Production and precipitation of rare earth elements in acidic to alkaline coal mine discharges, Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Stewart, B. W.; Capo, R. C.; Hedin, B. C.; Wallrich, I. L. R.; Hedin, R. S.

2016-12-01

Abandoned coal mine discharges are a serious threat to ground and surface waters due to their high metal content and often high acidity. However, these discharges represent a potential source of rare earth elements (REE), many of which are considered to be critical resources. Trace element data from 18 coal mine drainage (CMD) sites within the Appalachian Basin suggest CMD is enriched in total REE by 1-4 orders of magnitude relative to concentrations expected in unaffected surface or ground waters. When normalized to the North American Shale Composite (NASC), the discharges generally show a pattern of enrichment in the middle REE, including several identified as critical resources (Nd, Eu, Dy, Tb). In contrast, shale, sandstone and coal samples from Appalachian Basin coal-bearing units have concentrations and patterns similar to NASC, indicating that the REE in CMD are fractionated during interaction with rock in the mine pool. The highest total REE contents (up to 2800 mg/L) are found in low-pH discharges (acid mine drainage, or AMD). A precipitous drop in REE concentration in CMD with pH ≥6.6 suggests adsorption or precipitation of REE in the mine pool at circumneutral pH. Precipitated solids from 21 CMD active and passive treatment sites in the Appalachian Basin, including Fe oxy-hydroxides, Ca-Mg lime slurries, and Si- and Al-rich precipitates, are enriched in total REE content relative to the average CMD discharges by about four orders of magnitude. Similar REE trends in the discharges and precipitates, including MREE enrichment, suggest minimal fractionation of REE during precipitation; direct comparisons over multiple seasonal cycles are needed to confirm this. Although the data are limited, Al-rich precipitates generally have high REE concentrations, while those in iron oxy-hydroxides tend to be lower. Based on the area of mined coal in the Appalachian Basin, estimated infiltration rates, and the mean REE flux from discharges analyzed in this study and that of Cravotta and Brady (2015, Appl. Geochem. 62, 108-130), we estimate that coal mine drainage outflows in this region generate approximately 450 metric tons of dissolved REE per year, a portion of which could be targeted for resource recovery during CMD treatment.

Geochemical and multi-isotopic (87Sr/86Sr, 143Nd/144Nd, 238U/235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; Stewart, Brian W.

2018-02-01

We investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from -7.8 to -6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns. Limestone units thought to have formed under open ocean (oxic) conditions have δ238U values and REE patterns consistent with modern seawater. The δ238U values in whole rock shale and authigenic phases are greater than those of modern seawater and the upper crust. The δ238U values of reduced phases (the oxidizable fraction consisting of organics and sulfide minerals) are ∼0.6‰ greater than that of modern seawater. Bulk shale and carbonate cement extracted from the shale have similar δ238U values, and are greater than δ238U values of adjacent limestone units. We suggest these trends are due to the accumulation of chemically and, more likely, biologically reduced U from anoxic to euxinic bottom water as well as the influence of diagenetic reactions between pore fluids and surrounding sediment and organic matter during diagenesis and catagenesis.

Systematic Investigation of REE Mobility and Fractionation During Continental Shale Weathering Along a Climate Gradient

NASA Astrophysics Data System (ADS)

Jin, L.; Ma, L.; Dere, A. L. D.; White, T.; Brantley, S. L.

2014-12-01

Rare earth elements (REE) have been identified as strategic natural resources and their demand in the United States is increasing rapidly. REE are relatively abundant in the Earth's crust, but REE deposits with minable concentrations are uncommon. One recent study has pointed to the deep-sea REE-rich muds in the Pacific Ocean as a new potential resource, related to adsorption and concentration of REE from seawater by hydrothermal iron-oxyhydroxides and phillipsite (Kato et al., 2010). Finding new REE deposits will be facilitated by understanding global REE cycles: during the transformation of bedrock into soils, REEs are leached into natural waters and transported to oceans. At present, the mechanisms and factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we systematically studied soil profiles and bedrock in seven watersheds developed on shale bedrock along a climate transect in the eastern USA, Puerto Rico and Wales to constrain the mobility and fractionation of REE during chemical weathering processes. In addition, one site on black shale (Marcellus) bedrock was included to compare behaviors of REEs in organic-rich vs. organic-poor shale end members under the same environmental conditions. Our investigation focused on: 1) the concentration of REEs in gray and black shales and the release rates of REE during shale weathering, 2) the biogeochemical and hydrological conditions (such as redox, dissolved organic carbon, and pH) that dictate the mobility and fractionation of REEs in surface and subsurface environments, and 3) the retention of dissolved REEs on soils, especially onto secondary Fe/Al oxyhydroxides and phosphate mineral phases. This systematic study sheds light on the geochemical behaviors and environmental pathways of REEs during shale weathering along a climosequence.

The assessment of REE patterns and 143Nd/ 144Nd ratios in fish remains

NASA Astrophysics Data System (ADS)

Grandjean, Patricia; Cappetta, Henri; Michard, Annie; Albarède, Francis

1987-07-01

The REE content and isotopic composition of Sr and Nd have been determined in fish teeth ranging in age from the Trias to the present and from various localities mostly around the Atlantic. These measurements have been carried out on Selachian and Teleost remains from the same locality in Togo and show no appreciable difference, which suggests, with the help of a mass balance calculation of the Ce anomaly, that diagenetic effects are not responsible for the REE enrichment of biogenic phosphates. One group of fossil teeth has about 3 times the REE abundances of shale and a shale-normalized pattern with a minimum at Sm: it is thought to reflect deposition in the open-sea environment. A second group has REE concentration about 10 times higher than the first group with either a regular light REE enrichment or, more frequently, a maximum in the middle REE, both being probably indicative of deposition in estuarine or near-shore conditions. The shape of the REE spectra and the size of the Ce anomaly can be used semi-quantitatively to determine the depth of deposition. The results presented here on Late Cretaceous/Eocene fish teeth samples from Morocco reflect an increasing influx of deep waters with a lowLa/Yb ratio and strong negative Ce anomaly, which agrees well with the evolution of sediment chemistry and microfauna associations. In contrast, ɛ Nd is typical of the water mass in which the fish debris decayed. Examples of nearly isolated basins identified with Nd isotopes include the South Atlantic prior to the Lutetian (ɛ Nd ≈ -13.5), the Miocene Persian Gulf (ɛ Nd = -3.1), and Bolivia during the Late Cretaceous (ɛ Nd = -12.8). Togo and Guinea-Bissau results suggest that, in the South Atlantic, the meridional oceanic circulation had not started before 45 Ma ago. Combination of REE andɛ Nd data suggests that the assignment of Jurassic-Cretaceous samples measured so far to open-sea water masses is still ambiguous.

An impact of moss sample cleaning on uncertainty of analytical measurement and pattern profiles of rare earth elements.

PubMed

Dołęgowska, Sabina; Gałuszka, Agnieszka; Migaszewski, Zdzisław M

2017-12-01

The main source of rare earth elements (REE) in mosses is atmospheric deposition of particles. Sample treatment operations including shaking, rinsing or washing, which are made in a standard way on moss samples prior to chemical analysis, may lead to removing particles adsorbed onto their tissues. This in turn causes differences in REE concentrations in treated and untreated samples. For the present study, 27 combined moss samples were collected within three wooded areas and prepared for REE determinations by ICP-MS using both manual cleaning by shaking and triple rinsing with deionized water. Higher concentrations of REE were found in manually cleaned samples. The comparison of REE signatures and shale-normalized REE concentration patterns showed that the treatment procedure did not lead to fractionation of REE. All the samples were enriched in medium rare earth elements, and the δMREE factor remained practically unchanged after rinsing. Positive anomalies of Nd, Sm, Eu, Gd, Er and Yb were observed in both, manually cleaned and rinsed samples. For all the elements examined, analytical uncertainty was below 3.0% whereas sample preparation uncertainty computed with ANOVA, RANOVA, modified RANOVA and range statistics methods varied from 3.5 to 29.7%. In most cases the lowest s rprep values were obtained with the modified RANOVA method. Copyright © 2017 Elsevier Ltd. All rights reserved.

LA-ICP-MS analysis of isolated phosphatic grains indicates selective rare earth element enrichment during reworking and transport processes

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2016-04-01

Rare earth elements (REE) are a commonly used proxy to reconstruct water chemistry and oxygen saturation during the formation history of authigenic and biogenic phosphates in marine environments. In the modern ocean REE exhibit a distinct pattern with enrichment of heavy REE and strong depletion in Cerium. Studies of ancient phosphates and carbonates, however, showed that this 'modern' pattern is only rarely present in the geological past. Consequently, the wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry had to have been radically different in the earth's past. A wealth of studies has already shown that both early and late diagenesis can strongly affect REE signatures in phosphates and severely alter primary marine signals. However, no previous research was conducted on how alteration processes occurring prior to final deposition affect marine phosphates. Herein we present a dataset of multiple LA-ICP-MS measurements of REE signatures in isolated phosphate and carbonate grains deposited in a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene "Monterey event". The phosphates are represented by authigenic, biogenic and detrital grains emplaced in bioclastic grain- to packstones dominated by bryozoan and echinoderm fragments, as well as abundant benthic and planktic foraminifers. The results of 39 grain specific LA-ICP-MS measurements in three discrete rock samples reveals four markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Considering grain shape and REE patterns together indicate that authigenic, detrital and biogenic phosphates have distinct REE patterns irrespective of the sample. Our results show that the observed REE patterns in phosphates only broadly reflect water chemistry under certain well constrained circumstances of primary authigenesis. Are these conditions not met, REE patterns are more likely to reflect complex enrichment processes that likely already started to occur during reworking over geologically relatively short time frames. Similarities in the REE patterns of clearly detrital and biogenic phosphate further suggest that the often observed 'hat-shaped' pattern in biogenic phosphates can easily result from increased middle REE (Neodymium to Holmium) scavenging during taphonomic processes prior to final deposition. Finally, cluster analysis coupled with sedimentological considerations proved a valuable tool for the characterization of REE patterns of phosphates in terms of their formation conditions and depositional history, such as the distinction of phosphates formed in situ from reworked and transported phosphate grains.

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE PAGES

Yang, Jon; Verba, Circe; Torres, Marta; ...

2018-02-01

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jon; Verba, Circe; Torres, Marta

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Rare earth element scavenging in seawater

NASA Astrophysics Data System (ADS)

Byrne, Robert H.; Kim, Ki-Hyun

1990-10-01

Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

DOE PAGES

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; ...

2017-10-25

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Geochemical characteristics of dissolved rare earth elements in acid mine drainage from abandoned high-As coal mining area, southwestern China.

PubMed

Li, Xuexian; Wu, Pan

2017-09-01

Acid mine drainage (AMD) represents a major source of water pollution in the small watershed of Xingren coalfield in southwestern Guizhou Province. A detailed geochemical study was performed to investigate the origin, distribution, and migration of REEs by determining the concentrations of REEs and major solutes in AMD samples, concentrations of REEs in coal, bedrocks, and sediment samples, and modeling REEs aqueous species. The results highlighted that all water samples collected in the mining area are identified as low pH, high concentrations of Fe, Al, SO 4 2- and distinctive As and REEs. The spatial distributions of REEs showed a peak in where it is nearby the location of discharging of AMD, and then decrease significantly with distance away from the mining areas. Lots of labile REEs have an origin of coal and bedrocks, whereas the acid produced by the oxidation of pyrite is a prerequisite to cause the dissolution of coal and bedrocks, and then promoting REEs release in AMD. The North American Shale Composite (NASC)-normalized REE patterns of coal and bedrocks are enriched in light REEs (LREEs) and middle REEs (MREEs) relative to heavy REEs (HREEs). Contrary to these solid samples, AMD samples showed slightly enrichment of MREEs compared with LREEs and HREEs. This behavior implied that REEs probably fractionate during acid leaching, dissolution of bedrocks, and subsequent transport, so that the MREEs is primarily enriched in AMD samples. Calculation of REEs inorganic species for AMD demonstrated that sulfate complexes (Ln(SO 4 ) + and Ln(SO 4 ) 2 - ) predominate in these species, accounting for most of proportions for the total REEs species. The high concentrations of dissolved SO 4 2- and low pH play a decisive role in controlling the presence of REEs in AMD, as these conditions are necessary for formation of stable REEs-sulfate complexes in current study. The migration and transportation of REEs in AMD are more likely constrained by adsorption and co-precipitation of Fe-Al hydroxides/hydroxysulfate. In addition, the MREEs is preferentially captured by poorly crystalline Fe-Al hydroxides/hydroxysulfate, which favors that sediments also preserve NASC-normalized patterns with MREEs enrichment in the stream.

Seawater Phosphorites of the Seamount, Southwestern Pacific

NASA Astrophysics Data System (ADS)

Yoo, C.; Moon, J.; Kim, J.; Kim, K.; Lee, K.

2002-12-01

Phosphatized carbonate rocks associated with ferromanganese crusts (Fe-Mn crust) were investigated for better understanding of diagenetic evolution of the seamount (one of the Margellan Seamount Trail), southwestern Pacific. Three stages of phosphatization are inferred on the basis of paragenetic relation with Fe-Mn crusts, which are divided into four layers by their textures; 1) layer 1, massive, columnar growth structures with some porosity, 2) layer 2, porous, digitate growth structures with brown Fe-oxide filling, 3) layer 3, digitate and ovoidal growth structures with carbonate sediments filling, 4) layer 4, massive, parallel to undulatory laminated textures. Early phosphatization (phosphorite I) occurred before the formation of the oldest layer 4 crust. Foraminiferal-nannofossil limestones and shallow-water bioclastic limestones, encrusted by layer 4 crusts, are replaced by phosphorite I. Strontium isotope ratios (0.70743 to 0.70766) indicate that this phosphorite is formed at Late Cretaceous (85.2 to 73.5 Ma). Oxygen isotope values (-0.6 to 0.1% PDB) and shale-normalized REE pattern suggest that phosphorite I was formed in normal seawater. Phosphorite I appears as subhedral to euhedral, prismatic hexagonal crystallites approximately less than 5 æm in length. The second phosphorite (phosphorite II) is formed during the cessation of layer 4 crusts. Foraminiferal-nannofossil limestones filling the fractures developed within layer 4 crust are phosphatized during this episode. Age of phospatization II is defined as Late Eocene to Early Oligocene (36.5 to 31.6 Ma) from strontium isotope ratios (0.70777 to 0.70793). Oxygen isotope values (-2.9 to 2.9% PDB) and shale-normalized REE pattern of phosphorite II also suggest normal seawater origin. Phosphorite II replaced carbonate grain appears as anhedral, submicron-sized crystallites, whereas euhedral, prismatic hexagonal crystallites are filling the open space. Global climatic transition from a nonglacial to glacial period during Late Eocene to Early Oligocene intensified oceanic circulation and upwelling in deep-sea environment. Under this circumstance, phosphorite II may have been formed by redistribution of dissolved phosphous, accumulated in deep-sea during stable condition, to shallow environment. The last phosphatization (phosphorite III) occurred during or after the formation of layer 3 crust. Foraminiferal-nannofossil limestones filling the porosity and interstices within digitate layer 3 crust are phosphatized during this stage. Strontium isotope ratios (0.70827 to 0.70882) suggest that phosphorite III is formed from Oligocene/Miocene boundary to Middle Miocene (23.6 to 13.1 Ma). Shale-normalized REE pattern indicates this phosphorite was formed in normal seawater. Exclusively low oxygen isotope values (-10.7 to -2.4% PDB) suggest phosphorous ions responsible to phosphorite III probably provided during diagenesis of surrounding layer 3 crust.

Rare earth elements in river waters

NASA Technical Reports Server (NTRS)

Goldstein, Steven J.; Jacobsen, Stein B.

1988-01-01

To characterize the input to the oceans of rare earth elements (REE) in the dissolved and the suspended loads of rivers, the REE concentrations were measured in samples of Amazon, Indus, Mississippi, Murray-Darling, and Ohio rivers and in samples of smaller rivers that had more distinct drainage basin lithology and water chemistry. It was found that, in the suspended loads of small rivers, the REE pattern was dependent on drainage basin geology, whereas the suspended loads in major rivers had relatively uniform REE patterns and were heavy-REE depleted relative to the North American Shale composite (NASC). The dissolved loads in the five major rivers had marked relative heavy-REE enrichments, relative to the NASC and the suspended material, with the (La/Yb)N ratio of about 0.4 (as compared with the ratio of about 1.9 in suspended loads).

Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

PubMed

Janssen, René P T; Verweij, Wilko

2003-03-01

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.

Rare earth element contents of the Lusi mud: An attempt to identify the environmental origin of the hot mudflow in East Java - Indonesia

NASA Astrophysics Data System (ADS)

Agustawijaya, Didi Supriadi; Karyadi, Karyadi; Krisnayanti, Baiq Dewi; Sutanto, Sutanto

2017-12-01

The Sidoarjo mudflow in East Java, Indonesia, has been erupting since May 29th, 2006. The eruption has been known as the Lusi (lumpur Sidoarjo), which was previously considered as a remote seismic event consequence, but current geyser-like activities show an association with a geothermal phenomenon. A method of characterizing rare earth elements (REE) is commonly an effective tool for recognizing a geothermal system, and here it is adapted to particularly indicate the environmental origin of the Lusi mud. Results show that the Lusi hot mud is made of a porous smectite structure of a shale rock type, which becomes an ideal tank for trapping the REE, especially the light REE. Volcanic activities seem to be an important influence in the eruption; however, since there is a lack of significant isotopic evidences in the mobilization of the REE during the eruption, the chloride neutral pH water of the Lusi may hardly contain the REE. The moderate Ce and Eu anomalies found in the REE patterns of the mud strongly indicate a sea-floor basin as the most probable environment for the REE fractionation during the sedimentary rock formation, in which the weathering processes of volcanic rock origin enriched the Lusi shale with the REE.

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

NASA Astrophysics Data System (ADS)

Tang, Jianwu; Johannesson, Karen H.

2010-12-01

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH 3COO -) or strong (i.e., CO32-) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as "truly" dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., "colloidal" HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).

Excess europium content in Precambrian sedimentary rocks and continental evolution

NASA Technical Reports Server (NTRS)

Jakes, P.; Taylor, S. R.

1974-01-01

It is proposed that the europium excess in Precambrian sedimentary rocks, relative to those of younger age, is derived from volcanic rocks of ancient island arcs, which were the source materials for the sediments. Precambrian sedimentary rocks and present-day volcanic rocks of island arcs have similar REE patterns, total REE abundances, and excess Eu, relative to the North American shale composite. The present upper crustal REE pattern, as exemplified by that of sediments, is depleted in Eu, relative to chondrites. This depletion is considered to be a consequence of development of a granodioritic upper crust by partial melting in the lower crust, which selectively retains europium.

Environmental tracers for elucidating the weathering process in a phosphogypsum disposal site: Implications for restoration

NASA Astrophysics Data System (ADS)

Pérez-López, Rafael; Nieto, José M.; de la Rosa, Jesús D.; Bolívar, Juan P.

2015-10-01

This study provides geochemical data with the aim of identifying and tracing the weathering of phosphogypsum wastes stack-piled directly on salt-marshes of the Tinto River (Estuary of Huelva, SW Spain). With that purpose, different types of highly-polluted acid solutions were collected in the stack. Connection between these solutions and the estuarine environment was studied by geochemical tracers, such as rare earth elements (REE) and their North American Shale Composite (NASC)-normalized patterns and Cl/Br ratios. Phosphogypsum-related wastewaters include process water stored on the surface, pore-water contained in the phosphogypsum profile and edge outflow water emerging from inside the stack. Edge outflow waters are produced by waterlogging at the contact between phosphogypsum and the nearly impermeable marsh surface and discharge directly into the estuary. Process water shows geochemical characteristics typical of phosphate fertilizers, i.e. REE patterns with an evident enrichment of heavy-REE (HREE) with respect to middle-REE (MREE) and light-REE (LREE). By contrast, REE patterns of deeper pore-water and edge outflows are identical to those of Tinto River estuary waters, with a clear enrichment of MREE relative to LREE and HREE denoting influence of acid mine drainage. Cl/Br ratios of these solutions are very close to that of seawater, which also supports its estuarine origin. These findings clearly show that process water is not chemically connected with edge outflows through pore-waters, as was previously believed. Phosphogypsum weathering likely occurs by an upward flow of seawater from the marsh because of overpressure and permeability differences. Several recommendations are put forward in this study to route restoration actions, such as developing treatment systems to improve the quality of the edge outflow waters before discharging to the receiving environment.

Rare Earth Element Concentrations and Fractionation Patterns Along Groundwater Flow Paths in Two Different Aquifer Types (i.e., Sand vs. Carbonate)

NASA Astrophysics Data System (ADS)

Johannesson, K. H.; Tang, J.

2003-12-01

Groundwater samples were collected in two different types of aquifer (i.e., Carrizo Sand Aquifer, Texas and Upper Floridan carbonate Aquifer, west-central Florida) to study the concentrations, fractionation, and speciation of rare earth elements (REE) along groundwater flow paths in each aquifer. Major solutes and dissolved organic carbon (DOC) were also measured in these groundwaters. The Carrizo Sand aquifer was sampled in October 2002 and June 2003, whereas, to date, we have only sampled the Floridan once (i.e., June 2003). The data reveal no significant seasonal differences in major solute and REE concentrations for the Carrizo. In Carrizo sand aquifer, groundwaters from relatively shallow wells (i.e., less than 167 m) in the recharge zone are chiefly Ca-Na-HCO3-Cl type waters. With flow down-gradient the groundwaters shift composition to the Na-HCO3 waters. pH and alkalinity initially decrease with flow away from the recharge zone before increasing again down-gradient. DOC is generally low (0.65 mg/L) along the flow path. REE concentrations are highest in groundwaters from the recharge zone (Nd 40.5 pmol/kg), and decrease substantially with flow down-gradient reaching relatively low and stable values (Nd 4.1-8.6 pmol/kg) roughly 10 km from the recharge zone. Generally, Carrizo groundwaters exhibit HREE-enriched shale-normalized patterns. The HREE enrichments are especially strong for waters from the recharge zone [(Yb/Nd)SN =1.7-5.6], whereas down-gradient (deep) groundwaters have flatter patterns [(Yb/Nd)SN =0.7-2.5]. All groundwaters have slightly positive Eu anomalies (Eu/Eu* 0.09-0.14) and negative Ce anomalies (Ce/Ce* -0.85 - -0.07). In the Upper Floridan Aquifer, Ca, Mg, SO4, and Cl concentrations generally increase along groundwater flow path, whereas pH and alkalinity generally decrease. DOC is higher (0.64 - 2.29 mg/L) than in the Carrizo and initially increases along the flow path and then decreases down-gradient. LREE (Nd) concentrations generally increase along groundwater flow path, however, MREE (Gd) exhibit little change and HREE (Yb) concentrations tend to decreases along the flow path. Floridan groundwaters have HREE enriched shale-normalized patterns, although (Yb/Nd)SN values decrease along groundwater flow path. Thus, REE patterns of Floridan groundwaters tend to flatten with flow down-gradient. All groundwaters show positive Eu anomalies (0.06 - 0.17) and negative Ce anomalies (-0.12 - -0.63).

Rare earth and trace elements of fossil vertebrate bioapatite as palaeoenvironmental and sedimentological proxies

NASA Astrophysics Data System (ADS)

Žigaitė, Živilė; Fadel, Alexandre; Pérez-Huerta, Alberto; Jeffries, Teresa

2015-04-01

Rare earth (REE) and trace element compositions of fossil vertebrate dental microremains have been studied in Silurian and Devonian vertebrate dental scales and spines in-situ, using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Samples were selected from the well-known Silurian bone beds of Vesiku and Ohesaare in Saaremaa island of Estonia, and a number of Lower Devonian localities from Spitsbergen (Svalbard), Andrée Land group. Biomineral preservation was assessed using spot semi-quantitative elemental chemistry (SEM-EDS) and electron back-scatter difractometry (EBSD) for cristallinity imaging. The obtained PAAS shale-normalised REE concentrations were evaluated using basic geochemical calculations and quantifications. The REE patterns from the Lower Devonian vertebrate apatite from Andrée Land, Spitsbergen (Wood Bay and Grey Hœk formations) did not show any recognisable taxon-specific behavior, but had rather well expressed differences of REE compositions related to biomineral structure and sedimentary settings, suggesting REE instead to reflect burial environments and sedimentological history. The Eu anomaly recorded in two of the studied localities but not in the other indicate different taphonomic conditions and palaeoenvironment, while La/Sm, La/Yb ratios sugeest considerable influence of terrestrial freshwater during the early diagenesis. The La/Yb and La/Sm plots also agree with the average REE concentrations, reflecting domination of the adsoption over substitution as principal REE uptake mechanism in the fossils which had significantly lower overall REE concentrations, and vice versa. Vesiku (Homerian, Wenlock) microremains yielded very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with strong enrichment in middle REE and depletion in heavy REE. Negative Europium (Eu) anomaly was pronounced in all the profiles, but Cerium (Ce) anomalies were not detected suggesting possible suboxic to anoxic conditions of the bottom and pore waters during the formation of Vesiku bone bed. In Ohesaare (Pridoli), the REE compositions were nearly identical across all the morphotypes and histologies of acanthodian microremains showing flat REE patterns with slight depletion in HREE. There were no visible enrichment in MREE, indicating relatively good preservation of original bioapatite and likely absence of any pronounced fractionated REE incorporation during later stages of diagenesis. The shale normalised (La/Yb)SN and (La/Sm)SN REE ratio compilations showed addsorption as dominating REE uptake mechanism across all the studied microfossils. The absence of well-defined Ce anomaly suggest oxic palaeoseawater conditions, which agrees with existing interpretations of Ohesaare sequence as high-energy shoal and regressive open ocean sedimentary environment.

Rare earth elements and neodymium isotopes in sedimentary organic matter

NASA Astrophysics Data System (ADS)

Freslon, Nicolas; Bayon, Germain; Toucanne, Samuel; Bermell, Sylvain; Bollinger, Claire; Chéron, Sandrine; Etoubleau, Joel; Germain, Yoan; Khripounoff, Alexis; Ponzevera, Emmanuel; Rouget, Marie-Laure

2014-09-01

We report rare earth element (REE) and neodymium (Nd) isotope data for the organic fraction of sediments collected from various depositional environments, i.e. rivers (n = 25), estuaries (n = 18), open-ocean settings (n = 15), and cold seeps (n = 12). Sedimentary organic matter (SOM) was extracted using a mixed hydrogen peroxide/nitric acid solution (20%-H2O2-0.02 M-HNO3), after removal of carbonate and oxy-hydroxide phases with dilute hydrochloric acid (0.25 M-HCl). A series of experimental tests indicate that extraction of sedimentary organic compounds using H2O2 may be complicated occasionally by partial dissolution of sulphide minerals and residual carbonates. However, this contamination is expected to be minor for REE because measured concentrations in H2O2 leachates are about two-orders of magnitude higher than in the above mentioned phases. The mean REE concentrations determined in the H2O2 leachates for samples from rivers, estuaries, coastal seas and open-ocean settings yield relatively similar levels, with ΣREE = 109 ± 86 ppm (mean ± s; n = 58). The organic fractions leached from cold seep sediments display even higher concentration levels (285 ± 150 ppm; mean ± s; n = 12). The H2O2 leachates for most sediments exhibit remarkably similar shale-normalized REE patterns, all characterized by a mid-REE enrichment compared to the other REE. This suggests that the distribution of REE in leached sedimentary organic phases is controlled primarily by biogeochemical processes, rather than by the composition of the source from which they derive (e.g. pore, river or sea-water). The Nd isotopic compositions for organic phases leached from river sediments are very similar to those for the corresponding detrital fractions. In contrast, the SOM extracted from marine sediments display εNd values that typically range between the εNd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter (inferred from the analysis of local surface seawater). A notable exception is the case of organic matter (OM) fractions leached from cold seep sediment samples, which sometimes exhibit εNd values markedly different from both terrigenous and surface seawater signatures. This suggests that a significant fraction of organic compounds in these sediments may be derived from chemosynthetic processes, recycling pore water REE characterized by a distinct isotopic composition. Overall, our results confirm that organic matter probably plays an important role in the oceanic REE budget, through direct scavenging and remineralization within the water column. Both the high REE abundances and the shape of shale-normalized patterns for leached SOM also suggest that OM degradation in sub-surface marine sediments during early diagenesis could control, to a large extent, the distribution of REE in pore waters. Benthic fluxes of organic-bound REE could hence substantially contribute to the exchange processes between particulates and seawater that take place at ocean margins. Neodymium isotopes could provide useful information for tracing the origin (terrestrial versus marine) and geographical provenance of organic matter, with potential applications in paleoceanography. In particular, future studies should further investigate the potential of Nd isotopes in organic compounds preserved in sedimentary records for reconstructing past variations of surface ocean circulation.

The 'North American shale composite' - Its compilation, major and trace element characteristics

NASA Technical Reports Server (NTRS)

Gromet, L. P.; Dymek, R. F.; Haskin, L. A.; Korotev, R. L.

1984-01-01

North American shale composite (NASC) major element composition and compilation are presented, together with rare earth element (REE) redeterminations obtained by high precision analytical methods. The major element composition of the NASC compares closely with other average shale compositions, and significant portions of the REE and some other trace elements are contained in minor phases. The uneven REE distribution in NASC powder appears to yield the heterogeneity in analyzed aliquants. REE distributions of detrital sediments may to some extent be dependent on their minor mineral assemblages and the sedimentological factors controlling these assemblages.

Anthropogenic gadolinium anomalies and rare earth elements in the water of Atibaia River and Anhumas Creek, Southeast Brazil.

PubMed

de Campos, Francisco Ferreira; Enzweiler, Jacinta

2016-05-01

The concentrations of rare earth elements (REE), measured in water samples from Atibaia River and its tributary Anhumas Creek, Brazil, present excess of dissolved gadolinium. Such anthropogenic anomalies of Gd in water, already described in other parts of the world, result from the use of stable and soluble Gd chelates as contrast agents in magnetic resonance imaging. Atibaia River constitutes the main water supply of Campinas Metropolitan area, and its basin receives wastewater effluents. The REE concentrations in water samples were determined in 0.22-μm pore size filtered samples, without and after preconcentration by solid-phase extraction with bis-(2-ethyl-hexyl)-phosphate. This preconcentration method was unable to retain the anthropogenic Gd quantitatively. The probable reason is that the Gd chelates dissociate slowly in acidic media to produce the free ion that is retained by the phosphate ester. Strong correlations between Gd and constituents or parameters associated with effluents confirmed the source of most Gd in water samples as anthropogenic. The shale-normalized REE patterns of Atibaia River and Anhumas Creek water samples showed light and heavy REE enrichment trends, respectively. Also, positive Ce anomalies in many Atibaia River samples, as well as the strong correlations of the REE (except Gd) with terrigenous elements, imply that inorganic colloidal particles contributed to the REE measured values.

Residential heating contribution to level of air pollutants (PAHs, major, trace, and rare earth elements): a moss bag case study.

PubMed

Vuković, Gordana; Aničić Urošević, Mira; Pergal, Miodrag; Janković, Milan; Goryainova, Zoya; Tomašević, Milica; Popović, Aleksandar

2015-12-01

In areas with moderate to continental climates, emissions from residential heating system lead to the winter air pollution peaks. The EU legislation requires only the monitoring of airborne concentrations of particulate matter, As, Cd, Hg, Ni, and B[a]P. Transition metals and rare earth elements (REEs) have also arisen questions about their detrimental health effects. In that sense, this study examined the level of extensive set of air pollutants: 16 polycyclic aromatic hydrocarbons (PAHs), and 41 major elements, trace elements, and REEs using Sphagnum girgensohnii moss bag technique. During the winter of 2013/2014, the moss bags were exposed across Belgrade (Serbia) to study the influence of residential heating system to the overall air quality. The study was set as an extension to our previous survey during the summer, i.e., non-heating season. Markedly higher concentrations of all PAHs, Sb, Cu, V, Ni, and Zn were observed in the exposed moss in comparison to the initial values. The patterns of the moss REE concentrations normalized to North American Shale Composite and Post-Archean Australian Shales were identical across the study area but enhanced by anthropogenic activities. The results clearly demonstrate the seasonal variations in the moss enrichment of the air pollutants. Moreover, the results point out a need for monitoring of air quality during the whole year, and also of various pollutants, not only those regulated by the EU Directive.

Provenance and depositional history of continental slope sediments in the Southwestern Gulf of Mexico unraveled by geochemical analysis

NASA Astrophysics Data System (ADS)

Armstrong-Altrin, John S.; Machain-Castillo, María Luisa; Rosales-Hoz, Leticia; Carranza-Edwards, Arturo; Sanchez-Cabeza, Joan-Albert; Ruíz-Fernández, Ana Carolina

2015-03-01

The aim of this work is to constrain the provenance and depositional history of continental slope sediments in the Southwestern Gulf of Mexico (~1089-1785 m water depth). To achieve this, 10 piston sediment cores (~5-5.5 m long) were studied for mineralogy, major, trace and rare earth element geochemistry. Samples were analyzed at three core sections, i.e. upper (0-1 cm), middle (30-31 cm) and lower (~300-391 cm). The textural study reveals that the core sediments are characterized by silt and clay fractions. Radiocarbon dating of sediments for the cores at different levels indicated a maximum of ~28,000 year BP. Sediments were classified as shale. The chemical index of alteration (CIA) values for the upper, middle, and lower sections revealed moderate weathering in the source region. The index of chemical maturity (ICV) and SiO2/Al2O3 ratio indicated low compositional maturity for the core sediments. A statistically significant correlation observed between total rare earth elements (∑REE) versus Al2O3 and Zr indicated that REE are mainly housed in detrital minerals. The North American Shale Composite (NASC) normalized REE patterns, trace element concentrations such as Cr, Ni and V, and the comparison of REE concentrations in sediments and source rocks indicated that the study area received sediments from rocks intermediate between felsic and mafic composition. The enrichment factor (EF) results indicated that the Cd and Zn contents of the upper section sediments were influenced by an anthropogenic source. The trace element ratios and authigenic U content of the core sediments indicated the existence of an oxic depositional environment.

Thermal effects on rare earth element and strontium isotope chemistry in single conodont elements

NASA Astrophysics Data System (ADS)

Armstrong, H. A.; Pearson, D. G.; Griselin, M.

2001-02-01

A low-blank, high sensitivity isotope dilution, ICP-MS analytical technique has been used to obtain REE abundance data from single conodont elements weighing as little as 5 μg. Sr isotopes can also be measured from the column eluants enabling Sr isotope ratios and REE abundance to be determined from the same dissolution. Results are comparable to published analyses comprising tens to hundreds of elements. To study the effects of thermal metamorphism on REE and strontium mobility in conodonts, samples were selected from a single bed adjacent to a basaltic dyke and from the internationally used colour alteration index (CAI) "standard set." Our analyses span the range of CAI 1 to 8. Homogeneous REE patterns, "bell-shaped" shale-normalised REE patterns are observed across the range of CAI 1 to 6 in both sample sets. This pattern is interpreted as the result of adsorption during early diagenesis and could reflect original seawater chemistry. Above CAI 6 REE patterns become less predictable and perturbations from the typical REE pattern are likely to be due to the onset of apatite recrystallisation. Samples outside the contact aureole of the dyke have a mean 87Sr/ 86Sr ratio of 0.708165, within the broad range of published mid-Carboniferous seawater values. Our analysis indicates conodonts up to CAI 6 record primary geochemical signals that may be a proxy for ancient seawater.

Dissolved indium and rare earth elements in three Japanese rivers and Tokyo Bay: Evidence for anthropogenic Gd and In

NASA Astrophysics Data System (ADS)

Nozaki, Yoshiyuki; Lerche, Dorte; Alibo, Dia Sotto; Tsutsumi, Makoto

2000-12-01

New data on the dissolved (<0.04 μm) rare earth elements (REEs) and In in the Japanese Ara, Tama, and Tone river-estuaries and Tokyo Bay are presented. Unique shale-normalized REE patterns with a distinct positive Gd anomalies and a strong heavy-REE enrichment were seen throughout the data. The dissolved Gd anomaly is caused by local anthropogenic input mainly due to recent use of Gado-pentetic acid as a medical agent for magnetic resonance imaging (MRI) in hospitals. The heavy-REE enrichment may be attributed to fractionation during weathering and transport in the upstream of the rivers, and only partially to removal of light- and middle-REE enriched river colloids by the use of a new ultrafiltration technique. Dissolved In concentrations in the Japanese rivers are extraordinarily high as compared to those in the pristine Chao Phraya river of Thailand reported elsewhere (Nozaki et al., in press). Like Gd, the high dissolved In in the study area can also be ascribed to recent use of In-containing organic compound, In(DTPA) 2- in medical diagnosis. Thus, in the highly populated and industrialized area, dissolved heavy metal concentrations in rivers and estuaries may be significantly perturbed by human activities and the fate of those anthropogenic soluble substances in the marine environment needs to be investigated further.

Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

PubMed Central

Wang, Lingqing; Liang, Tao

2015-01-01

Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg−1 with an average value of 4.67 × 103 mg·kg−1, which was significantly higher than the average value in China (181 mg·kg−1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China.

PubMed

Wang, Lingqing; Liang, Tao

2015-07-22

Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China's largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 10(4) mg·kg(-1) with an average value of 4.67 × 10(3) mg·kg(-1), which was significantly higher than the average value in China (181 mg·kg(-1)). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La(N)/Yb(N), La(N)/Sm(N) and Gd(N)/Yb(N)). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind.

Geochemical variations of rare earth elements in Marcellus shale flowback waters and multiple-source cores in the Appalachian Basin

NASA Astrophysics Data System (ADS)

Noack, C.; Jain, J.; Hakala, A.; Schroeder, K.; Dzombak, D. A.; Karamalidis, A.

