth element mineral deposits: The global landscape

Four conventional mineral deposit types—carbonatite, alkaline igneous, heavy mineral sand, and regolith-hosted ion-adsorption clay deposits—currently supply global markets with the rare earth elements (REEs) and rare earth oxides (REOs) necessary to meet the technological needs of global communities. The unique properties of REEs make them useful in a wide variety of applications, such as alloys, batteries, catalysts, magnets, phosphors, and polishing compounds. Rare earth element minerals are complex in both composition and structure. Carbonate, oxide, silicate, and phosphate-type minerals contain highly variable amounts of rare earths. Most rare earth-bearing minerals contain mainly lighter rare earths, a mixture of all the rare earths, or only the heavier rare earths. Diverse technological applications require the full range of light, middle, and heavy rare earths. The production of these elements, in particular the heavy rare earths, remains highly dependent on deposits from China. Diversification of rare earth supply chains is contingent on expanded knowledge of globally distributed resources and an understanding of the degree to which those resources have been explored and evaluated. The knowledge of tectonic setting, typical rock associations, deposit morphology, and deposit genesis has led to the discovery of many conventional-type rare earth deposit types. Recent developments are anticipated to result in further discoveries that have the potential to meet the ever-expanding applications of REEs and REOs to address modern societal needs.

Book chapter

A robust, finite element model for hydrostatic surface water flows

A finite element scheme is introduced for the 2-dimensional shallow water equations using semi-implicit methods in time. A semi-Lagrangian method is used to approximate the effects of advection. A wave equation is formed at the discrete level such that the equations decouple into an equation for surface elevation and a momentum equation for the horizontal velocity. The convergence rates and relative computational efficiency are examined with the use of three test cases representing various degrees of difficulty. A test with a polar-quadrant grid investigates the response to local grid-scale forcing and the presence of spurious modes, a channel test case establishes convergence rates, and a field-scale test case examines problems with highly irregular grids.A finite element scheme is introduced for the 2-dimensional shallow water equations using semi-implicit methods in time. A semi-Lagrangian method is used to approximate the effects of advection. A wave equation is formed at the discrete level such that the equations decouple into an equation for surface elevation and a momentum equation for the horizontal velocity. The convergence rates and relative computational efficiency are examined with the use of three test cases representing various degrees of difficulty. A test with a polar-quadrant grid investigates the response to local grid-scale forcing and the presence of spurious modes, a channel test case establishes convergence rates, and a field-scale test case examines problems with highly irregular grids.

Communications in Numerical Methods in Engineering

Trace element geochemistry (Li, Ba, Sr, and Rb) using Curiosity's ChemCam: early results for Gale crater from Bradbury Landing Site to Rocknest

The ChemCam instrument package on the Mars rover, Curiosity, provides new capabilities to probe the abundances of certain trace elements in the rocks and soils on Mars using the laser-induced breakdown spectroscopy technique. We focus on detecting and quantifying Li, Ba, Rb, and Sr in targets analyzed during the first 100 sols, from Bradbury Landing Site to Rocknest. Univariate peak area models and multivariate partial least squares models are presented. Li, detected for the first time directly on Mars, is generally low (<15 ppm). The lack of soil enrichment in Li, which is highly fluid mobile, is consistent with limited influx of subsurface waters contributing to the upper soils. Localized enrichments of up to ~60 ppm Li have been observed in several rocks but the host mineral for Li is unclear. Bathurst_Inlet is a fine-grained bedrock unit in which several analysis locations show a decrease in Li and other alkalis with depth, which may imply that the unit has undergone low-level aqueous alteration that has preferentially drawn the alkalis to the surface. Ba (~1000 ppm) was detected in a buried pebble in the Akaitcho sand ripple and it appears to correlate with Si, Al, Na, and K, indicating a possible feldspathic composition. Rb and Sr are in the conglomerate Link at abundances >100 ppm and >1000 ppm, respectively. These analysis locations tend to have high Si and alkali abundances, consistent with a feldspar composition. Together, these trace element observations provide possible evidence of magma differentiation and aqueous alteration.

