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Role of sediment-trace element chemistry in water-quality monitoring and the need for standard analytical methods

Multiple linear regression models calculated from readily obtainable chemical and physical parameters can explain a high percentage (70% or greater) of observed sediment trace-element variance for Cu, Zn, Pb, Cr, Ni, Co, As, Sb, Se, and Hg. Almost all the factors used in the various models fall into the category of operational definitions (e.g., grain size, surface area, and geochemical substrates such as amorphous iron and manganese oxides). Thus, the concentrations and distributions used in the various models are operationally defined, and are subject to substantial change depending on the method used to determine them. Without standardized procedures, data from different sources are not comparable, and the utility and applicability of the various models would be questionable.

Conference Paper↗

Magmatic (silicates/saline/sulfur-rich/CO2) immiscibility and zirconium and rare-earth element enrichment from alkaline magma chamber margins : Evidence from Ponza Island, Pontine Archipelago, Italy

Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Th as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424??C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite. arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536??C (54 to 65 wt. % NaCI equivalent) whereas total homogenization is between 640 and 755??C. The occurrence of silicate-melt inclusions and high-temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic. The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and incompatible elements.

European Journal of Mineralogy↗

Lead-isotopic, sulphur-isotopic, and trace-element studies of galena from the Silesian-Cracow Zn-Pb ores, polymetallic veins from the Gory Swietokrzyskie MTS, and the Myszkow porphyry copper deposit, Poland

Lead-isotopic data on galena samples collected from a paragenetically constrained suite of samples from the Silesian-Cracow ore district show no regional or paragenetically controlled lead-isotopic trends within the analytical reproducibility of the measurements. Furthermore, the new lead-isotopic data agree with previously reported lead-isotopic results (R. E. Zartman et al., 1979). Sulfur-isotopic analyses of ores from the Silesian-Cracow district as well as from vein ore from the Gory Swietokrzyskie Mts. and the Myszkow porphyry copper deposit, when coupled with trace-element data from the galena samples, clearly discriminate different hydrothermal ore-forming events. Lead-isotopic data from the Permian and Miocene evaporite deposits in Poland indicate that neither of these evaporite deposits were a source of metals for the Silesian-Cracow district ores. Furthermore, lead-isotopic data from these evaporite deposits and the shale residues from the Miocene halite samples indicate that the crustal evolution of lead in the central and western European platform in southern Poland followed normal crustal lead-isotopic growth, and that the isotopic composition of crustal lead had progressed beyond the lead-isotopic composition of lead in the Silesian-Cracow ores by Permian time. Thus, Mesozoic and Tertiary sedimentary flysch rocks can be eliminated as viable source rocks for the metals in the Silesian-Cracow Mississippi Valley-type (MVT) deposits. The uniformity of the isotopic composition of lead in the Silesian-Cracow ores, when coupled with the geologic evidence that mineralization must post-date Late Jurassic faulting (E. Gorecka, 1991), constrains the geochemical nature of the source region. The source of the metals is probably a well-mixed, multi-cycle molasse sequence of sedimentary rocks that contains little if any Precambrian metamorphic or granitic clasts (S. E. Church, R. B. Vaughn, 1992). If ore deposition was post Late Jurassic (about 150 m. y.) or later as indicated by the geologic evidence, the source rocks probably contained elevated concentrations of Zn and Pb (75-100 ppm), and relatively low concentrations of U and Th (2 and 8 ppm or less, respectively). The Carboniferous coal-bearing molasse rocks of the Upper Silesian Coal Basin are a prime candidate for such a source region. The presence of ammonia and acetate in the fluid inclusions (Viets et al., 1996a) also indicate that the Carboniferous coal-bearing molasse sequence in the Upper Silesian Coal Basin may have been a suitable pathway for the MVT ore fluids. The lead-isotopic homogeneity, when coupled with the sulfur-isotopic heterogeneity of the ores suggests that mixing of a single metal-bearing fluid with waters from separate aquifers containing variable sulfur-isotopic compositions in karsts in the Muschelkalk Formation of Middle Triassic age may have been responsible for the precipitation of the ores of the Silesian-Cracow district.