2013-12-01

Rare earth elements (REE) - encompassing the naturally occurring lanthanides, yttrium, and scandium - are potential tracers for subsurface groundwater-brine flows and geochemical processes. Application of these elements as naturally occurring tracers during shale gas development is reliant on accurate quantitation of trace metals in hypersaline brines. We have modified and validated a liquid-liquid technique for extraction and pre-concentration of REE from saline produced waters from shale gas extraction wells with quantitative analysis by ICP-MS. This method was used to analyze time-series samples of Marcellus shale flowback and produced waters. Additionally, the total REE content of core samples of various strata throughout the Appalachian Basin were determined using HF/HNO3 digestion and ICP-MS analysis. A primary goal of the study is to elucidate systematic geochemical variations as a function of location or shale characteristics. Statistical testing will be performed to study temporal variability of inter-element relationships and explore associations between REE abundance and major solution chemistry. The results of these analyses and discussion of their significance will be presented.

Trace Element Inputs to the Upper West Pacific from Nd Isotopes and Rare Earth Elements

NASA Astrophysics Data System (ADS)

Behrens, M. K.; Pahnke, K.; Schnetger, B.; Brumsack, H. J.

2015-12-01

Neodymium isotopes (143Nd/144Nd, expressed as ɛNd) and rare earth element (REE) concentrations in the ocean trace water mass transport and margin-seawater exchange processes. The distinct ɛNd and REE signatures of the lithogenic components of margin sediments of the West Pacific allow characterization of trace element inputs to the Pacific Ocean. We present dissolved ɛNdand REE concentrations from twelve vertical profiles of a transect from South Korea to Fiji. Near South Korea, surface waters are marked by unradiogenic ɛNd (as low as -7.3), high REE concentrations (e.g., Nd = 15.3 pmol/kg) and low salinity. Towards the open ocean, these parameters gradually change towards typical Pacific open ocean values (ɛNd = -3.3, [Nd] = 5.55 pmol/kg). Subsurface waters show REE depletions, followed by the typical REE increase with increasing water depth. These distributions indicate trace element input near South Korea and enhanced subsurface scavenging, as indicated by strong heavy REE to light REE fractionation. In the tropical West Pacific (10°N-15°S), high surface and subsurface water ɛNd values (+0.7) and positive Eu anomalies trace the influence of volcanic islands. Yet, absolute REE concentrations are extremely low at these depths (e.g., Nd = 2.77 pmol/kg). Using shale-normalized Nd/Er and Ho/Dy ratios, that show a much stronger surface to subsurface decrease in coastal waters compared to the open ocean, we suggest enhanced scavenging in this area. Eastward flowing intermediate waters (NPIW, AAIW) have ɛNd values up to +1.9 (NPIW) and +3.7 (AAIW) higher than those entering the tropical West Pacific from north and south, respectively. Modified ɛNd at intermediate depths and no change in REE patterns suggest that boundary exchange along volcanic island margins modifies the seawater ɛNd without changing the REE budget.

Quantification of diagenesis in Cenozoic sharks: Elemental and mineralogical changes

NASA Astrophysics Data System (ADS)

Labs-Hochstein, Joann; MacFadden, Bruce J.

2006-10-01

Diagenesis of bone during fossilization is pervasive, however, the extent of this process varies with depositional environment. This study quantifies diagenesis of shark vertebral centra through analysis of a suite of physical and chemical characters including crystallinty index (CI), carbonate content, and elemental concentrations. Although shark skeletons are initially cartilaginous, the soft cartilage of the vertebral centra is replaced with carbonate hydroxyapatite during growth. Nine vertebral centra are analyzed from lamnoid (Lamnoidea) sharks ranging in age from the cretaceous to recent using Fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma mass spectrometry (ICPMS). The variables CI, carbonate content, rare earth element (REE) concentrations, Ca/P, Ba/Ca, Sr/Ba, (La/Yb) N, (La/Y) N, (La/Yb) N vs. (La/Sm) N, La/Yb, and Ce anomalies elucidate the diagenetic and depositional environments of the seven fossil vertebral centra. The two extant centra demonstrate the initial, unaltered end-member conditions for these variables. Two fossil vertebral centra ( Carcharodon megalodon and Isurus hastalis) demonstrate a strong terrestrial influence during diagenesis (distinctive flattening of shale-normalized REE patterns) that masked the seawater signal. Three centra ( Carcharodon auriculatus, Carcharodon angustidens, and Creotxyrhina mantelli) have indications of some terrestrial influx evident by some flattening of the REE patterns relative to seawater. The terrestrial influence in these five shark centra ( C. megalodon, I. hastalis, C. auriculatus, C. angustidens and C. mantelli) are interpreted to represent a primarily nearshore habitat for these species. In contrast, the two Otodus obliquus centra have REE patterns that represent the original seawater signal and have no indications of terrigenous input. These results indicate that fossil shark vertebral centra have the potential to understand diagenesis and reconstruct paleooceanographic environments.

Rare earth elements (REE) as natural and applied tracers in the catchment area of Gessental valley, former uranium mining area of Eastern Thuringia, Germany

NASA Astrophysics Data System (ADS)

Buechel, G.; Merten, D.; Geletneky, J. W.; Kothe, E.

2003-04-01

Between 1947 and 1990 about 113.000 t of uranium were excavated at the former uranium mining site of Ronneburg (Eastern Thuringia, Germany). The legacy consists of more than 200 million m^3 of metasedimentary rocks rich in organic matter, sulfides and heavy metals originally deposited in mining heaps at the surface. The metasedimentary rocks formed under anoxic conditions about a 400 Mio. years ago are now exposed to oxic conditions. The oxidation of markasite and pyrite results in the formation of H_2SO_4. The formation of acid mine drainage (AMD) leads to high concentrations of uranium, rare earth elements (REE) and other heavy metals in surface water, seepage water and groundwater. This mobilization is due to alteration enhanced by high microbial activity and low pH. The tolerance mechanisms towards heavy metal pollution of soil substrate and surface/groundwater has allowed the selection of microbes which have, e.g. specific transporter genes and which are associated to plants in symbiotic interactions like mycorrhiza. In order to follow the processes linking alteration of metasedimentary rocks to biological systems the use of tracers is needed. One group of such tracers occuring in high concentrations in the water phase at the Ronneburg mining site are the REE (La-Lu) which are featured by very similar chemical behaviour. They show smooth but continuous variations of their chemical behaviour as a function of atomic number. For seepage water of the waste rock dump Nordhalde - sampled over a period of two years - the shale normalized REE patterns show enrichment of heavy REE and only minor variations, although the concentration differs. At sampling points in the surface water and in groundwater rather similar REE patterns were observed. Thus, REE can be used as tracers to identify diffuse inflow of REE-rich acid mine drainage of the dumps into the creek and the sediments. The absolute concentrations of REE in the creek and in ground water are up to 1000 times less than in seepage water due to mixing and (co)precipitation of REE. Lu/La and Sm/La relations show a significant decrease with increasing distance from the dump caused by preferential (co)precipitation of heavy REE with amorphous Fe-hydroxides along the Gessenbach. Thus, REE patterns can not only be used as tracers but also to study processes. In contrast to the patterns of the seepage, the REE patterns of the Silurian rocks as determined by LA-ICP-MS feature rather flat patterns with enrichment of middle REE (Sm - Dy). Results from batch experiments show preferentially leaching of heavy REE for all investigated source rocks. The highest absolute concentrations of REE appear in the eluates of the Silurian 'Ockerkalk'. Since the REE pattern closely reflects the pattern found in the seepage water it is assumed to be the most important source for the occurence of the REE pattern observed in seepage water. Studies of microbial heavy metal retention were performed by direct incubation of seepage water using well characterized fungal and bacterial strains. Using the bacterium Escherichia coli for incubation of seepage water sorption of heavy metals to biomass was observed. Use of the fungus Schizophyllum commune for incubation, however, has a much more pronounced effect including significant fractionation of REE pointing to the possibility of a specific active uptake mechanism. Bioextraction with bacteria and fungal mycelia might be an alternative to plant growth and phytoextraction and might be preferable for AMD water treatment since no soil substrate is necessary. Future research must be directed towards genes for active transport, intra- or extracellular storage proteins and their application. Biotechnological use of such genes in, e.g., strains of E. coli, might yield highly useful bioremediation strains that can help to reduce the ecological effects of pollution resulting from former mining activities.

Submarine groundwater discharge of rare earth elements: Evidence of an important trace element flux to coastal waters

NASA Astrophysics Data System (ADS)

Johannesson, K. H.; Chevis, D.; Burdige, D. J.; Cable, J. E.; Martin, J. B.; Roy, M.

2008-12-01

Johannesson and Burdige [2007, EPSL 253, 129] suggested that submarine groundwater discharge (SGD) represents a substantial, unrecognized source of Nd to the oceans. Based on a globally averaged terrestrial SGD flux equal to 6 percent of the global river discharge and mean groundwater Nd concentrations obtained from the literature, we estimated a global SGD Nd flux that was within a factor of 2 of the previously proposed missing global Nd flux. To test our hypothesis that SGD is an important source of Nd to the oceans, rare earth element (REE) concentrations were measured in SGD samples collected beneath a coastal lagoon on the Florida Atlantic coast (Indian River Lagoon). Shale (PAAS)-normalized REE patterns for all SGD samples exhibit substantial enrichments in the heavy REEs (HREE) compared to the light REEs (LREE) as shown by their PAAS-normalized Yb/Nd ratios, which range from 5 to 73 (mean = 16). SGD from piezometers located 10 m and 22.5 m from shore exhibit PAAS-normalized REE plots that are most similar to the patterns of the overlying lagoon (surface) water. For example, mean PAAS-normalized Yb/Nd ratios for groundwaters sampled from the 10 m and 22.5 m piezometers are 6.7 and 8.3, which compare well with the PAAS- normalized Yb/Nd ratio of water column samples (8.7). In contrast, the mean PAAS-normalized Yb/Nd ratio of terrestrial-derived groundwater from the piezometer at the shoreline is 41. Neodymium concentrations of the SGD samples range from 230 to 2400 pmol/kg (mean = 507 pmol/kg), and thus are substantially higher than reported for open ocean seawater (typical Nd = 20 pmol/kg). Based on SGD fluxes previously determined with seepage meters, porewater Cl concentrations, and Rn-222 deficiencies of porewaters [Martin et al., 2007, Water Resour. Res. 43, W0544, doi: 10.1029/2006WR005266], we estimate daily inputs of Nd to the Indian River Lagoon of 50 to 2100 umoles for the terrestrial-derived component of SGD, and 171 mmoles for the marine component of SGD (81 to 3400 times greater). Residence times of Nd in the portion of the lagoon studied are estimated to range from 6 to more than 250 years based on the terrestrial-derived SGD flux of Nd, compared to 26 days using the marine-derived SGD flux of Nd. The substantially shorter residence time determined using the marine-derived SGD component compares well with the estimated flushing time for this portion of the estuary (~3 weeks). The similarity between SGD and lagoon water Nd concentrations and PAAS-normalized REE patterns, in conjunction with the larger, marine-derived SGD flux of Nd, strongly suggests that recirculation of lagoon water and subsequent SGD exerts the principal control on Nd concentrations in the lagoon. The elevated Nd concentration for deep groundwater (186 cmbsf) located 22.5 m from shore also agrees well with another study that reported recirculated, marine SGD as a source of REEs to coastal waters [Duncan and Shaw, 2003, Aquatic Geochem. 9, 233]. Thus, our observations demonstrate the importance of recirculated, marine SGD to these lagoon surface waters, and further support our hypothesis that SGD contributes substantial fluxes of Nd to the coastal oceans.

Do Leached Authigenic Fractions Reflect the Neodymium Seawater Composition?

NASA Astrophysics Data System (ADS)

Pimbert, A.; Gourlan, A. T.; Chauvel, C.

2016-12-01

Leaching of marine sediment is often used to recover past Nd seawater composition and reconstruct past ocean circulation. It is assumed to reliably extract REE from the authigenic fraction of sediment [1]. However, while most studies assume that the recovered signal is that of past seawater, very few report complete isotopic and trace element data that clearly demonstrate it is the case. We present new ɛNd values and REE contents measured on leachates of sediments from two Cretaceous marine sections deposited at shallow water depth (Taghazoute in Morocco) and at greater depth in the Atlantic (DSDP Site 367). REE patterns of leachates vary according to lithology: bell-shaped patterns or positive Ce anomalies for organic-poor samples and seawater-like patterns (negative Ce anomaly, low Nd/Yb ratio) for black shales. ɛNd values also vary: between -5.6 and -9.6 at Taghazoute and between -10 and -8.1 at Site 367. Interestingly, ɛNd values correlate with Ce anomalies for Taghazoute black shales. Samples with the largest Ce negative anomalies have the highest ɛNd while samples with no Ce anomalies have much lower ɛNd. This suggests the presence in the leached material of detritus mixed up with the authigenic fraction for sediments deposited in shallow environment. This confirms the findings made by Huck et al. [2] for fish teeth in a similar environment. In such environment, recovering the pristine seawater signal requires (a) the acquisition of both Nd isotopes and trace element contents, and (b) selection of the only Nd isotopic compositions associated to clear seawater trace element characteristics. For sediments deposited in open-ocean setting (Site 367), no detrital contamination affects leached fractions. The REE patterns vary depending on the nature of authigenic fraction but ɛNd remains constant. Here, ɛNd values can be used to discuss oceanic reconstructions. [1] Martin et al. (2010), Chem. Geol, 269, 414-431. [2] Huck et al. (2016), G3, 17, 679-698.

Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

USGS Publications Warehouse

Gammons, C.H.; Wood, S.A.; Nimick, D.A.

2005-01-01

Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in magnitude to estimates in the literature for adsorption of divalent metal cations onto clays and hydrous metal oxides. The results of this study have important implications to the use of REE as hydrogeochemical tracers in streams. Copyright ?? 2005 Elsevier Ltd.

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

USGS Publications Warehouse

Piper, D.Z.; Baedecker, P.A.; Crock, J.G.; Burnett, W.C.; Loebner, B.J.

1988-01-01

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 ?? 10-3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment. Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris. ?? 1988.

On the origin of a phosphate enriched interval in the Chattanooga Shale (Upper Devonian) of Tennessee-A combined sedimentologic, petrographic, and geochemical study

NASA Astrophysics Data System (ADS)

Li, Yifan; Schieber, Juergen

2015-11-01

The Devonian Chattanooga Shale contains an uppermost black shale interval with dispersed phosphate nodules. This interval extends from Tennessee to correlative strata in Kentucky, Indiana, and Ohio and represents a significant period of marine phosphate fixation during the Late Devonian of North America. It overlies black shales that lack phosphate nodules but otherwise look very similar in outcrop. The purpose of this study is to examine what sets these two shales apart and what this difference tells us about the sedimentary history of the uppermost Chattanooga Shale. In thin section, the lower black shales (PBS) show pyrite enriched laminae and compositional banding. The overlying phosphatic black shales (PhBS) are characterized by phosbioclasts, have a general banded to homogenized texture with reworked layers, and show well defined horizons of phosphate nodules that are reworked and transported. In the PhBS, up to 8000 particles of P-debris per cm2 occur in reworked beds, whereas the background black shale shows between 37-88 particles per cm2. In the PBS, the shale matrix contains between 8-16 phosphatic particles per cm2. The shale matrix in the PhBS contains 5.6% inertinite, whereas just 1% inertinite occurs in the PBS. The shale matrix in both units is characterized by flat REE patterns (shale-normalized), whereas Phosbioclast-rich layers in the PhBS show high concentrations of REEs and enrichment of MREEs. Negative Ce-anomalies are common to all samples, but are best developed in association with Phosbioclasts. Redox-sensitive elements (Co, U, Mo) are more strongly enriched in the PBS when compared to the PhBS. Trace elements associated with organic matter (Cu, Zn, Cd, Ni) show an inverse trend of enrichment. Deposited atop a sequence boundary that separates the two shale units, the PhBS unit represents a transgressive systems tract and probably was deposited in shallower water than the underlying PBS interval. The higher phosphate content in the PhBS is interpreted as the result of a combination of lower sedimentation rates with reworking/winnowing episodes. Three types of phosphatic beds that reflect different degrees of reworking intensity are observed. Strong negative Ce anomalies and abundant secondary marcasite formation in the PhBS suggests improved aeration of the water column, and improved downward diffusion of oxygen into the sediment. The associated oxidation of previously formed pyrite resulted in a lowering of pore water pH and forced dissolution of biogenic phosphate. Phosphate dissolution was followed by formation of secondary marcasite and phosphate. Repeated, episodic reworking caused repetitive cycles of phosphatic dissolution and reprecipitation, enriching MREEs in reprecipitated apatite. A generally "deeper" seated redox boundary favored P-remineralization within the sediment matrix, and multiple repeats of this process in combination with wave and current reworking at the seabed led to the formation of larger phosphatic aggregates and concentration of phosphate nodules in discrete horizons.

Paleoenvironmental signals and paleoclimatic condition of the Early Maastrichtian oil shales from Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Fathy, Douaa; Wagreich, Michael; Zaki, Rafat; Mohamed, Ramadan S. A.

2016-04-01

Early Maastrichtian oil shales are hosted in the Duwi Formation of the Central Eastern Desert, Egypt. The examined member represents up to 20% of the total Duwi Formation. This interval is mainly composed of siliciclastic facies, phosphorites facies and carbonate facies. Oil shales microfacies is mainly composed of smectite, kaolinite, calcite, fluorapatite, quartz and pyrite. They are enriched in a number of major elements and trace metals in particular Ca, P, V, Ni, Cr, Sr, Zn, Mo, Nb, U and Y compared to the post-Archaean Australian shale (PAAS). Chondrite-normalized REEs patterns of oil shales for the studied area display light rare earth elements enrichment relatively to heavy rare earth elements with negative Ce/Ce* and Eu/Eu* anomalies. The most remarkable indicators for redox conditions are enrichments of V, Mo, Ni, Cr, U content and depletion of Mn content. Besides, V/V+Ni, V/Ni, U/Th, Ni/Co, authigentic uranium ratios with presence of framboidal shape of pyrite and its size are reflecting the deposition of these shales under marine anoxic to euxinic environmental conditions. Additionally, the ratio of Strontium (Sr) to Barium (Ba) Sr/Ba reflected highly saline water during deposition. Elemental ratios critical to paleoclimate and paleoweathering (Rb /Sr, Al2O3/TiO2), CIA values, binary diagram between (Al2O3+K2O+Na2O) and SiO2 and types of clay minerals dominated reflect warm to humid climate conditions prevailing during the accumulation of these organic-rich petroleum source rocks.

Some chemical aspects of diagenetic carbonates from the Miocene of Sitakund, Bangladesh

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akhter, S.H.; Chowdhury, S.Q.; Kandaker, N.I.

1990-05-01

A preliminary chemical and petrological study was done of the Miocene limestone and its comparison with surrounding and overlying marine shales. The material for these studies was obtained from the Miocene Surma sediments exposed in Sitakund region, Cluttagong, Bangladesh. These limestones occur in a predominantly marine shale sequence and show an apparent angular structural relationship with respect to the host marine shales. Three types of carbonates are recognized: banded limestone, dark laminated limestone, and argillaceous limestone. These are devoid of any skeletal remains and often show recrystallization phenomena. Carbonate mineral phases included calcite, aragonite, dolomite, and more rarely magnesite andmore » ankerite. Noncarbonate fraction shows quartz, although very fine grained, is intricately intergrown, indicating that it is at least recrystallized, if not authigenic. Petrographic study of these carbonates show a great variability in terms of texture and composition and suggest a complex multistep and presumably continuous diagenesis. Relatively high REE (rare earth elements) abundances in these carbonates are most likely due to diagenesis and incorporation of mobile REE from local detrital phases into diagenetic carbonates. The anomalously low abundances of cerium in all the carbonates indicates a predominantly marine source for the REE. Recrystallization of carbonate resulted in the extensive exchange of Sr and O between carbonate and diagenetic fluid, the latter being low in REE/Ca ratios. Associated marine shales have quite dissimilar trace-element signatures. This may reflect uncommon crustal sources of REE for the carbonates and clastics. The enrichment of Ni and Zn in marine shales are related to the proximality of local bedrock source areas and clay minerals in the marine sediments.« less

Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

NASA Astrophysics Data System (ADS)

Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

2006-08-01

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

Sources and distribution of yttrium and rare earth elements in surface sediments from Tagus estuary, Portugal.

PubMed

Brito, Pedro; Prego, Ricardo; Mil-Homens, Mário; Caçador, Isabel; Caetano, Miguel

2018-04-15

The distribution and sources of yttrium and rare-earth elements (YREE) in surface sediments were studied on 78 samples collected in the Tagus estuary (SW Portugal, SW Europe). Yttrium and total REE contents ranged from 2.4 to 32mg·kg -1 and 18 to 210mg·kg -1 , respectively, and exhibited significant correlations with sediment grain-size, Al, Fe, Mg and Mn, suggesting a preferential association to fine-grained material (e.g. aluminosilicates but also Al hydroxides and Fe oxyhydroxides). The PAAS (Post-Archean Australian Shale) normalized patterns display three distinct YREE fractionation pattern groups along the Tagus estuary: a first group, characterized by medium to coarse-grained material, a depleted and almost flat PAAS-normalized pattern, with a positive anomaly of Eu, representing one of the lithogenic components; a second group, characterized mainly by fine-grained sediment, with higher shale-normalized ratios and an enrichment of LREE relative to HREE, associated with waste water treatment plant (WWTP) outfalls, located in the northern margin; and, a third group, of fine-grained material, marked by a significant enrichment of Y, a depletion of Ce and an enrichment of HREE over LREE, located near an inactive chemical-industrial complex (e.g. pyrite roast plant, chemical and phosphorous fertilizer industries), in the southern margin. The data allow the quantification of the YREE contents and its spatial distribution in the surface sediments of the Tagus estuary, identifying the main potential sources and confirming the use of rare earth elements as tracers of anthropogenic activities in highly hydrodynamic estuaries. Copyright © 2017 Elsevier B.V. All rights reserved.

Geochemistry of ferromanganese nodule-sediment pairs from Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2011-01-01

Fourteen ferromanganese nodule-sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule-sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo - (307, 273), Ni - (71, 125), Mn - (64, 87), Cu - (43, 80), Co - (23, 75), Pb - (15, 24), Zn - (9, 11) and V - (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation ( r ⩾ 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.

Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

NASA Astrophysics Data System (ADS)

Johannesson, Kevin H.; Zhou, Xiaoping

1999-01-01

-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

NASA Astrophysics Data System (ADS)

Censi, P.; Raso, M.; Yechieli, Y.; Ginat, H.; Saiano, F.; Zuddas, P.; Brusca, L.; D'Alessandro, W.; Inguaggiato, C.

2017-03-01

Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

Rare earth element compositions of core sediments from the shelf of the South Sea, Korea: Their controls and origins

NASA Astrophysics Data System (ADS)

Jung, Hoi-Soo; Lim, Dhongil; Choi, Jin-Yong; Yoo, Hae-Soo; Rho, Kyung-Chan; Lee, Hyun-Bok

2012-10-01

Rare earth elements (REEs) of bulk sediments and heavy mineral samples of core sediments from the South Sea shelf, Korea, were analyzed to determine the constraints on REE concentrations and distribution patterns as well as to investigate their potential applicability for discriminating sediment provenance. Bulk sediment REEs showed large variation in concentrations and distribution patterns primarily due to grain size and carbonate dilution effects, as well as due to an abundance of heavy minerals. In the fine sandy sediments (cores EZ02-15 and 19), in particular, heavy minerals (primarily monazite and titanite/sphene) largely influenced REE compositions. Upper continental crust-normalized REE patterns of these sand-dominated sediments are characterized by enriched light REEs (LREEs), because of inclusion of heavy minerals with very high concentrations in LREEs. Notably, such a strong LREE enrichment is also observed in Korean river sediments. So, a great care must be taken when using the REE concentrations and distribution patterns of sandy and coarse silty shelf sediments as a proxy for discriminating sediment provenance. In the fine-grained muddy sediments with low heavy mineral abundance, in contrast, REE fractionation ratios and their UCC-normalized patterns seem to be reliable proxies for assessing sediment provenance. The resultant sediment origin suggested a long lateral transportation of some fine-grained Chinese river sediments (probably the Changjiang River) to the South Sea of Korea across the shelf of the northern East China Sea.

Rare earth elements geochemistry in springs from Taftan geothermal area SE Iran

NASA Astrophysics Data System (ADS)

Shakeri, Ata; Ghoreyshinia, Sayedkazem; Mehrabi, Behzad; Delavari, Morteza

2015-10-01

Concentrations of rare earth elements (REEs) were determined in springs and andesitic-dacitic rocks of Taftan geothermal field. Hydrochemical results of major ions indicate that thermal springs are Na-SO4-Cl and Ca-SO4-Cl types. Concentrations of REEs are in ranges of 10- 4 to 1.2 and 49 to 62 times of chondrite for springwater and rock samples, respectively. The thermal (STS and TTS) and the cold (APS) springs with low pH values exhibit a very high REE contents (0.64 to 3.15 mg/l). Saturation index indicates that Fe and Al phases can control dissolved REE concentration in FTS and PF cold springs. The speciation of REE complexes indicates dominant presence of LnSO4+ and free ion in the Taftan thermal springs. In APS cold spring with pH 4, fluoride complexes are dominate over the free ion and sulfate species, while in PF and FTS cold springs with pH 6.4 and 7, respectively, carbonate complexes (LnCO3+) are predominant species. Chondrite-normalized pattern for the low-pH waters show very distinctive gull-wing patterns, characteristic feature of acid-sulfate geothermal systems, and are similar to those of the host rocks. Chemical characteristics of rare earth elements in spring and volcanic rock samples indicate that REEs are originated from the andesitic-dacitic host rocks. Whole-rock-normalized REE patterns and petrographic evidences show that rare earth elements leached mainly from marginal alteration of minerals and matrix decomposition in volcanic rocks. In chondrite-normalized REE patterns, significant negative Eu anomaly in the cold springs compare to the thermal and acidic springs indicates that alteration of plagioclase is more intense in the later, corresponding to increasing in temperature and acidic state of reactant water.

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

NASA Astrophysics Data System (ADS)

Leybourne, Matthew I.; Johannesson, Karen H.

2008-12-01

We have collected ˜500 stream waters and associated bed-load sediments over an ˜400 km 2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into "dissolved" (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm] NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce ∗] NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu ∗] NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm] NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb] NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce ∗] NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu ∗] NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm] NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb] NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced. The partial extraction recovered, on average ˜20% of the Fe in the total sediment, ˜80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO 2/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.

Examination of Martian sedimentary rocks to understand possible paleo-ocean and its age

NASA Technical Reports Server (NTRS)

Tanaka, T.

1988-01-01

It is well known that the terrestrial marine sediments have large cerium anomaly on their chondrite-normalized REE pattern. Siliceous shale and calcaleous sediments have negative Ce-anomaly. Ferromanganese nodule have positive or negative Ce-anomaly. The Ce-anomaly is considered to be a result of tetravalent state of cerium rather than common trivalent. Ferromanganese nodule which formed under reducing condition has negative Ce-anomaly. Then, combined study of Ce-anomaly with Ce isotopes is expected to play an important role in geochemistry. La-138 decays to Ce-138 and Ba-138 with a total half life of about 1 x 10 to the 11th years. Cerium anomalies (positive or negative) are expected in Martian paleo-ocean and in sediments as observed in the terrestrial environment. A list of things to be examined is given.

Analyzing Solutions High in Total Dissolved Solids for Rare Earth Elements (REEs) Using Cation Exchange and Online Pre-Concentration with the seaFAST2 Unit; NETL-TRS-7-2017; NETL Technical Report Series; U.S. Department of Energy, National Energy Technology Laboratory: Albany, OR, 2017; p 32

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, J.; Torres, M.; Verba, C.

The accurate quantification of the rare earth element (REE) dissolved concentrations in natural waters are often inhibited by their low abundances in relation to other dissolved constituents such as alkali, alkaline earth elements, and dissolved solids. The high abundance of these constituents can suppress the overall analytical signal as well as create isobaric interferences on the REEs during analysis. Waters associated with natural gas operations on black shale plays are characterized by high salinities and high total dissolved solids (TDS) contents >150,000 mg/L. Methods used to isolate and quantify dissolved REEs in seawater were adapted in order to develop themore » capability of analyzing REEs in waters that are high in TDS. First, a synthetic fluid based on geochemical modelling of natural brine formation fluids was created within the Marcellus black shale with a TDS loading of 153,000 mg/L. To this solution, 1,000 ng/mL of REE standards was added based on preliminary analyses of experimental fluids reacted at high pressure and temperature with Marcellus black shale. These synthetic fluids were then run at three different dilution levels of 10, 100, and 1,000–fold dilutions through cation exchange columns using AG50-X8 exchange resin from Eichrom Industries. The eluent from the cation columns were then sent through a seaFAST2 unit directly connected to an inductively coupled plasma mass spectrometer (ICP-MS) to analyze the REEs. Percent recoveries of the REEs ranged from 80–110% and fell within error for the external reference standard used and no signal suppression or isobaric interferences on the REEs were observed. These results demonstrate that a combined use of cation exchange columns and seaFAST2 instrumentation are effective in accurately quantifying the dissolved REEs in fluids that are >150,000 mg/L in TDS and have Ba:Eu ratios in excess of 380,000.« less

Climatic and hydrological control on trace element variations in a speleothem from the Chauvet Cave, France

NASA Astrophysics Data System (ADS)

Bourdin, C.; Genty, D.; Douville, E.

2009-04-01

An ICPMS quantitative analysis of Ca, Mg, Ba, Sr, U, Mn, Y and 14 Rare Earth Elements (REE) has been performed on a speleothem from the Chauvet cave (south-east of France). The Chau-stm-6 stalagmite that grew from 33 ky to 11.5 ky before present had been previously dated by U-Th series method and the published d13C and d18O profile is used as a paleoclimatic benchmark. Chau-stm-6 recorded that major element Ca ratios (Mg, Ba, Sr), U and REY (REE + Y) responded to early deglaciation (15 ky). Their concentrations show relative variations of 40% to 75%. Ba and Sr profiles are significantly correlated (r = 0.85) and show a two-step increase during early deglaciation. Mg and U are weakly correlated and display a decreasing trend from 15 ky to 11.5 ky. REY concentrations decrease during early deglaciation (15 ky to 14.5 ky). The clear onset of Younger Dryas as recorded by both d13C and d18O profiles is not well marked by any of these trace elements though the averaged Sr concentration is slightly lower in the more recent part of the profile. Sr and Ba increase is best explained by the tenfold rise of the growth rate rather than changes in water residence time in the karst which would also increase Mg. The incongruent dissolution of dolomite upstream is invalidated by the absence of reported dolomite in the Chauvet karst system. No correlation was found between REY and Mn (an element strongly bound with colloidal and particular phases in water), suggesting that REY were mainly dissolved (and likely to be complexed) in groundwater. Due to the poorly developed soil above the cave, REY are thought to come mainly from the dissolution of the limestone bedrock. Bedrock samples display a rather flat pattern, only slightly depleted in LREE (light REE) and with a weak cerium (Ce) anomaly (0.6 to 1). In comparison Chau-stm-6 patterns show a marked depletion in LREE and a more pronounced Ce anomaly (0.3 to 0.75). This shale-normalized pattern is construed as coming from REY fractionation during mobilization or transport of the elements in seepage water rather than from the mixing of several REY sources. Preferential removal of LREE may come from their stronger affinity with particles and from a weaker carbonate complexation. The different climatic and environmental conditions don't seem to have affected REY fractionation - LREE/HREE (light REE on heavy REE) remained quite constant, although the ratio peaks or fall sharply at the climatic transitions. This could be the result of brief periods of intense leaching of colloids or particles. A weak anticorrelation was found between the Y/REE ratio and Ce anomaly. Moreover glacial conditions correspond to a high Y/REE-low Ce pattern whereas milder climate correspond to the opposite situation. The probable higher concentration of particles during the warmer period could explain both the better transport of REE relative to Y that has a slower particle-reactivity and larger scavenging of all REE that smoothes Ce anomaly. pH and Eh could also control the selective removal of Ce. Again no significant difference between Bolling-Allerod and Younger Dryas samples could be observed on REY patterns. This study is one of the first steps towards the use of REY as paleohydrologic and paleoclimatic proxies in continental environments.

Rare earth element and uranium-thorium variations in tufa deposits from the Mono Basin, CA

NASA Astrophysics Data System (ADS)

Wilcox, E. S.; Tomascak, P. B.; Hemming, N.; Hemming, S. R.; Rasbury, T.; Stine, S.; Zimmerman, S. R.

2009-12-01

Samples of fossil tufa deposits from several localities in the Mono Basin, eastern California, were analyzed for trace element concentrations in order to better understand changes in lake composition in the past. These deposits were formed during the last glacial cycle, mostly during deglaciation (Benson et al., 1990, PPP). Three elevations are represented by the analyses. Samples from near Highway 167 were sampled between 2063 and 2069 m asl. Samples from near Thompson Road were sampled between 2015 and 2021 m. One layered mound was sampled at 1955 m. Concentrations of the lanthanide rare earth elements (REE), in particular the heavy/light (HREE/LREE) distributions, have been shown to be sensitive to alkalinity in modern saline lakes (e.g., Johannesson et al., 1994, GRL, 21, 773-776), and the same has been suggested for U/Th (Anderson et al., 1982, Science, 216, 514-516). Holocene to near-modern tufa towers exist in shallow water and around the current shoreline (1945 m). Tufa towers above 2000 m include a characteristic morphology termed thinolite, interpreted to represent pseudomorphs after the very cold water mineral ikaite. Most lower elevation towers do not have the thinolite morphology, but some layered tufa mounds at low elevations include several layers of thinolite, such as the one sampled for this project. Analyses were made on millimeter-scale bulk samples from tufa towers. Measurements were made on sample solutions with a Varian 820MS quadrupole ICP-MS. Mono Basin tufa samples have total REE concentrations ranging from 0.029 to 0.77 times average shales. Samples have flat to moderately HREE-enriched shale-normalized patterns with limited overall variability ([La/Lu]SN of 1.8 to 9.6) but with some variability in the slope of the HREE portion of the patterns. Tufa towers sampled from three elevations have (Gd/Lu)SN of 0.40 to 1.5. The REE patterns of most samples have small positive Ce anomalies, but a minority of samples, all from the layered tufa mound, have small negative Ce anomalies. Concentrations of U and Th range from 0.5 to 12 ppm and from 0.2 to 12 ppm, respectively, with substantial variability in U/Th (0.08 to 20). Relative to modern Mono Lake water (Johannesson and Lyons, 1994, Limn. Oc., 39, 1141-1154) the tufa samples have 29 to 144000 times the total REE contents, but the water has HREE/LREE nearly twice as high as the most HREE-enriched fossil tufa. There is a general trend in which samples from higher elevation have lower average total REE, (Gd/Lu)SN and Th and higher average U and U/Th, the latter ranging from 0.52 in the locality at lowest elevation to 10.5 at the highest. In general the results show promise for the application of this approach to paleo-alkalinity, although analyses of modern precipitates as well as laboratory precipitation experiments are needed to fully address the processes.

Evaluation of carbonate diagenesis: A comparative study of minor elements, trace elements, and rare-earth elements (REE + Y) between Pleistocene corals and matrices from Grand Cayman, British West Indies

NASA Astrophysics Data System (ADS)

Li, Rong; Jones, Brian

2014-12-01

On Grand Cayman, the Pleistocene Ironshore Formation consists of six unconformity-bounded units of limestones that have been partially or completely altered to calcite by post-depositional meteoric diagenesis. In order to examine the diagenetic history from the perspective of geochemical elements, the concentrations of minor element (Sr, Na, Mg), trace elements (Ba, Fe, Mn, Al, Si), and rare-earth elements (REE) and yttrium (Y) were determined for 105 corals and 84 matrices collected from the Rogers Wreck Point (RWP), Western Onshore area (WO), and offshore George Town (GT) areas. With the transformation of aragonite to calcite, the Sr, Na, and Ba values decreased, but Mg increased, which are indicative of diagenetic alteration in an open water system. Due to intrinsic "vital effects" and the extrinsic diagenetic environment, the variations of Sr, Na, Ba, and Mg concentrations between Acropora and Montastrea from the GT area are different to those of their counterparts from RWP and WO. The signatures of Sr, Na, Ba, and Mg are in good agreement with the diagenetic history as determined from petrographic and stable isotopic criteria. The REE + Y (REY) concentrations (ΣREY) are higher in the matrices (0.2-6.9 ppm, average 2.6 ppm) than in the associated corals (0.1-5.4 ppm, average 0.6 ppm). Shale-normalized REY patterns of the Pleistocene Ironshore Formation are similar to those of oxygenated seawater, which are characterized by (1) light REE depletion relative to heavy REE (average DySN/SmSN = 1.7, n = 35), (2) positive La anomalies (average Pr/Pr* = 1.17, n = 53), and (3) negative Ce anomalies (average Ce/Ce* = 0.49, n = 53). The preserved seawater-like REY distribution pattern, the lack of correlation between ΣREY and mineralogy, and the lack of correlation between ΣREY and diagenesis-sensitive stable oxygen isotope (δ18O) indicate that meteoric diagenesis did not have a major impact on the REY distribution patterns. The matrices and corals in the GT area, compared to their counterparts from RWP and WO, have relatively less depleted LREE and lower Y in REY distribution pattern, suggesting contamination by minor amounts of detrital sediments. This is supported by the fact that limestones from the GT area contain abnormally high contents of detrital elements (Al, Si). The variations in ΣREY in carbonate rocks from locality to locality probably reflect variations that existed in the local depositional environments where these deposits originally formed.