Journal of Geophysical Research E: Planets

Trace-element accumulation by Hygrohypnum ochraceum in the upper Rio Grande Basin, Colorado and New Mexico, USA

Transplanted bryophytes can provide an indication of bioavailability. Rates of accumulation were related to the magnitude of ambient trace-element concentrations; maximal uptake occurred during the first 10 d of exposure. Trace-element concentrations in transplanted bryophytes could potentially be used to predict water and sediment concentrations that represent an integration of conditions over short to intermediate lengths of time, rather than instantaneous conditions as measured using water samples.

Environmental Toxicology and Chemistry

Organochlorine and trace element contamination in wintering and migrating diving ducks in the southern Great Lakes, USA, since the zebra mussel invasion

Because of the potential for increased trophic transfer of contaminants by zebra mussels ( Dreissena sp. ) to higher trophic levels, we collected four species of waterfowl (n = 65 ducks) from four locations in Lake Erie, Lake St. Clair, and Lake Michigan, USA, between 1991 and 1993 for organochlorine contaminant and trace element analyses. Geometric mean concentrations of total polychlorinated biphenyls (PCBs) and p , p ′-dichlorodiphenyldichloroethylene (DDE) were 1.35 and 0.15 μg/g wet weight in lesser scaup ( Aythya affinis ) carcasses and were below known effect levels. Total PCBs in 80% of carcasses, however, were above the U.S. Food and Drug Administration's threshold of 3.0 μg/g lipid weight for consumption of poultry. With the exception of selenium, trace elements were also at background or no-effect levels. Selenium concentrations in livers of 95% of lesser scaup, 90% of bufflehead ( Bucephala albeola ), and 72% of common goldeneye ( Bucephala clangula ) were in the elevated (>10 μg/g dry wt) or potentially harmful range (>33 μg/g dry wt). The effects of these high selenium concentrations are unknown but should be investigated further based on reproductive effects observed in field and laboratory studies of dabbling ducks and because lesser scaup populations are declining. Concentrations of total PCBs in dreissenid mussels in western Lake Erie were 10 times higher than in the upper Mississippi River but were similar to concentrations in other industrialized rivers in Europe and the United States. Metal concentrations were similar to other industrialized sites where zebra mussels have been sampled.

Indiana, Michigan, Ohio

The role of sediment ingestion in exposing bottom-feeding fish to chemical elements

Digesta were collected from the intestines of seven species of bottom-feeding fish to better understand the role of incidental ingestion of sediment in exposing fish to inorganic contaminants. A composite sediment tracer variable, based on concentrations of Co, Cr, Ni, Ti, V, and Y in digesta and in sediment, was calculated to estimate sediment content of digesta. Concentration factors (mg/kg in digesta divided by mg/kg in sediment) of eight elements of interest were linearly regressed on this tracer variable. The relative importance of sediment ingestion to oral exposure was quantified. Zinc, Cd, and Cu were ingested mainly from sediment-free food. Arsenic, Cr, Ni, Al, and Pb, in contrast, were ingested mainly from sediment. As an example, 93% of the Ni in digesta from a brown bullhead ( Ameiurus nebulosus ) was from sediment and only 7% from food. Regressions of Al and Pb in digesta of suckers (Catostomidae) suggested an additional oral source, possibly from oxides coating biotic or abiotic surfaces. Overall, concentrations of 12 of 21 elements studied were positively correlated with sediment content ( p < 0.005). Including sediment ingestion as a pathway for bottom-feeding fish is essential for accurately estimating exposures in toxicological studies.