Prace - Panstwowego Instytutu Geologicznego↗

Isotopic and trace element compositions of upper mantle and lower crustal xenoliths, Cima volcanic field, California: Implications for evolution of the subcontinental lithospheric mantle

Ultramafic and mafic xenoliths from the Cima volcanic field, southern California, provide evidence of episodic modification of the upper mantle and underplating of the crust beneath a portion of the southern Basin and Range province. The upper mantle xenoliths include spinel peridotite and anhydrous and hydrous pyroxenite, some cut by igneous-textured pyroxenite-gabbro veins and dikes and some by veins of amphibole ?? plagioclase. Igneous-textured pyroxenites and gabbros like the dike rocks also occur abundantly as isolated xenoliths inferred to represent underplated crust. Mineral and whole rock trace element compositions among and within the different groups of xenoliths are highly variable, reflecting multiple processes that include magma-mantle wall rock reactions, episodic intrusion and it filtration of basaltic melts of varied sources into the mantle wall rock, and fractionation. Nd, Sr, and Pb isotopic compositions mostly of clinopyroxene and plagioclase mineral separates show distinct differences between mantle xenoliths (??Nd = -5.7 to +3.4; 87Sr/86Sr = 0.7051 - 0.7073; 206Pb/204Pb = 19.045 - 19.195) and the igneous-textured xenoliths (??Nd = +7.7 to +11.7; 87Sr/86Sr = 0.7027 - 0.7036 with one carbonate-affected outlier at 0.7054; and 206Pb/204Pb = 18.751 - 19.068), so that they cannot be related. The igneous-textured pyroxenites and gabbros are similar in their isotopic compositions to the host basaltic rocks, which have ??Nd of+5.1 to +9.3; 87Sr/86Sr of 0.7028 - 0.7050, and 206Pb/204Pb of 18.685 - 21.050. The igneous-textured pyroxenites and gabbros are therefore inferred to be related to the host rocks as earlier cogenetic intrusions in the mantle and in the lower crust. Two samples of peridotite, one modally metasomatized by amphibole and the other by plagioclase, have isotopic compositions intermediate between the igneous-textured xenoliths and the mantle rock, suggesting mixing, but also derivation of the metasomatizing magmas from two separate and distinct sources. Sm-Nd two-mineral "isochrons" yield apparent ages for petrographically identical rocks believed to be coeval ranging from -0 to 113 ?? 26 Ma, indicating the unreliability of dating these rocks with this method. Amphibole and plagioclase megacrysts are isotopically like the host basalts and probably originate by mechanical breakup of veins comagmatic with the host basaltic rocks. Unlike other Basin and Range localities, Cima Cr-diopside group isotopic compositions do not overlap with those of the host basalts. Copyright 1997 by the American Geophysical Union.

Journal of Geophysical Research B: Solid Earth↗

Incorporation of rare earth elements in titanite: Stabilization of the A2/a dimorph by creation of antiphase boundaries

The atomic arrangement of a natural rare-earth-rich titanite and two synthetic rare-earth-doped titanites have been refined in space group A2/a, and the atomic arrangement of an undoped P21/a synthetic titanite was also refined for comparison. Previous work has shown that titanite possesses a domain structure, with domains formed of like-displaced Ti atoms in the [100] octahedral chains. P21/a titanite results when the crystal is formed of a single domain, but as Ti-reversal sites occur in the octahedral chain the apparent A2/a structure results from the average of antiphase domains. Antiphase boundaries occur at O1, which is alternately overbonded or underbonded at the boundaries, depending on the displacement of the neighboring Ti atoms. Type 2 antiphase boundaries exist where two Ti atoms are displaced away from the intervening O1 atom and are energetically unfavorable because of underbonding of that O1 atom. However, substitution of a trivalent rare earth element in the adjacent Ca2+ site relieves that underbonding, favoring the creation of type 2 antiphase boundaries and stabilization of the A2/a dimorph. The results of high-precision crystal structure analyses demonstrate that rare earth substituents for Ca stabilize the A2/a dimorph at lower substitution levels than required for octahedral substitutions.