Tetrad effects in REE abundance patterns of chondrules from CM meteorites: Implications for aqueous alteration on the CM parent asteroid

NASA Astrophysics Data System (ADS)

Inoue, Mutsuo; Nakamura, Noboru; Kimura, Makoto

2009-09-01

Lanthanide tetrad effect in bulk chondrules from two moderately altered CM chondrites, Murchison and Yamato-793321 (Y-793321), are reported for the first time. Twenty-three chondrules were petrographically characterized and analyzed for 10 rare earth elements (REE) and other trace and major elements (Ba, Sr, Rb, K, Ca, Mg and Fe) using the precise isotope dilution technique. The results indicate systematic depletion (several times) of alkali and alkaline earths compared to CV and CO chondrules. Most of the porphyritic olivine (8 PO) and olivine-pyroxene (4 POP), porphyritic and radial pyroxene (2 PP, 1 RP), and granular olivine (1 GO) chondrules show a light-REE (L-REE) depleted, heavy-REE (H-REE) smoothly fractionated pattern composed of four (upward convex) segments possessing a relatively large negative Eu anomaly (CI-normalized La/Sm, Lu/Er and Eu/Eu* ratios = 0.3-1: Eu*, normal value). On the other hand, all barred-olivine (5 BO) chondrules, a few PO and POP indicate almost a flat L-REE pattern. In addition, regardless of their textural types, nearly half of the chondrules have a variable degree of Ce and Yb anomalies, and/or L/H-REE discontinuity, which is similar to CV and CO chondrules. The observed L- and H-convex REE patterns accompanied with the negative Eu anomaly is the first known case for chondrules as well as meteoritic materials, but have been previously reported for geological samples such as sedimentary rocks, late stage igneous and metamorphic rocks, and are explained as the lanthanide tetrad effect, which plausibly results from fluid-rock interaction. We suggest that the marked REE fractionations occurred by the selective incorporation of L-, H-REEs and Eu into alteration products in the matrix during alteration processes on the CM parent body, but that the gas/solid REE fractionation characteristics established in the nebula have basically remained unchanged. We suggest that the tetrad effects observed here represent a new index of physico-chemical conditions of fluid-rock interactions prevalent on the CM parent body.

REE enrichment in granite-derived regolith deposits of the southeast United States: Prospective source rocks and accumulation processes

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.; Simandl, G.J.; Neetz, M.

2015-01-01

The Southeastern United States contains numerous anorogenic, or A-type, granites, which constitute promising source rocks for REE-enriched ion adsorption clay deposits due to their inherently high concentrations of REE. These granites have undergone a long history of chemical weathering, resulting in thick granite-derived regoliths, akin to those of South China, which supply virtually all heavy REE and Y, and a significant portion of light REE to global markets. Detailed comparisons of granite regolith profiles formed on the Stewartsville and Striped Rock plutons, and the Robertson River batholith (Virginia) indicate that REE are mobile and can attain grades comparable to those of deposits currently mined in China. A REE-enriched parent, either A-type or I-type (highly fractionated igneous type) granite, is thought to be critical for generating the high concentrations of REE in regolith profiles. One prominent feature we recognize in many granites and mineralized regoliths is the tetrad behaviour displayed in REE chondrite-normalized patterns. Tetrad patterns in granite and regolith result from processes that promote the redistribution, enrichment, and fractionation of REE, such as late- to post- magmatic alteration of granite and silicate hydrolysis in the regolith. Thus, REE patterns showing tetrad effects may be a key for discriminating highly prospective source rocks and regoliths with potential for REE ion adsorption clay deposits.

Temporal changes in Ce-anomalies in biogenic apatite from the Upper Cretaceous-Lower Eocene phosphate beds of Morocco. Is there a link to global paleoceanography?

NASA Astrophysics Data System (ADS)

Kocsis, L.; Gheerbrant, E.; Mouflih, M.; Cappetta, H.; Ulianov, A.

2012-12-01

Shallow marine phosphorites are widespread along the western coast of Morocco. These sediments were deposited in three, first order transgressive-regressive cycles during the late Cretaceous-early Eocene. The layers are exceptionally rich in marine vertebrate fossils and three periods - Maastrichtian, Danian-Thanetian and Ypresian - can be distinguished by the especially abundant selachian fauna. A comprehensive geochemical study is carried out on these biogenic apatite fossils, and here we present trace element data analyzed on enameloid and dentin of shark teeth, coprolites, and bones coming from the Ouled Abdoun and Ganntour Basins. A clear separation is apparent between enameloid and the other archives in terms of the former has lower Cu, Ba, rare earth elements (REE) and U, and higher Zn and Sr concentrations. The REE and U in phosphatic fossils originate almost entirely from early diagenetic pore fluid and thus they can be used as a fingerprint of burial conditions. The above observed differences in the trace element concentrations relate to the originally different structure of these fossils, which means the better crystallized and denser enameloid interacted less with the burial fluid than the other remains. All the fossils revealed very similar shale normalized REE patterns, with negative Ce-anomaly and heavy REE enrichment, which mimics the REE distribution of typical modern seawater. This would indicate that the early diagenetic pore fluid was dominated by seawater, when these fossils gained their REE composition. However, the patterns show small differences with lower La/Sm, and higher La/Yb and Sm/Yb ratios in the coprolites, dentine and bones, which would appear as slight flattening of the patterns on the heavy REE end. This signifies again that these latter archives are more susceptible to interaction with the pore fluid. In contrast, the Ce-anomaly does not vary among the different remains and the values are very similar in a given layer. However, more interestingly a gradual shift towards lower Ce/Ce* values from older to younger beds is evident. Three major causes could be responsible for this temporal Ce-anomaly shift. First is enhanced REE uptake with time and gradually less oxygenated early diagenetic environment in the deeper and older beds. This would predict higher total REE content in the older fossils, which is not observable in our record. Second is varying water depth in the basins that may relate to alternation in redox conditions in the burial environment. Clearly, sea-level fluctuation had an impact on the sedimentation in these shallow marine basins. However, Ce-anomaly appears to change before major sedimentary gaps. Third and our preferred interpretation is the negative Ce-anomaly shift indicates the presence of more oxygenated seawater in the basins. This region was controlled by upwelling currents from the Atlantic Ocean, hence the observed changes are presumed to be in this source. This would point to development of more oxygenated deepwater in the North Atlantic by the end of the Paleocene, which may link to the extended opening of the North Atlantic and its connection to the South Atlantic.

Back-arc with frontal-arc component origin of Triassic Karmutsen basalt, British Columbia, Canada

USGS Publications Warehouse

Barker, F.; Sutherland, Brown A.; Budahn, J.R.; Plafker, G.

1989-01-01

The largely basaltic, ???4.5-6.2-km-thick, Middle to Upper Triassic Karmutsen Formation is a prominent part of the Wrangellian sequence. Twelve analyses of major and minor elements of representative samples of pillowed and massive basalt flows and sills from Queen Charlotte and Vancouver Islands are ferrotholeiites that show a range of 10.2-3.8% MgO (as normalized, H2O- and CO2-free) and related increases in TiO2 (1.0-2.5%), Zr (43-147 ppm) and Nb (5-16 ppm). Other elemental abundances are not related simply to MgO: distinct groupings are evident in Al2O3, Na2O and Cr, but considerable scatter is present in FeO* (FeO + 0.9Fe2O3) and CaO. Some of the variation is attributed to alteration during low-rank metamorphism or by seawater - including variation of Ba, Rb, Sr and Cu, but high-field-strength elements (Sc, Ti, Y, Zr and Nb) as well as Cr, Ni, Cu and rare-earth elements (REE's) were relatively immobile. REE's show chondrite-normalized patterns ranging from light-REE depleted to moderately light-REE enriched. On eleven discriminant plots these analyses fall largely into or across fields of within-plate basalt (WIP), normal or enriched mid-ocean-ridge tholeiite (MORB) and island-arc tholeiite (IAT). Karmutsen basalts are chemically identical to the stratigraphically equivalent Nikolai Greenstone of southern Alaska and Yukon Territory. These data and the fact that the Karmutsen rests on Sicker Group island-arc rocks of Paleozoic age suggest to us that: 1. (1) the basal arc, after minor carbonate-shale deposition, underwent near-axial back-arc rifting (as, e.g., the Mariana arc rifted at different times); 2. (2) the Karmutsen basalts were erupted along this rift or basin as "arc-rift" tholeiitite; and 3. (3) after subsequent deposition of carbonates and other rocks, and Jurassic magmatism, a large fragment of this basalt-sediment-covered island arc was accreted to North America as Wrangellia. The major- and minor-elemental abundances of Karmutsen basalt is modeled by first mixing primitive arc magma with enriched basaltic liquid derived either from garnet peridotite or metasomatized mantle, followed by fractionation of olivine, pyroxenes, plagioclase and spinel. ?? 1989.

Time-resolved interaction of seawater with gabbro: An experimental study of rare-earth element behavior up to 475 °C, 100 MPa

NASA Astrophysics Data System (ADS)

Beermann, Oliver; Garbe-Schönberg, Dieter; Bach, Wolfgang; Holzheid, Astrid

2017-01-01

High metal and rare-earth element (REE) concentrations with unusual ('atypical') normalized REE patterns are documented in fluids from active hydrothermal vent fields on the Mid-Atlantic Ridge, 5°S and the East Scotia Ridge. Those fluids show relative enrichment of middle heavy REEs and almost no Eu anomalies in chondrite-normalized patterns. To understand the processes that produce such atypical REE patterns we ran a series of experiments, in which natural bottom seawater or aqueous solutions (NaCl, NaCl-MgCl2, or NaCl-CaCl2) were reacted with gabbro and gabbro mineral assemblages from 300 to 475 °C and 40 and 100 MPa. These P-T conditions are representative for water-rock interactions in hydrothermal root and discharge zones. Fluid flux variability and kinetics were addressed in the experiments by varying the water-to-rock mass ratio (w/r) from 0.5-10 and using different run durations from 3-720 h. Only seawater and synthetic MgCl2-bearing fluid mobilized significant amounts of REEs, Si, Ca, Fe, and Mn from gabbro, from clinopyroxene, and from plagioclase. At 425 °C and 40 MPa, fluids were initially acidic with pH (25 °C) of ∼2 increasing to values between ∼4 and 7 upon progressing reactions. Rare earth element and Fe contents peaked within 3-6 h after interaction with gabbroic mineral grains (125-500 μm) at w/r of 5 (REEs) and 2-5 (Fe) but decreased with continuing reaction without strong REE fractionation. Most of the REEs that were leached from primary minerals and dissolved in the fluids early became redeposited into solid reaction products after 720 h. Contents of dissolved SiO2 were pressure-dependent, being about twofold higher at 100 MPa than at 40 MPa (425 °C) and were below quartz saturation with gabbro and clinopyroxene as solid starting material and close to quartz saturation with plagioclase reactant. However, Si in fluids from the rock-dominated experiments at 100 MPa with gabbro (w/r 0.5-1) dropped to very low contents. A concomitant decrease in chlorinity suggests that these changes may be due to the breakdown of olivine and the formation of serpentine and Fe-hydroxy chlorides. Regardless of the starting solid reactants, fluid REE patterns were dominantly controlled by w/r. Atypical fluid REE patterns and high fluid REE contents were obtained at high w/r (⩾5). Whereas typical REE patterns known from many mid-ocean ridge vent fluids, showing relative enrichments of light REEs and a positive Eu anomaly, were obtained at low w/r of 0.5-1. Our results hence clearly show that REE contents and patterns of vent fluids are sensitive to variations in the w/r.

Do manganese nodules grow or dissolve after burial? Results from the Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2007-07-01

Fifty buried manganese nodules at different depth intervals were recovered in 12 sediment cores from the Central Indian Ocean Basin (CIOB). A maximum of 15 buried nodules were encountered in one sediment core (AAS-22/GC-07) and the deepest nodule was recovered at 5.50 m below seafloor in core AAS-04/GC-5A. Approximately 80% of the buried nodules are small in size (˜2 cm diameter) in contrast to the Atlantic Ocean and Peru Basin (Pacific Ocean) where the majority of the buried nodules are large, ˜8 cm and >6 cm, respectively. Buried nodule size decreases with core depth and this distribution appears to be similar to the phenomenon of "Brazil Nut Effect". Buried nodules exhibit both smooth and rough surface textures and are ellipsoidal, elongated, rounded, sub rounded, irregular and polynucleated. Buried nodules from siliceous ooze are enriched in Mn, Cu, Ni, Zn, Mo, Ga, V and Rb whereas those from red clay are enriched in Fe, Co, Ti, U, Th, Y, Cr, Nb and Rare Earth Elements (REE). Buried nodules from siliceous ooze suggest their formation under hydrogenetic, early digenetic and diagenetic processes whereas those from red clay are of hydrogenetic origin. REE are enriched more than 1.5 times in buried nodules from red clay compared to siliceous ooze. However, the mode of incorporation of REE into buried nodules from both sedimentary environments is by a single authigenic phase consisting of Fe-Ti-P. Shale-normalized REE patterns and Ce anomalies suggest that nodules from siliceous ooze formed under more oxidizing conditions than those from red clay. Nodules buried at depths between 1.5 and 2.5 m are diagenetic (Mn/Fe ratio 10-15), formed in highly oxic environments (large positive Ce anomalies) and record aeolian dust (high Eu anomalies). Chemical composition, surface texture and morphology of buried nodules are similar to those of surface nodules from the same basin. Furthermore, buried nodule compositions do not exhibit any distinct patterns within the core depth, suggesting that buried nodules neither grow nor dissolve after their burial in the sediment column.

Mineralogy, geochemistry, and radiocarbon ages of deep sea sediments from the Gulf of Mexico, Mexico

NASA Astrophysics Data System (ADS)

Armstrong-Altrin, John S.; Machain-Castillo, María Luisa

2016-11-01

The mineralogy, geochemistry, and radiocarbon ages of two sediment cores (GMX1 and GMX2) collected from the deep sea area of the Southwestern Gulf of Mexico (∼876-1752 m water depth) were studied to infer the sedimentation rate, provenance, heavy metal contamination, and depositional environment. The sediments are dominated by silt and clay fractions. The mineralogy determined by X-Ray diffractometry for the sediment cores reveals that montmorillonite and muscovite are the dominant clay minerals. The sections between 100 and 210 cm of the sediment cores GMX1 and GMX2, respectively, are characterized by the G. menardii group and G. Inflata planktonic foraminiferal species, which represent the Holocene and Pleistocene, respectively. The radiocarbon-age measurements of mixed planktonic foraminifera varied from ∼268 to 45,738 cal. years B.P and ∼104 to 25,705 cal. years B.P, for the sediment cores GMX1 and GMX2, respectively. The variation in age between the two sediment cores is due to a change in sediment accumulation rate, which was lowest at the location GMX1 (0.006 cm/yr) and highest at the location GMX2 (0.017 cm/yr). The chemical index of alteration (CIA), chemical index of weathering (CIW), and index of chemical maturity (ICV) values indicated a moderate intensity of weathering in the source area. The total rare earth element concentrations (∑REE) in the cores GMX1 and GMX2 vary from ∼94 to 171 and ∼78 to 151, respectively. The North American Shale Composite (NASC) normalized REE patterns showed flat low REE (LREE), heavy REE (HREE) depletion with low negative to positive Eu anomalies, which suggested that the sediments were likely derived from intermediate source rocks. The enrichment factor of heavy metals indicated that the Cd and Zn concentrations in the sediment cores were impacted by an anthropogenic source. The redox-proxy trace element ratios such as V/Cr, Ni/Co, Cu/Zn, (Cu + Mo)/Zn, and Ce/Ce* indicated that the sediments were deposited under an oxic depositional environment. The similarity in major element concentrations, REE content, and the NASC normalised REE patterns between the cores GMX1 and GMX2 revealed that the provenance of sediments remained relatively uniform or constant during deposition for ∼4.5 Ma. The major and trace element based multidimensional discrimination diagrams showed a rift setting for the core sediments, which is consistent with the geology of the Gulf of Mexico.

Mineralogy and Geochemistry of Vanadium-Bearing Black Shales at Zhangcun and Zhengfang, Eastern Jiangxi Province, China

NASA Astrophysics Data System (ADS)

Long, H.; Long, H.; Nekvasil, H.; Liu, Y.

2001-12-01

As a member of Hetang Formation, lower Cambrian, the Zhangcun-Zhengfang vanadium-bearing black shales are spread in the sea basin outside of the Ancient Jiangnan Island Arc. The composition of black shales is silicalite + siltstone + detrital carbonate. A large amount of hyalophane has been discovered in the shales and the hyalophane-rich rock is the major type of vanadium-host rock. The barium content in the hyalophane is up to 18.91%. The vanadium mainly exists in vanadiferous illite and several Ti-V oxides, possibly including a new mineral. The chemical formula of this kind of Ti-V oxide is V2O3¡nTiO2, n=4¡ª9, according to the electronic microprobe studies. The micro X-ray diffraction studies show the new mineral may be triclinic. The shales are rich in Ba, K, V and contain only trace Na and Mn while all the compositions of the shales except carbonate have a low content of Mg and Ca. According to the authors¡_ study, V obviously has a relationship with Ba and Se, which are from the volcano or hydrothermal activities, and the basic elements Cr, Co, Ni, Ti and Fe. It may present that they are from the same source. Thus, it seems that they are not from the ¡rnormal¡_ sedimentary environment and may be from the hydrothermal deposition. The REE models show that silicalite may be the hydrothermal deposit that does not mix with seawater while the REE models of hyalopahne-rich rock is similar to some modern hydrothermal deposits in the seafloor. The subtle negative anomaly of Yb may reflect the REE model of basalt in the seafloor. The geology and geochemistry of the shales indicate that the shales may be of hydrothermal genesis. Silicalite may be the typical ¡r pure¡_ hydrothermal sediment and hyalophane-rich rock may be the product of hydrothermal activity while the hydrothermal fluid passes the continent source material in the sedimentary process. V, Ti, Ba and Si may be from the volcanic rock in the seafloor and the Al and K may be from the continent.

A novel approach for acid mine drainage pollution biomonitoring using rare earth elements bioaccumulated in the freshwater clam Corbicula fluminea.

PubMed

Bonnail, Estefanía; Pérez-López, Rafael; Sarmiento, Aguasanta M; Nieto, José Miguel; DelValls, T Ángel

2017-09-15

Lanthanide series have been used as a record of the water-rock interaction and work as a tool for identifying impacts of acid mine drainage (lixiviate residue derived from sulphide oxidation). The application of North-American Shale Composite-normalized rare earth elements patterns to these minority elements allows determining the origin of the contamination. In the current study, geochemical patterns were applied to rare earth elements bioaccumulated in the soft tissue of the freshwater clam Corbicula fluminea after exposure to different acid mine drainage contaminated environments. Results show significant bioaccumulation of rare earth elements in soft tissue of the clam after 14 days of exposure to acid mine drainage contaminated sediment (ΣREE=1.3-8μg/gdw). Furthermore, it was possible to biomonitor different degrees of contamination based on rare earth elements in tissue. The pattern of this type of contamination describes a particular curve characterized by an enrichment in the middle rare earth elements; a homologous pattern (E MREE =0.90) has also been observed when applied NASC normalization in clam tissues. Results of lanthanides found in clams were contrasted with the paucity of toxicity studies, determining risk caused by light rare earth elements in the Odiel River close to the Estuary. The current study purposes the use of clam as an innovative "bio-tool" for the biogeochemical monitoring of pollution inputs that determines the acid mine drainage networks affection. Copyright © 2017 Elsevier B.V. All rights reserved.

REE controls in ultramafic hosted MOR hydrothermal systems: An experimental study at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Allen, Douglas E.; Seyfried, W. E.

2005-02-01

A hydrothermal experiment involving peridotite and a coexisting aqueous fluid was conducted to assess the role of dissolved Cl - and redox on REE mobility at 400°C, 500 bars. Data show that the onset of reducing conditions enhances the stability of soluble Eu +2 species. Moreover, Eu +2 forms strong aqueous complexes with dissolved Cl - at virtually all redox conditions. Thus, high Cl - concentrations and reducing conditions can combine to reinforce Eu mobility. Except for La, trivalent REE are not greatly affected by fluid speciation under the chemical and physical condition considered, suggesting control by secondary mineral-fluid partitioning. LREE enrichment and positive Eu anomalies observed in fluids from the experiment are remarkably similar to patterns of REE mobility in vent fluids issuing from basalt- and peridotite-hosted hydrothermal systems. This suggests that the chondrite normalized REE patterns are influenced greatly by fluid speciation effects and secondary mineral formation processes. Accordingly, caution must be exercised when using REE in hydrothermal vent fluids to infer REE sources in subseafloor reaction zones from which the fluids are derived. Although vent fluid patterns having LREE enrichment and positive Eu anomalies are typically interpreted to suggest plagioclase recrystallization reactions, this need not always be the case.

Continental crustal composition and lower crustal models

NASA Technical Reports Server (NTRS)

Taylor, S. R.

1983-01-01

The composition of the upper crust is well established as being close to that of granodiorite. The upper crustal composition is reflected in the uniform REE abundances in shales which represent an homogenization of the various REE patterns. This composition can only persist to depths of 10-15 km, for heat flow and geochemical balance reasons. The composition of the total crust is model dependent. One constraint is that it should be capable of generating the upper granodioritic (S.L.) crust by partial melting within the crust. This composition is based on the andesite model, which assumes that the total crust has grown by accretion of island arc material. A representation of the growth rate of the continental crust is shown. The composition of the lower crust, which comprises 60-80% of the continental crust, remains a major unknown factor for models of terrestrial crustal evolution. Two approaches are used to model the lower crust.

Provenance of the Neogene Surma Group from the Chittagong Tripura Fold Belt, southeast Bengal Basin, Bangladesh: Constraints from whole-rock geochemistry and detrital zircon U-Pb ages

NASA Astrophysics Data System (ADS)

Rahman, M. Julleh Jalalur; Xiao, Wenjiao; McCann, Tom; Songjian, Ao

2017-10-01

Miocene Surma Group from the Chittagong Tripura Fold Belt (CTFB), southeast Bengal Basin has been analyzed to evaluate their provenance, tectonic settings and paleoweathering conditions. The sandstones show moderate to high contents of SiO2 (65-80%; 75% on average), and Al2O3 (9.94% on average), with Fe2O3 (total Fe as Fe2O3) + MgO contents of 5.1%, TiO2 (0.57% on average). Compared to the upper continental crust (UCC), the sandstones are depleted in CaO (1.49%) and enriched in Al2O3, Fe2O3 and Na2O. The Neogene shales of the Surma Group are in fair concurrence when compared to the NASC (North American Shale Composite), UCC (the upper continental crust) with the exception of the low content of CaO but when compared with the PAAS (Post-Archaean Australian Shale), the Neogene shales are a little more depleted in Al2O3 content. Sandstones and shales have Eu/Eu∗ ∼0.61 and ∼0.65, (La/Lu)N ∼9.06 and ∼8.70, La/Sc- ∼3.90 and ∼2.86, Th/Sc ∼1.19 and ∼1.41, La/Co- ∼3.69 and ∼2.42, Th/Co ∼1.08 and ∼1.20 and Cr/Th ∼7.90 and ∼5.88 ratios as well as Chondrite-normalized REE patterns with flat HREE, LREE enrichment, and negative Eu anomalies indicate the derivation from predominantly felsic sources subjected to low to moderate chemical weathering [Chemical index of alteration (CIA) values of sandstones- 31.11-74.46, av. 60.08); shales- 43.96-73.07, av. 61.80]. Integrated geochemical and zircon U-Pb studies reveal that main sediment input might have been from the Himalaya with mixing influence from the east of the Indo-Burman Ranges in an active margin setting at the convergence of the Indian and Burmese plates.

Complementary rare earth element patterns in unique achondrites, such as ALHA 77005 and shergottites, and in the earth

NASA Technical Reports Server (NTRS)

Ma, M.-S.; Schmitt, R. A.; Laul, J. C.

1982-01-01

Abundances of major, minor, and trace elements are determined in the Antarctic achondrite Allan Hills (ALHA) 77005 via sequential instrumental and radiochemical neutron activation analysis. The rare earth element (REE) abundances of ALHA 77005 reveal a unique chondritic normalized pattern; that is, the REEs are nearly unfractionated from La to Pr at approximately 1.0X chondrites, monotonically increased from Pr to Gd at approximately 3.4X with no Eu anomaly, nearly unfractionated from Gd and Ho and monotonically decreased from Ho to Lu at approximately 2.2X. It is noted that this unique REE pattern of ALHA 77005 can be modeled by a melting process involving a continuous melting and progressive partial removal of melt from a light REE enriched source material. In a model of this type, ALHA 77005 could represent either a crystallized cumulate from such a melt or the residual source material. Calculations show that the parent liquids for the shergottites could also be derived from a light REE enriched source material similar to that for ALHA 77005.

RARE EARTH ELEMENTS IN FLY ASHES AS POTENTIAL INDICATORS OF ANTHROPOGENIC SOIL CONTAMINATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mattigod, Shas V.

2003-08-01

Studies of rare earth element (REE) content of disposed fly ashes and their potential mobility were neglected for decades because these elements were believed to be environmentally benign. A number of recent studies have now shown that REE may pose a long-term risk to the biosphere. Therefore, there is a critical need to study the REE concentrations in fly ash and their potential mobilization and dispersal upon disposal in the environment. We analyzed the REE content of bulk, size fractionated, and density separated fractions of three fly ash samples derived from combustion of sub bituminous coals from the western Unitedmore » States and found that the concentrations of these elements in bulk ashes were within the range typical of fly ashes derived from coals from the North American continent. The concentrations of light rare earth elements (LREE) such as La, Ce, and Nd, however, tended towards the higher end of the concentration range whereas, the concentrations of middle rare earth elements (MREE) (Sm and Eu) and heavy rare earth elements (HREE) (Lu) were closer to the lower end of the observed range for North American fly ashes. The concentrations of REE did not show any significant enrichment with decreasing particle size, this is typical of nonvolatile lithophilic element behavior during the combustion process. The lithophilic nature of REE was also confirmed by their concentrations in heavy density fractions of these fly ashes being on average about two times more enriched than the concentrations in the light density fractions. Shale normalized average of REE concentrations of fly ashes and coals revealed significant positive anomalies for Eu and Dy. Because of these distinctive positive anomalies of Eu and Dy, we believe that fly ash contamination of soils can be fingerprinted and distinguished from other sources of anthropogenic REE inputs in to the environment.« less

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

USGS Publications Warehouse

Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

1996-01-01

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive YSN and GdSN anomalies in seawater.

REE and actinide microdistribution in Sahara 97072 and ALHA77295 EH3 chondrites: A combined cosmochemical and petrologic investigation

NASA Astrophysics Data System (ADS)

Gannoun, A.; Boyet, M.; El Goresy, A.; Devouard, B.

2011-06-01

We report the results of rare earth elements (REEs) and U-Th inventory of individual minerals (oldhamite, enstatite and niningerite) in two of the most unequilibrated and primitive EH3 known so far, ALHA77295 and Sahara 97072. Under the highly reducing condition that prevailed during the formation of enstatite chondrites, REEs are mainly chalcophile and concentrated in oldhamite. The study is guided by detailed petrographic investigations of the individual minerals in chondrules, complex sulfide-metal clasts and enstatite-dominated matrices. We developed two textural parameters in order to resolve the evolution of oldhamite condensates and their residence in the solar gas prior to their accretion in the individual objects or in matrices and relate these textural features to the measured REE patterns of the individual oldhamite crystals. These textural parameters are the crystal habit of oldhamite grains (idiomorphic or anhedral) and their host assemblages. REE concentrations were measured by SIMS and LA-ICPMS. Oldhamite grains display REE enrichments (10-100 × CI). Four types of REE patterns are encountered in oldhamite in ALHA77295. In general the REE distributions cannot be assigned to a specific oldhamite-bearing assemblage. The most represented REE pattern is characterized by both slight to large positive Eu and Yb anomalies and is enriched in light REEs relative to heavy REEs. This pattern is present in 97% of oldhamite in Sahara 97072, suggesting a different source region in the reduced part of the nebula or different parental EH asteroids for the two EH3 chondrites. Different parental asteroids are also supported by MgS-FeS zoning profiles in niningerite grains adjacent to troilite revealing both normal and reverse zoning trends and different MnS contents. The observed homogeneity of REE distribution in oldhamite grains in Sahara 97072 is not related to the mild metamorphic event identified in this meteorite that caused breakdown of the major K- and Rb-bearing sulfide (djerfisherite). REE concentrations in enstatite range between 0.2 and 8 × CI. Hence, enstatite is an important REE host next to oldhamite. Most patterns are characterized by negative Eu and Yb anomalies. Niningerites are negligible contributors to bulk EH3 REE inventory. Average positive Eu and Yb anomalies observed in most oldhamite are complimentary to the negative ones in enstatite thus explaining the flat patterns of the bulk meteorites. The condensation calculations based on cosmic abundances predict that the first oldhamite condensates should have flat REE patterns with Eu and Yb depletions since Eu and Yb condense at lower temperature than other REE. However, this pattern is seen in enstatite. Our findings are at odds with the predicted negative Eu and Yb anomalies in oldhamite earliest condensates from a closed system in a reduced solar source. Our petrographic, mineral chemistry and REE abundances of oldhamite, enstatite and niningerite discards an origin of oldhamite by impact melting ( Rubin et al., 2009). Our results do not support in first order the scenario of the incorporation of REE in the Earth's core to explain 142Nd excess in terrestrial samples relative to chondrites because oldhamite is the major REE carrier phase and has super-chondritic Sm/Nd ratios.

High resolution rare-earth elements analyses of natural apatite and its application in geo-sciences: Combined micro-PIXE, quantitative CL spectroscopy and electron spin resonance analyses

NASA Astrophysics Data System (ADS)

Habermann, D.; Götte, T.; Meijer, J.; Stephan, A.; Richter, D. K.; Niklas, J. R.

2000-03-01

The rare-earth element (REE) distribution in natural apatite is analysed by micro-PIXE, cathodoluminescence (CL) microscopy and spectroscopy and electron spin resonance (ESR) spectroscopy. The micro-PIXE analyses of an apatite crystal from Cerro de Mercado (Mexico) and the summary of 20 analyses of six francolite (conodonts of Triassic age) samples indicate that most of the REEs are enriched in apatite and francolite comparative to average shale standard (NASC). The analyses of fossil francolite revealing the REE-distribution not to be in balance with the REE-distribution of seawater and fish bone debris. Strong inhomogenous lateral REE-distribution in fossil conodont material is shown by CL-mapping and most probably not being a vital effect. Therefore, the resulting REE-signal from fossil francolite is the sum of vital and post-mortem incorporation. The necessary charge compensation for the substitution of divalent Ca by trivalent REE being done by different kind of electron defects and defect ions.

Trace elements and REE geochemistry of Middle Devonian carbonate mounds (Maïder Basin, Eastern Anti-Atlas, Morocco): Implications for early diagenetic processes

NASA Astrophysics Data System (ADS)

Franchi, Fulvio; Turetta, Clara; Cavalazzi, Barbara; Corami, Fabiana; Barbieri, Roberto

2016-08-01

Trace and rare earth elements (REEs) have proven their utility as tools for assessing the genesis and early diagenesis of widespread geological bodies such as carbonate mounds, whose genetic processes are not yet fully understood. Carbonates from the Middle Devonian conical mud mounds of the Maïder Basin (eastern Anti-Atlas, Morocco) have been analysed for their REE and trace element distribution. Collectively, the carbonates from the Maïder Basin mud mounds appear to display coherent REE patterns. Three different geochemical patterns, possibly related with three different diagenetic events, include: i) dyke fills with a normal marine REE pattern probably precipitated in equilibrium with seawater, ii) mound micrite with a particular enrichment of overall REE contents and variable Ce anomaly probably related to variation of pH, increase of alkalinity or dissolution/remineralization of organic matter during early diagenesis, and iii) haematite-rich vein fills precipitated from venting fluids of probable hydrothermal origin. Our results reinforce the hypothesis that these mounds were probably affected by an early diagenesis induced by microbial activity and triggered by abundance of dispersed organic matter, whilst venting may have affected the mounds during a later diagenetic phase.

Trace element mobility in dolomitic argillites of the Mesoproterozoic Belt-Purcell Supergroup, Western North America

NASA Astrophysics Data System (ADS)

González-Álvarez, Ignacio; Kerrich, Robert

2011-04-01

The Belt-Purcell Supergroup comprises dolomite-rich stratigraphic units in a dominantly siliciclastic succession, where sedimentation spans 1400-1470 Ma. Dolomitic units are variable mixtures of co-sedimented argillite and primary carbonate post-depositionally converted to secondary dolomite. Based on rare earth element (REE) relationships three distinct REE patterns are identified in the dolomite-rich units: Type 1 (T1d; d = dolomitic sample) with REE patterns parallel to post-Archean Upper Continental Crust (PA-UCC), albeit at lower absolute abundances due to dilution by carbonate content; Type 2 (T2d) with Heavy REE (HREE) enrichment but Light REE (LREE) depletion relative to T1d; and Type 3 (T3d) with enrichment in LREE and HREE relative to T1d, but erratic Middle REE (MREE) patterns. There is a progressive increase of ΣREE from T1d through T2d to T3d, whereas for ΣLREE/ΣHREE T2d < T1d < T3d. T1d-T2d and T3d represent three different "snapshots" of a continuous process. In terms of timing, dolomitization of calcite primary sediment in all samples likely took place broadly during burial diagenesis, as inferred for most Proterozoic dolomites. T1d is easily explained by provenance: however, T2d and T3d cannot be related to provenance, weathering or sedimentary sorting processes to explain higher concentrations of HREE referenced to PA-UCC and consequently developed in the sediment from a T1d precursor. The same three REE signatures have been described in previous studies in counterpart siliciclastic counterparts throughout the Belt-Purcell Supergroup at three different locations. Mobility of normally stable REE is accompanied by mobility of normally isochemical high field strength elements (HFSE) in T2d and T3d to give REE/REE, HFSE/HFSE, REE/HFSE and Y/HREE fractionations. No specific REE-HFSE signatures are apparent in the carbonate-rich units as compared to their non-dolomitic siliciclastic counterparts. This unusual mobility of REE and HFSE reflected in T2d and T3d is attributed to alkaline oxidizing post-depositional brines. Salinity was derived from seawater-sediment reactions, dissolution of evaporite minerals, and the smectite-illite transformation, whereas alkaline oxidizing conditions were promoted by groundwater interaction with mafic units in the basin, CO 2 introduced into the system during episodic rifting with mantle degassing, and interaction of syn-sedimentary mafic intrusions with carbonate units at early stages of BPS deposition. Intermittent brine activity, inducing T2d and T3d patterns, spanned >1 Ga as recorded by secondary monazite grains with age distributions that correspond to large scale tectono-thermal events in Laurentia. Post-depositional processes and redistribution of carbonate can have an impact on transitional stratigraphic contacts between dolomitic and siliciclastic units which may have been incorrectly described as primary due to sedimentary environment changes.

Rare earth and trace element signatures for assessing an impact of rock mining and processing on the environment: Wiśniówka case study, south-central Poland.

PubMed

Migaszewski, Zdzisław M; Gałuszka, Agnieszka; Dołęgowska, Sabina

2016-12-01

A detailed hydrogeochemical study was performed in the Wiśniówka mining area (south-central Poland). This covered three acid pit bodies, historic tailings acid ponds, acid pools, and additionally two neighboring rivers. All these acid mine drainage (AMD) waters are characterized by the pH in the range of 1.7 (pools) to 3.5 (tailings ponds). The most interesting is the Podwiśniówka acid pit lake that shows a very low pH (2.2-2.5) and very high concentrations of SO 4 2- (2720-5460 mg/L), Fe (545-1140 mg/L), Al (86.2 mg/L), As (9603-24,883 μg/L), Co (1317-3458 μg/L), Cr (753-2047 μg/L), Cu (6307-18,879 μg/L), Ni (1168-3127 μg/L), and rare earth element (REE) (589-1341 μg/L). In addition, seeps that drain the Podwiśniówka mine tailings and partly aggregate piles form strong acid pools in the mining area. Along with these pools, in which As and REE contents reach 369,726 and 6288 μg/L, respectively, these waters are among the most distinctive As- and REE-rich AMD surface waters across the world. It is noteworthy that the Podwiśniówka acid pit lake and Wiśniówka Duża acid pit sump exhibit different element signatures and REE concentration patterns normalized to North American Composite Shale (NASC): the Podwiśniówka acid pit lake always shows a characteristic roof-shaped medium REE (MREE) profile with distinct enrichments in Gd, Eu, and Tb whereas the other one displays a step-shaped heavy REE (HREE) profile with positive Tb and Gd anomalies. The REE undergo fractionation during weathering and the subsequent leaching of dissolved and suspended fractions from rocks to acid water bodies where these and other elements are further fractionated by geochemical processes. This study shows that the individual REE have greater affinities for Mn, HREE for Fe and SO 4 2- , and only La and Ce for Al. This specific water geochemistry has enabled us to (i) pinpoint the location of AMD "hot spots" originated from quartzite mining and processing operations conducted by current and previous mining companies, (ii) predict the directions and effects of future strip mining for quartzites in the Wiśniówka Duża and Podwiśniówka open pits, and (iii) evaluate the potential impact of mining and processing effluents on the quality of rivers.

The controls on the major and trace element variation of shales, siltstones, and sandstones of Pennsylvanian-Permian age from uplifted continental blocks in Colorado to platform sediment in Kansas, USA

NASA Astrophysics Data System (ADS)

Cullers, Robert L.