Environmental Toxicology and Chemistry

The effect of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, USA. Part III. Downstream effects: The Spokane River Basin

During 1998/1999, surface and subsurface sediment samples were collected along the entire length of the Spokane River from its outlet at the northern end of Lake Coeur d'Alene (CDA), Idaho, to Lake Roosevelt on the Columbia River, Washington. The study was conducted to determine if the trace element enrichments observed in Lake CDA and on the floodplain and in the CDA River extend through the Spokane River Basin (SRB). As in Lake CDA, surface sediments in the SRB are enriched in Pb, Zn, As, Cd, Sb and Hg relative to local background levels. Pb, Cd and Zn are the most elevated, with maximum enrichment occurring in the upper Spokane River in close proximity to Lake CDA. On average, enrichment decreases downstream, apparently reflecting both increased distance from the inferred source (the CDA River Basin), as well as increased dilution by locally derived but unenriched materials. Only Cd and Zn display marked enrichment throughout the SRB. Pb, Zn and Cd seem to be associated mainly with an operationally defined iron oxide phase, whereas the majority of the As and Sb seem to be matrix-held. Subsurface sediments also are enriched in Pb, Zn, As, Cd, Sb and Hg relative to background levels. Based on 137Cs and excess 210Pb dating, trace element enrichment began in the middle part of the SRB (Long Lake) between 1900 and 1920. This is contemporaneous with similar enrichments observed in Lake CDA, as well as the completion of Long Lake Dam (1913). In the most downstream part of the basin (Spokane River Arm of Lake Roosevelt), enrichment began substantially later, between 1930 and 1940. The temporal difference in enrichment between Long Lake and the River Arm may reflect the latter's greater distance from the presumed source of the enrichment (the CDA River Basin); however, the difference is more likely the result of the completion of Grand Coulee Dam (1934-1941), which formed Lake Roosevelt, backed up the Spokane River, and increased water levels in the River Armby about 30 m.

Hydrological Processes

A domain decomposition approach to implementing fault slip in finite-element models of quasi-static and dynamic crustal deformation

We employ a domain decomposition approach with Lagrange multipliers to implement fault slip in a finite-element code, PyLith, for use in both quasi-static and dynamic crustal deformation applications. This integrated approach to solving both quasi-static and dynamic simulations leverages common finite-element data structures and implementations of various boundary conditions, discretization schemes, and bulk and fault rheologies. We have developed a custom preconditioner for the Lagrange multiplier portion of the system of equations that provides excellent scalability with problem size compared to conventional additive Schwarz methods. We demonstrate application of this approach using benchmarks for both quasi-static viscoelastic deformation and dynamic spontaneous rupture propagation that verify the numerical implementation in PyLith.

Journal of Geophysical Research B: Solid Earth

Distribution of elements in biotite-hornblende pairs and in an orthopyroxene-clinopyroxene pair from zoned plutons, northern Sierra Nevada, California

Distribution of major and minor elements has been determined for five hornblende-biotite pairs from hornblende-biotite quartz diorite and monzotonalite and for a clinopyroxene-orthopyroxene pair from pyroxene diorite collected from the border zones and centers of zoned plutons in the northern Sierra Nevada, California. The distribution coefficients K d [Mg/Fe] for biotite/hornblende are of the same magnitude (0.61–0.67) for both the mafic border zone and the silicic center. For comparison, K D [Mg/Fe] values for biotite/hornblende from plutonic rocks of the central Sierra Nevada and the southern California batholith were calculated from data published by others. Rocks of the oldest age group (ca. 150 m.y.) in the central Sierra Nevada have an average distribution coefficient, K D , of 0.64, close to the average K D in the study area, where K-Ar dates are 143 to 129 m.y. The intermediate age group has an average K D =0.81, and the youngest group has K D =0.77. K D [Mg/Fe] for biotite/hornblende from the southern California batholith is 0.83, close to the average of the intermediate age group in the central Sierra Nevada. The calculated difference in pressure of crystallization between rocks of the Feather River area and the southern California batholith is 1 kb; the rocks of the Feather River area being crystallized at a higher pressure. This is in good agreement with the low-pressure contact metamorphism in the south (pyroxene hornfels facies), as compared with a medium-pressure metamorphism around the northern plutons, where andalusitesillimanite-cordierite and andalusite-staurolite subfacies of the amphibolite facies indicate pressures of about 4 kb. Trace elements Cr, V, Ni, Co, Ga are distributed equally between biotite and hornblende, whereas Ba and possibly Cu are concentrated in biotite and Sr and Sc and possibly Zr in hornblende.

California