American Mineralogist↗

Test functions for three-dimensional control-volume mixed finite-element methods on irregular grids

Numerical methods based on unstructured grids, with irregular cells, usually require discrete shape functions to approximate the distribution of quantities across cells. For control-volume mixed finite-element methods, vector shape functions are used to approximate the distribution of velocities across cells and vector test functions are used to minimize the error associated with the numerical approximation scheme. For a logically cubic mesh, the lowest-order shape functions are chosen in a natural way to conserve intercell fluxes that vary linearly in logical space. Vector test functions, while somewhat restricted by the mapping into the logical reference cube, admit a wider class of possibilities. Ideally, an error minimization procedure to select the test function from an acceptable class of candidates would be the best procedure. Lacking such a procedure, we first investigate the effect of possible test functions on the pressure distribution over the control volume; specifically, we look for test functions that allow for the elimination of intermediate pressures on cell faces. From these results, we select three forms for the test function for use in a control-volume mixed method code and subject them to an error analysis for different forms of grid irregularity; errors are reported in terms of the discrete L2 norm of the velocity error. Of these three forms, one appears to produce optimal results for most forms of grid irregularity.

Conference Paper↗

Measuring mercury and other elemental components in tree rings

There has been considerable interest in measuring heavy metal pollution, such as mercury, using tree ring analysis. Since 1970, this method has provided a historical snapshot of pollutant concentrations near hazardous waste sites. Traditional methods of analysis have long been used with heavy metal pollutants such as mercury. These methods, such as atomic fluorescence and laser ablation, are sometimes time consuming and expensive to implement. In recent years, ion beam techniques, such as Particle Induced X-Ray Emission (PIXE), have been used to measure large numbers of elements. Most of the existing research in this area has been completed for low to medium atomic number pollutants, such as titanium, cobalt, nickel, and copper. Due to the reduction of sensitivity, it is often difficult or impossible to use traditional low energy (few MeV) PIXE analysis for pollutants with large atomic numbers. For example, the PIXE detection limit for mercury was recently measured to be about 1 ppm for a spiked Southern Magnolia wood sample [ref. 1]. This presentation will compare PIXE and standard chemical concentration results for a variety of wood samples.

Conference Paper↗

Measuring mercury and other elemental components in tree rings

There has been considerable interest in measuring heavy metal pollution, such as mercury, using tree ring analysis. Since 1970, this method has provided a historical snapshot of pollutant concentrations near hazardous waste sites. Traditional methods of analysis have long been used with heavy metal pollutants such as mercury. These methods, such as atomic fluorescence and laser ablation, are sometimes time consuming and expensive to implement. In recent years, ion beam techniques, such as Particle Induced X-Ray Emission (PIXE), have been used to measure large numbers of elements. Most of the existing research in this area has been completed for low to medium atomic number pollutants, such as titanium, cobalt, nickel, and copper. Due to the reduction of sensitivity, it is often difficult or impossible to use traditional low energy (few MeV) PIXE analysis for pollutants with large atomic numbers. For example, the PIXE detection limit for mercury was recently measured to be about 1 ppm for a spiked Southern Magnolia wood sample [ref. 1]. This presentation will compare PIXE and standard chemical concentration results for a variety of wood samples. Copyright 2004 by ISA.

Conference Paper↗

Monitoring suspended sediment and associated trace element and nutrient fluxes in large river basins in the USA

In 1996, the US Geological Survey converted its occurrence and distribution-based National Stream Quality Accounting Network (NASQAN) to a national, flux-based water-quality monitoring programme. The main objective of the revised programme is to characterize large USA river basins by measuring the fluxes of selected constituents at critical nodes in various basins. Each NASQAN site was instrumented to determine daily discharge, but water and suspended sediment samples are collected no more than 12-15 times per year. Due to the limited sampling programme, annual suspended sediment fluxes were determined from site-specific sediment rating (transport) curves. As no significant relationship could be found between either discharge or suspended sediment concentration (SSC) and suspended sediment chemistry, trace element and nutrient fluxes are estimated using site-specific mean or median chemical levels determined from a number of samples collected over a period of years, and under a variety of flow conditions.