1994-11-01

Shales, siltstones, and sandstones of Pennsylvanian-Permian age from near the source in Colorado to those in the platform in eastern Colorado and Kansas have been analyzed for major elements and a number of trace elements, including the REEs. The near-source sandstones are significantly more enriched (Student t-test at better than the 99% confidence level) in SiO 2 and Na 2O concentrations and more depleted in Al 2O 3, Fe 2O 3 (total), TiO 2, Th, Hf, Sc, Cr, Cs, REEs, Y, and Ni concentrations and La/Co and La/Ni ratios than the near-source shales and siltstones, most likely due to more plagioclase and quartz and less clay minerals in the sandstones than in the shales and siltstones. There are no significant differences in K 2O and Sr concentrations and Eu/Eu∗, La/Lu, La/Se, Th/Sc, Th/Co, and Cr/Th ratios between the near-source sandstones and the near-source shales and siltstones. Samples of the Molas, Hermosa, and Cutler formations near the source that were formed in different environments in the same area contain no significant difference in Eu/Eu∗, La/Lu, La/Sc, Th/Sc, Th/Co, and Cr/Th ratios, so a generally silicic source and not the environment of deposition was most important in producing these elemental ratios. For example, Cr/Th ratios of near-source shales, siltstones, and sandstones range from 2.5 to 17.5 and Eu/Eu∗ range from 0.48 to 0.78, which are in the range of sources of sediments derived from mainly silicic and not basic sources. Near-source shales and siltstones contain significantly higher (Student t-test) and more varied concentrations of most elements (Al 2O 3, Fe 2O 3, MnO, TiO 2, Ba, Th, Hf, Ta, Co, Sc, REEs, Nb, Y) but significantly lower concentrations of Na 2O and Eu/Eu∗ than platform shales and siltstones in Kansas (e.g., La = 65.7 ± 40 and Eu/Eu∗ = 0.55 ± 0.07 in near-source shales and siltstones and La = 23.7 ± 8.7 and Eu/Eu∗ = 0.64 ± 0.08 in platform shales and siltstones). The SiO 2 and CaO concentrations are not significantly different in platform shales and siltstones compared to the near-source shales and siltstones, so dilution of other minerals by quartz and calcite is not the main reason for the lower concentration of most elements in the platform relative to the near-source shales and siltstones. Rather the lesser concentrations of most elements in clay minerals of the platform shales and siltstones can account for the lower concentration of most elements compared to corresponding near-source shales and siltstones. The lower concentrations of many elements in clay minerals in the platform shales and siltstones may be a result of having been derived from recycling of clay minerals from older rocks. The greater homogeneity of elemental concentrations of the platform shales and siltstones compared to those in the source is also consistent with homogeneous mixing of such recycled material. Also there is no significant difference in Th/Sc, La/Co, Th/Co, La/Ni, and Cr/Th ratios of the near-source sedimentary rocks in Colorado to the platform shales and siltstones in Kansas, and the latter are also consistent with derivation from mostly silicic source rocks.

Seasonal and spatial variations in rare earth elements and yttrium of dissolved load in the middle, lower reaches and estuary of the Minjiang River, southeastern China

NASA Astrophysics Data System (ADS)

Zhu, Xuxu; Gao, Aiguo; Lin, Jianjie; Jian, Xing; Yang, Yufeng; Zhang, Yanpo; Hou, Yuting; Gong, Songbai

2017-09-01

With the aim of elucidating the spatial and seasonal behaviors of rare earth elements (REEs), we investigated the dissolved REE concentrations of surface water collected during four seasons from middle, lower reaches and estuary of the Minjiang River, southeastern China. The results display that the REE abundances in Minjiang River, ranging from 3.3-785.9 ng/L, were higher than those of many of the major global rivers. The total REE concentrations (ΣREE) were seasonally variable, averaging in 5 937.30, 863.79, 825.65 and 1 065.75 ng/L during second highest flow (SHF), normal flow (NF), low flow (LF) and high flow (HF) season, respectively. The R (L/M) and R (H/M) ratios reveal the spatial and temporal variations of REE patterns, and particularly vary apparently in the maximum turbidity zone and estuary. REE patterns of dissolved loads are characterized by progressing weaker LREEs-enrichment and stronger HREEs-enrichment downstream from middle reaches to estuary during all four seasons. Comparing with NF and LF seasons, in which REE patterns are relatively flat, samples of SHF season have more LREE-enriched and HREE-depleted patterns that close to parent rocks, while samples of HF season are more LREEs-depleted and HREE-enriched. REE fractionations from the middle to lower reaches are stronger in the SHF and HF seasons than those in NF and LF seasons. Generally, spatial and seasonal variations in REE abundance and pattern are presumably due to several factors, such as chemical weathering, mixture with rainfall and groundwater, estuarine mixing, runoff, biological production and mountain river characters, such as strong hydrodynamic forces and steep slopes. The highest Gd/Gd* always occurs at north ports during all four seasons, where most of the large hospitals are located. This suggests Gd anomalies are depended on the density of modern medical facilities. Y/Ho ratios fluctuate and positively correlate to salinity in estuary, probably because of the geochemical behavior differences between Y and Ho.

[Rare earth elements contents and distribution characteristics in nasopharyngeal carcinoma tissue].

PubMed

Zhang, Xiangmin; Lan, Xiaolin; Zhang, Lingzhen; Xiao, Fufu; Zhong, Zhaoming; Ye, Guilin; Li, Zong; Li, Shaojin

2016-03-01

To investigate the rare earth elements(REEs) contents and distribution characteristics in nasopharyngeal carcinoma( NPC) tissue in Gannan region. Thirty patients of NPC in Gannan region were included in this study. The REEs contents were measured by tandem mass spectrometer inductively coupled plasma(ICP-MS/MS) in 30 patients, and the REEs contents and distribution were analyzed. The average standard deviation value of REEs in lung cancer and normal lung tissues was the minimum mostly. Light REEs content was higher than the medium REEs, and medium REEs content was higher than the heavy REEs content. REEs contents changes in nasopharyngeal carcinoma were variable obviously, the absolute value of Nd, Ce, Pr, Gd and other light rare earth elements were variable widely. The degree of changes on Yb, Tb, Ho and other heavy rare earth elements were variable widely, and there was presence of Eu, Ce negative anomaly(δEu=0. 385 5, δCe= 0. 523 4). The distribution characteristic of REEs contents in NPC patients is consistent with the parity distribution. With increasing atomic sequence, the content is decline wavy. Their distribution patterns were a lack of heavy REEs and enrichment of light REEs, and there was Eu , Ce negative anomaly.

Rare earth elements in apatite: Uptake from H{sub 2}O-bearing phosphate-fluoride melts and the role of volatile components

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleet, M.E.; Pan, Yuanming

The partitioning of rare earth elements (REEs) between fluorapatite (FAp) and H{sub 2}O- bearing phosphate-fluoride melts has been studied at about 700 and 800{degrees}C and 0.10-0.15 GPa. REE uptake patterns, i.e., plots of D(REE:FAp/melt), are convex upwards and peak near Nd for single-REE substituted FAp at minor (0.03-0.25 wt% REE{sub 2}O{sub 3}) abundances, and binary (LREE + HREE)-substituted FAp, and hexa-REE-substituted FAp at minor to major (0.25-7.8 wt% REE{sub 2}O{sub 3}) abundances. Partition coefficients for minor abundances of REE and depolymerized phosphate melts are about 5, 8, and 1 for La, Nd, and Lu, respectively and broadly comparable to thosemore » for early fluorapatite in the fractionation of melts of basaltic composition. The Ca2 site exerts marked control on the selectivity of apatite for REE because it preferentially incorporates LREE and its effective size varies with substitution of the A-site volatile anion component (F, Cl, OH). Using simple crystal-chemical arguments, melt(or fluid)-normalized REE patterns are predicted to peak near Nd for fluorapatite and be more LREE-enriched for chlorapatite. These predictions are consistent with data from natural rocks and laboratory experiments. The wide variation in D(REE:apatite/melt) in nature (from <1 for whitlockite-bearing lunar rocks to about 100 for evolved alkalic rocks) is attributed largely to the influence of the volatile components. 49 refs., 8 figs., 3 tabs.« less

Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control

USGS Publications Warehouse

Morgan, J.W.; Wandless, G.A.

1980-01-01

Rare earth element (REE) abundances were measured by neutron activation analysis in anhydrite (CaSO4), barite (BaSO4), siderite (FeCO3) and galena (PbS). A simple crystal-chemical model qualitatively describes the relative affinities for REE substitution in anhydrite, barite, and siderite. When normalized to 'crustal' abundances (as an approximation to the hydrothermal fluid REE pattern), log REE abundance is a surprisingly linear function of (ionic radius of major cation-ionic radius of REE)2 for the three hydrothermal minerals, individually and collectively. An important exception, however, is Eu, which is anomalously enriched in barite and depleted in siderite relative to REE of neighboring atomic number and trivalent ionic radius. In principle, REE analyses of suitable pairs of co-existing hydrothermal minerals, combined with appropriate experimental data, could yield both the REE content and the temperature of the parental hydrothermal fluid. The REE have only very weak chalcophilic tendencies, and this is reflected by the very low abundances in galena-La, 0.6 ppb; Sm, 0.06 ppb; the remainder are below detection limits. ?? 1980.

Importance of nanoparticles and colloids from volcanic ash for riverine transport of trace elements to the ocean: evidence from glacial-fed rivers after the 2010 eruption of Eyjafjallajökull Volcano, Iceland.

PubMed

Tepe, Nathalie; Bau, Michael

2014-08-01

Volcanic ashes are often referenced as examples for natural nanoparticles, yet the particle size distribution <1000 nm is only rarely documented. We here report results of a geochemical study of glacial-fed rivers, glacial surface runoff, glacial base flow, and pure glacial meltwater from southern Iceland, that had been sampled 25 days after the explosive eruptions at Eyjafjallajökull in 2010. In addition to the dissolved concentrations of rare earth elements (REE), Zr, Hf, Nb, and Th in the 450 nm-filtered waters, we also studied the respective filter residues (river particulates >450 nm) and volcanic ash. In spite of the low solubilities and high particle-reactivities of the elements studied, most water samples show high dissolved concentrations, such as up to 971 ng/kg of Ce and 501 ng/kg of Zr. Except for the pure glacial meltwater and glacial base flow, all waters display the same shale-normalized REE patterns with pronounced light and heavy REE depletion and positive Eu anomalies. While such patterns are unusual for river waters, they are similar to those of the respective river particulates and the volcanic ash, though at different concentration levels. The distribution of dissolved Zr, Hf, Nb, and Th in the waters also matches that of filter residues and ash. This strongly suggests that in all 450 nm-filtered river waters, the elements studied are associated with solid ash particles smaller than 450 nm. This reveals that volcanic ash-derived nanoparticles and colloids are present in these glacial-fed rivers and that such ultrafine particles control the trace element distribution in the surface runoff. Subsequent to explosive volcanic eruptions, these waters provide terrigenous input from landmasses to estuaries, that is characterized by a unique trace element signature and that subsequent to modification by estuarine processes delivers a pulse of nutrients to coastal seawater in regions not affected by plume fall-out. Copyright © 2014 Elsevier B.V. All rights reserved.

In situ U-Th-Pb ages of the Miaoya carbonatite complex in the South Qinling orogenic belt, central China

NASA Astrophysics Data System (ADS)

Ying, Yuancan; Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Yang, Yueheng

2017-10-01

The Miaoya carbonatite complex in the South Qinling orogenic belt hosts one of the largest rare earth element (REE)-Nb deposits in China that is composed of carbonatite and syenite. The emplacement age of the complex and the geochronological relationship between the carbonatite and syenite have long been debated. In this study, in situ U-Th-Pb ages have been obtained for the constituent minerals zircon, monazite and columbite from carbonatite and syenite of the Miaoya complex, together with their chemical and isotopic compositions. In situ trace element compositions for zircon from carbonatite and syenite are highly variable. The zircon displays slightly heavy REE (HREE)-enriched chondrite-normalized patterns with no Eu anomaly and various light REE (LREE) contents. In situ Th-Pb dating for zircon from the Miaoya complex by laser ablation ICP-MS yields ages of 442.6 ± 4.0 Ma (n = 53) for syenite and 426.5 ± 8.0 Ma (n = 23) for carbonatite. Monazite from carbonatite and syenite shows similar chondrite-normalized REE patterns and yields a consistent Th-Pb age of 240 Ma. Based on petrographic and chemical composition, columbite from the carbonatite can be identified into two groups. The columbite dispersed within carbonatite is characterized by slightly LREE-enriched chondrite-normalized REE patterns, whereas columbite associated with apatite is characterized by LREE-depleted trends. Columbite has been further determined to have a weighted mean 206Pb/238U age of 232.8 ± 4.5 Ma (n = 9) using LA-ICP-MS. Detailed geochronological and chemical investigations suggest that there were two major episodes of magmatic/metasomatic activities in the formational history of the Miaoya carbonatite complex. The early alkaline magmatism emplaced in the Silurian was related to the opening of the Mianlue Ocean, whereas the late metasomatism or hydrothermal overprint occurred during the Triassic South Qinling orogeny. The latter serves as the major ore formation period for both REE (e.g., monazite) and Nb (e.g., columbite).

Rare earth element metasomatism in hydrothermal systems: The Willsboro-Lewis wollastonite ores, New York, USA

USGS Publications Warehouse

Whitney, P.R.; Olmsted, J.F.

1998-01-01

Wollastonite ores and garnet-pyroxene skarns in the Willsboro-Lewis district, New York, USA were formed in a complex hydrothermal system associated with the emplacement of a large anorthosite pluton. Contact-metamorphic marbles were replaced by wollastonite, garnet, and clinopyroxene during infiltration metasomatism involving large volumes of water of chiefly meteoric origin. Rare earth elements (REE) in these rocks show large departures from the protolith REE distribution, indicative of substantial REE mobility. Three types of chondrite-normalized REE distribution patterns are present. The most common, found in ores and skarns containing andradite-rich garnet, is convex-up in the light REE (LREE) with a maximum at Pr and a positive Eu anomaly. Europium anomalies and Pr/Yb ratios are correlated with X(Ad) in garnet. This pattern (type C) results from uptake of REE from hydrothermal fluids by growing crystals of calcsilicate minerals, principally andradite, with amounts of LREE controlled by the difference in ionic radius between Ca++ and REE3+ in garnet X sites. The Eu anomaly results either from prior interaction of the fluids with plagioclase-rich, Eu-positive anorthositic rocks in and near the ore zone, or by enrichment of divalent Eu on growth surfaces of garnet followed by entrapment, or both. Relative enrichment in heavy REE (type H) occurs in ores and skarn where calcsilicates, including grossularitic garnet, in contact-metamorphic marble have been concentrated by dissolution of calcite. In most cases a negative Eu anomaly is inherited from the marble protolith. Skarns containing titanite and apatite exhibit high total REE, relative light REE enrichment, and negative Eu anomalies (type L). These appear to be intrusive igneous rocks (ferrodiorites or anorthositic gabbros) that have been converted to skarn by Ca metasomatism. REE, sequestered in titanite, apatite, and garnet, preserve the approximate REE distribution pattern of the igneous protolith. Post-ore granulite facies metamorphism homogenized zoned mineral grains without causing complete intergranular reequilibration and does not appear to have significantly affected the whole-rock REE distributions. These results demonstrate that extensive REE metasomatism can occur in hydrothermal systems at shallow to intermediate depths and that REE geochemistry may be useful in discerning the origin of skarns and skarn-related ore deposits.

Continental shelves as potential resource of rare earth elements.

PubMed

Pourret, Olivier; Tuduri, Johann

2017-07-19

The results of this study allow the reassessment of the rare earth elements (REE) external cycle. Indeed, the river input to the oceans has relatively flat REE patterns without cerium (Ce) anomalies, whereas oceanic REE patterns exhibit strong negative Ce anomalies and heavy REE enrichment. Indeed, the processes at the origin of seawater REE patterns are commonly thought to occur within the ocean masses themselves. However, the results from the present study illustrate that seawater-like REE patterns already occur in the truly dissolved pool of river input. This leads us to favor a partial or complete removal of the colloidal REE pool during estuarine mixing by coagulation, as previously shown for dissolved humic acids and iron. In this latter case, REE fractionation occurs because colloidal and truly dissolved pools have different REE patterns. Thus, the REE patterns of seawater could be the combination of both intra-oceanic and riverine processes. In this study, we show that the Atlantic continental shelves could be considered potential REE traps, suggesting further that shelf sediments could potentially become a resource for REE, similar to metalliferous deep sea sediments.

Distribution pattern of rare earth ions between water and montmorillonite and its relation to the sorbed species of the ions.

PubMed

Takahashi, Yoshio; Tada, Akisa; Shimizu, Hiroshi

2004-09-01

REE (rare earth element) distribution coefficients (Kd) between the aqueous phase and montmorillonite surface were obtained to investigate the relation between the REE distribution patterns and the species of REE sorbed on the solid-water interface. It was shown that the features in the REE patterns, such as the slope of the REE patterns, the tetrad effect, and the Y/Ho ratio, were closely related to the REE species at the montmorillonite-water interface. In a binary system (REE-montmorillonite) below pH 5, three features (a larger Kd value for a lighter REE, the absence of the tetrad effect, and the Y/Ho ratio being unchanged from its initial value) suggest that hydrated REE are directly sorbed as an outer-sphere complex at the montmorillonite-water interface. Above pH 5.5, the features in the REE patterns, the larger Kd value for heavier REE, the M-type tetrad effect, and the reduced Y/Ho ratio, showed the formation of an inner-sphere complex of REE with -OH group at the montmorillonite surface. In addition, the REE patterns in the presence of humic acid at pH 5.9 were also studied, where the REE patterns became flat, suggesting that the humate complex is dominant as both dissolved and sorbed species of REE in the ternary system. All of these results were consistent with the spectroscopic data (laser-induced fluorescence spectroscopy) showing the local structure of Eu(III) conducted in the same experimental system. The present results suggest that the features in the REE distribution patterns include information on the REE species at the solid-water interface.

Geochemical investigation of Archaean Bimodal and Dwalile metamorphic suites, Ancient Gneiss Complex, Swaziland

USGS Publications Warehouse

Hunter, D.R.; Barker, F.; Millard, H.T.

1984-01-01

The bimodal suite (BMS) comprises leucotonalitic and trondhjemitic gneisses interlayered with amphibolites. Based on geochemical parameters three main groups of siliceous gneiss are recognized: (i) SiO2 14%, and fractionated light rare-earth element (REE) and flat heavy REE patterns; (ii) SiO2 and Al2O3 contents similar to (i) but with strongly fractionated REE patterns with steep heavy REE slopes; (iii) SiO2 > 73%, Al2O3 < 14%, Zr ??? 500 ppm and high contents of total REE having fractionated light REE and flat heavy REE patterns with large negative Eu anomalies. The interlayered amphibolites have major element abundances similar to those of basaltic komatiites, Mg-tholeiites and Fe-rich tholeiites. The former have gently sloping REE patterns, whereas the Mg-tholeiites have non-uniform REE patterns ranging from flat (??? 10 times chondrite) to strongly light REE-enriched. The Fe-rich amphibolites have flat REE patterns at 20-30 times chondrite. The Dwalile metamorphic suite, which is preserved in the keels of synforms within the BMS, includes peridotitic komatiites that have depleted light REE patterns similar to those of compositionally similar volcanics in the Onverwacht Group, Barberton, basaltic komatiites and tholeiites. The basaltic komatiites have REE patterns parallel to those of the BMS basaltic komatiites but with lower total REE contents. The Dwalile tholeiites have flat REE patterns. The basic and ultrabasic liquids were derived by partial melting of a mantle source which may have been heterogeneous or the heterogeneity may have resulted from sequential melting of the mantle source. The Fe-rich amphibolites were derived either from liquids generated at shallow levels or from liquids generated at depth which subsequently underwent extensive fractionation. ?? 1984.

The controls on the major and trace element variations of shales, siltstones, and sandstones of Pennsylvanian-Permian age from uplifted continental blocks in Colorado to platform sediment in Kansas, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullers, R.L.

Shales, siltstones, and sandstones of Pennsylvanian-Permian age from near the source in Colorado to those in the platform in eastern Colorado and Kansas have been analyzed for major elements and a number of trace elements, including the REEs. The near-source sandstones are significantly more enriched (Student t-test at better than the 99% confidence level) in SiO[sub 2] and Na[sub 2]O concentrations and more depleted in Al[sub 2]O[sub 3], Fe[sub 2]O[sub 3] (total), TiO[sub 2], Th, Hf, Sc, Cr, Cs, REEs, Y, and Ni concentrations and La/Co and La/Ni ratios than the near-source shales and siltstones, most likely due to moremore » plagioclase and quartz and less clay minerals in the sandstones than in the shales and siltstones. There are no significant differences in K[sub 2]O and Sr concentrations and Eu/Eu*, La/Lu, La/SC, Th/Sc, Th/Co, and Cr/Th ratios between the near-source sandstones and the near-source shales and siltstones. Samples of the Molas, Hermosa, and Cutler formations near the source that were formed in different environments in the same area contain no significant difference in Eu/Eu, La/Lu, La/Sc, Th/Sc, Th/Co, and Cr/Th ratios, so a generally silicic source and not the environment of deposition was most important in producing these elemental ratios.« less

Li and δ 7Li in mudrocks from the British Caledonides: Metamorphism and source influences

NASA Astrophysics Data System (ADS)

Qiu, Lin; Rudnick, Roberta L.; McDonough, William F.; Merriman, Richard J.

2009-12-01

Mudrocks from three lower Paleozoic basins in the British Caledonides (southern Lake District, northern Lake District and Southern Uplands) were investigated to determine the influence of sub-greenschist facies metamorphism on Li and the factors that control Li in fine-grained terrigenous sedimentary rocks. Metamorphic grade, as determined by KI (Kübler index) does not correlate with Li content ([Li]) and δ 7Li, indicating that sub-greenschist facies metamorphism has negligible effect on Li in these rocks. Collectively, the data for all three basins show a negative correlation between [Li] and δ 7Li and a positive correlation between [Li] and the Chemical Index of Alteration (CIA), suggesting that provenance exerts the greatest control on Li in mudrocks. Samples from the northern Lake District, which were deposited in an extensional basin, have homogeneous REE patterns, similar to shale composites (PAAS), the highest CIA, Th/U and [Li] and the lowest δ 7Li and ɛNd, consistent with their derivation from a highly weathered, ancient continental source. By contrast, mudrocks from the Southern Uplands range to the lowest CIA, Th/U and [Li] and have the highest δ 7Li and ɛNd. These samples were deposited in a forearc basin on the southern margin of the Laurentian craton and contain volcanic detritus. Their REE patterns are the most variable, ranging from average shale-like patterns to less LREE-enriched patterns. The compositional heterogeneity within the Southern Uplands mudrocks is consistent with a mixed provenance that includes juvenile crustal materials (lower [Li], ɛNd and Th/U, higher δ 7Li), likely derived from the arc, as well as more highly weathered continental detritus. Mudrocks from the southern Lake District were deposited in a foreland basin, and exhibit geochemical characteristics intermediate between the northern Lake District and the Southern Uplands mudrocks, indicating their derivation from a mixed source. Our study shows that Li concentrations and δ 7Li can provide additional information on the degree of weathering of the provenance of mudrocks.

Metal loading levels influence on REE distribution on humic acid: Experimental and Modelling approach

NASA Astrophysics Data System (ADS)

Marsac, R.; Davranche, M.; Gruau, G.; Dia, A.

2009-04-01

In natural organic-rich waters, rare earth elements (REE) speciation is mainly controlled by organic colloids such as humic acid (HA). Different series of REE-HA complexation experiments performed at several metal loading (REE/C) displayed two pattern shapes (i) at high metal loading, a middle-REE (MREE) downward concavity, and (ii) at low metal loading, a regular increase from La to Lu (e.g. Sonke and Salters, 2006; Pourret et al., 2007). Both REE patterns might be related to REE binding with different surface sites on HA. To understand REE-HA binding, REE-HA complexation experiments at various metals loading were carried out using ultrafiltration combined with ICP-MS measurements, for the 14 REE simultaneously. The patterns of the apparent coefficients of REE partition between HA and the inorganic solution (log Kd) evolved regularly according to the metal loading. The REE patterns presented a MREE downward concavity at low loading and a regular increase from La to Lu at high loading. The dataset was modelled with Model VI by adjusting two specific parameters, log KMA, the apparent complexation constant of HA low affinity sites and DLK2, the parameter increasing high affinity sites binding strength. Experiments and modelling provided evidence that HA high affinity sites controlled the REE binding with HA at low metal loading. The REE-HA complex could be as multidentate complexes with carboxylic or phenolic sites or potentially with sites constituted of N, P or S as donor atoms. Moreover, these high affinity sites could be different for light and heavy REE, because heavy REE have higher affinity for these sites, in low density, and could saturate them. These new Model VI parameter sets allowed the prediction of the REE-HA pattern shape evolution on a large range of pH and metal loading. According to the metal loading, the evolution of the calculated REE patterns was similar to the various REE pattern observed in natural acidic organic-rich waters (pH<7 and DOC>10 mg L-1). As a consequence, the metal loading could be the key parameter controlling the REE pattern in organic-rich waters.

Rare Earth Element Behavior During Incongruent Weathering and Varying Discharge Conditions in Silicate Dominated River Systems: The Australian Victorian Alps

NASA Astrophysics Data System (ADS)

Hagedorn, K. B.; Cartwright, I.

2008-12-01

The distribution of rare earth elements (REE) and trace elements was measured by ICP-MS on fresh, slightly weathered and weathered granite and surface water samples from a network of 11 pristine rivers draining the Australian Victorian Alps during (i) high and (ii) low discharge conditions. River water REE concentrations are largely derived from atmospheric precipitation (rain, snow), as indicated by similar Chondrite normalized REE patterns (higher LREE over HREE; negative Ce anomalies, positive Eu anomalies) and similar total REE concentrations during both dry and wet seasons. Calculations based on the covariance between REE and Cl concentrations and oxygen and hydrogen isotopes indicate precipitation input coupled with subsequent evaporation may account for 30% o 100% of dissolved REE in stream waters. The dissolved contribution to the granitic substratum to stream water comes mainly from the transformation of plagioclase to smectite, kaolinite and gibbsite and minor apatite dissolution. However, since most REE of the regional granite are present in accessory minerals (titanite, zircon, etc.) they do not significantly contribute to the river REE pool. REE concentrations drop sharply downstream as a result of dilution and chemical attenuation. A trend of downstream enrichment of the heavier REE is due to selective partitioning of the lighter REE (as both free REE or REECO3 complexes) to hydrous oxides of suspended Al which, in turn, is controlled by a downstream increase of pH to values > 6.1 (for free REE) and > 7.3 (for REECO3 complexes). Although most circumneutral waters were supersaturated with REE phosphate compounds, precipitation of LnPO4 is not believed to have been a dominant process because the predicted phosphate fractionation pattern is inconsistent with the observed trends. Negative saturation indices of hydrous ferric oxides also militate against surface complexation onto goethite. Instead, REE attenuation most likely resulted from adsorption onto hydrous aluminium oxide. Seasonally, higher total REE concentrations during the dry season are due to longer residence time of water within rock fractures as well as high rainfall REE concentrations which, for the summer of 2007, might be related to organic carbon rich dust released after bushfires in the region. Lower pH values and low oxidation potentials at that time also contribute to raise REE concentrations through desorption.

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

Rare earth elements in fine-grained sediments of major rivers from the high-standing island of Taiwan

NASA Astrophysics Data System (ADS)

Li, Chuan-Shun; Shi, Xue-Fa; Kao, Shuh-Ji; Liu, Yan-Guang; Lyu, Hua-Hua; Zou, Jian-Jun; Liu, Sheng-Fa; Qiao, Shu-Qing

2013-06-01

Thirty-eight sediment samples from 15 primary rivers on Taiwan were retrieved to characterize the rare earth element (REE) signature of fluvial fine sediment sources. Compared to the three large rivers on the Chinese mainland, distinct differences were observed in the REE contents, upper continental crust normalized patterns and fractionation factors of the sediment samples. The average REE concentrations of the Taiwanese river sediments are higher than those of the Changjiang and Huanghe, but lower than the Zhujiang. Light rare earth elements (LREEs) are enriched relative to heavy rare earth elements (HREEs) with ratios from 7.48 to 13.03. We found that the variations in (La/Lu)UCC-(Gd/Lu)UCC and (La/Yb)UCC-(Gd/Yb)UCC are good proxies for tracing the source sediments of Taiwanese and Chinese rivers due to their distinguishable values. Our analyses indicate that the REE compositions of Taiwanese river sediments were primarily determined by the properties of the bedrock, and the intensity of chemical weathering in the drainage areas. The relatively high relief and heavy rainfall also have caused the REEs in the fluvial sediments from Taiwan to be transported to the estuaries down rivers from the mountains, and in turn delivered nearly coincidently to the adjacent seas by currents and waves. Our studies suggest that the REE patterns of the river sediments from Taiwan are distinguishable from those from the other sources of sediments transported into the adjacent seas, and therefore are useful proxies for tracing the provenances and dispersal patterns of sediments, as well as paleoenvironmental changes in the marginal seas.

Rare earth elements mobility processes in an AMD-affected estuary: Huelva Estuary (SW Spain).

PubMed

Lecomte, K L; Sarmiento, A M; Borrego, J; Nieto, J M

2017-08-15

Huelva Estuary is a transition zone where REE-rich acidic waters interact with saline-alkaline seawater. This mixing process influences the geochemical and mineralogical characteristics of particulate and dissolved fractions. The Tinto River has >11,000μgL -1 dissolved REE (pH=1.66), whereas seawater only reaches 8.75·10 -2 μgL -1 dissolved REE (pH=7.87). REE-normalized patterns in "pH<6 solutions" are parallel and show similarities, diminishing their concentration as pH increases. Sequential extraction performed on the generated precipitates of mixed solutions indicates that most REE are associated to the residual phase. In a second order, REE are associated with soluble salts at pH3 and 3.5 whereas in sediments generated at pH4 and 5, they are distributed in salts (1° extraction), poorly crystallized Fe-bearing minerals (schwertmannite, 3° extraction) and well crystallized Fe-bearing minerals (goethite - hematite, 4° extraction). Finally, precipitated REE are highest at pH6 newly formed minerals with a release to solution in higher pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geochemistry of rare earth elements in minesoils from São Domingos mining district (Iberian Pyrite Belt)

NASA Astrophysics Data System (ADS)

Delgado, Joaquin; Perez-Lopez, Rafael; Nieto, Jose Miguel; Ayora, Carles

2010-05-01

The São Domingos mine is one of the most emblematic mining districts in the lower part of the Guadiana River Basin (SW of Iberian Peninsula). It is located in Portugal (about 5 km from the Spanish border), in the northern sector of the Iberian Pyrite Belt (IPB), one of the largest metallogenetic provinces of massive sulphides in the world. Although mining activity has ceased at present, the large-scale exploitation of this deposit between the second half of the XIX century and the first half of the XX century, has favoured the production of enormous waste dumps, where oxidation of pyrite and associated sulphides is resulting in the production of acid mine drainage (AMD). Mining wastes, minesoils, and acid mine drainage have been analyzed for their major ions and rare earth elements (REE) with the aim of understanding the REE mobility during sulphide weathering so that lanthanoid series can be used both as a proxy for the extent of water-rock interaction and as a tool for identifying impacts of AMD on natural ecosystems. Chemical speciation of REE in extracts from minesoils indicates that REE sulphate complexes (mainly LnSO4+) are the primary aqueous form (60-90%), and free ionic species (Ln3+, 10-40%) are the next most abundant form of soil water-soluble fraction and controls the REE speciation model. The REE from this fraction have NASC-normalized patterns with middle-REE (MREE) enriched signature compared to the light-REE (LREE) and heavy-REE (HREE), showing convex MREE-signatures and convexity index values of +1.29 +/- 1.13. These results are consistent with the typical REE fractionation patterns reported for AMD. Poorly crystalline iron oxyhydroxysulphates act as a source of labile MREE by dissolution and/or desorption processes and could explain the MREE-enriched signatures in solution.

Rare earth elements in street dust and associated health risk in a municipal industrial base of central China.

PubMed

Sun, Guangyi; Li, Zhonggen; Liu, Ting; Chen, Ji; Wu, Tingting; Feng, Xinbin

2017-12-01

The content levels, distribution characteristics, and health risks associated with 15 rare earth elements (REEs) in urban street dust from an industrial city, Zhuzhou, in central China were investigated. The total REE content (∑REE) ranged from 66.1 to 237.4 mg kg -1 , with an average of 115.9 mg kg -1 , which is lower than that of Chinese background soil and Yangtze river sediment. Average content of the individual REE in street dust decreased in the order Ce > La > Nd > Y > Pr > Sm > Gd > Dy > Er > Yb > Eu > Ho > Tb > Tm > Lu. The chondrite-normalized REE pattern indicated light REE (LREE) enrichment, a relatively steep LREE trend, heavy REE (HREE) depletion, a flat HREE trend, a Eu-negative anomaly and a Ce-positive anomaly. Foremost heavy local soil and to less degree anthropogenic pollution are the main sources of REE present in street dust. Health risk associated with the exposure of REE in street dust was assessed based on the carcinogenic and non-carcinogenic effect and lifetime average daily dose. The obtained cancer and non-cancer risk values prompt for no augmented health hazard. However, children had greater health risks than that of adults.

Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China

USGS Publications Warehouse

Zheng, Lingyun; Liu, Gaisheng; Chou, C.-L.; Qi, C.; Zhang, Y.

2007-01-01

The rare earth elements (REEs) in coals are important because of: (a) REE patterns can be an indicator of the nature of source rocks of the mineral matter as well as sedimentary environments; (b) REEs abundance in coal may have industrial-significance. In this study, a total of thirty-four samples of Permian coal, partings, roof, and floor were collected from the Huaibei Coalfield, Anhui Province, China. Abundances of rare earth elements (REEs) and other elements in the samples were determined by inductively coupled-plasma mass spectrometry (ICP-MS) and inductively coupled-plasma atomic emission spectrometry (ICP-AES). The results show that the REEs are enriched in coals in the Huaibei Coalfield as compared with Chinese and U.S. coals and the world coal average. Coals in the Lower Shihezi Formation (No. 7, 5, and 4 Coals) and Upper Shihezi Formation (No. 3) have higher REE abundances than the coals in Shanxi Formation (No. 10). Magmatic intrusion resulted in high enrichment of REEs concentrations in No. 5 and 7 Coals. The REE abundances are positively correlated with the ash content. The mineral matter in these coals is mainly made up of clay minerals and carbonates. The REEs are positively correlated with lithophile elements including Si, Al, Ti, Fe, and Na, which are mainly distributed in clay minerals, indicating that REEs are contained mainly in clay minerals. The REE abundances in coals normalized by the ash are higher than that in partings. REEs abundances of coals cannot be accounted for by the REE content in the mineral matter, and some REEs associated with organic matter in coals. ?? 2007 Elsevier Ltd. All rights reserved.

Determination and distribution of rare earth elements in beach rock samples using instrumental neutron activation analysis (INAA)

NASA Astrophysics Data System (ADS)

Ravisankar, R.; Manikandan, E.; Dheenathayalu, M.; Rao, Brahmaji; Seshadreesan, N. P.; Nair, K. G. M.

2006-10-01

Beach rocks are a peculiar type of formation when compared to other types of rocks. Rare earth element (REE) concentrations in beach rock samples collected from the South East Coast of Tamilnadu, India, have been measured using the instrumental neutron activation analysis (INAA) single comparator K0 method. The irradiations were carried out using a thermal neutron flux of ˜10 11 n cm -2 s -1 at 20 kW power using the Kalpakkam mini reactor (KAMINI), IGCAR, Kalpakkam, Tamilnadu. Accuracy and precision were evaluated by assaying irradiated standard reference material (SRM 1646a estuarine sediment). The results being found to be in good agreement with certified values. REE elements have been determined from 15 samples using high-resolution gamma spectrometry. The geochemical behavior of REE in beach rock, in particular REE (chondrite-normalized) pattern has been studied.

Trace element evaluation of a suite of rocks from Reunion Island, Indian Ocean

USGS Publications Warehouse

Zielinski, R.A.

1975-01-01

Reunion Island consists of an olivine-basalt shield capped by a series of flows and intrusives ranging from hawaiite through trachyte. Eleven rocks representing the total compositional sequence have been analyzed for U, Th and REE. Eight of the rocks (group 1) have positive-slope, parallel, chondrite-normalized REE fractionation patterns. Using a computer model, the major element compositions of group 1 whole rocks and observed phenocrysts were used to predict the crystallization histories of increasingly residual liquids, and allowed semi-quantitative verification of origin by fractional crystallization of the olivine-basalt parent magma. Results were combined with mineral-liquid distribution coefficient data to predict trace element abundances, and existing data on Cr, Ni, Sr and Ba were also successfully incorporated in the model. The remaining three rocks (group 2) have nonuniform positive-slope REE fractionation patterns not parallel to group 1 patterns. Rare earth fractionation in a syenite is explained by partial melting of a source rich in clinopyroxene and/or hornblende. The other two rocks of group 2 are explained as hybrids resulting from mixing of syenite and magmas of group 1. ?? 1975.

Indicators of Provenance Weathering: Li and δ7Li in Mudrocks from the British Caledonides

NASA Astrophysics Data System (ADS)

Qiu, L.; Rudnick, R. L.; McDonough, W. F.; Merriman, R. J.

2008-12-01

We determined the Li concentration [Li] and isotopic composition (δ7Li), as well as major, trace element and Sr and Nd isotopic compositions of mudrocks (mudstone, shale, slate) from three Lower Paleozoic basins within the British Caledonides in order to determine the effects of sub-greenschist facies metamorphism on Li and the factors that control Li in mudrocks. [Li] varies widely, from 29 to 139 ppm, with mudrocks from the northern Lake District generally having higher concentrations (56-136 ppm, average 102 ppm) than those from the Scottish Southern Uplands (28-74 ppm, average 50 ppm) or southern Lake District (40-91 ppm, average 52 ppm) basins. δ7Li of mudrocks from the northern Lake District (δ7Li =-3.2 ±1.6 permil, 2σ) are relatively constant compared to those of the mudrocks from the southern Lake District (-3.4 permil to 0 permil) and the Southern Uplands (-4.4 permil to +3.7 permil). Metamorphic grade, determined by the Kübler index method, does not correlate with [Li] or δ7Li, indicating that sub-greenschist facies metamorphism had little effect on Li in these mudrocks. Collectively, the data for all three basins show a negative correlation between [Li] and δ7Li and a positive correlation between [Li] and the chemical index of alteration (CIA), suggesting that provenance exerts the greatest control on Li in mudrocks. Samples from the northern Lake District, which were deposited in an extensional basin, have homogeneous REE patterns, similar to shale composites (PAAS and NASC), the highest CIA, Th/U and [Li] and the lowest δ7Li and ɛNd, consistent with their derivation from a highly weathered ancient continental source. By contrast, mudrocks from the Southern Uplands range to the lowest CIA, Th/U and [Li] and have the highest δ7Li and ɛNd. These samples were deposited in a subudction zone on the southern margin of the Laurentian craton and contain volcanic detritus derived from a proximal arc. They have the most variable REE patterns, ranging from average shale-like patterns to less LREE-enriched patterns. The heterogeneity within the Southern Uplands mudrocks points to a mixed provenance that includes juvenile crustal materials (lower [Li], ɛNd and Th/U, higher δ7Li), likely derived from the arc, as well as more weathered cratonic detritus. Mudrocks from the southern Lake District deposited in a foreland basin, exhibit geochemical characteristics intermediate between the northern Lake District and the Southern Uplands mudrocks indicating their derivation from a mixed source. Our study shows that Li and δ7Li can provide addition information on the nature of the provenance of mudrocks.

Multistage metasomatism in lithospheric mantle beneath V. Grib pipe (Arkhangelsk diamondiferous province, Russia): evidence from REE patterns in garnet xenocrysts.

NASA Astrophysics Data System (ADS)

Shchukina, Elena; Alexei, Agashev; Nikolai, Pokhilenko

2015-04-01

150 garnet xenocrysts from V. Grib kimberlite pipe were analyzed for major and trace elements compositions. 70 % of garnet belong to lherzolite field; 14 % - megacrysts and pyroxenites; 11 % - eclogites; 4 % - harzburgite; 1 % (1- wehrlite defined by Sobolev (1973). Harzburgite garnets: sinusoidal REE patterns Smn/Ern > 5 (5.2 - 19.8). low Y (0.5 - 3.9 ppm), Zr (1.1 - 44.6 ppm), Ti (54 - 1322 ppm). Wehrlite garnetd: close to sinusoidal REE patterns, Smn/Ern - 1.8. Megacrysts and pyroxenites garnets: normal REE patterns Smn/Ern < 1 (0.2 - 0.6), high TiO2 (0.9 - 1.3 wt %). Lherzolite garnets 70 % show four groups of REE patterns similar to peridotite xenoliths (Shchukina et al., 2013, 2015). 1-st contains MREE at С1 level, Sm/Ern - 0.03, La/Ybn - 0.002. increasing La -Yb range, low Y, Zr, Ti indicating residual nature. 2-nd: MREE at 2 - 13 chondrite units, Smn/Ern (0.16 - 0.98), La/Ybn - 0.001 - 0.040 and flat pattern from MREE to HREE. 3-rd -MREE at 5 - 14 chondrite units, Sm/Ern > 1 (1.05 - 4.81) La/Ybn - 0.010-0.051 increasing an hump at MREE decreasing to HREE. 4-th: sinusoidal REE, Sm/Ern 4.2 - 27.2. and harzburgite Y, Zr, Ti . Average Cr2O3 content increases from 2-nd to the 3-rd group (3.3 to 5.7 wt%) and 4th (7.9 wt %). Average Y/Zr decreases from 2-nd (0.6) to 3rd (0.2) and 4th group (0.08). REE and Y, Zr, Ti indicate the metasomatic origin of garnets of 2, 3. 4 groups. Modeling of TREfor equilibrated melts and fractional crystallization 2nd group close to Turyino field basalts and 3-rd - to Izmozero field picrites of Arkhangelsk diamondiferous province (ADP). Basing on geochemical data of garnet xenocrysts and garnets and clinopyroxenes in peridotites (Shchukina et al., 2013, 2015) we suppose at least 3 stage of high-temperature metasomatic enrichment. 1st stage - is enrichment of residual garnets (found only in peridotite garnets) in LREE by the influence of carbonatite melt close to the Mela field carbonatites of ADP. REE patterns in clinopyroxenes from these peridotite samples and the geochemical modeling results show that clinopyroxenes are also in equilibrium with carbonatite melt. Formation of garnet with the sinusoidal REE pattern could also occurs during carbonatite stage of mantle metasomatism. The 2- nd stage - is formation of garnets of group 3 from the melt of composition close to Izhmozero field picrites. Garnets of group 3 are of lherzolite paragenesis on the content of CaO and Cr2O3, but their REE patterns are close to sinusoidal patterns. The final stage of mantle metasomatism is the formation of garnets of group 2 exposed to the melt of composition close to Turyino field basalts. Garnets of group 2 have low Cr2O3 that indicate the significant amounts of basaltic component in the resulting melt composition or direct crystallization from the melt in case of most low-chromium garnets and megacrysts garnets. Modeling results show that the formation of the garnets of group 2 in peridotites associated with crystallization of the clinopyroxenes. At this stage of mantle metasomatism garnets have typical major and trace element lherzolite composition.

Typical aqueous rare earth element behavior in co-produced Brines, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nye, Charles; Quillinan, Scott; McLing, Travis

Normalization of Rare Earth Elements (REEs) is important to remove the distracting effects of the Oddo–Harkins rule and provide a meaningful baseline. Normalizations for rocks are well developed and include chondritic meteorites, UCC, PM, PAAS, and NASC. However normalizations for aqueous REEs are limited to oceanic regions such as the North Pacific Deep Water or North Atlantic Surface Water. This leaves water in contact with continental lithologies without a suitable normalization. We present a preliminary continental aqueous REE normalization derived from 38 deep basin hydrocarbon brines in Wyoming. The REEs in these waters are seven orders of magnitude more dilutemore » than NASC but with significant europium enrichment. Gromet 1984 reports NASC Eu/Eu* is 0.2179, whereas in the normalization offered here, Eu/Eu* is 3.868. These waters also are free from the distracting reduction-oxidation cerium behavior found in ocean normalizations. Because these samples exhibit both the uniform behavior of NASC and the absolute concentration of seawater, a normalization based upon them offers a unique combination of the advantages of both. We used single-peak gaussian analysis to quantify the mean values for each REE and estimate the distribution variability. Additional sample collection during the last year revealed that the Powder River Basin (PRB) is atypical relative to the other sampled basins of Wyoming. Those other basins are the Wind River Basin (WRB) Green River Basin (GRB) and Wamsutter Area (WA). A pre-normalization gadolinium anomaly (Gd/Gd*) of between 4 and 23 with a mean of 11.5, defines the PRB samples. Other basins in this study range from 1 to 7 with a mean of 2.8. Finally, we present a preliminary model for ligand-based behavior of REEs in these samples. This model identifies bicarbonate, bromide, and chloride as forming significant complexes with REEs contributing to REE solubility. The ligand model explains observed REEs in the sampled Cretaceous and Paleocene clastic reservoirs. However, the presence of more REEs than predicted in six samples suggests that there is an additional, unconsidered ligand contributing to REE dissolution. Further work will identify this ligand, which appears to be confined to calcium-cemented and dolostone systems.« less

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

USGS Publications Warehouse

James, O.B.; Floss, C.; McGee, J.J.

2002-01-01

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = CREE in low-Ca pyroxene/CREE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals. Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. "Equilibrium" liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates. Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occured significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ??Nd will be in error. Copyright ?? 2002 Elsevier Science Ltd.

Geochemistry of loess-paleosol sediments of Kashmir Valley, India: Provenance and weathering

NASA Astrophysics Data System (ADS)

Ahmad, Ishtiaq; Chandra, Rakesh

2013-04-01

Middle to Late Pleistocene loess-paleosol sediments of Kashmir Valley, India, were analyzed for major, trace and REE elements in order to determine their chemical composition, provenance and intensity of palaeo-weathering of the source rocks. These sediments are generally enriched with Fe2O3, MgO, MnO, TiO2, Y, Ni, Cu, Zn, Th, U, Sc, V and Co while contents of SiO2, K2O, Na2O, P2O5, Sr, Nb and Hf are lower than the UCC. Chondrite normalized REE patterns are characterized by moderate enrichment of LREEs, relatively flat HREE pattern (GdCN/YbCN = 1.93-2.31) and lack of prominent negative Eu anomaly (Eu/Eu* = 0.73-1.01, average = 0.81). PAAS normalized REE are characterized by slightly higher LREE, depleted HREE and positive Eu anomaly. Various provenance discrimination diagrams reveal that the Kashmir Loess-Paleosol sediments are derived from the mixed source rocks suggesting large provenance with variable geological settings, which apparently have undergone weak to moderate recycling processes. Weathering indices such as CIA, CIW and PIA values (71.87, 83.83 and 80.57 respectively) and A-CN-K diagram imply weak to moderate weathering of the source material.

Examination of rare earth element concentration patterns in freshwater fish tissues.

PubMed

Mayfield, David B; Fairbrother, Anne

2015-02-01

Rare earth elements (REEs or lanthanides) were measured in ten freshwater fish species from a reservoir in Washington State (United States). The REE distribution patterns were examined within fillet and whole body tissues for three size classes. Total concentrations (ΣREE) ranged from 0.014 to 3.0 mg kg(-1) (dry weight) and averaged 0.243 mg kg(-1) (dry weight). Tissue concentration patterns indicated that REEs accumulated to a greater extent in organs, viscera, and bone compared to muscle (fillet) tissues. Benthic feeding species (exposed to sediments) exhibited greater concentrations of REEs than pelagic omnivorous or piscivorous fish species. Decreasing REE concentrations were found with increasing age, total length or weight for largescale and longnose suckers, smallmouth bass, and walleye. Concentration patterns in this system were consistent with natural conditions without anthropogenic sources of REEs. These data provide additional reference information with regard to the fate and transport of REEs in freshwater fish tissues in a large aquatic system. Copyright © 2014 Elsevier Ltd. All rights reserved.

REE partitioning between apatite and melt in a peralkaline volcanic suite, Kenya Rift Valley

USGS Publications Warehouse

Macdonald, R.; Baginski, B.; Belkin, H.E.; Dzierzanowski, P.; Jezak, L.

2009-01-01

Electron microprobe analyses are presented for fluorapatite phenocrysts from a benmoreite-peralkaline rhyolite volcanic suite from the Kenya Rift Valley. The rocks have previously been well characterized petrographically and their crystallization conditions are reasonably well known. The REE contents in the M site increase towards the rhyolites, with a maximum britholite component of ~35 mol.%. Chondrite-normalized REE patterns are rather flat between La and Sm and then decrease towards Yb. Sodium and Fe occupy up to 1% and 4%, respectively, of the M site. The major coupled substitution is REE3+ + Si4+ ??? Ca2+ + P5+. The substitution REE3+ + Na+ ??? 2Ca2+ has been of minor importance. The relatively large Fe contents were perhaps facilitated by the low fo2 conditions of crystallization. Zoning is ubiquitous and resulted from both fractional crystallization and magma mixing. Apatites in some rhyolites are relatively Y-depleted, perhaps reflecting crystallization from melts which had precipitated zircon. Mineral/glass (melt) ratios for two rhyolites are unusually high, with maxima at Sm (762, 1123). ?? 2008 The Mineralogical Society.

Rare earth elements as a fingerprint of soil components solubilization

NASA Astrophysics Data System (ADS)

Davranche, M.; Grybos, M.; Gruau, G.; Pédrot, M.; Dia, A.

2009-04-01

The retention of rare earth element (REE) in the soil profile are mainly controlled by three factors, (i) the stability of the primary REE-carrying minerals, (ii) the presence of secondary phases as clays and Fe- and Mn-oxyhydroxides and (ii) the concentration of colloidal organic matter (OM). Considering that each soil phases (mineral or organic) displays (ii) various surface properties, such as specific area, surface sites density and nature and (ii) their own REE distribution inherited from the rock weathering, their mobilization through various chemical reactions (dissolution, colloidal release….) may involve the development of various shaped REE patterns in the soil solutions. REE fractionation from the different soil phases may therefore be used to identify the response of the soil system to a particular chemical process such as reductive and/or acidic dissolution. To test this purpose, an organic-rich wetland soil sample was incubated under anaerobic condition at both pH 5 and uncontrolled pH. The REE patterns developed in the soil solution were then compared to the REE patterns obtained through either aerobic at pH 3 and 7 incubations or a chemical reduction experiment (using hydroxylamine). REE patterns in anaerobic and aerobic at pH 7 experiments exhibited the same middle rare earth element (MREE) downward concavity significant of the complexation of REE with soil OM. By contrast, under acidic condition, the REE pattern exhibited a positive Eu anomaly due to the dissolution of soil feldspar. Finally, REE pattern obtained from the chemical reducing experiment showed an intermediary flat shape corresponding to a mixing between the soil organic and mineral phases dissolution. The comparison of the various REE pattern shapes allowed to conclude that (i) biological reduction of wetland soil involved amorphous Fe(III) colloids linked to OM and, (ii) that the REE mobility was controlled by the dynamic of OM in wetland soil. They also evidence the potential of REE to be use as a tracer of the soil phases involved in the various chemical processes running in soil solutions.

Rare Earth Elements in Alberta Oil Sand Process Streams

DOE PAGES

Roth, Elliot; Bank, Tracy; Howard, Bret; ...

2017-04-05

The concentrations of rare earth elements in Alberta, Canada oil sands and six oil sand waste streams were determined using inductively coupled plasma mass spectrometry (ICP–MS). The results indicate that the rare earth elements (REEs) are largely concentrated in the tailings solvent recovery unit (TSRU) sample compared to the oil sand itself. The concentration of lanthanide elements is ~1100 mg/kg (1100 ppm or 0.11 weight %), which represents a >20× increase in the concentration compared to the oil sand itself and a >7× increase compared to the North American Shale Composite (NASC). The process water, which is used to extractmore » the oil from oil sands, and the water fraction associated with the different waste streams had very low concentrations of REEs that were near or below the detection limits of the instrument, with the highest total concentration of REEs in the water fraction being less than 10 μg/L (ppb). Size and density separations were completed, and the REEs and other potentially interesting and valuable metals, such as Ti and Zr, were concentrated in different fractions. These results give insights into the possibility of recovering REEs from waste streams generated from oil sand processing.« less

Rare Earth Elements in Alberta Oil Sand Process Streams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roth, Elliot; Bank, Tracy; Howard, Bret

The concentrations of rare earth elements in Alberta, Canada oil sands and six oil sand waste streams were determined using inductively coupled plasma mass spectrometry (ICP–MS). The results indicate that the rare earth elements (REEs) are largely concentrated in the tailings solvent recovery unit (TSRU) sample compared to the oil sand itself. The concentration of lanthanide elements is ~1100 mg/kg (1100 ppm or 0.11 weight %), which represents a >20× increase in the concentration compared to the oil sand itself and a >7× increase compared to the North American Shale Composite (NASC). The process water, which is used to extractmore » the oil from oil sands, and the water fraction associated with the different waste streams had very low concentrations of REEs that were near or below the detection limits of the instrument, with the highest total concentration of REEs in the water fraction being less than 10 μg/L (ppb). Size and density separations were completed, and the REEs and other potentially interesting and valuable metals, such as Ti and Zr, were concentrated in different fractions. These results give insights into the possibility of recovering REEs from waste streams generated from oil sand processing.« less

Issues in characterizing resting energy expenditure in obesity and after weight loss

PubMed Central

Bosy-Westphal, Anja; Braun, Wiebke; Schautz, Britta; Müller, Manfred J.

2013-01-01

Limitations of current methods: Normalization of resting energy expenditure (REE) for body composition using the 2-compartment model fat mass (FM), and fat-free mass (FFM) has inherent limitations for the interpretation of REE and may lead to erroneous conclusions when comparing people with a wide range of adiposity as well as before and after substantial weight loss. Experimental objectives: We compared different methods of REE normalization: (1) for FFM and FM (2) by the inclusion of %FM as a measure of adiposity and (3) based on organ and tissue masses. Results were compared between healthy subjects with different degrees of adiposity as well as within subject before and after weight loss. Results: Normalizing REE from an “REE vs. FFM and FM equation” that (1) was derived in obese participants and applied to lean people or (2) was derived before weight loss and applied after weight loss leads to the erroneous conclusion of a lower metabolic rate (i) in lean persons and (ii) after weight loss. This is revealed by the normalization of REE for organ and tissue masses that was not significantly different between lean and obese or between baseline and after weight loss. There is evidence for an increasing specific metabolic rate of FFM with increasing %FM that could be explained by a higher contribution of liver, kidney and heart mass to FFM in obesity. Using “REE vs. FFM and FM equations” specific for different levels of adiposity (%FM) eliminated differences in REE before and after weight loss in women. Conclusion: The most established method for normalization of REE based on FFM and FM may lead to spurious conclusions about metabolic rate in obesity and the phenomenon of weight loss-associated adaptive thermogenesis. Using %FM-specific REE prediction from FFM and FM in kg may improve the normalization of REE when subjects with wide differences in %FM are investigated. PMID:23532370

Transfer of rare earth elements from natural metalliferous (copper and cobalt rich) soils into plant shoot biomass of metallophytes from Katanga (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Pourret, Olivier; Lange, Bastien; Jitaru, Petru; Mahy, Grégory; Faucon, Michel-Pierre

2014-05-01

The geochemical behavior of rare earth elements (REE) is generally assessed for the characterization of the geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. REE behavior is investigated according to their concentrations normalized with respect to the upper continental crust. In this study, the geochemical fingerprint of REE in plant shoot biomass of an unique metallicolous flora (i.e., Crepidorhopalon tenuis and Anisopappus chinensis) was investigated. The plants originate from extremely copper and cobalt rich soils, deriving from Cu and Co outcrops in Katanga, Democratic Republic of Congo. Some of the species investigated in this study are able to accumulate high amounts of Cu and Co in shoot hence being considered as Cu and Co hyperaccumulators. Therefore, assessing the behavior of REE may lead to a better understanding of the mechanisms of metal accumulation by this flora. The data obtained in this study indicate that REE uptake by plants is not primarily controlled by their concentration and speciation in the soil as previously shown in the literature (Brioschi et al. 2013). Indeed, the REE patterns in shoots are relatively flat whereas soils patterns are Middle REE enriched. In addition, it is worth noting that Eu enrichments occur in aerial parts of the plants. These positive Eu anomalies suggest that Eu3 + can form stable organic complexes replacing Ca2 + in several biological processes as in xylem fluids associated with the general nutrient flux. Therefore, is is possible that the Eu mobility in these fluids is enhanced by its reductive speciation as Eu2 +. Eventually, the geochemical behavior of REE illustrates that metals accumulation in aerial parts of C. tenuis and A. chinensis is mainly driven by dissolved complexation. Brioschi, L., Steinmann, M., Lucot, E., Pierret, M., Stille, P., Prunier, J., Badot, P., 2013. Transfer of rare earth elements (REE) from natural soil to plant systems: implications for the environmental availability of anthropogenic REE. Plant and Soil, 366, 143-163.

Rb-Sr systematics and REE abundances in Shalka and several other diogenites

NASA Astrophysics Data System (ADS)

Takahashi, K.; Yabuki, S.; Kagi, H.; Masuda, A.

1994-07-01

The diogenites have been regarded as igneous products in the early solar system and they have been considered to have genetically close relationship with eucrites. Depsite their simple mineralogical compositions and narrow range for major-element compositions, diogenites have been known to show wide Rare Earth Elements (REE) variations in absolute concentration and in mutual abundance ratios. Furthermore, some diogenites have peculiar Rb-Sr isotope systematics (ages younger than 4.5 b.y.). The Shalka meteorite belongs to the diogenites, and a unique REE abundance pattern has been reported. We performed Rb-Sr isotopic analyses and measured REE abundances in the Shalka diogenite with several other diogenites to discuss their genesis. Roughly speaking, REE patterns in diogenites are characterized by the negative Eu anomaly and the depletion of light REE. For Shalka, some heterogeneity in REE abundance patterns have been observed. While one sample chip shows the REE pattern with a large negative Eu anomaly and depleted light REE, particularly characterized by the concave curvature for the La-Nd span, other samples show the pattern nearly flat or the pattern enriched in light REE. These variations could not be explained easily by the simple mixing process of LREE-depleted components and LREE-enriched melt, but they imply some metamorphism process. The Rb-Sr isotopic data for Shalka are shown with the data for other several diogenites. These observations indicate that Shalka would undergo a significant extent of metamorphism followed by redistribution of REE and the disturbance of the Rb-Sr systematics. We are going to do further studies on Shalka to discuss the metamorphic process and compare it with other diogenites.

Off-line separation and determination of rare earth elements associated with chloroplast pigments of hyperaccumulator Dicranopteris dichotoma by normal-phase liquid chromatography and ICP-MS.

PubMed

Wei, Z G; Hong, F S; Yin, M; Li, H X; Hu, F; Zhao, G W; Wong, J W C

2004-10-01

An off-line normal-phase liquid chromatography-ICP-MS method has been used for separation and determination of the rare earth elements (REE) associated with chloroplast pigments of Dicranopteris dichotoma. The stability of REE-bound pigments was tested, and almost no destruction of REE-bound pigments occurred during the so-called normal-phase liquid chromatography. The accumulated free REE ions on the microcrystalline cellulose column were cleaned by elution with 5 mmol L(-1) 2-ethylhexyl hydrogen 2-ethylhexylphosphonate (P507), to avoid exchange of these free ions with metals from the pigments. When these precautions were taken, the method was applied to the study of REE-bound pigments in D. dichotoma. ICP-MS results showed REE were present in chlorophylls and lutein, although REE concentrations in carotene and pheophytin were both below procedural blank levels. By careful analysis of the eluate fractions containing chlorophyll a it was found that REE-bound chlorophyll a in D. dichotoma was slightly enriched in the fractions with relatively short retention time. Results indicated that the retention time of REE-bound chlorophyll a might be slightly less than that of magnesium chlorophyll a, and REE-bound chlorophylls might be of relatively low polarity in comparison with magnesium bound chlorophylls. This phenomenon could be explained by the special double-decker sandwich-structure of REE-bound chlorophylls, as was reported by us and other authors. On the basis of these results we preferred to consider that REE can replace magnesium in chlorophyll a of D. dichotoma, and that the role of REE-bound chlorophylls in photosynthesis cannot be neglected. These data might be useful for understanding of both the properties of REE-bound pigments and the effect of REE on plant photosynthesis.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

REE Distribution in Cultivated and No Cultivated Soils in Two Viticultural Areas of Central Chile: Mineralogical, Pedological and Anthropic Influences

NASA Astrophysics Data System (ADS)

Castillo, P.; Townley, B.; Aburto, F.

2017-12-01

Within the scope of a Corfo-Innova Project (I+D Wines of Chile-University of Chile) we have recognized remarkable REE patterns in soils of two vineyards located in traditional vinicultural areas: Casablanca and Santa Cruz. Both vineyards have granitic parent rock, with similar petrographic features and REE patterns. We studied REE distribution on twelve cultivated soil profiles at each vineyard, where a full mineralogical, geochemical and pedogenic sampling and characterization was performed. To establish the effect of management no cultivated soil profiles were included from each vineyard location. REE in soil samples were measured by ICP-MS using two digestion methods: lithium metaborate/tetraborate fusion to obtain REE contents in total soil and MMI® partial extraction technique for REE contents on bioavailable phases.Soils display similar signatures of REEs respect to the rock source at both vineyards, but showing relative enrichments in soils of Casablanca and depletion in soils of Santa Cruz. Bioavailable phase data indicates a relative depletion of LREEs compared to HREEs and different anomalies for Ce (positive vs negative) in different areas of the same vineyard. Similar patterns of soils and parent rock suggest that REEs are adequate tracers of lithological source. Enrichments and/or depletions of REE patterns in soils respect to the rock source and Ce anomalies, evidence differential pedogenetic processes occurring at each sampled site. Results of bioavailable phase are coherent with the immobilization and fractionation of LREEs by stable minerals within soils as clays and Fe oxides. Mineralogical results in soil thin sections of Casablanca evidence the occurrence of Ti phases as sphene, ilmenite and rutile, which probably control the relative REE enrichment, since these minerals are considered more stable under pedogenic conditions.Finally, cultivated soils show a depleted but analogous pattern of REE regarding to no cultivated soil, indicating the REEs loss due to agricultural land use. Our preliminary hypothesis is the existence of organometallic complexes that retain REEs in natural soils, which are degraded with vinicultural management. However other factors as differential weathering rates of minerals, clays mineralogy and fractionation of REE by plants must be considered.

U, Th, Pb and REE abundances and Pb 207/Pb 206 ages of individual minerals in returned lunar material by ion microprobe mass analysis.

NASA Technical Reports Server (NTRS)

Andersen, C. A.; Hinthorne, J. R.

1972-01-01

Results of ion microprobe analyses of Apollo 11, 12 and 14 material, showing that U, Th, Pb and REE are concentrated in accessory minerals such as apatite, whitlockite, zircon, baddeleyite, zirkelite, and tranquillityite. Th/U ratios are found to vary by over a factor of 40 in these minerals. K, Ba, Rb and Sr have been localized in a K rich, U and Th poor glass phase that is commonly associated with the U and Th bearing accessory minerals. Li is observed to be fairly evenly distributed between the various accessory phases. The phosphates have been found to have REE abundance patterns (normalized to the chondrite abundances) that are fairly flat, while the Zr bearing minerals have patterns that rise steeply, by factors of ten or more, from La to Gd. All the accessory minerals have large negative Eu anomalies. Radiometric age dates (Pb 207/Pb 206) of the individual U and Th bearing minerals compare favorably with the Pb 207/Pb 206 age of the bulk rocks.

An ion microprobe study of the intra-crystalline behavior of REE and selected trace elements in pyroxene from mare basalts with different cooling and crystallization histories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shearer, C.K.; Papike, J.J.; Simon, S.B.

1989-05-01

To study the effects of crystallization sequence and rate on trace element zoning characteristics of pyroxenes, the authors used combined electron microprobe-ion microprobe techniques on four nearly isochemical Apollo 12 and 15 pigeonite basalts with different cooling rates and crystallization histories. Major and minor element zoning characteristics are nearly identical to those reported in the literature. All the pyroxenes have similar chondrite-normalized REE patterns: negative Eu anomalies, positive slopes as defined by Yb/Ce, and slopes of REE patterns from Ce to Sm much steeper than from Gd to Yb. These trace element zoning characteristics in pyroxene and the partitioning ofmore » trace elements between pyroxene and the melt are intimately related to the interplay among the efficiency of the crystallization process, the kinetics at the crystal-melt interface, the kinetics of plagioclase nucleation and the characteristics of the crystal chemical substitutions within both the pyroxene and the associated crystallizing phases (i.e. plagioclase).« less

The Hydrogeochemistry of Qingshui Geothermal Field, Northeastern Taiwan.

NASA Astrophysics Data System (ADS)

Yu-Wen, Chen; Cheng-Kuo, Lin; Wayne, Lin; Yu-Te, Chang; Pei-Shan, Hsieh

2015-04-01

The Qingshui geothermal field is located at the upstream valley of Lanyang Creek, northeastern Taiwan. It is renowned as a geothermal field. The previous studies demonstrated a higher geothermal gradient, 100oC/km warmer than a normal geotherm. However, Qingshui geothermal field has not been well developed due to the higher mining costs. In the recent years, the Taiwan government has been focusing on developing alternative and renewable energy and initiated a 10 year project, Nation Energy Program. This study is part of this project In general, it is very difficult to collect deep downhole samples without considerable change of hydro- and gas- chemistry of water under high temperature and pressure. A new sampling tool, GTF Sampler, was designed by the research team, Green Energy and Environment Laboratories, Industrial Technology Research Institute. This tool can simultaneously collect high quality geothermal water and gas sample and moreover, the sampling depth can reach up to 800 meters. Accordingly, a more accurate measurements can be conducted in the laboratory. In this study, 10 geothermal samples were collected and measured. The results demonstrate that geothermal water samples are characterized with Na(K)-HCO3 water type and located at the mature water area in Giggenbach Na-K-Mg diagram. Several geothermometers, including silica and cation geothermometry, were used to estimate potential temperature in the geothermal reservoir systems. In general, the geothermoters of Na-K and Na-K-Ca obtain reservoir temperatures between 120-190oC and 130-210oC, respectively, but the silica geothermometer indicates a lower reservoir temperature between 90 and 170oC. There is no big difference among them. It is worth to note that all calculated temperatures are lower than those of in-situ downhole measurements; therefore, more detailed and advanced researches would be needed for the inconsistency. To examine the argument about igneous heat source in the previous studies, rare earth elements (REEs) were also measured in this study. The results normalized by North America Shale REEs (NASC) show a flat pattern and a distinct europium positive anomaly. It possibly indicates a chemical interaction between meteoric water and sedimentary rock, which excludes the possibility of an igneous source.

Lanthanide and actinide chemistry at high C/O ratios in the solar nebula

NASA Technical Reports Server (NTRS)

Lodders, Katharina; Fegley, Bruce, Jr.

1993-01-01

Chemical equilibrium calculations were performed to study the condensation chemistry of the REE and actinides under the highly reducing conditions which are necessary for the formation of the enstatite chondrites. Our calculations confirm that the REE and actinides condensed into oldhamite (CaS), the major REE and actinide host phase in enstatite chondrites, at a carbon-oxygen (C/O) ratio not less than 1 in an otherwise solar gas. Five basic types of REE abundance patterns, several of which are analogous to REE abundance patterns observed in the Ca, Al-rich inclusions in carbonaceous chondrites, are predicted to occur in meteoritic oldhamites. All of the reported REE patterns in oldhamites in enstatite chondrites can be interpreted in terms of our condensation calculations. The observed patterns fall into three of the five predicted categories. The reported Th and U enrichments and ratios in meteoritic oldhamites are also consistent with predictions of the condensation calculations. Pure REE sulfides are predicted to condense in the 10 exp -6 to 10 exp -9 bar range and may be found in enstatite chondrites if they formed in this pressure range.

Anthropogenic rare earth elements and their spatial distributions in the Han River, South Korea.

PubMed

Song, Hyeongseok; Shin, Woo-Jin; Ryu, Jong-Sik; Shin, Hyung Seon; Chung, Heesun; Lee, Kwang-Sik

2017-04-01

Rare earth elements (REE) consist of lanthanides (from La to Lu), together with yttrium and scandium, in which anthropogenic REE, such as gadolinium (Gd), lanthanum (La), and samarium (Sm), has emerged as micro-contaminants in natural waters in highly developed countries. Here, we collected water samples in the Han River (HR) and its tributaries flowing through Seoul Capital Area, the world's second largest metropolitan area in order to examine how and to what extent anthropogenic REE anomalies may occur. Water samples show higher light REE concentrations than heavy REE concentrations, while wastewater treatment plant (WWTP) samples display much higher heavy REE concentrations due to high Gd concentration. The PAAS-normalized REE patterns indicate that WWTP samples display the pronounced positive Gd anomalies, in which anthropogenic Gd from magnetic resonance imaging (MRI) diagnostic system occurs as a form of Gd complexation with either Cl - or SO 4 2- . Due to the WWTP, both the HR and tributaries show also positive Gd anomalies and the anthropogenic Gd concentrations increase as a function of the distance from the Paldang dam. This result indicates a positive correlation between populaton, number of MRI instruments, and positive Gd anomaly. Similarly, positive La and Sm anomalies exist in the HR, indicating that the HR is also affected by their point sources. Based on the discharge rate and anthropogenic REE concentrations, their fluxes are estimated to be 952 ± 319 kg/yr, suggesting that this amount of fluxes could disturb REE distribution in the Yellow Sea, and pose harmful effects on aquatic ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

The rare earth element compositions of the Changjiang (Yangtze) and Huanghe (Yellow) river sediments

NASA Astrophysics Data System (ADS)

Yang, Shou Ye; Jung, Hoi Soo; Choi, Man Sik; Li, Cong Xian

2002-07-01

Thirty-four samples from the Changjiang and Huanghe were analyzed to characterize their rare earth element (REE) compositions. Although REE concentrations in the Changjiang sediments are higher than those of the Huanghe sediments, the former are less variable. Bulk samples and acid-leachable fractions have convex REE patterns and middle REE enrichments relative to upper continental crust, whereas flat patterns are present in the residual fractions. Source rock composition is the primary control on REE composition, and weathering processes play a minor role. Grain size exerts some influence on REE composition, as demonstrated by the higher REE contents of clay minerals in sediments from both rivers. Heavy minerals contribute about 10-20% of the total REE in the sediments. Apatite is rare in the river sediments, and contributes less than 2% of the REE content, but other heavy minerals such as sphene, allanite and zircon are important reservoirs of residual REE fractions. The Fe-Mn oxides phase accounts for about 14% of bulk REE content in the Changjiang sediments, which could be one of the more important factors controlling REE fractionation in the leachable fraction.

Rare earth elements in coastal sediments of the northern Galician shelf: Influence of geological features

NASA Astrophysics Data System (ADS)

Prego, Ricardo; Caetano, Miguel; Bernárdez, Patricia; Brito, Pedro; Ospina-Alvarez, Natalia; Vale, Carlos

2012-03-01

The Northern coast of Galicia, NW Iberian Peninsula, exhibits a variety of geological features: Ortegal allochthonous complex, Ollo-de-Sapo autochthonous domain and massifs of Bares, Barqueiro and San-Ciprian. In order to examine the influence of terrestrial lithologies on coastal sediments, 103 samples were collected in the Rias of Ortigueira, Barqueiro and Viveiro, their neighbouring shelf and the estuaries of Mera, Sor and Landro rivers. Aluminium, Fe, Sc, particulate inorganic and organic carbon and rare earth elements (REE) were determined in the <2 mm fraction. In addition, calcite, muscovite, quartz and riebeckite minerals were identified and quantified in 33 selected samples. The distributions of riebeckite and Fe reflect the influence of Ortegal complex on the coastal areas around the Cape Ortegal. The highest concentrations of ΣREE were found in fine sediments from confined inner parts of the Rias (up to 233 mg kg-1), while most of the sands contained 11-70 mg kg-1. ΣREE normalised to European Shale (ES) highlights the relative abundance of lanthanides (ΣREEN>6) near Cape Ortegal and the innermost ria zones. The ratio between light and heavy REE (L/H) showed lower values (4-11) around Cape Ortegal and the shelf while higher ratios (15-23) were detected in west of the Cape Estaca-de-Bares and in the inner Viveiro Ria due to elevated contributions of La and Ce. The L/H values normalised to ES reflects the importance of HREE in the adjacent area to Ortegal Complex (LN/HN<0.8) and the LREE (LN/HN>1.4) in the inner estuaries and west Cape Estaca-de-Bares. The highest REE individual ES normalised were measured in fine-grained sediments of the Mera and Sor estuaries. Sediments from the eastern shelf of Cape Ortegal presented enhanced ratios only for HREE. These results indicate that distribution of REE in the northern Galician region is highly depending on the neighbouring lithological pattern, contrasting with the situation found in the western Galician shelf and the Bay of Biscay. Lanthanides can, thus, provide a useful tool to follow the sediment pathway in the land-sea boundary zones, denoting continental geochemical imprint or fluvial outputs accordingly to the existing hydrological and geological conditions.

Early Proterozoic crustal evolution: Geochemical and NdPb isotopic evidence from metasedimentary rocks, southwestern North America

NASA Astrophysics Data System (ADS)

McLennan, S. M.; Hemming, S. R.; Taylor, S. R.; Eriksson, K. A.

1995-03-01

Early Proterozoic (1.8-1.7 Ga) metasedimentary rocks in northern New Mexico and southern Colorado, USA, can be divided into turbidite successions (commonly volcanogenic) associated with mafic/felsic metavolcanic successions (e.g., Irving Fm.) and stable shelf quartzite-pelite successions of shallow marine origin (e.g., Hondo Gp.). Metapelites from the turbidite successions reported here have low K2O/Na2O, low Th/U (<3.0), low to moderate Th/Sc (0.1-0.6), and slight negative Eu-anomalies, although regionally, negative Eu-anomalies in such rocks are common. At the time of sedimentation (ca. 1.7-1.8 Ga), ɛNd values were in the range +3 to +7, indistinguishable from associated metavolcanic and plutonic rocks. Similarly, lead isotopic data scatter about a 1.7 Ga reference isochron. Low κ (232Th/238U) values for the Irving Formation are consistent with derivation from crustal sources similar to the southern Colorado/northern New Mexico lead isotope crustal province. These data are further consistent with a volcanic arc related origin. In contrast, stable shelf metapelites have high K2O/Na2O, variable but commonly high Th/U (2.0-7.0), moderate to high Th/Sc (0.5-1.4), and substantial negative Eu-anomalies. Although compositions are rather variable, they are typical of post-Archean shales. Neodymium isotopes are surprisingly radiogenic with ɛNd(1.7 Ga) in the range -0.2 to +4. Lead isotopic data for the least radiogenic samples also are consistent with a dominantly juvenile source and on a 207Pb/204Pb vs. 206Pb/204Pb diagram, data scatter slightly above the 1.7 Ga reference isochron, suggesting minor components of significantly older material. Lead isotopic systematics suggest that a major component of the provenance was derived from the immediately associated metavolcanic-plutonic terranes, consistent with suggestions of a first-cycle origin, but with an Archean component. Isotopic data restrict the Archean component to about 10%, on average, and no more than 25% in any sample. This older crustal component may be derived either by direct erosion of Archean rocks, such as the Wyoming Province, or indirectly through assimilation into Early Proterozoic igneous rocks. Although the stable shelf sedimentary rocks are derived from a provenance with similar ages as the volcanogenic turbidites, the geochemical characteristics of the provenance are significantly different. Accordingly, these data are consistent with especially rapid and widespread crustal growth and evolution in southwestern North America during the period 1.9-1.7 Ga. Several samples from the Hondo Group and Uncompahgre Formation have REE patterns that are rotated to LREE depletion and perhaps HREE enrichment. The change in REEs correlate with Mo, U, and V abundances and Pb isotopic characteristics suggesting sedimentary processes similar to those operating in black shales affected these REE patterns. REE patterns and Th/U ratios of Early Proterozoic volcanogenic turbidites examined in this and other studies differ on average from turbidites found in Archean greenstone belts. Negative Eu-anomalies are common, HREE-depletion is seen but comparatively rare, and Th/U ratios are commonly below 3.0. Accordingly, these data are consistent with models suggesting that the upper crust had a different composition in the Archean.