Conference Paper↗

Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

Indian Journal of Marine Sciences↗

Rare earth element ore geology of carbonatites

For nearly 50 years, carbonatites have been the primary source of niobium and rare earth elements (REEs), in particular the light REEs, including La, Ce, Pr, and Nd. Carbonatites are a relatively rare type of igneous rock composed of greater than 50 vol % primary carbonate minerals, primarily calcite and/or dolomite, and contain the highest concentrations of REEs of any igneous rocks. Although there are more than 500 known carbonatites in the world, currently only four are being mined for REEs: the Bayan Obo, Maoniuping, and Dalucao deposits in China, and the Mountain Pass deposit in California, United States. The carbonatite-derived laterite deposit at Mount Weld in Western Australia is also a REE producer. In addition to REEs, carbonatite-related deposits are the primary source of Nb, with the Araxá deposit, a carbonatite-derived laterite in Minas Gerais state, Brazil, being the dominant producer. Other commodities produced from carbonatite-related deposits include phosphates, iron, fluorite, copper, vanadium, titanium, uranium, and calcite. Types of ores include those formed as primary magmatic minerals, from late magmatic hydrothermal fluids, and by supergene enrichment in weathered horizons. Although the principal REE-bearing mineral phases include fluorocarbonates (bastnäsite, parisite, and synchysite), hydrated carbonates (ancylite), and phosphates (monazite and apatite), the dominant mineral exploited at most mines is bastnäsite. Bastnäsite typically is coarse grained and contains approximately 75 wt % RE 2 O 3 (rare earth oxides; REOs). Processes responsible for REE enrichment include fractional crystallization of the carbonatitic magma, enrichment of REEs in orthomagmatic or hydrothermal fluids and subsequent precipitation or subsolidus metasomatic redistribution of REEs, and breakdown of primary carbonatitic mineral phases by chemical weathering and sequestration of REEs in secondary minerals or in association with clays. Carbonatites are primarily associated with continental rifting, but some carbonatites are associated with orogenic activity. Although there is debate on how carbonatite magmas are generated, the parental magma and REEs are clearly derived from mantle sources.

Book chapter↗

Resolving the percentage of component terrains within single resolution elements

An approximate maximum likelihood technique employing a widely available (BMD) discriminant analysis program has been developed for resolving the percentage of component terrains within single resolution elements. The method employs all four channels of Landsat data simultaneously and does not require prior knowledge of the percentage of components in mixed pixels. For five test cases, the method proved to be superior to single band weighted average and linear regression techniques and permitted an estimate of the total area occupied by component terrains to within 6 percent of the true area covered. It is believed this accuracy should be sufficient for many geologic applications of Landsat multispectral data.

Photogrammetric Engineering and Remote Sensing↗

Size distribution of rare earth elements in coal ash

Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported.

Conference Paper↗

A Galerkin, finite-element analysis of steady-state flow and heat transport in the shallow hydrothermal system in the East Mesa area, Imperial Valley, California

A steady-state simulation model was applied to the shallow hydrothermal system in the East Mesa area of Imperial Valley, Calif. The steady-state equations of flow and heat transport were solved by use of a Galerkin, finite-element method. A solution was obtained by iterating between the temperature and pressure equations, using updated densities and viscosities. Temperature and pressure were obtained for each node, and corresponding head values were calculated. The simulated temperature and pressure patterns correlated well with the observed patterns. Additional data, mainly from test drilling, would be required for construction of a similar model of the deep hydrothermal system.