Recovery and Separation of Rare Earth Elements Using Salmon Milt

PubMed Central

Takahashi, Yoshio; Kondo, Kazuhiro; Miyaji, Asami; Watanabe, Yusuke; Fan, Qiaohui; Honma, Tetsuo; Tanaka, Kazuya

2014-01-01

Recycling rare earth elements (REEs) used in advanced materials such as Nd magnets is important for the efficient use of REE resources when the supply of several REEs is limited. In this work, the feasibility of using salmon milt for REE recovery and separation was examined, along with the identification of the binding site of REEs in salmon milt. Results showed that (i) salmon milt has a sufficiently high affinity to adsorb REEs and (ii) the adsorption capacity of the milt is 1.04 mEq/g, which is comparable with that of commercial cation exchange resin. Heavier REEs have higher affinity for milt. A comparison of stability constants and adsorption patterns of REEs discussed in the literature suggests that the phosphate is responsible for the adsorption of REE in milt. The results were supported by dysprosium (Dy) and lutetium (Lu) LIII-edge extended x-ray absorption fine structure (EXAFS) spectroscopy. The REE-P shell was identified for the second neighboring atom, which shows the importance of the phosphate site as REE binding sites. The comparison of REE adsorption pattern and EXAFS results between the milt system and other adsorbent systems (cellulose phosphate, Ln-resin, bacteria, and DNA-filter hybrid) revealed that the coordination number of phosphate is correlated with the slope of the REE pattern. The separation column loaded with milt was tested to separate REE for the practical use of salmon milt for the recovery and separation of REE. However, water did not flow through the column possibly because of the hydrophobicity of the milt. Thus, sequential adsorption–desorption approach using a batch-type method was applied for the separation of REE. As an example of the practical applications of REE separation, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste by a batch-type method using salmon milt. PMID:25490035

Milankovitch climate cyclicity and its effect on relative sea level changes and organic carbon storage, Late Cretaceous black shales of Colombia and Venezuela

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villamil, T.; Kauffman, E.G.

1993-02-01

The Late Cretaceous Villeta Group and La Luna Formation shows remarkable depositional cyclicity attributable to Milankovitch climate cycles. Each 30-60 cm thick hemicycle is composed of a basal gray shale, a medial black, organic-rich shale, and an upper gray shale with a dense argillaceous limestone cap. Fourier time-series analysis revealed peak frequencies of 500, 100, and 31 ka (blending 21 and 42 ka data). ThiS cyclicity reflects possibly wet cooler (shale) to dry, possibly warm (limestone) climatic changes and their influence on relative sea level, sedimentation rates/patterns, productivity, water chemistry and stratification. Wet/cool hemicycles may produce slight lowering of sealevel,more » increased rates of clay sedimentation, diminished carbonate production, water stratification, increased productivity among noncalcareous marine plankton, and increased Corg production and storage. Dry/warm hemicycles may produce a slight rise in sealevel, and return to normal marine conditions with low Corg storage. Source rock quality may depend upon the predominance of wet over dry climatic phases. Differences between climate-forced cyclicity and random facies repetition, are shown by contrasting observed lithological patterns and geochemical signals with litho- and chemostratigraphy generated from random models. Accomodation space plots (Fischer plots) for cyclically interbedded black shale-pelagic limestone sequences, allowed prediction of facies behavior, shoreline architecture, and quantitative analysis of relative sea level. The synchroneity of Milankovitch cycles and changes in hemicycle stacking patterns, were tested against a new high-resolution event-chronostratigraphic and biostratigraphic framework for NW South America. Geochemical spikes and hemicycle stacking patterns occur consistently throughout the sections measured, supporting the correlation potential of cyclostratigraphy.« less

Provenance and paleogeography of the Devonian Durazno Group, southern Parana Basin in Uruguay

NASA Astrophysics Data System (ADS)

Uriz, N. J.; Cingolani, C. A.; Basei, M. A. S.; Blanco, G.; Abre, P.; Portillo, N. S.; Siccardi, A.

2016-03-01

A succession of Devonian cover rocks occurs in outcrop and in the subsurface of central-northern Uruguay where they were deposited in an intracratonic basin. This Durazno Group comprises three distinct stratigraphic units, namely the Cerrezuelo, Cordobés and La Paloma formations. The Durazno Group does not exceed 300 m of average thickness and preserves a transgressive-regressive cycle within a shallow-marine siliciclastic shelf platform, and is characterized by an assemblage of invertebrate fossils of Malvinokaffric affinity especially within the Lower Devonian Cordobés shales. The sedimentary provenance of the Durazno Group was determined using petrography, geochemistry, and morphological studies of detrital zircons as well as their U-Pb ages. Sandstone petrography of Cerrezuelo and La Paloma sequences shows that they have a dominantly quartz-feldspathic composition with a minor contribution of other minerals. Whole-rock geochemical data indicate that alteration was strong in each of the three formations studied; chondritic-normalized REE patterns essentially parallel to PAAS, the presence of a negative Eu-anomaly, and Th/Sc and La/Hf ratios point to an average source composition similar to UCC or slightly more felsic. Within the Cerrezuelo Formation, recycling of older volcano-metasedimentary sources is interpreted from Zr/Sc ratios and high Hf, Zr, and REE concentrations. U-Pb detrital zircon age populations of the Cerrezuelo and La Paloma formations indicate that the principal source terranes are of Neoproterozoic age, but include also minor populations derived from Mesoproterozoic and Archean-Paleoproterozoic rocks. A provenance from the Cuchilla Dionisio-Dom Feliciano, Nico Pérez and Piedra Alta terranes of Uruguay and southern Brazil is likely. This study establishes an intracratonic extensional tectonic setting during Durazno time. Considering provenance age sources, regional paleocurrent distributions and the established orogenic history recorded in SW Gondwana, we suggest that the basin fill was derived from paleohighs located in what is currently SE Uruguay.

Trace-element abundances in several new ureilites

NASA Technical Reports Server (NTRS)

Boynton, William V.; Hill, Dolores H.

1993-01-01

Four new ureilites are analyzed for trace-element abundances. Frontier Mountain (FRO) 90054 is an augite-rich ureilite and has high rare earth element (REE) abundances with a pattern expected of augite. FRO 90036 and Acfer 277 have REE patterns similar to the V-shape pattern of other ureilites. Nuevo Mercurio (b) has very high REE abundances, but they look like they are due to terrestrial alteration. The siderophile-element pattern of these ureilites are similar to those of known ureilites.

Rare earth element geochemistry characteristics of seawater and porewater from deep sea in western Pacific.

PubMed

Deng, Yinan; Ren, Jiangbo; Guo, Qingjun; Cao, Jun; Wang, Haifeng; Liu, Chenhui

2017-11-28

Deep-sea sediments contain high concentrations of rare earth element (REE) which have been regarded as a huge potential resource. Understanding the marine REE cycle is important to reveal the mechanism of REE enrichment. In order to determine the geochemistry characteristics and migration processes of REE, seawater, porewater and sediment samples were systematically collected from the western Pacific for REE analysis. The results show a relatively flat REE pattern and the HREE (Heavy REE) enrichment in surface and deep seawater respectively. The HREE enrichment distribution patterns, low concentrations of Mn and Fe and negative Ce anomaly occur in the porewater, and high Mn/Al ratios and low U concentrations were observed in sediment, indicating oxic condition. LREE (Light REE) and MREE (Middle REE) enrichment in upper layer and depletion of MREE in deeper layer were shown in porewater profile. This study suggests that porewater flux in the western Pacific basin is a minor source of REEs to seawater, and abundant REEs are enriched in sediments, which is mainly caused by the extensive oxic condition, low sedimentation rate and strong adsorption capacity of sediments. Hence, the removal of REEs of porewater may result in widespread REE-rich sediments in the western Pacific basin.

Resting energy expenditure per lean body mass determined by indirect calorimetry and bioelectrical impedance analysis in cats.

PubMed

Center, S A; Warner, K L; Randolph, J F; Wakshlag, J J; Sunvold, G D

2011-01-01

Resting energy expenditure (REE) approximates ≥60% of daily energy expenditure (DEE). Accurate REE determination could facilitate sequential comparisons among patients and diseases if normalized against lean body mass (LBM). (1) Validate open-flow indirect calorimetry (IC) system and multifrequency bioelectrical impedance analysis (MF-BIA) to determine REE and LBM, respectively, in healthy nonsedated cats of varied body conditions; (2) normalize REE against LBM. Fifty-seven adult neutered domestic short-haired cats with stable BW. Continuous (45-min) IC-measurements determined least observed metabolism REE. Cage gas flow regulated with mass flow controllers was verified using nitrogen dilution; span gases calibrated gas measurements. Respiratory quotient accuracy was verified using alcohol combustion. IC-REE was compared to DEE, determined using doubly labeled water. MF-BIA LBM was validated against criterion references (deuterium, sodium bromide). Intra- and interassay variation was determined for IC and MF-BIA. Mean IC-REE (175 ± 38.7 kcal; 1.5-14% intra- and interassay CV%) represented 61 ± 14.3% of DEE. Best MF-BIA measurements were collected in sternal recumbency and with electrodes in neck-tail configuration. MF-BIA LBM was not significantly different from criterion references and generated LBM interassay CV% of 6.6-10.1%. Over- and underconditioned cats had significantly (P ≤ .05) lower and higher IC-REE (kcal/kg) respectively, compared with normal-conditioned cats. However, differences resolved with REE/LBM (approximating 53 ± 10.3 kcal/LBM [kg]). IC and MF-BIA validated herein reasonably estimate REE and LBM in cats. REE/LBM(kg) may permit comparison of energy utilization in sequential studies or among different cats. Copyright © 2011 by the American College of Veterinary Internal Medicine.

Source and mobility of Rare Earth Elements in a sedimentary aquifer system: Aquitaine basin (Southern France)

NASA Astrophysics Data System (ADS)

Negrel, P. J.; Petelet-Giraud, E.; Millot, R.; Malcuit, E.

2011-12-01

The study of rare earth elements (REEs) in natural waters initially involved an examination of their occurrence and behavior in seawater and coastal waters such as estuaries. Since the 1990s, REE geochemistry has been applied to continental waters such as rivers and lakes and groundwaters. Rare earth elements) are of great interest because of their unique characteristics and have been used in the study of many geological processes like weathering and water-rock interaction processes, provenance of sediments, etc... With the evolution of analytical techniques like new generation ICP-MS, much attention had been paid towards the water geochemistry of REEs. However, there is a need of more investigations devoted to REEs in large groundwater systems, especially on the understanding of the distribution of REEs and their evolution in such systems. In this frame, large sedimentary aquifer systems often constitute strategic water resources for drinking water supply, agriculture irrigation and industry, but can also represent an energetic resource for geothermal power. Large water abstractions can induce complete modification of the natural functioning of such aquifer systems. These large aquifer systems thus require water management at the basin scale in order to preserve both water quantity and quality. The large Eocene Sand aquifer system of the Aquitaine sedimentary basin was studied through various hydrological, chemical and isotopic tools. This system extends over 116,000 km2 in the South west part of the French territory. The aquifer being artesian in the west of the district and confined with piezometric levels around 250-m depth in the east. The 'Eocene Sands', composed of sandy Tertiary sediments alternating with carbonate deposits, is a multi-layer system with high permeability and a thickness of several tens of metres to a hundred metres. The Eocene Sand aquifer system comprises at least five aquifers: Paleocene, Eocene infra-molassic sands (IMS), early Eocene, middle Eocene, and late Eocene. One important feature, in these confined systems isolated from anthropogenic influence, is the range in salinities by a factor of 10, from 250 mg/L up to 2.5 g/L. The ΣREE, in the range 2-54 ng/L, with a dependence on salinity when expressed in % HCO3 or SO4, reflect the carbonate or evaporite source of REEs. The UCC normalized-REE patterns show a large variability as exemplified by the REE flat patterns-low SREE associated with salinity controlled by HCO3. In the present work, the REEs are investigated in terms of saturation indices, speciation modelling, REE patterns in order to recognize the aquifer type hosting groundwater and decipher the origin of the salinity of the groundwater as some part of the aquifer display in the groundwater concentration of chemical element exceeding the drinking water standard (SO4, F...). Such high concentrations of naturally-occurring substances (e.g. unaffected by human activities) can have negative impacts on groundwater thresholds and deciphering their origin by means of geochemical tools like REE is a remaining challenge.

Rare earth elements distribution in grapevine varieties grown on volcanic soils: an example from Mount Etna (Sicily, Italy).

PubMed

D'Antone, Carmelisa; Punturo, Rosalda; Vaccaro, Carmela

2017-04-01

A geochemical and statistical approach has allowed identifying in rare earth elements (REEs) absorption a good fingerprinting mark for determining the territoriality and the provenance of Vitis vinifera L. in the district of Mount Etna (southern Italy). Our aim is to define the REEs distribution in different parts of the plants which grow in the same volcanic soil and under the same climate conditions, and therefore to assess whether REEs distribution may reflect the composition of the provenance soil or if plants can selectively absorb REEs in order to recognize the fingerprint in the Etna Volcano soils as well as the REEs pattern characteristic of each cultivar of V. vinifera L. The characteristic pattern of REEs has been determined by ICP-MS analyses in the soils and in the selected grapevine varieties for all the following parts: leaves, seeds, juice, skin, and berries. These geochemical criteria, together with the multivariate statistical analysis of the principal component analysis (PCA) and of the linear discriminant analysis (LDA) that can be summarized with the box plot, suggest that leaves mostly absorb REEs than the other parts of the plant. This work investigates the various parts of the plant in order to verify if each grape variety presents a characteristic geochemical pattern in the absorption of REEs in relationship with the geochemical features of the soil so to highlight the individual compositional fingerprint. Based on REE patterns, our study is a useful tool that allows characterizing the differences among the grape varieties and lays the foundation for the use of REEs in the geographic origin of the Mount Etna wine district.

A survey of the selenochemistry of major, minor and trace elements.

NASA Technical Reports Server (NTRS)

Schmitt, R. A.; Laul, J. C.

1973-01-01

Average data for igneous and/or metaigneous rocks and soils from seven lunar sites are presented. There are compositional similarities between Apollo 11 and Luna 16 eastern maria, Ap 12 and 15 western maria, and between Ap 16 and L 20 highlands. Subtle differences do exist between the paired mare sites and the two highland sites and striking differences between the eastern and western maria. Chondritic normalized REE (rare earth element) patterns for igneous rocks and soils from all sites range from 7-350 generally with negative Eu anomalies. Anorthositic gabbroes to anorthosites, presumably highland material, exhibit a positive Eu anomaly. The REE patterns or Sr isotopic ratios suggest two lava flows each for the L 16 and Ap 14 sites, at least four lava flows for the Ap 11 and 12 site and about six for the Ap 15 site.

Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

USGS Publications Warehouse

Huebner, J.S.; Flohr, M.J.K.; Grossman, J.N.

1992-01-01

Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes. ?? 1992.

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

NASA Astrophysics Data System (ADS)

Elderfield, H.; Hawkesworth, C. J.; Greaves, M. J.; Calvert, S. E.

1981-04-01

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. 143Nd /144Nd ratios in the nodules (˜0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.

A first report of rare earth elements in northwestern Mediterranean seaweeds.

PubMed

Squadrone, Stefania; Brizio, Paola; Battuello, Marco; Nurra, Nicola; Sartor, Rocco Mussat; Benedetto, Alessandro; Pessani, Daniela; Abete, Maria Cesarina

2017-09-15

The concentrations of rare earth elements (REE) were determined by ICP-MS in dominant seaweed species, collected from three locations of the northwestern Mediterranean Sea. This is the first study to define levels and patterns of REE in macro algae from these coastal areas. Rare elements are becoming emerging inorganic contaminants in marine ecosystems, due to their worldwide increasing applications in industry, technology, medicine and agriculture. Significant inter-site and interspecies differences were registered, with higher levels of REE in brown and green macro algae than in red seaweeds. Levels of light REE were also observed to be greater compared to heavy REE in all samples. One of the investigated locations (Bergeggi, SV) had higher REE and ΣREE concentrations, probably due to its proximity to an important commercial and touristic harbor, while the other two sites were less affected by anthropogenic contaminations, and showed comparable REE patterns and lower concentrations. Rare earth elements in seaweeds. Copyright © 2017 Elsevier Ltd. All rights reserved.

The surface sediment types and their rare earth element characteristics from the continental shelf of the northern south China sea

NASA Astrophysics Data System (ADS)

Wang, Shuhong; Zhang, Nan; Chen, Han; Li, Liang; Yan, Wen

2014-10-01

The grain size as well as some major and trace elements, including rare earth element (REE), for 273 surface sediment samples collected from the continental shelf of the northern South China Sea were analyzed in this study. The sediment types are mainly sandy silt and silt, making up 60% of the whole samples, and secondly are mud, sandy mud, muddy sand and silty sand, making up 28% of the whole samples, based on grain-size in which the Folk's classification was used. The total REE content (ΣREE) show a wide variation from 21 ppm to 244 ppm with an average value of 155 ppm, which similar to the average ΣREE of the China loess, but much different from that in deep-sea clay, showing a significant terrigenous succession. The REE contents in different sediment types vary greatly, mainly enriching in silt, sandy silt, mud and sandy mud. The REE distribution contours parallel to the coastal, presenting like strips and their contents gradually reduce with increasing distance from the coast. The high content of the western Pearl River Mouth, Shang/Xiachuan Islands and Hailing Bay might be regarded to the coastal current developed from the east to the west along to the Pearl River Mouth in the northern South China Sea. But the chondrite-normalized REE patterns in various sediment types have no difference, basically same as those of coastal rivers and upper crust. They all show relative enrichments in light rare earth element (LREE), noticeable negative Eu anomaly and no Ce anomaly, indicating that those sediments are terrigenous sediments and from the same source region. Further analysis suggest that the sedimentary environment in the study area is relatively stable and granite widely distributed in the South China mainland is the main source of REE, which are transported mainly by the Pearl River. The late diagenesis has little effect on the REE.

Nature of parent rocks, mineralization styles and ore genesis of regolith-hosted REE deposits in South China: An integrated genetic model

NASA Astrophysics Data System (ADS)

Li, Yan Hei Martin; Zhao, Wen Winston; Zhou, Mei-Fu

2017-10-01

Regolith-hosted rare earth element (REE) deposits, also called ion-adsorption or weathered crust elution-deposited REE deposits are distributed over Jiangxi, Guangdong, Fujian, Hunan, Guangxi and Yunnan provinces in South China. In general, these deposits can be categorized into the HREE-dominated type, for example the famous Zudong deposit in southern Jiangxi province and the LREE-dominated type, such as the Heling and Dingnan deposits in southern Jiangxi province. Most of these deposits form from weathering of biotite and muscovite granites, syenites, monzogranites, granodiorites, granite porphyries, and rhyolitic tuffs. The parent rocks are generally peraluminous, siliceous, alkaline and contain a variety of REE-bearing minerals. Mostly, REE patterns of regolith are inherited from the parent rocks, and therefore, characteristics of the parent rocks impose a significant control on the ore formation. Data compilation shows that autometasomatism during the latest stage of granite crystallization is likely essential in forming the HREE-enriched granites, whereas LREE-enriched granites could form through magmatic differentiation. These deposits are normally two- to three-fold, but could be up to ten-fold enrichment in REE compared to the parent granites, where the maximum enrichment usually occurs from the lower B to the upper C horizon. Ce shows different behavior with the other REEs. Strongly positive Ce anomalies commonly occur at the upper part of weathering profiles, likely due to oxidation of Ce3+ to Ce4+ and removal of Ce from soil solutions through precipitation of cerianite. Vertical pH and redox gradients in weathering crusts facilitate dissolution of REE-bearing minerals at shallow level and fixation of REE at depth through either adsorption on clay minerals or precipitation of secondary minerals. At the same time, mass removal of major elements plays an important role in concentrating REE in regolith. Combination of mass removal and eluviation-illuviation dynamics is the main mechanism for REE accumulation in weathering crusts. Favorable exogenetic factors facilitate the accumulation of REE in regolith and preservation of the ore bodies. These include quasi-equilibrium between denudation and exhumation at regional scales, local geomorphology dominated by low-lying gentle slopes, adequate rainfall, and favorable groundwater conditions. Continuous operation of such a dynamic weathering system is essential in the formation of regolith-hosted REE deposits.

Age-Dependent Changes in Resting Energy Expenditure (REE): Insights from Detailed Body Composition Analysis in Normal and Overweight Healthy Caucasians

PubMed Central

Geisler, Corinna; Braun, Wiebke; Pourhassan, Maryam; Schweitzer, Lisa; Glüer, Claus-Christian; Bosy-Westphal, Anja; Müller, Manfred J.

2016-01-01

Age-related changes in organ and tissue masses may add to changes in the relationship between resting energy expenditure (REE) and fat free mass (FFM) in normal and overweight healthy Caucasians. Secondary analysis using cross-sectional data of 714 healthy normal and overweight Caucasian subjects (age 18–83 years) with comprehensive information on FFM, organ and tissue masses (as assessed by magnetic resonance imaging (MRI)), body density (as assessed by Air Displacement Plethysmography (ADP)) and hydration (as assessed by deuterium dilution (D2O)) and REE (as assessed by indirect calorimetry). High metabolic rate organs (HMR) summarized brain, heart, liver and kidney masses. Ratios of HMR organs and muscle mass (MM) in relation to FFM were considered. REE was calculated (REEc) using organ and tissue masses times their specific metabolic rates. REE, FFM, specific metabolic rates, the REE-FFM relationship, HOMA, CRP, and thyroid hormone levels change with age. The age-related decrease in FFM explained 59.7% of decreases in REE. Mean residuals of the REE-FFM association were positive in young adults but became negative in older subjects. When compared to young adults, proportions of MM to FFM decreased with age, whereas contributions of liver and heart did not differ between age groups. HOMA, TSH and inflammation (plasma CRP-levels) explained 4.2%, 2.0% and 1.4% of the variance in the REE-FFM residuals, but age and plasma T3-levels had no effects. HMR to FFM and MM to FFM ratios together added 11.8% on to the variance of REE-FFM residuals. Differences between REE and REEc increased with age, suggesting age-related changes in specific metabolic rates of organs and tissues. This bias was partly explained by plasmaT3-levels. Age-related changes in REE are explained by (i) decreases in fat free mass; (ii) a decrease in the contributions of organ and muscle masses to FFM; and (iii) decreases in specific organ and tissue metabolic rates. Age-dependent changes in the REE-FFMassociation are explained by composition of FFM, inflammation and thyroid hormones. PMID:27258302

Age-Dependent Changes in Resting Energy Expenditure (REE): Insights from Detailed Body Composition Analysis in Normal and Overweight Healthy Caucasians.

PubMed

Geisler, Corinna; Braun, Wiebke; Pourhassan, Maryam; Schweitzer, Lisa; Glüer, Claus-Christian; Bosy-Westphal, Anja; Müller, Manfred J

2016-06-01

Age-related changes in organ and tissue masses may add to changes in the relationship between resting energy expenditure (REE) and fat free mass (FFM) in normal and overweight healthy Caucasians. Secondary analysis using cross-sectional data of 714 healthy normal and overweight Caucasian subjects (age 18-83 years) with comprehensive information on FFM, organ and tissue masses (as assessed by magnetic resonance imaging (MRI)), body density (as assessed by Air Displacement Plethysmography (ADP)) and hydration (as assessed by deuterium dilution (D₂O)) and REE (as assessed by indirect calorimetry). High metabolic rate organs (HMR) summarized brain, heart, liver and kidney masses. Ratios of HMR organs and muscle mass (MM) in relation to FFM were considered. REE was calculated (REEc) using organ and tissue masses times their specific metabolic rates. REE, FFM, specific metabolic rates, the REE-FFM relationship, HOMA, CRP, and thyroid hormone levels change with age. The age-related decrease in FFM explained 59.7% of decreases in REE. Mean residuals of the REE-FFM association were positive in young adults but became negative in older subjects. When compared to young adults, proportions of MM to FFM decreased with age, whereas contributions of liver and heart did not differ between age groups. HOMA, TSH and inflammation (plasma CRP-levels) explained 4.2%, 2.0% and 1.4% of the variance in the REE-FFM residuals, but age and plasma T3-levels had no effects. HMR to FFM and MM to FFM ratios together added 11.8% on to the variance of REE-FFM residuals. Differences between REE and REEc increased with age, suggesting age-related changes in specific metabolic rates of organs and tissues. This bias was partly explained by plasmaT3-levels. Age-related changes in REE are explained by (i) decreases in fat free mass; (ii) a decrease in the contributions of organ and muscle masses to FFM; and (iii) decreases in specific organ and tissue metabolic rates. Age-dependent changes in the REE-FFMassociation are explained by composition of FFM, inflammation and thyroid hormones.

Hydrothermal barite mineralization at Chenarvardeh deposit, Markazi Province, Iran: Evidences from REE geochemistry and fluid inclusions

NASA Astrophysics Data System (ADS)

Ehya, Farhad; Mazraei, Shaghayegh Moalaye

2017-10-01

Barite mineralization occurs at Chenarvardeh deposit as layers and lenses in Upper Eocene volcanic and pyroclastic rocks. The host rocks are intensely saussuritized in most places. Barite is accompanied by calcite, Mn-oxides, galena and malachite as subordinate minerals. The amount of Sr in barites is low and varies between 0.11 and 0.30 wt%. The concentration of Rb, Zr, Y, Ta and Hf is also low (<5 ppm) in barite samples. The amount of total REEs (∑REE) is low in barites, ranging from 7.51 to 30.50 ppm. Chondrite-normalized REE patterns reveal LREE enrichment with respect to HREE, and positive Ce anomalies. Fluid inclusions are common in barite samples, being dominantly from liquid-rich two phase (L + V) type. Salinity values in fluid inclusions range from 9.41 to 18.69 wt% NaCl equivalent with most frequent salinities falling in the range of 10-15 wt% NaCl equivalent. Homogenization temperatures (Th) range between 160 and 220 °C, being the 180-200 °C range as the most common Th interval. A combination of factors, including geologic setting, host rock, mineral assemblages, REE geochemistry and fluid inclusion data are consistent with a submarine volcanic hydrothermal model for barite formation at the Chenarvardeh deposit. Mineral-forming fluids originated from solutions related to submarine hydrothermal activities deposited barite on seafloor as they encountered sulfate-bearing seawater.

Porites corals as recorders of mining and environmental impacts: Misima Island, Papua New Guinea

NASA Astrophysics Data System (ADS)

Fallon, Stewart J.; White, Jamie C.; McCulloch, Malcolm T.

2002-01-01

In 1989 open-cut gold mining commenced on Misima Island in Papua New Guinea (PNG). Open-cut mining by its nature causes a significant increase in sedimentation via the exposure of soils to the erosive forces of rain and runoff. This increased sedimentation affected the nearby fringing coral reef to varying degrees, ranging from coral mortality (smothering) to relatively minor short-term impacts. The sediment associated with the mining operation consists of weathered quartz feldspar, greenstone, and schist. These rocks have distinct chemical characteristics (rare earth element patterns and high abundances of manganese, zinc, and lead) and are entering the near-shore environment in considerably higher than normal concentrations. Using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), we analyzed eight colonies (two from high sedimentation, two transitional, two minor, and two unaffected control sites) for Y, La, Ce, Mn, Zn, and Pb. All sites show low steady background levels prior to the commencement of mining in 1988. Subsequently, all sites apart from the control show dramatic increases of Y, La, and Ce associated with the increased sedimentation as well as rapid decreases following the cessation of mining. The elements Zn and Pb exhibit a different behavior, increasing in concentration after 1989 when ore processing began and one year after initial mining operations. Elevated levels of Zn and Pb in corals has continued well after the cessation of mining, indicating ongoing transport into the reef of these metals via sulfate-rich waters. Rare earth element (REE) abundance patterns measured in two corals show significant differences compared to Coral Sea seawater. The corals display enrichments in the light and middle REEs while the heavy REEs are depleted relative to the seawater pattern. This suggests that the nearshore seawater REE pattern is dominated by island sedimentation. Trace element abundances of Misima Island corals clearly record the dramatic changes in the environmental conditions at this site and provide a basis for identifying anthropogenic influences on corals reefs.

Distribution of Some Rare and Trace Elements in Ice-Rafted Sediments in the Yermak Plateau Area, the Arctic Ocean

NASA Astrophysics Data System (ADS)

Shevchenko, V. P.; Maslov, A. V.; Stein, R.

2017-11-01

The distribution of V, Co, Ni, Sr, Nb and rare earth elements (REE) in ice-rafted sediments (IRS) collected in the Yermak Plateau area (the Arctic Ocean) during cruise ARK-XX/3 of the R/V Polarstern in September 2004 has been analyzed. It was determined that the Nb/V ratio in these IRS has an intermediate value between the average ratio values in suspended particulate matter of the Yenisei and Khatanga rivers and Mesozoic-Cenozoic basalts, on the one hand, and suspended matter of the Ob and Lena rivers and post-Archean Australian Shale (PAAS), on the other hand. The REE distribution demonstrates the same pattern. The IRS data points in Nb-Sr, Ni-Co, and Co-Sr and some other diagrams are close mainly to the average chemical composition of suspended particulate matter of the Ob and Lena rivers, i.e., waterways draining watersheds composed predominantly of sedimentary rocks. The Nb, Sr, Ni, and Co contents in the studied IRS samples are close to those in the PAAS. In accordance with this, we were able to conclude that the main provenance areas of the studied IRS samples are situated in the eastern part of the Laptev Sea and the East Siberian Sea, on shelf of which the erosion products of sedimentary and metamorphic rocks of the Verkhoyansk Fold Belt dominate.

Occurrence of Two Different Types of Paleoarchean TTGs in Singhbhum craton, Eastern India: Insight from Geochemistry and Zircon Saturation Thermometry

NASA Astrophysics Data System (ADS)

Mitra, A.; Dey, S.

2017-12-01

Paleoarchean era is marked as an active period of continental crust genesis. A large part of the paleoarchean crust is made up of grey sodic granitoids collectively referred as Tonalite Trondjhemite Granodiorite (TTG). Generation and evolution of TTGs are still highly debated, though researchers agree on their generation through partial melting of hydrated basalt at garnet or amphibole stability field. Discrete remnants of paleoarchean TTGs are exposed in several parts of the Singhbhum craton, eastern India. Our study exhibits occurrence of two different types of TTGs based on REE pattern in a chondrite normalized REE diagram. Accordingly, TTGs have been grouped into two different types, namely (1) High HREE TTG [low SiO2; high HREE avg. (Gd/Er)n=2.23; less fractionated REE avg. (La/Yb)n=27.9 and relatively low Sr/Y avg. Sr/Y=53.59] and Low HREE TTG [high SiO2; depleted HREE avg. (Gd/Er)n=3.23; steeply fractionated REE avg. (La/Yb)n=46.11 and relatively high Sr/Y avg. Sr/Y= 95.49]. The two types of TTGs mainly differ in pressure sensitive signatures like Sr/Y and (La/Yb)n ratio. Considering the major element composition both the types are consistent with a low-K mafic source. This indicates, melting occurred at different crustal levels from a same/similar source. Moderate Al2O3, high Sr contents coupled with depleted HREE and Y are linked to the presence of garnet in either residual or fractionating phase. However, HREE variation is controlled by the amount of Garnet retained in the restite. Thus, in spite of melting of the source rock in garnet stability field, only the minor change in depth of melting and in turn different amount of retention of garnet in the source caused the difference in HREE pattern. Zircon saturation temperature (TZr) calculated on the basis of whole rock Zr concentration ranges from 735˚C to 760 ˚C (avg. 749˚C) for high HREE TTG and 750 ˚C to 802˚C (avg. 773˚C) for low HREE TTG. Absence of zircon xenocryst depicts zircon undersaturated melt, thus calculated TZr provides minimum estimate of the real magma temperature. High temperature magmas (Low HREE) formed at deeper level retained more garnet in source compare to low temperature magma (High HREE). Hence, temperature difference in TTG magmas is consistent with differences in REE pattern and grouping of TTGs, considering a normal geothermal gradient.

Rare earth elements in freshwater, marine, and terrestrial ecosystems in the eastern Canadian Arctic.

PubMed

MacMillan, Gwyneth Anne; Chételat, John; Heath, Joel P; Mickpegak, Raymond; Amyot, Marc

2017-10-18

Few ecotoxicological studies exist for rare earth elements (REEs), particularly field-based studies on their bioaccumulation and food web dynamics. REE mining has led to significant environmental impacts in several countries (China, Brazil, U.S.), yet little is known about the fate and transport of these contaminants of emerging concern. Northern ecosystems are potentially vulnerable to REE enrichment from prospective mining projects at high latitudes. To understand how REEs behave in remote northern food webs, we measured REE concentrations and carbon and nitrogen stable isotope ratios (∂ 15 N, ∂ 13 C) in biota from marine, freshwater, and terrestrial ecosystems of the eastern Canadian Arctic (N = 339). Wildlife harvesting and tissue sampling was partly conducted by local hunters through a community-based monitoring project. Results show that REEs generally follow a coherent bioaccumulation pattern for sample tissues, with some anomalies for redox-sensitive elements (Ce, Eu). Highest REE concentrations were found at low trophic levels, especially in vegetation and aquatic invertebrates. Terrestrial herbivores, ringed seal, and fish had low total REE levels in muscle tissue (∑REE for 15 elements <0.1 nmol g -1 ), yet accumulation was an order of magnitude higher in liver tissues. Age- and length-dependent REE accumulation also suggest that REE uptake is faster than elimination for some species. Overall, REE bioaccumulation patterns appear to be species- and tissue-specific, with limited potential for biomagnification. This study provides novel data on the behaviour of REEs in ecosystems and will be useful for environmental impact assessment of REE enrichment in northern regions.

Anomalous REE patterns in unequilibrated enstatite chondrites: Evidence and implications

NASA Technical Reports Server (NTRS)

Crozaz, Ghislaine; Hsu, Weibiao

1993-01-01

We present here a study of Rare Earth Element (REE) microdistributions in unequilibrated enstatite chondrites (EOC's). Although the whole rock REE contents are similar in both unequilibrated and equilibrated chondrites, the host minerals of these refractory elements are different. In the least equilibrated ordinary chondrites (UOC's), the REE reside mainly in glass whereas, in their more equilibrated counterparts, the bulk of the REE is in calcium phosphate, a metamorphic mineral that formed by oxidation of phosphorous originally contained in metal. In the smaller group of enstatite (E) chondrites, calcium phosphate is absent and the phase that contains the highest REE concentrations is a minor mineral, CaS (oldhamite), which contains approximately 50 percent of the total Ca present. In E chondrites, elements typically considered to be lithophiles (such as Ca and Mn) occur in sulfides rather than silicates. This indicates formation under extremely reducing conditions, thus in a region of the solar nebula distinct from those that supplied the more abundant ordinary and carbonaceous chondrites. Previously, we observed a variety of REE patterns in the oldhamite of UEC's; they range from almost flat to some with pronounced positive Eu and Yb anomalies. Here, we searched for complementary REE patterns in other minerals from E chondrites and found them in the major mineral, enstatite. Whenever Eu and Yb anomalies are present in this mineral, they are always negative.

Rare earths in the Leadville Limestone and its marble derivates

USGS Publications Warehouse

Jarvis, J.C.; Wildeman, T.R.; Banks, N.G.

1975-01-01

Samples of unaltered and metamorphosed Leadville Limestone (Mississippian, Colorado) were analyzed by neutron activation for ten rare-earth elements (REE). The total abundance of the REE in the least-altered limestone is 4-12 ppm, and their distribution patterns are believed to be dominated by the carbonate minerals. The abundances of the REE in the marbles and their sedimentary precursors are comparable, but the distribution patterns are not. Eu is enriched over the other REE in the marbles, and stratigraphically upward in the formation (samples located progressively further from the heat source), the light REE become less enriched relative to the heavy REE. The Eu anomaly is attributed to its ability, unique among the REE, to change from the 3+ to 2+ oxidation state. Whether this results in preferential mobilization of the other REE or whether this reflects the composition of the pore fluid during metamorphism is unknown. Stratigraphically selective depletion of the heavy REE may be attributed to more competition for the REE between fluid and carbonate minerals in the lower strata relative to the upper strata. This competition could have been caused by changes in the temperature of the pore fluid or to the greater resistance to solution of the dolomite in the lower parts of the formation than the calcite in the upper parts. ?? 1975.

Petrography and geochemistry of clastic sedimentary rocks as evidences for provenance of the Lower Cambrian Lalun Formation, Posht-e-badam block, Central Iran

NASA Astrophysics Data System (ADS)

Etemad-Saeed, N.; Hosseini-Barzi, M.; Armstrong-Altrin, John S.

2011-09-01

Petrography and geochemistry (major, trace and rare earth elements) of clastic rocks from the Lower Cambrian Lalun Formation, in the Posht-e-badam block, Central Iran, have been investigated to understand their provenance. Petrographical analysis suggests that the Lalun conglomerates are dominantly with chert clasts derived from a proximal source, probably chert bearing Precambrian Formations. Similarly, purple sandstones are classified as litharenite (chertarenite) and white sandstones as quartzarenite types. The detrital modes of purple and white sandstones indicate that they were derived from recycled orogen (uplifted shoulders of rift) and stable cratonic source. Most major and trace element contents of purple sandstones are generally similar to upper continental crust (UCC) values. However, white sandstones are depleted in major and trace elements (except SiO 2, Zr and Co) relative to UCC, which is mainly due to the presence of quartz and absence of other Al-bearing minerals. Shale samples have considerably lower content in most of the major and trace elements concentration than purple sandstones, which is possibly due to intense weathering and recycling. Modal composition (e.g., quartz, feldspar, lithic fragments) and geochemical indices (Th/Sc, La/Sc, Co/Th, Cr/Th, Cr/V and V/Ni ratios) of sandstones, and shales (La/Sc and La/Cr ratios) indicate that they were derived from felsic source rocks and deposited in a passive continental margin. The chondrite-normalized rare earth element (REE) patterns of the studied samples are characterized by LREE enrichment, negative Eu anomaly and flat HREE similar to an old upper continental crust composed chiefly of felsic components in the source area. The study of paleoweathering conditions based on modal composition, chemical index of alteration (CIA), plagioclase index of alteration (PIA) and A-CN-K (Al 2O 3 - CaO + Na 2O - K 2O) relationships indicate that probably chemical weathering in the source area and recycling processes have been more important in shale and white sandstones relative to purple sandstones. The results of this study suggest that the main source for the Lalun Formation was likely located in uplifted shoulders of a rifted basin (probably a pull-apart basin) in its post-rift stage (Pan-African basement of the Posht-e-badam block).

Rare Earth Element Measurements of Melilite and Fassaite in Allende Cai by Nanosims

NASA Technical Reports Server (NTRS)

Ito, M.; Messenger, Scott

2009-01-01

The rare earth elements (REEs) are concentrated in CAIs by approx. 20 times the chondritic average [e.g., 1]. The REEs in CAIs are important to understand processes of CAI formation including the role of volatilization, condensation, and fractional crystallization [1,2]. REE measurements are a well established application of ion microprobes [e.g., 3]. However the spatial resolution of REE measurements by ion microprobe (approx.20 m) is not adequate to resolve heterogeneous distributions of REEs among/within minerals. We have developed methods for measuring REE with the NanoSIMS 50L at smaller spatial scales. Here we present our initial measurements of REEs in melilite and fassaite in an Allende Type-A CAI with the JSC NanoSIMS 50L. We found that the key parameters for accurate REE abundance measurements differ between the NanoSIMS and conventional SIMS, in particular the oxide-to-element ratios, the relative sensitivity factors, the energy distributions, and requisite energy offset. Our REE abundance measurements of the 100 ppm REE diopside glass standards yielded good reproducibility and accuracy, 0.5-2.5 % and 5-25 %, respectively. We determined abundances and spatial distributions of REEs in core and rim within single crystals of fassaite, and adjacent melilite with 5-10 m spatial resolution. The REE abundances in fassaite core and rim are 20-100 times CI abundance but show a large negative Eu anomaly, exhibiting a well-defined Group III pattern. This is consistent with previous work [4]. On the other hand, adjacent melilite shows modified Group II pattern with no strong depletions of Eu and Yb, and no Tm positive anomaly. REE abundances (2-10 x CI) were lower than that of fassaite. These patterns suggest that fassaite crystallized first followed by a crystallization of melilite from the residual melt. In future work, we will carry out a correlated study of O and Mg isotopes and REEs of the CAI in order to better understand the nature and timescales of its formation process and subsequent metamorphic history.

Rare earth elements in Hamersley BIF minerals

NASA Astrophysics Data System (ADS)

Alibert, Chantal

2016-07-01

Minerals from the Hamersley banded iron formation, Western Australia, were analyzed for Y and rare earth elements (YREEs) by laser ablation ICP-MS to investigate diagenetic pathways, from precursor phases to BIF minerals. One group of apatites carries the seawater REE signature, giving evidence that P and REEs, thoroughly scavenged from the water column by Si-ferrihydrite particles, were released upon microbial Fe3+ reductive dissolution of Si-ferrihydrite in pore-water and finally sequestered mainly in authigenic apatite. The absence of fractionation between apatite and seawater suggests that REE were first incorporated into an amorphous calcium phosphate as fully hydrated cations, i.e. as outer-sphere complexes. The iron oxides and carbonates carry only a small fraction of the whole-rock REE budget. Their REE patterns are distinctly enriched in Yb and show some M-type tetrad effect consistent with experimental Kd(REE) between solid and saline solution with low carbonate ion concentrations. It is deduced that hematite formed at an incipient stage of Fe2+-catalyzed dissolution of Si-ferrihydrite, via a dissolution-reprecipitation pathway. The REE pattern of greenalite, found as sub-micron particles in quartz in a chert-siderite sample, is consistent with its authigenic origin by precipitation in pore-water after dissolution of a small amount of Si-ferrihydrite. Magnetite carries very low YREEs (ppb-level), has an homogeneous pattern distinctly enriched in the mid-REEs compared to hematite, and includes a late population depleted in light-REEs, Ba and As. Magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid-aided hematite-magnetite re-equilibration or transformation at low-grade metamorphic temperatures.

Geochemical constraints on the petrogenesis of the pyroclastic rocks in Abakaliki basin (Lower Benue Rift), Southeastern Nigeria

NASA Astrophysics Data System (ADS)

Chukwu, Anthony; Obiora, Smart C.

2018-05-01

The pyroclastic rocks in the Cretaceous Abakaliki basin occur mostly as oval-shaped bodies, consisting of lithic/lava and vitric fragments. They are commonly characterized by parallel and cross laminations, as well contain xenoliths of shale, mudstone and siltstones from the older Asu River Group of Albian age. The rocks are basic to ultrabasic in composition, comprising altered alkali basalts, altered tuffs, minor lapillistones and agglomerates. The mineral compositions are characterized mainly by laths of calcic plagioclase, pyroxene (altered), altered olivines and opaques. Calcite, zeolite and quartz represent the secondary mineral constituents. Geochemically, two groups of volcaniclastic rocks, are distinguished: alkaline and tholeiitic rocks, both represented by fresh and altered rock samples. The older alkali basalts occur within the core of the Abakaliki anticlinorium while the younger tholeiites occur towards the periphery. Though most of the rocks are moderate to highly altered [Loss on ignition (LOI, 3.43-22.07 wt. %)], the use of immobile trace element such as Nb, Zr, Y, Hf, Ti, Ta and REEs reflect asthenospheric mantle source compositions. The rocks are enriched in incompatible elements and REEs (∑REE = 87.98-281.0 ppm for alkaline and 69.45-287.99 ppm for tholeiites). The ratios of La/Ybn are higher in the alkaline rocks ranging from 7.69 to 31.55 compared to the tholeiitic rocks which range from 4.4 to 16.89 and indicating the presence of garnet-bearing lherzolite in the source mantle. The spidergrams and REEs patterns along with Zr/Nb, Ba/Nb, Rb/Nb ratios suggest that the rocks were generated by a mantle plume from partial melting of mixed enriched mantle sources (HIMU, EMI and EMII) similar to the rocks of the south Atlantic Ocean such as St. Helena (alkaline rocks) and Ascension rocks (tholeiitic rocks). The rocks were formed in a within-plate setting of the intra-continental rift type similar to other igneous rocks in the Benue Rift and are not related to any subduction event as previously suggested.

Weathering behavior of REE-Y in a granitic soil profile (Case of Strengbach watershed)

NASA Astrophysics Data System (ADS)

Gangloff, Sophie; Stille, Peter; Chabaux, François

2017-04-01

Rare earth elements and yttrium (REE-Y) can be used as tracers of bedrock weathering and soil formation. One of the aims of this study is to better understand the different phenomena which impact the REE-Y mobilization and modify the REE-Y pattern along a soil profile. Our study has been performed on a granitic soil profile and soil solutions corresponding, sampled in a forest parcel covered with spruces from the Strengbach catchment. The behavior of the REE-Y pattern are compared with previously published results. The samples were collected from 2009 to 2013 and ultra-filtered to determine the spatial and temporal influence as well as that of the colloidal and dissolved fractions on the evolution of the REE-Y patterns. The EFTi of the soil indicates that during alteration process, phosphate minerals and zircon might be dissolved and induce the formation of secondary mineral phase like xenotime in the deeper soil horizons. The ultra-filtered soil solutions from humic horizon show that the REE-Y are principally enriched in the colloidal fraction controlling the REE-Y dynamic while in the deeper soil solutions colloidal and dissolved fractions influence the REE-Y. The mobility of REE-Y is controlled by the dissolution of the zircon and phosphate minerals, the precipitation of the REE-Y(PO4) and the evolution of OC with depth. The comparative study of the soil profile, soil water extracts and soil solutions show that (Eu*/Eu)DS anomaly reflects weathering of plagioclase in the micropores and the migration of the released Eu to the macropores, the (Ce*/Ce) anomaly, is stabilized by the electron shuttling of the humic acid (aromaticity) and provides information on the redox conditions only in the deeper soil horizons depleted in humic acid and finally the HREE enrichment in the deeper soil solutions results from the partial dissolution of secondary minerals in the upper soil horizons (above 30 cm depth).

Watson: A new link in the IIE iron chain

NASA Technical Reports Server (NTRS)

Olsen, Edward; Davis, Andrew; Clarke, Roy S., Jr.; Schultz, Ludolf; Weber, Hartwig W.; Clayton, Robert; Mayeda, Toshiko; Jarosewich, Eugene; Sylvester, Paul; Grossman, Lawrence

1994-01-01

Watson, which was found in 1972 in South Australia, contains the largest single silicate rock mass seen in any known iron meteorite. A comprehensive study has been completed on this unusual meteorite: petrography, metallography, analyses of the silicate inclusion (whole rock chemical analysis, INAA, RNAA, noble gases, and oxygen isotope analysis) and mineral compositions (by electron microprobe and ion microprobe). The whole rock has a composition of an H-chondrite minus the normal H-group metal and troilite content. The oxygen isotope composition is that of the silicates in the IIE iron meteorites and lies along an oxygen isotope fractionation line with the H-group chondrites. Trace elements in the metal confirm Watson is a new IIE iron. Whole rock Watson silicate shows an enrichment in K and P (each approximately 2X H-chondrites). The silicate inclusion has a highly equilibrated igneous (peridotite-like) texture with olivine largely poikilitic within low-Ca pyroxene: olivine (Fa20), opx (Fs17Wo3), capx (Fs9Wo14)(with very fine exsolution lamellae), antiperthite feldspar (An1-3Or5) with less than 1 micron exsolution lamellae (An1-3Or greater than 40), shocked feldspar with altered stoichiometry, minor whitlockite (also a poorly characterized interstitial phosphate-rich phase) and chromite, and only traces of metal and troilite. The individual silicate minerals have normal chondritic REE patterns, but whitlockite has a remarkable REE pattern. It is very enriched in light REE (La is 720X C1, and Lu is 90X C1, as opposed to usual chonditic values of approximately 300X and 100-150X, respectively) with a negative Eu anomaly. The enrichment of whole rock K is expressed both in an unusually high mean modal Or content of the feldspar, Or13, and in the presence of antiperthite.

Provenance and geochemical behavior of fluorine in the soils of an endemic fluorosis belt, central Iran

NASA Astrophysics Data System (ADS)

Dehbandi, Reza; Moore, Farid; Keshavarzi, Behnam

2017-05-01

The concentration of fluorine, major, trace and rare earth elements (REEs) were used to estimate the probable sources and provenance of fluorine in the soils of an endemic fluorosis belt in central Iran. Total fluorine (TF) in soils varied from 146 to 406 mg/kg with a mean of 277.5 mg/kg. Calculated enrichment factor (EF) and single factor pollution index (SFPI) revealed that the majority of soil samples were moderately contaminated by fluorine. The very strong positive correlation of TF with weathering indices and soil's fine sized fractions indicated that chemical weathering and alteration of parent rocks/soils are the main controlling factors of fluorine behavior in soils. Fluorine affinity to immobile transition trace elements and REEs suggested the role of heavy minerals as the potential F host phases. Modal mineralogy along with SEM-EDX analysis indicated that apatite, fluorapophyllite, epidote, biotite, muscovite and chlorite, as well as, clay minerals are the main F-bearing minerals in the studied soils. Discriminant, bivariate and ternary diagrams of elemental compositions displayed similar geochemical signature of soils to intermediate-acidic rocks and local shales. Based on the weathering indices, soils were immature and showed a non-steady state weathering trend from upper continental crust (UCC), acidic and intermediate igneous source rocks towards shale composition possibly due to mixing of moderately weathered and un-weathered sources of different primary compositions.

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

NASA Astrophysics Data System (ADS)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle forming sub-surface injections or surface flows. These ores have formed during magmatism as immiscible liquids (silicate and Fe-P-rich magmatic liquids) which separated from strongly differentiated magmas aided by a large volatile and alkali element content. Separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits. We proposed that the separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits.

Crystallization process of zircon and fergusonite during hydrothermal alteration in Nechalacho REE deposit, Thor Lake, Canada

NASA Astrophysics Data System (ADS)

Hoshino, M.; Watanabe, Y.; Murakami, H.; Kon, Y.; Tsunematsu, M.

2012-04-01

The core samples of two drill holes, which penetrate sub-horizontal mineralized horizons at Nechalacho REE deposit in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify magmatic and hydrothermal processes that enriched HFSE (e.g. Zr, Nb, Y and REE). Zircon is the most common REE minerals in Nechalacho REE deposit. The zircon is divided into five types as follows: Type-1 zircon occurs as single grain in phlogopite and the chondrite-normalized REE pattern is characterized by a steeply-rising slope from the LREE to the HREE with a positive Ce-anomaly and negative Eu-anomaly. This chemical characteristic is similar to that of igneous zircon. Type-2 zircon consists of HREE-rich magmatic porous core and LREE-Nb-F-rich hydrothermal rim. This type zircon is mostly included in phlogopite and fluorite, and occasionally in microcline. Type-3 zircon is characterized by euhedral to anhedral crystal, occurring in a complex intergrowth with REE fluorocarbonates. Type-3 zircons have high contents of REE, Nb and fluorine. Type-4 zircon consists of porous-core and -rim zones, but their chemical compositions are similar to each other. This type zircon is a subhedral crystal rimmed by fergusonite. Type-5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircons are filled by fergusonite. Type-4 and -5 zircons show low REE and Nb contents. Occurrences of these five types of zircon are different according to the depth and degree of the alteration by hydrothermal solutions rich in F- and CO3 of the two drill holes, which permit a model for evolution of the zircon crystallization in Nechalacho REE deposit as follows: (1) type-1 (single magmatic zircon) is formed in miaskitic syenite. (2) LREE-Nb-F-rich hydrothermal zircon formed around HREE-rich magmatic zircon (type-2 zircon); (3) type-3 zircon crystallized thorough F and CO3-rich hydrothermal alteration of type-2 zircon which formed the complex intergrowth with REE fluorocarbonates; (4) the CO3-rich hydrothermal fluid corroded type-3, forming Nb-REE-poor zircons (type-3). Niobium and REE was no longer stable in the zircon structure and crystallized as fergusonite around the REE-Nb-leached zircon (type-4); (5) type-5 zircons are formed from more CO3-rich hydrothermal alteration of type-3 zircon. Therefore, type-4 and -5 zircons are often included in ankerite. Type 3-5 zircons at Nechalacho REE deposit were formed by leaching and/or dissolution of type-2 zircon in the presence of F- and/or CO3-rich hydrothermal fluid. The above mineral association indicates that three hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (1) F-rich hydrothermal stage caused the crystallization of REE-Nb-rich zircon (type-2 rim and type-3), with abundant formation of phlogophite and fluorite, (2) F-CO3-rich hydrothermal stage led to the replacement of a part of REE-Nb-F-rich zircon by REE fluorocarbonate and (3) hydrothermal stage rich in CO3 resulted in crystallization of REE-Nb-F-poor zircon and fergusonite, with ankerite. Increases of HFSE contents, REE-Nb-F-poor zircon (type-4 and -5) and fergusonite contents during progress of hydrothermal alteration show that REE and Nb in hydrothermal fluid in the Nechalacho REE deposit were finally concentrated into fergusonite by way of zircon.

Distribution characteristics of rare earth elements in children's scalp hair from a rare earths mining area in southern China.

PubMed

Tong, Shi-Lu; Zhu, Wang-Zhao; Gao, Zhao-Hua; Meng, Yu-Xiu; Peng, Rui-Ling; Lu, Guo-Cheng

2004-01-01

In order to demonstrate the validity of using scalp hair rare earth elements (REEs) content as a biomarker of human REEs exposure, data were collected on REEs exposure levels from children aged 11-15 years old and living in an ion-adsorptive type light REEs (LREEs) mining and surrounding areas in southern China. Sixty scalp hair samples were analyzed by ICP-MS for 16 REEs (La Lu, Y and Sc). Sixteen REEs contents in the samples from the mining area (e.g., range: La: 0.14-6.93 microg/g; Nd: 0.09-5.27 microg/g; Gd: 12.2-645.6ng/g; Lu: 0.2-13.3 ng/g; Y: 0.03-1.27 microg/g; Sc: 0.05-0.30 microg/g) were significantly higher than those from the reference area (range: La: 0.04-0.40 microg/g; Nd: 0.04-0.32 microg/g; Gd: 8.3-64.6 ng/g; Lu: 0.4-3.3ng/g; Y: 0.03-0.29 microg/g; Sc: 0.11-0.36 microg/g) and even much higher than those published in the literature. The distribution pattern of REEs in scalp hair from the mining area was very similar to that of REEs in the mine and the atmosphere shrouding that area. In conclusion, the scalp hair REEs contents may indicate not only quantitatively but also qualitatively (distribution pattern) the absorption of REEs from environmental exposure into human body. The children living in this mining area should be regarded as a high-risk group with REEs (especially LREEs) exposure, and their health status should be examined from a REEs health risk assessment perspective.

Fusion Bead Procedure for Nuclear Forensics Employing Synthetic Enstatite to Dissolve Uraniferous and Other Challenging Materials Prior to Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

PubMed

Reading, David G; Croudace, Ian W; Warwick, Phillip E

2017-06-06

There is an increasing demand for rapid and effective analytical tools to support nuclear forensic investigations of seized or suspect materials. Some methods are simply adapted from other scientific disciplines and can effectively be used to rapidly prepare complex materials for subsequent analysis. A novel sample fusion method is developed, tested, and validated to produce homogeneous, flux-free glass beads of geochemical reference materials (GRMs), uranium ores, and uranium ore concentrates (UOC) prior to the analysis of 14 rare earth elements (REE) via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The novelty of the procedure is the production of glass beads using 9 parts high purity synthetic enstatite (MgSiO 3 ) as the glass former with 1 part of sample (sample mass ∼1.5 mg). The beads are rapidly prepared (∼10 min overall time) by fusing the blended mixture on an iridium strip resistance heater in an argon-purged chamber. Many elements can be measured in the glass bead, but the rare earth group in particular is a valuable series in nuclear forensic studies and is well-determined using LA-ICP-MS. The REE data obtained from the GRMs, presented as chondrite normalized patterns, are in very good agreement with consensus patterns. The UOCs have comparable patterns to solution ICP-MS methods and published data. The attractions of the current development are its conservation of sample, speed of preparation, and suitability for microbeam analysis, all of which are favorable for nuclear forensics practitioners and geochemists requiring REE patterns from scarce or valuable samples.

Large sedimentary aquifer systems functioning. Constraints by classical isotopic and chemical tools, and REE in the Eocene sand aquifer, SW France

NASA Astrophysics Data System (ADS)

Petelet-Giraud, E.; Negrel, P. J.; Millot, R.; Guerrot, C.; Brenot, A.; Malcuit, E.

2010-12-01

Large sedimentary aquifer systems often constitute strategic water resources for drinking water supply, agriculture irrigation and industry, but can also represent an energetic resource for geothermal power. Large water abstractions can induce complete modification of the natural functioning of such aquifer systems, e.g. with seepage between aquifer layers that can lead to water quality degradation. These large aquifer systems thus require rational water management at the sedimentary basin scale in order to preserve both water quantity and quality. In addition to hydrogeological modelling mainly dealing with water quantity, chemical and isotopic methods were applied to evidence the spatial variability of water characteristics and to turn this into better understanding of hydrosystems functioning. The large Eocene Sand aquifer system of the Adour-Garonne sedimentary basin was studied through various hydrological, chemical and isotopic tools. This system extends over 116,000 km2 (one-fifth of the French territory, located in the South west part). The aquifer being artesian in the west of the district and confined with piezometric levels around 250-m depth in the east. The ‘Eocene Sands’, composed of sandy Tertiary sediments alternating with carbonate deposits, is a multi-layer system with high permeability and a thickness of several tens of metres to a hundred metres..The Eocene Sand aquifer system comprises at least five aquifers: Paleocene, Eocene infra-molassic sands (IMS), early Eocene, middle Eocene, and late Eocene. According to δ18O and δ2H values and estimated 14C ages, both present-day recharge (mainly located in the north of the area) and old recharge (16-35 ky) can be evidenced. High spatial variability was evidenced within a same aquifer layer, with temporal variability over one hydrological cycle limited to a few points located in the recharge areas. These results and especially the very old waters recharged under colder climate combined with the continuous decrease of water levels in the IMS aquifer for instance constitute major indicators to be taken into account for water management at the aquifer system scale. Major elements variability was interpreted in terms of water-rock interactions in these confined systems isolated from anthropogenic influence, with the main role played by evaporites on the water salinity (up to 2.5 g.L-1). Rare Earth Elements (REE) were also analysed in some groundwater samples, resulting in a large variability of UCC normalized-REE patterns, ΣREE ranging from 1.9 to 50.6 µg.L-1, with no dependence on TDS. For instance, interaction with carbonates delivers REE flat patterns and highest ΣREE. The REE patterns and control by key parameters are investigated in order to test REE as a potential supplementary geochemical tracer to recognize the aquifer type hosting groundwater.

Tracking the depleted mantle signature in melt inclusions and host glass of basaltic martian shergottites using secondary ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Peters, T. J.; Simon, J. I.; Jones, J. H.; Usui, T.; Economos, R. C.; Schmitt, A. K.; McKeegan, K. D.

2013-12-01

Trace element abundances of depleted shergottite magmas recorded by olivine-hosted melt inclusions (MI) and interstitial mesostasis glass were measured using the CAMECA ims-1270 ion microprobe. Two meteorites: Tissint, an olivine-phyric basaltic shergottite which fell over Morocco July 18th 2001; and the Antarctic meteorite Yamato 980459 (Y98), an olivine-phyric basaltic shergottite with abundant glassy mesostasis have been studied. Chondrite-normalized REE patterns for MI in Tissint and Y98 are characteristically LREE depleted and, within analytical uncertainty, parallel those of their respective whole rock composition; supporting each meteorite to represent a melt composition that has experienced closed-system crystallization. REE profiles for mesostasis glass in Y98 lie about an order of magnitude higher than those from the MI; with REE profiles for Tissint MI falling in between. Y98 MI have the highest average Sm/Nd and Y/Ce ratios, reflecting their LREE depletion and further supporting Y98 as one of our best samples to probe the depleted shergotitte mantle. In general, Zr/Nb ratios overlap between Y98 and Tissint MI, Ce/Nb ratios overlap between Y98 MI and mesostasis glass, and Sm/Nd ratios overlap between Y98 mesostasis glass and Tissint MI. These features support similar sources for both, but with subtle geochemical differences that may reflect different melting conditions or fractionation paths during ascent from the mantle. Interestingly, the REE patterns for all analyses in Y98 and possibly for those from Tissint as well display a flattening of the LREE that suggests an early crustal contribution to the shergottite mantle.

Tracking the Depleted Mantle Signature in Melt Inclusions and Residual Glass of Basaltic Martian Shergottites using Secondary Ionization Mass Spectrometry

NASA Technical Reports Server (NTRS)

Peters, Timothy J.; Simon, Justin I.; Jones, John H.; Usui, Tomohiro; Economos, Rita C.; Schmitt, Axel K.; McKeegan, Kevin D.

2013-01-01

Trace element abundances of depleted shergottite magmas recorded by olivine-hosted melt inclusions (MI) and interstitial mesostasis glass were measured using the Cameca ims-1270 ion microprobe. Two meteorites: Tissint, an olivine-­phyric basaltic shergottite which fell over Morocco July 18th 2001; and the Antarctic meteorite Yamato 980459 (Y98), an olivine-phyric basaltic shergottite with abundant glassy mesostasis have been studied. Chondrite-­normalized REE patterns for MI in Tissint and Y98 are characteristically LREE depleted and, within analytical uncertainty, parallel those of their respective whole rock composition; supporting each meteorite to represent a melt composition that has experienced closed-­system crystallization. REE profiles for mesostasis glass in Y98 lie about an order of magnitude higher than those from the MI; with REE profiles for Tissint MI falling in between. Y98 MI have the highest average Sm/Nd and Y/Ce ratios, reflecting their LREE depletion and further supporting Y98 as one of our best samples to probe the depleted shergotitte mantle. In general, Zr/Nb ratios overlap between Y98 and Tissint MI, Ce/Nb ratios overlap between Y98 MI and mesostasis glass, and Sm/Nd ratios overlap between Y98 mesostasis glass and Tissint MI. These features support similar sources for both, but with subtle geochemical differences that may reflect different melting conditions or fractionation paths during ascent from the mantle. Interestingly, the REE patterns for both Y98 bulk and MI analyses display a flattening of the LREE that suggests a crustal contribution to the Y98 parent melt. This observation has important implications for the origins of depleted and enriched shergottites.

Source and path identification of metals pollution in a mining area by PMF and rare earth element patterns in road dust.

PubMed

Tian, Shuhan; Liang, Tao; Li, Kexin; Wang, Lingqing

2018-08-15

To better assess pollution and offer efficient protection for local residents, it is necessary to both conduct an exhaustive investigation into pollution levels and quantify its contributing sources and paths. As it is the biggest light rare earth element (REE) reserve in the world, Bayan Obo deposit releases large amounts of heavy metals into the surrounding environment. In this study, road dust from zones located at different distances to the mining area was collected and sieved using seven sizes. This allowed for subsequent analysis of size-dependent influences of mining activities. A receptor model was used to quantitatively assess mine contributions. REE distribution patterns and other REE parameters were compared with those in airborne particulates and the surrounding soil to analyze pollution paths. Results showed that 27 metals were rated as moderately to extremely polluted (2

The association of a high drive for thinness with energy deficiency and severe menstrual disturbances: confirmation in a large population of exercising women.

PubMed

Gibbs, Jenna C; Williams, Nancy I; Scheid, Jennifer L; Toombs, Rebecca J; De Souza, Mary Jane

2011-08-01

A high drive-for-thinness (DT) score obtained from the Eating Disorder Inventory-2 is associated with surrogate markers of energy deficiency in exercising women. The purposes of this study were to confirm the association between DT and energy deficiency in a larger population of exercising women that was previously published and to compare the distribution of menstrual status in exercising women when categorized as high vs. normal DT. A high DT was defined as a score ≥7, corresponding to the 75th percentile for college-age women. Exercising women age 22.9 ± 4.3 yr with a BMI of 21.2 ± 2.2 kg/m2 were retrospectively grouped as high DT (n = 27) or normal DT (n = 90) to compare psychometric, energetic, and reproductive characteristics. Chi-square analyses were performed to compare the distribution of menstrual disturbances between groups. Measures of resting energy expenditure (REE) (4,949 ± 494 kJ/day vs. 5,406 ± 560 kJ/day, p < .001) and adjusted REE (123 ± 16 kJ/LBM vs. 130 ± 9 kJ/LBM, p = .027) were suppressed in exercising women with high DT vs. normal DT, respectively. Ratio of measured REE to predicted REE (pREE) in the high-DT group was 0.85 ± 0.10, meeting the authors' operational definition for an energy deficiency (REE:pREE <0.90). A greater prevalence of severe menstrual disturbances such as amenorrhea and oligomenorrhea was observed in the high-DT group (χ2 = 9.3, p = .003) than in the normal-DT group. The current study confirms the association between a high DT score and energy deficiency in exercising women and demonstrates a greater prevalence of severe menstrual disturbances in exercising women with high DT.

The potential of sedimentary foraminiferal rare earth element patterns to trace water masses in the past

NASA Astrophysics Data System (ADS)

Osborne, Anne H.; Hathorne, Ed C.; Schijf, Johan; Plancherel, Yves; Böning, Philipp; Frank, Martin

2017-04-01

Dissolved rare earth element (REE) concentration data from intermediate and deep seawater form an array characterized by higher middle-REE enrichments (MREE/MREE*) in the North Atlantic and a progressive increase in heavy-to-light REE ratios (HREE/LREE) as water masses age. The REEs in foraminifera are fractionated toward higher MREE/MREE* and lower HREE/LREE relative to seawater. Calculations based on a scavenging model show that the REE patterns in uncleaned core-top foraminifera resemble those adsorbed onto calcite, particulate organic material, and hydrous ferric oxides but the full extent of the REE fractionation measured in foraminifera was not reproduced by the model. However, differences in the HREE/LREE and MREE/MREE* ratios and the cerium anomaly between ocean basins are preserved and are in agreement with the seawater REE distribution. Under oxic conditions, the HREE/LREE and MREE/MREE* compositions of uncleaned foraminifera at the sediment/seawater boundary are preserved during burial but the cerium anomaly is sensitive to burial depth. In suboxic sedimentary environments, all uncleaned foraminiferal REE concentrations are elevated relative to core-top values indicating addition of REEs from pore waters. The HREE/LREE ratio is highest when sedimentation rates were greatest and when high Fe/Ca ratios in the uncleaned foraminifera indicate that Fe was mobile. In sediments that have not experienced suboxic conditions during burial, uncleaned foraminifera preserve the seawater signal taken up at the sediment/seawater interface and are therefore suggested to be a suitable archive of changes in the REE signal of past bottom waters.

Fish debris record the hydrothermal activity in the Atlantis II deep sediments (Red Sea)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oudin, E.; Cocherie, A.

1988-01-01

The REE and U, Th, Zr, Hf, Sc have been analyzed in samples from Atlantis II and Shaban/Jean Charcot Deeps in the Red Sea. The high Zr/Hf ratio in some sediments indicates the presence of fish debris or of finely crystallized apatite. The positive ..sigma..REE vs P/sub 2/O/sub 5/ and ..sigma..REE vs Zr/Hf correlations show that fish debris and finely crystallized apatite are the main REE sink in Atlantis II Deep sediments as in other marine environments. The hydrothermal sediments and the fish debris concentrates have similar REE patterns, characterized by a LREE enrichment and a large positive Eu anomaly.more » This REE pattern is also observed in E.P.R. hydrothermal solutions. Fish debris from marine environments acquire their REE content and signature mostly from sea water during early diagenesis. The hydrothermal REE signature of Atlantis II Deep fish debris indicate that they probably record the REE signature of their hydrothermal sedimentation and diagenetic environment. The different REE signatures of the Shaban/Jean Charcot and Atlantis II Deep hydrothermal sediments suggest a sea water-dominated brine in the Shaban/Jean Charcot Deep as opposed to the predominantly hydrothermal brine in Atlantis II Deep. Atlantis II Deep fish debris are also characterized by their high U but low Th contents. Their low Th contents probably reflect the low Th content of the various possible sources (sea water, brine, sediments). Their U contents are probably controlled by the redox conditions of sedimentation.« less

Rare earth element behavior during groundwater – seawater mixing along the Kona Coast of Hawaii

USGS Publications Warehouse

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph; Prouty, Nancy G.; Swarzenski, Peter W.; Chevis, Darren A.; Telfeyan, Katherine; White, Christopher D.; Burdige, David J.

2017-01-01

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previous investigations showed that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries. Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were mixed with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO3)2-] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Taken together, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3 – 2.6 mmol Nd day-1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.

Rare earth element behavior during groundwater–seawater mixing along the Kona Coast of Hawaii

DOE PAGES

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph; ...

2016-11-14

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previously we saw that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries.more » Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were conducted with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO 3) 2 -] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Altogether, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3–2.6 mmol Nd day -1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.« less

Rare earth element behavior during groundwater–seawater mixing along the Kona Coast of Hawaii

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previously we saw that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries.more » Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were conducted with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO 3) 2 -] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Altogether, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3–2.6 mmol Nd day -1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.« less

Host-rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo REEFe-Nb ore deposit, Inner Mongolia, P.R.C.

USGS Publications Warehouse

Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Yinchen, R.

1992-01-01

Bayan Obo, a complex rare earth element (REE)FeNb ore deposit, located in Inner Mongolia, P.R.C. is the world's largest known REE deposit. The deposit is chiefly in a marble unit (H8), but extends into an overlying unit of black shale, slate and schist unit (H9), both of which are in the upper part of the Middle Proterozoic Bayan Obo Group. Based on sedimentary structures, the presence of detrital quartz and algal fossil remains, and the 16-km long geographic extent, the H8 marble is a sedimentary deposit, and not a carbonatite of magmatic origin, as proposed by some previous investigators. The unit was weakly regionally metamorphosed (most probably the lower part of the green schist facies) into marble and quartzite prior to mineralization. Tectonically, the deposit is located on the northern flank of the Sino-Korean craton. Many hypotheses have been proposed for the origin of the Bayan Obo deposit; the studies reported here support an epigenetic, hydrothermal, metasomatic origin. Such an origin is supported by field and laboratory textural evidence; 232Th/208Pb internal isochron mineral ages of selected monazite and bastnaesite samples; 40Ar/39Ar incremental heating minimum mineral ages of selected alkali amphiboles; chemical compositions of different generations of both REE ore minerals and alkali amphiboles; and evidence of host-rock influence on the various types of Bayan Obo ores. The internal isochron ages of the REE minerals indicate Caledonian ages for various episodes of REE and Fe mineralization. No evidence was found to indicate a genetic relation between the extensive biotite granitic rocks of Hercynian age in the mine region and the Bayan Obo are deposit, as suggested by previous workers. ?? 1992.

Petrology and Geochemistry of Tethyan Mélange and Flysch Units Adjacent to the Yarlung Zangbo Suture Zone (YZSZ), Southern Tibet

NASA Astrophysics Data System (ADS)

Dupuis, C.; Hebert, R.; Wang, C.; Li, Y.; Li, Z.

2004-05-01

Located north of the Himalayas, the E-W trending YZSZ is mainly composed of remnants of the Neo-Tethys ocean-floor and marks the suture between Indian and Eurasian plates. This project aims to define geological units immediately South of the YZSZ ophiolites : the serpentinized ophiolitic mélange, the Jurassic-Cretaceous wildflysch and the Triassic flysch. The ophiolitic mélange is characterized by ultramafic rocks, which can be divided into 3 groups. Cpx-harzburgites contain brownish aluminous spinels with Mg# of 0.7-0.75 and Cr# of 0.15-0.27. They resemble fertile abyssal peridotites with generally smooth LREE-depleted and fairly flat MREE-HREE profiles. Transitional harzburgites contain reddish spinels with Mg# of 0.57-0.66 and Cr# of 0.35-0.46. They resemble depleted abyssal or supra-subduction zone peridotites in that MREE-HREE profiles have positive slopes indicative of high degrees of partial melting. LREE profiles vary from depleted to slightly enriched, consistent with some trapped or interacting melt or aqueous fluids. Harzburgites and dunites contain dark reddish spinels with Mg# of 0.47-0.68 and Cr# of 0.40-0.63. They have U-shaped profiles characteristics of interaction between LREE-enriched melt and REE-depleted mantle residues. Spinel compositions and fractional melting modelling indicate that Cpx-harburgites may be the residues from 5-15% melting, transitional harzburgites from 15-23% melting, and harzburgites and dunites from 22-29% melting. The South Sandwich arc-basin system is considered a modern analog of initial geodynamic setting. Mafic rocks (gabbros, diabases and basalts) are ubiquitous and can be geochemically subdivided according to their source unit. LREE-depleted profiles with average (La/Yb)N of 0.5 and slight negative Nb-Ta and Ti anomalies indicate that rocks from the ophiolitic mélange formed in a back-arc basin, such as back-arc-basin mafic rocks of the Izu-Bonin Arc. REE patterns of rocks from the wildflysch are LREE-enriched with average (La/Yb)N of 5.3. These rocks are of intraplate affinity and are geochemically similar to volcanic rocks of the South Tethyan suture zone of Pakistan, which are interpreted to represent an early expression of the Réunion hotspot. Rocks from the flysch show the most LREE-enriched profiles with average (La/Yb)N of 6.9 and slight negative Nb-Ta and Ti anomalies, which suggest continental lithospheric assimilation. Similarly to volcanic rocks of the Deccan Traps, these rocks are thus interpreted to derive from an enriched mantle source of intraplate type (Réunion hotspot?), with additional contamination from the Indian continental crust (ICC). The geochemical signature of greywackes, red and black shales from the wildflysch and flysch units are all concordant with a continental passive margin setting. Despite fairly important chemical weathering, the signature was not affected by significant sedimentary recycling nor heavy-mineral accumulation. REE patterns show a LREE enrichment typical of shales and indicate an old upper CC provenance for the turbidites. Multi-element patterns indicate both mafic and felsic contributions to the source. The mafic contribution (slight positive Ti anomalies) could originate from mafic blocks of enriched intraplate geochemical affinity found in the sedimentary units, whereas the felsic contribution (slight LREE enrichment and negative NB-Ta anomalies) probably derives from remnants of evolved migmatitic batholith of the ICC.

Geochemical and Geochronologic Investigations of Zircon-hosted Melt Inclusions in Rhyolites from the Mesoproterozoic Pea Ridge IOA-REE Deposit, St. Francois Mountains, Missouri

NASA Astrophysics Data System (ADS)

Watts, K. E.; Mercer, C. N.; Vazquez, J. A.