California↗

Annual fluxes of sediment-associated trace/major elements, carbon, nutrients, and sulfur from US coastal rivers

About 260–270 Mt of suspended sediment are discharged annually from the conterminous USA; approximately 69% derives from Gulf rivers (n = 36), 24% from Pacific rivers (n = 42), and 7% from Atlantic rivers (n = 54). Elevated sediment-associated chemical concentrations relative to baseline levels occur in the reverse order of sediment discharges: Atlantic rivers (49%) > Pacific rivers (40%) > Gulf rivers (23%). Elevated trace element concentrations (e.g. Cu, Zn) tend to occur in association with present/former industrial areas and/or urban centres, particularly along the northeast Atlantic coast. Elevated nutrient concentrations occur along both the Atlantic and Gulf coasts, but are dominated by rivers in the urban northeast and by southeastern and Gulf coast “blackwater” streams. Elevated Ca, Mg, K and Na levels appear to reflect local petrology whereas elevated Ti, S, Fe, and Al concentrations are ubiquitous, possibly because they have both natural and anthropogenic sources. Almost all the elevated sediment-associated chemical concentrations/fluxes are lower than worldwide averages.

United States coastal rivers↗

Lateritic, supergene rare earth element (REE) deposits

Intensive lateritic weathering of bedrock under tropical or sub-tropical climatic conditions can form a variety of secondary, supergene-type deposits. These secondary deposits may range in composition from aluminous bauxites to iron and niobium, and include rare earth elements (REE). Over 250 lateritic deposits of REE are currently known and many have been important sources of REE. In southeastern China, lateritic REE deposits, known as ion-adsorption type deposits, have been the world’s largest source of heavy REE (HREE). The lateritized upper parts of carbonatite intrusions are being investigated for REE in South America, Africa, Asia and Australia, with the Mt. Weld deposit in Australia being brought into production in late 2012. Lateritic REE deposits may be derived from a wide range of primary host rocks, but all have similar laterite and enrichment profiles, and are probably formed under similar climatic conditions. The weathering profile commonly consists of a depleted zone, an enriched zone, and a partially weathered zone which overlie the protolith. Lateritic weathering may commonly extend to depths of 30 to 60 m. REE are mobilized from the breakdown of primary REE-bearing minerals and redeposited in the enriched zone deeper in the weathering horizon as secondary minerals, as colloids, or adsorbed on other secondary minerals. Enrichment of REE may range from 3 to 10 times that of the source lithology; in some instances, enrichment may range up to 100 times.

Conference Paper↗

Documenting the use of the Long Term Resource Monitoring element’s fish monitoring methodologies throughout the Midwest

The Upper Mississippi River Restoration (UMRR) Program’s Long Term Resource Monitoring (LTRM) element is designed to monitor and assess long term trends in the Upper Mississippi River System (UMRS). To accomplish this, standardized methods are used that allow for comparisons across pools and rivers. In recent years, other projects and other agencies have adopted the LTRM fish methodologies for use outside the UMRR. To determine how widespread the use of the Fish Component’s methods are, a twelve question survey was delivered via SurveyMonkey.com through the states comprising the American Fisheries Society (AFS) North Central Division and the Upper Mississippi River Conservation Committee. Approximately 2,000 professionals were reached with ≈11 percent participating. Results indicate that nearly all (95 percent) respondents use standardized methods in their sampling and 48 percent are familiar with the LTRM fish methodologies. Roughly one-third (35 percent) of all respondents have used the methods in the past and most (78 percent) of those have modified the methods to suit the information needs specific to their fishery. Results indicate that the LTRM methods have indeed spread outside the UMRR and are now a well-known and potentially widely used technique to sample fish communities.

Illinois, Iowa, Minnesota, Missouri, Wisconsin↗

Transmission of atmospherically deposited trace elements through an undeveloped, forested Maryland watershed

Retention and transmission of atmospherically-derived major (H + , Na + , K + , Ca 2+ , Mg 2+ , HCO 3 - , NO 3 - , SO 4 -2 , Cl - , SiO 2 ) and trace (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se, and Zn) species were evaluated in an undeveloped forested watershed underlain by a rather inert quartzite lithology (Bear Branch, Catoctin State Forest, Thrumont, Maryland). These comparisons were based on atmospheric input to stream export over a period of 16 months. Both wet (precipitation) and total (bulk, including vegetative throughfall) atmospheric loading to the catchment were determined. Stream export was gauged based on systematic sampling of the stream under varied flow regimes. Additionally, watershed export of both dissolved and particulate trace element phases was examined during three high run-off intensives associated with summer storms.

Maryland↗