2015-12-01

Silicic volcanic and plutonic rocks of an eroded Mesoproterozoic caldera complex were intruded and replaced by iron ore, and cross-cut by REE-enriched breccia pipes (~12% total REO) to form the Pea Ridge iron-oxide-apatite-REE (IOA-REE) deposit. Igneous activity, iron ore formation, and REE mineralization overlapped in space and time, however the source of REEs and other metals (Fe, Cu, Au) integral to these economically important deposits remains unclear. Melt inclusions (MI) hosted in refractory zircon phenocrysts are used to constrain magmatic components and processes in the formation of the Pea Ridge deposit. Homogenized (1.4 kbar, 1000°C, 1 hr) MI in zircons from rhyolites ~600 ft (PR-91) and ~1200 ft (PR-12) laterally from the ore body were analyzed for major elements by EPMA and volatiles and trace elements (H2O, S, F, Cl, REEs, Rb, Sr, Y, Zr, Nb, U, Th) by SHRIMP-RG. Metals (including Cu, Au) will be measured in an upcoming SHRIMP-RG session. U-Pb ages, Ti and REE were determined by SHRIMP-RG for a subset of zircon spots adjacent to MI (1458 ± 18 Ma (PR-12); 1480 ± 45 Ma (PR-91)). MI glasses range from fresh and homogeneous dacite-rhyolite (65-75 wt% SiO2) to heterogeneous, patchy mixtures of K-spar and quartz (PR-12, 91), and more rarely mica, albite and/or anorthoclase (PR-91). MI are commonly attached to monazite and xenotime, particularly along re-entrants and zircon rims (PR-91). Fresh dacite-rhyolite glasses (PR-12) have moderate H2O (~2-2.5 wt%), Rb/Sr ratios (~8) and U (~5-7 ppm), and negative (chondrite-normalized) Eu anomalies (Eu ~0.4-0.7 ppm) (typical of rhyolites), whereas HREEs (Tb, Ho, Tm) are elevated (~2-3 ppm). Patchy K-spar and quartz inclusions (PR-12, 91) have flat LREE patterns, and positive anomalies in Tb, Ho, and Tm. One K-spar inclusion (PR-91) has a ~5-50 fold increase in HREEs (Tb, Dy, Ho, Er, Tm) and U (35 ppm) relative to other MI. U-Pb and REE analyses of its zircon host are not unusual (1484 ± 21 Ma); its irregular shape surrounded by a CL-bright zone (Ti-in-zircon = 713°C) is a commonly observed texture and suggests resorption. Silicic magmatism at Pea Ridge was complex, with zircons trapping both pristine melt and poly-phase mixtures that span a range of REE contents. Most MI have lower REE contents than would be expected for significant magmatic REE contribution to the Pea Ridge IOA-REE deposit.

Rare earth elements in pore waters from Cabo Friós western boundary upwelling system

NASA Astrophysics Data System (ADS)

Smoak, J. M.; Silva-Filho, E. V.; Rousseau, T.; Albuquerque, A. L.; Caldeira, P. P.; Moreira, M.

2015-12-01

Rare earth elements (REE) are a group of reactive trace elements in aqueous media, they have a coherent chemical behavior with however a subtle and gradual shift in physicochemical properties allowing their use as tracers of sources and processes. Uncertainties on their oceanic inputs and outputs still remains [Arsouze et al., 2009; Siddall et al., 2008; Tachikawa et al., 2003]. The water-sediment interface were early on identified as a relevant REE source due to the high distribution coefficient between sediments and pore waters [Elderfield and Sholkovitz, 1987] and substantially higher concentration then the water column [Abbott et al., 2015; Haley et al., 2004; Sholkovitz et al., 1989; Soyol-Erdene and Huh, 2013]. Here we present a cross shelf transect of 4 short pore waters REE profiles on a 680 km2 mud bank located in the region of Cabo Frio, Brazil. This study reveals similar trends at the four sites: a REE production zone reflected by a maximum in concentration at the top of the sediment evolving with depth toward a REE consumption zone reflected by a minimum in REE concentrations. PAAS normalized patterns shows 1) a progressive depletion in LREE with depth with HREE/LREE ratios comprised between 1.1 and 1.6 in the 2 first centimeters evolving gradually to ratios comprised between 2.8 and 4.7 above 7 cm 2) A sharp gradient in negative Ce anomaly with Ce/Ce* values reaching 0.3. With maximum Nd concentrations comprised between 780 and 1200 pmol.kg and considering that seawater Nd concentrations of Brazilian shelf bottom waters are comprised between 24 and 50 pmol.Kg-1 we apply the Fick´s First Law of diffusion and estimate that 340 +/- 90 nmol. m-2 Y-1 of Nd is released in the Cabo frio´s mudbank. This flux is in the same order of magnitude of recent estimates by [Abbott et al., 2015] in the slope of Oregon´s margin. Unraveling processes responsible for the REE production zone will help to refine the global REE fluxes estimates.

The effect of tissue structure and soil chemistry on trace element uptake in fossils

NASA Astrophysics Data System (ADS)

Hinz, Emily A.; Kohn, Matthew J.

2010-06-01

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H 2O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO 3. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element "plumes" down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ˜5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients ( Kd's). Although acid leaches and bulk digestion of soils yield comparable fossil-soil Kd's among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H 2O leachates instead reveal radically different Kd's in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE Kd's and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading Kd's for many trace elements, especially the REE, and H 2O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.

RNA sequencing confirms similarities between PPI-responsive oesophageal eosinophilia and eosinophilic oesophagitis.

PubMed

Peterson, K A; Yoshigi, M; Hazel, M W; Delker, D A; Lin, E; Krishnamurthy, C; Consiglio, N; Robson, J; Yandell, M; Clayton, F

2018-06-04

Although current American guidelines distinguish proton pump inhibitor-responsive oesophageal eosinophilia (PPI-REE) from eosinophilic oesophagitis (EoE), these entities are broadly similar. While two microarray studies showed that they have similar transcriptomes, more extensive RNA sequencing studies have not been done previously. To determine whether RNA sequencing identifies genetic markers distinguishing PPI-REE from EoE. We retrospectively examined 13 PPI-REE and 14 EoE biopsies, matched for tissue eosinophil content, and 14 normal controls. Patients and controls were not PPI-treated at the time of biopsy. We did RNA sequencing on formalin-fixed, paraffin-embedded tissue, with differential expression confirmation by quantitative polymerase chain reaction (PCR). We validated the use of formalin-fixed, paraffin-embedded vs RNAlater-preserved tissue, and compared our formalin-fixed, paraffin-embedded EoE results to a prior EoE study. By RNA sequencing, no genes were differentially expressed between the EoE and PPI-REE groups at the false discovery rate (FDR) ≤0.01 level. Compared to normal controls, 1996 genes were differentially expressed in the PPI-REE group and 1306 genes in the EoE group. By less stringent criteria, only MAPK8IP2 was differentially expressed between PPI-REE and EoE (FDR = 0.029, 2.2-fold less in EoE than in PPI-REE), with similar results by PCR. KCNJ2, which was differentially expressed in a prior study, was similar in the EoE and PPI-REE groups by both RNA sequencing and real-time PCR. Eosinophilic oesophagitis and PPI-REE have comparable transcriptomes, confirming that they are part of the same disease continuum. © 2018 John Wiley & Sons Ltd.

Rare Earth Elements of the Permian-Triassic Conodonts from Shelf Basin to Shallow Platform: Implications for Oceanic Redox Conditions immediately After the End-Permian Mass Extinction

NASA Astrophysics Data System (ADS)

Li, Y.; Zhao, L.; Chen, Z.; Chen, J.; Chen, Y.

2013-12-01

Rare-earth elements (REEs) can provide information regarding the influence of weathering fluxes and hydrothermal inputs on seawater chemistry as well as processes that fractionate REEs between solid and aqueous phases. Of these, cerium (Ce) distributions may provide information about variations in dissolved oxygen in seawater, and thus assess the redox conditions. The short residence times of REEs in seawater (~300-1,000 yr) can result in unique REE signatures in local watermasses. REE patterns preserved in biogenic apatite such as conodonts are ideal proxies for revealing original seawater chemistry. Here, we measured the REE content of in-situ, single albid crowns using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in combination with an ArF (λ=193 nm) excimer laser (Lambda Physiks GeoLas 2005) and quadrupole ICP-MS (Agilent 7500a). LA-ICP-MS is ideally suited for analyzing conodonts due to its ability to measure compositional variation within single conodont elements. It has the capability to determine, with high spatial resolution, continuous compositional depth profiles through the concentric layered structure of component histologies. To evaluate paleoceanographic conditions immediately after the Permian-Triassic (P-Tr) mass extinction in various depositional settings, we sampled a nearly contemporaneous strata unit, the P-Tr boundary bed, just above the extinction horizon from six sections in South China. They represent various depositional settings from shelf basin (Chaohu and Daxiakou sections), lower part of ramp (Meishan section), normal shallow platform (Yangou section), and platform microbialite (Chongyang and Xiushui sections). The sampled unit is constrained by conodonts Hindeodus changxingensis, H. parvus, and H. staeschei Zones in Meishan. REE results obtained from conodont albid crowns show that the seawater in lower ramp and shelf basin settings contains much higher REE concentrations than that in shallow platform. Ce/Ce* ratios in shelf basin and lower ramp are similar to one another, ranging from 0.7-1.0. The same ratios, however, are much lower in shallow platform and microbialite settings, ranging from 0.17-0.22 and 0.2-0.45, respectively. Eu/Eu+ ratios also show similar patterns: 0.7-1.0 in shelf basin and lower ramp and 0.3-0.7 in shallow platform. If the Ce/Ce* was truly influenced by environmental redox conditions, then Ce/Ce* values of 0.7-1.0 in shelf basin and lower ramp settings are indicative of a suboxic to anoxic depositional system, while the same proxy of 0.17-0.45 in shallow platform and microbialite points to a well-oxygenated setting immediately after the P-Tr mass extinction.

Iridium anomalies and fractionated siderophile element patterns in impact ejecta, Brockman Iron Formation, Hamersley Basin, Western Australia: evidence for a major asteroid impact in simatic crustal regions of the early Proterozoic earth

NASA Astrophysics Data System (ADS)

Glikson, Andrew; Allen, Charlotte

2004-04-01

A stratigraphically consistent <20-cm-thick unit of microkrystite spherule and microtektite-bearing impact fallout ejecta overlying volcanic tuff of the 4th Shale Macroband (DGS4) of the Dales Gorge Member (2.47-2.50 Ga), Brockman Iron Formation, Hamersley Group, Western Australia, displays anomalous platinum group element (PGE) and other trace metal patterns. The unit has high Ir (13 ppb) and Pt (35 ppb), and low Pd (2.7 ppb) and Au (1.55-1.88 ppb). The low Pd/Ir ratios and low Cr/V suggest depletion in volatile PGE and metals relative to refractory PGE and V, contrasted to the ubiquitous high Pd/Ir of most terrestrial rocks. Marked depletion in the volatile Rare Earth Element (REE) abundances in stilpnomelane spherule cores is consistent with this model. The loss of volatile PGE, analogous to relations in 3.24 Ga impact fallout units of the Barberton greenstone belt (S3 and S4), suggests fractionation related to atmospheric spherule condensation. The microkrystite spherule unit locally incorporate fragments and up to meter-scale boulders of banded chert and stromatolite carbonate, suggesting tsunami transport postdating spherule deposition. DGS4 microkrystite spherules are dominated by stilpnomelane mantled by K-feldspar shells, which consist of inward-radiating fibrous feldspar aggregates suggestive of devitrification. The K and REE enrichment of spherule margins are contrasted to flat REE patterns of the stilpnomelane cores, suggesting adsorption of lithophile elements during settling of the spherules through the hydrosphere. K-feldspar shells contain submicron-scale Ni metal, oxide, sulfide and arsenide grains and euhedral needles of feldspar-exsolved ilmenite. Associated magnetite may have high nickel (<1.25% NiO). The generally mafic composition of the spherules and high Ni/Cr and Ni/Co are consistent with a target mafic-ultramafic crust, consistent with the lack of shock-metamorphosed quartz. Mixing calculations suggest a contribution of 2.5-3% projectile component to the impact-generated volatile cloud. Conservative mass balance estimates derived from the Ir and Pt flux, assuming global extent of a 10-cm-thick spherule unit and chondritic projectile composition, suggest an asteroid diameter on the scale of ˜30 km. Similar estimates are obtained from spherule sizes, which in DGS4 reach a mean diameter of ˜2.0 mm in aerodynamically elongate spherules. The evidence implies formation of an impact basin on the scale of 400 km in simatic/oceanic regions of the early Proterozoic crust.

Evaluation of water quality in surface water and shallow groundwater: a case study of a rare earth mining area in southern Jiangxi Province, China.

PubMed

Hao, Xiuzhen; Wang, Dengjun; Wang, Peiran; Wang, Yuxia; Zhou, Dongmei

2016-01-01

This study was conducted to evaluate the quality of surface water and shallow groundwater near a rare earth mining area in southern Jiangxi Province, China. Water samples from paddy fields, ponds, streams, wells, and springs were collected and analyzed. The results showed that water bodies were characterized by low pH and high concentrations of total nitrogen (total N), ammonium nitrogen (NH4 (+)-N), manganese (Mn), and rare earth elements (REEs), which was likely due to residual chemicals in the soil after mining activity. A comparison with the surface water standard (State Environmental Protection Administration & General Administration of Quality Supervision, Inspection and Quarantine of China GB3838, 2002) and drinking water sanitary standard (Ministry of Health & National Standardization Management Committee of China GB5749, 2006) of China revealed that 88 % of pond and stream water samples investigated were unsuitable for agricultural use and aquaculture water supply, and 50 % of well and spring water samples were unsuitable for drinking water. Moreover, significant cerium (Ce) negative and heavy REEs enrichment was observed after the data were normalized to the Post-Archean Australian Shales (PAAS). Principal component analysis indicated that the mining activity had a more significant impact on local water quality than terrace field farming and poultry breeding activities. Moreover, greater risk of water pollution and adverse effects on local residents' health was observed with closer proximity to mining sites. Overall, these findings indicate that effective measures to prevent contamination of surrounding water bodies from the effects of mining activity are needed.

Stable isotope, chemical, and mineral compositions of the Middle Proterozoic Lijiaying Mn deposit, Shaanxi Province, China

USGS Publications Warehouse

Yeh, Hsueh-Wen; Hein, James R.; Ye, Jie; Fan, Delian

1999-01-01

The Lijiaying Mn deposit, located about 250 km southwest of Xian, is a high-quality ore characterized by low P and Fe contents and a mean Mn content of about 23%. The ore deposit occurs in shallow-water marine sedimentary rocks of probable Middle Proterozoic age. Carbonate minerals in the ore deposit include kutnahorite, calcite, Mn calcite, and Mg calcite. Carbon (−0.4 to −4.0‰) and oxygen (−3.7 to −12.9‰) isotopes show that, with a few exceptions, those carbonate minerals are not pristine low-temperature marine precipitates. All samples are depleted in rare earth elements (REEs) relative to shale and have negative Eu and positive Ce anomalies on chondrite-normalized plots. The Fe/Mn ratios of representative ore samples range from about 0.034 to <0.008 and P/Mn from 0.0023 to <0.001. Based on mineralogical data, the low ends of those ranges of ratios are probably close to ratios for the pure Mn minerals. Manganese contents have a strong positive correlation with Ce anomaly values and a moderate correlation with total REE contents. Compositional data indicate that kutnahorite is a metamorphic mineral and that most calcites formed as low-temperature marine carbonates that were subsequently metamorphosed. The braunite ore precursor mineral was probably a Mn oxyhydroxide, similar to those that formed on the deep ocean-floor during the Cenozoic. Because the Lijiaying precursor mineral formed in a shallow-water marine environment, the atmospheric oxygen content during the Middle Proterozoic may have been lower than it has been during the Cenozoic.

Lunar Ferroan Anorthosite Petrogenesis: Clues from Trace Element Distributions in FAN Subgroups

NASA Astrophysics Data System (ADS)

Floss, Christine; James, Odette B.; McGee, James J.; Crozaz, Ghislaine

1998-04-01

The rare earth elements (REE) and selected other trace elements were measured in plagioclase and pyroxene from nine samples of the lunar ferroan anorthosite (FAN) suite of rocks. Samples were selected from each of four FAN subgroups previously defined by James et al. (1989). Plagioclase compositions are homogeneous within each sample, but high- and low-Ca pyroxenes from lithic clasts typically have different REE abundances from their counterparts in the surrounding granulated matrices. Measured plagioclase/low-Ca pyroxene concentration ratios for the REE have steeper patterns than experimentally determined plagioclase/low-Ca pyroxene partition coefficients in most samples. Textural and trace element evidence suggest that, although subsolidus equilibration may be responsible for some of the discrepancy, plagioclase compositions in most samples have been largely unaffected by intermineral redistribution of the REE. The REE systematics of plagioclase from the four subgroups are broadly consistent with their derivation through crystallization from a single evolving magma. However, samples from some of the subgroups exhibit a decoupling of plagioclase and pyroxene compositions that probably reflects the complexities inherent in crystallization from a large-scale magmatic system. For example, two anorthosites with very magnesian mafic minerals have highly evolved trace element compositions; major element compositions in plagioclase also do not reflect the evolutionary sequence recorded by their REE compositions. Finally, a noritic anorthosite breccia with relatively ferroan mafic minerals contains several clasts with high and variable REE and other trace element abundances. Although plagioclase REE compositions are consistent with their derivation from a magma with a KREEPy trace element signature, very shallow REE patterns in the pyroxenes suggest the addition of a component enriched in the light REE.

A new method for the determination of Gadolinium in ppq levels

NASA Astrophysics Data System (ADS)

Brünjes, Robert; Bichler, Andrea; Hofmann, Thilo

2015-04-01

The use of Gadolinium (Gd) complexes as a contrast agent in Magnetic Resonance Imaging (MRI) results in an enhanced Gd input in the aquatic environment. Gd-complexes are excreted by humans unmetabolized within 12h after application. Passing the sewage systems with almost no degradation taking place, they successively reach surface waters, which make Gd a capable tracer for surface water/groundwater (SW/GW) interactions. The natural background concentration of Gd and other rare earth elements (REE) occur at ultratrace levels [low ng/L]. Crust-normalized REE patterns show positive Gd-anomalies in surface water, groundwater, and recently also in tap water. The difference between the total concentration and its natural background concentration estimated by the REE pattern is the anthropogenic Gd. Not only densely populated areas are affected by the presence of anthropogenic Gd. Studies have shown that even in rural areas without MRI facilities, anthropogenic Gd can be detected, since people are sent home after treatment. However, low input concentrations and mixing with natural waters lead to a decrease of Gd concentration below the current limit of quantification (LOQ) [1-5ng/L]. Often anthropogenic Gd cannot be calculated, although it is present, because natural background concentration cannot be determined with current methods, in particular in areas with low waste water load (e.g. headwater catchments). A new method using an on-line preconcentration system "SeaFAST" (Elemental Scientific Inc., USA), in combination with a desolvation system "Apex Q" (Elemental Scientific Inc., USA) and a QQQ-ICP-MS instrument (Agilent Technologies, Japan) does lower the LOQ for REE by a factor of 10 to 20. The SeaFAST-system uses a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate specifically REE as they are exclusively trivalent while anions, alkali and alkaline earth cations are washed out. The Apex Q interface is also supposed to significantly lower oxide interferences. We also evaluate a pretreatment in order to degrade the complexes and reach high recoveries of anthropogenic Gd. Our method will provide a determination of REE in ppq-levels, that significantly improves the differentiation between naturally and anthropogenic Gd. This will allow the detection of less than 1% waste water in SW and GW and finally increase the areas where studies of anthropogenic Gd could be conducted. A first application of our method was conducted during a field study in November 2014.

Comparing REE distribution in GEMAS agricultural soils and FOREGS topsoils-subsoils in Italy and Sweden

NASA Astrophysics Data System (ADS)

Petrosino, Paola; Sadeghi, Martiya; Andersson, Madelen; Albanese, Stefano; Dinelli, Enrico; Valera, Paolo; Ladenberger, Anna; Morris, George; Uhlbäck, Jo; Lima, Annamaria; De Vivo, Benedetto

2014-05-01

Scientific interest on Rare Earth Elements (REEs)-bearing media is increasing as a consequence of the rapidly growing demand of these important chemical resources, which are currently used in a large number of technical applications. In this study, Italian and Swedish REE data from the FOREGS database on topsoil and subsoils samples have been compared to the distribution of REEs in the GEMAS samples of agricultural soil (Ap), pertaining to regularly ploughed land to a depth of 20 cm. Principal Component Analysis (PCA) was carried out to identify patterns within both data sets. Investigation of the spatial distribution of REEs in FOREGS topsoil-subsoil and GEMAS Ap media for both countries revealed the prominent role of the geogenic component in the general REE geochemical pattern of the three solid media. Despite a similar REE content in the underlying parent material or bedrocks (alkaline igneous rocks, both intrusive and effusive in Italy, alkaline granites and pegmatites in Sweden), several distinct differences emerged between the two countries driven by climate, topography, age of the rock units and sediments, presence of mineralisations, type of soils and presence of glacial deposits. GEMAS agricultural soils form both countries show higher REEs contents than the corresponding subsoils and topsoils, which could be ascribed to the analytical method specifically set for REEs and the last generation ICP-MS instrument used by SGS Lab to analyze REEs in Ap soils. The REE content in Italian topsoil and subsoil is similar and there is a good agreement between the topsoils and Ap soils, which were collected from similar depth. Swedish subsoil is on the contrary more enriched in REEs with respect to topsoil, and Ap soils even display REE contents higher than subsoils. This anomalous REE concentrations in agricultural soil may originate from the fact that most of the arable land in Sweden has been located on glacial and postglacial deposits, rich in clay which has tendency to accumulate secondary REEs. We concluded that the fingerprints of anthropic activity due to agricultural activities does not influence the geogenic signal. Both in Italy and Sweden, in fact, REE trends in GEMAS agricultural soils are well comparable with those obtained for FOREGS soils sampled from unoccupied and undisturbed regions.

Chemistry of the older supracrustals of Archaean age around Sargur

NASA Technical Reports Server (NTRS)

Janardhan, A. S.; Shadaksharaswamy, N.; Capdevila, R.

1988-01-01

In the Archaeans of the Karnataka craton two stratigraphically distinct volcano-sedimentary sequences occur, namely the older supracrustals of the Sargur type and the younger Dharwar greenstones. The dividing line between these is the 3 by old component of the Peninsular gneiss. The trace and rare earth element chemistry of the Sargur metasediments show, in general, marked similarity to the Archaean sediments. The significant departures are in the nickel and chromium abundances. The REE data of the Sargur pelites of the Terakanambi region represented by Silli-gt-bio-feldspar schists and paragneisses show LREE enrichment and flat to depleted HREE pattern. Banded iron formations have very low REE abundance. They show slightly enriched LREE and flat to depleted HREE pattern. REE abundance in the Mn-horizons is comparable to that of the Archaean sediments. Mn-horizons show enriched LREE and flat HREE with anamolous Eu. REE patterns of these bands is well evolved and has similarities with PAAS.

Fractionation in the solar nebula - Condensation of yttrium and the rare earth elements

NASA Technical Reports Server (NTRS)

Boynton, W. V.

1975-01-01

The condensation of Y and the rare earth elements (REE) from the solar nebula may be controlled by thermodynamic equilibrium between gas and condensed solids. Highly fractionated REE patterns may result if condensates are removed from the gas before condensation is complete. It is found that the fractionation is not a smooth function of REE ionic radius but varies in an extremely irregular pattern. Both Yb and Eu are predicted to be extremely depleted in the early condensate without the requirement of condensation in the divalent state. The model is discussed with respect to a highly fractionated pattern observed by Tanaka and Masuda (1973), in a pink Ca-Al-rich inclusion from the Allende meteorite and can account for the abundances of each REE determined. According to the model this inclusion represents a condensate from a previously fractionated gas rather than from a gas of solar composition. Before the condensation of this inclusion, an earlier condensate was formed and was removed from equilibrium with the gas.

Comparison of energy expenditure, body composition, metabolic disorders, and energy intake between obese children with a history of craniopharyngioma and children with multifactorial obesity.

PubMed

Bomer, Ilanit; Saure, Carola; Caminiti, Carolina; Ramos, Javier Gonzales; Zuccaro, Graciela; Brea, Mercedes; Bravo, Mónica; Maza, Carmen

2015-11-01

Craniopharyngioma is a histologically benign brain malformation with a fundamental role in satiety modulation, causing obesity in up to 52% of patients. To evaluate cardiovascular risk factors, body composition, resting energy expenditure (REE), and energy intake in craniopharyngioma patients and to compare the data with those from children with multifactorial obesity. All obese children and adolescents who underwent craniopharyngioma resection and a control group of children with multifactorial obesity in follow-up between May 2012 and April 2013. Anthropometric measurements, bioelectrical impedance, indirect calorimetry, energy intake, homeostatic model assessment insulin resistance (HOMA-IR), and dyslipidemia were evaluated. Twenty-three patients with craniopharyngioma and 43 controls were included. Children with craniopharyngioma-related obesity had a lower fat-free mass percentage (62.4 vs. 67.5; p=0.01) and a higher fat mass percentage (37.5 vs. 32.5; p=0.01) compared to those with multifactorial obesity. A positive association was found between %REE and %fat-free mass in subjects with multifactorial obesity (68±1% in normal REE vs. 62.6±1% in low REE; p=0.04), but not in craniopharyngioma patients (62±2.7 in normal REE vs. 61.2±1.8% in low REE; p=0.8). No differences were found in metabolic involvement or energy intake. REE was lower in craniopharyngioma patients compared to children with multifactorial obesity regardless of the amount of fat-free mass, suggesting that other factors may be responsible for the lower REE.

The formation and trace elements of garnet in the skarn zone from the Xinqiao Cu-S-Fe-Au deposit, Tongling ore district, Anhui Province, Eastern China

NASA Astrophysics Data System (ADS)

Xiao, Xin; Zhou, Tao-fa; White, Noel C.; Zhang, Le-jun; Fan, Yu; Wang, Fang-yue; Chen, Xue-feng

2018-03-01

Xinqiao is a large copper-gold deposit and consists of two major mineralization types: stratabound and skarn. The skarn occurs along the contact between a quartz diorite intrusion and Carboniferous-Triassic limestone. Xinqiao has a strongly developed skarn zone, including endoskarn and exoskarn; the exoskarn is divided into proximal and distal exoskarn. We present systematic major, trace and rare earth element (REE) concentrations for garnets from the skarn zone, discuss the factors controlling the incorporation of trace elements into the garnets, and constrain the formation and evolution of the garnet from skarn zone in Xinqiao deposit. Grossular (Adr20-44Grs56-80) mostly occurs in endoskarn and has typical HREE-enriched and LREE-depleted patterns, with small Eu anomalies and low ∑REE. Garnets from the exoskarn show complex textures and chemical compositions. The composition of garnets range from Al-rich andradite (Adr63-81Grs19-47) to andradite (Adr67-98Grs2-33). Garnet in endoskarn has typical HREE-enriched and LREE-depleted patterns. Al-rich andradite in proximal skarn has small Eu anomalies and moderate ∑REE. Andradite from distal exoskarn shows strong positive Eu anomalies and has variable ∑REE. The U, Y, Fe and Al relationship with ∑REE shows that two mechanisms controlled incorporation of REE into the garnets: crystal chemistry (substitution and interstitial solid solution) mainly controlled in the endoskarn garnet (grossular) and the proximal exoskarn (Al-rich andradite), and fluid and rock chemistry (surface adsorption and occlusion) controlled REEs in the distal exoskarn. Furthermore, Al has a negative relationship with ∑REE indicating that REE3+ did not follow a coupled, YAG-type substitution into the garnets. Variations in textures and trace and rare earth elements of garnets suggest that the garnets in the endoskarn formed by slow crystal growth at low W/R ratios and near-neutral pH in a closed system during periods of diffusive metasomatism. The garnets in the exoskarn formed rapidly from externally derived fluids during advective metasomatism, and adsorption had a major control on the REE patterns in distal exoskarn. With the end of water-rock reaction, the contents of REE decreased in the hydrothermal fluid, and the system became nearly closed.

Rare earth element patterns in Archean high-grade metasediments and their tectonic significance

NASA Technical Reports Server (NTRS)

Taylor, Stuart Ross; Rudnick, Roberta L.; Mclennan, Scott M.; Eriksson, Kenneth A.

1986-01-01

REE data on metasedimentary rocks from two different types of high-grade Archean terrains are presented and analyzed. The value of REEs as indicators of crustal evolution is explained; the three geologic settings (in North America, Southern Africa, and Australia) from which the samples were obtained are described; and the data are presented in extensive tables and graphs and discussed in terms of metamorphic effects, the role of accessory phases, provenance, and tectonic implications (recycling, the previous extent of high-grade terrains, and a model of Archean crustal growth). The diversity of REE patterns in shallow-shelf metasediments is attributed to local provenance, while the Eu-depleted post-Archean patterns are associated with K-rich plutons from small, stable early Archean terrains.

Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

USGS Publications Warehouse

Piper, David Z.; Bau, Michael

2013-01-01

The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

Geochemical, oxygen, and neodymium isotope compositions of metasediments from the Abitibi greenstone belt and Pontiac Subprovince, Canada: Evidence for ancient crust and Archean terrane juxtaposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, R.; Kerrich, R.; Maas, R.

1993-02-01

The Abitibi greenstone belt (AGB) and Pontiac Subprovince (PS) in the southwestern Superior Province are adjacent greenstone-plutonic and metasedimentary-dominated terranes, respectively, separated by a major fault zone. Metasediments from these two contrasting terranes are compared in terms of major- and trace-element and O- and Nd-isotope compositions, and detrital zircon ages. The following two compositional populations of metasediments are present in the low-grade, Abitibi southern volcanic zone: (1) a mafic-element-enriched population (MEP) characterized by flat, depleted REE patterns; enhanced Mg, Cr, Co, Ni, and Sc; low-incompatible-element contents; and minor or absent normalized negative troughs at Nb, Ta, and Ti; and (2)more » a low-mafic-element population (LMEP) featuring LREE-enriched patterns; enhanced Rb, Cs, Ba, Th, and U contents; and pronounced normalized negative troughs at Nb, Ta, and Ti. These geochemical features are interpreted to indicate that the MEP sediments were derived from an ultramafic- and mafic-dominated oceanic provenance, whereas the LMEP sediments represent mixtures of mafic and felsic are source rocks. The PS metasediments are essentially indistinguishable from Abitibi LMEP on the basis of major-element and transition metal abundances, suggesting comparable types of source rocks and degrees of maturity, but are distinct in terms of some trace elements and O-isotope compositions. The Pontiac metasediments are depleted in [sup 18]O and enriched in Cs, Ba, Pb, Th, U, Nb, Ta, Hf, Zr, and total REE and also have higher ratios of Rb/K, Cs/Rb, Ba/Rb, Ta/Nb, Th/La, and Ba/La relative to the Abitibi LMEP. Two subtypes of REE patterns have been identified in PS metasediments. The first subtype is interpreted to be derived from provenances of mixed mafic and felsic volcanic rocks, whereas the Eu-depleted type has features that are typical of post-Archean sediments or Archean K-rich granites and volcanic equivalents. 100 refs., 9 figs., 4 tabs.« less

Geochemistry of pillow lavas and sheeted dikes from Nain and Ashin ophiolites (Central Iran)

NASA Astrophysics Data System (ADS)

Saccani, Emilio; Pirnia Naeini, Tahmineh; Torabi, Ghodrat

2017-04-01

An extensive, worldwide database on the geochemistry of basalts from well-known tectonic settings is available. Knowing the chemistry of basalts on one hand, and the tectonic setting of their origin on the other hand, resulted in the development of tectonic discrimination diagrams. Recently developed discrimination diagrams allow us to determine the tectonic setting of volcanics with almost neglectable probability of misclassification (<1%). One major application of these diagrams lies in discriminating the tectonic setting of formation of ophiolites, particularly in poorly-known areas. A good example is the Inner ophiolite belt of Iran, located in Central Iran. The geodynamic significance of the inner ophiolites is still poorly known. From the Inner ophiolites, either no volcanic section is reported, or, the data are highly limited and poorly-reliable due the high degree of alteration of the studied samples. We have been able to overcome this problem by spotting relatively well-preserved outcrops of pillow lavas and sheeted dikes from two ophiolite mélanges of Central Iran, Nain and Ashin ophiolites. The two mélanges are located in the west of Central-East Iranian microplate. In total, 28 samples have been collected from the pillow lavas and sheeted dikes outcrops. The studied volcanic rocks consist mainly of basalts and minor ferrobasalts and basaltic andesites, all showing a clear subalkaline nature (e.g., Nb/Y = 0.03-0.21). Two samples from the Nain ophiolite are characterized by N-MORB normalized incompatible element patterns showing marked Th positive anomalies and Ta, Nb, Ti negative anomalies. Chondrite-normalized REE patterns show LREE/HREE (light REE/heavy REE) enrichment, with LaN/YbN=3.2-4.3. These rocks are chemically similar to the calc-alkaline basalts (CAB), as also highlighted by many discrimination diagrams. These rocks are interpreted to have generated in a cordilleran-type volcanic arc setting. All other samples from both the Nain and Ashin ophiolites display a wide range of chemical composition. However, the relatively less fractionated basalts are characterized by low TiO2 (0.60-1 wt%), P2O5 (0.03-0.08 wt%), Zr (23-75 ppm) and Y (9-27) contents. Cr (38-619 ppm) and Ni (22-220 ppm) contents show a wide range of variation. N-MORB normalized incompatible element patterns show rather flat trends and a general depletion (from 0.4 to 0.8 times N-MORB composition) coupled with a slight Th enrichment (1-3 times N-MORB). Chondrite-normalized REE patterns are generally flat and are characterized by either a slight depletion or a slight enrichment in LREE compared to HREE (LaN/YbN=0.7-1.2). These overall chemical features resemble those of island arc tholeiites from many ophiolitic complexes. The depletion in incompatible elements compared to N-MORB suggest that these rocks were derived from partial melting of a depleted mantle source. Th enrichment with respect to Nb (ThN/NbN = 2.6-12.4) suggests that mantle sources underwent enrichment in subduction-derived chemical components prior melting. Our data suggest that the Nain and Ashin ophiolites were formed in a subduction-related tectonic setting during the Late Cretaceous. The chemistry of the studied rocks is compatible with transition zone either from forearc to arc or from arc to backarc.

Geochemical Evidence for Recent Hydrothermal Alteration of Marine Sediments in Mid-Okinawa Trough, Southwest Japan

NASA Astrophysics Data System (ADS)

Tanaka, A.; Abe, G.; Yamaguchi, K. E.

2014-12-01

Recent studies have shown that submarine hydrothermal system supports diverse microbial life. Bio-essential metals supporting such microbial communities were released from basalts by high-temperature water-rock interaction in deeper part of the oceanic crust and carried by submarine fluid flow. Its total quantity in global hydrothermal settings has been estimated to be on the order of ~1019 g/yr, which is surprisingly on the same order of the total river flows (Urabe et al., 2011). Therefore, it is important to explore how submarine river system works, i.e., to understand mechanism and extent of elemental transport, which should lead to understanding of the roles of hydrothermal circulation in oceanic crust in controlling elemental budget in the global ocean and geochemical conditions to support deep hot biosphere. 　We performed REE analysis of marine sediments influenced by submarine hydrothermal activity in Mid-Okinawa Trough. The sediment samples used in this study are from IODP site at Iheya North region and JADE site at Izena region. The samples show alternation between volcanic and clastic sediments. Hydrothermal fluids of this area contain elevated concentrations of volatile components such as H2, CO2, CH4, NH4+, and H2S, supporting diverse chemoautotrophic microbial community (Nakagawa et al., 2005). The purpose of this study is to examine the effect of hydrothermal activity on the REE signature of the sediments. Chondrite-normalized REE patterns of the samples show relative enrichment of light over heavy REEs, weak positive Ce anomalies, and variable degrees of negative Eu anomalies. The REE patterns suggest the sediments source was mainly basalt, suggesting insignificant input of continental materials. Negative Eu anomalies found in the IODP site become more pronounced with increasing depth, suggesting progressive increase of hydrothermal alteration where Eu was reductively dissolved into fluids by decomposition of feldspars. Contrary, at the JADE site, magnitude of negative Eu anomalies was variable independent of the sediment depth. This suggests changes in the redox conditions, most likely due to occasional invasions of O2-bearing seawater into sediments. Different regimes of hydrothermal fluid flows govern the chemical environments of marine sediments in active hydrothermal areas.

Neodymium Isotope associated with planktonic foraminifera as a proxy of deglacial changes in Pacific ocean circulation

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

Neodymium isotopes of ferromanganese oxide coatings precipitated on planktonic foraminifera have been intensively used as a proxy for water mass reconstruction in the deep Atlantic and Indian Ocean, but their suitability is not well constrained in the Pacific and may be affected by enhanced inputs and scavenging relative to advection. In this study, Nd isotopes and Rare Earth Element (REE) concentrations of planktonic foraminifera from ~60 sites widely distributed throughout the Pacific are presented. We found that the REE pattern associated with planktonic foraminifera in our study and Fe-Mn oxides/coatings in the global ocean have a common heavy REE depleted pattern when normalized to their ambient seawater due to preferential removal of light REEs onto particles relative to heavy REEs during scavenging. The core-top ɛNd results agree with the proximal seawater compositions, indicating that planktonic foraminiferal coatings can give a reliable record of past changes in bottom water Nd isotopes in the Pacific. A good correlation between foraminifera Nd isotopes and seawater phosphate suggests that Nd with a predominantly radiogenic isotopic composition was probably added gradually along continental boundaries so that the Nd isotopic composition change paralleled the accumulation of nutrients in the deep Pacific. By confirming Nd isotopes as a reliable water mass tracer in the Pacific Ocean, this proxy is then applied to reconstruct how the water mass circulation changes during the Last Glacial Maximum (LGM). Most of the cores in deep North Pacific show essentially invariant Nd isotopic compositions during the LGM compared with core-top values, suggesting that Nd isotope of Pacific end-member did not change during glacial times. However, the LGM Southwest Pacific cores have more radiogenic ɛNd than core-tops corroborating the previous findings of reduced inflow of North Atlantic Deep Water. The Eastern Equatorial Pacific cores above ~2 km showed consistently lower LGM ɛNd values, which might suggest a reduced influence of more radiogenic North Pacific Deep Water return flow. Taken together, our results indicate a slower Pacific overturning circulation during the glacial times, and the inflow and return flow of the Pacific meridional overturning were closely linked in the glacial-interglacial cycles.

Effects of a Tripeptide Iron on Iron-Deficiency Anemia in Rats.

PubMed

Xiao, Chen; Lei, Xingen; Wang, Qingyu; Du, Zhongyao; Jiang, Lu; Chen, Silu; Zhang, Mingjie; Zhang, Hao; Ren, Fazheng

2016-02-01

This study aims to investigate the effects of a tripeptide iron (REE-Fe) on iron-deficiency anemia rats. Sprague-Dawley rats were randomly divided into seven groups: a normal control group, an iron-deficiency control group, and iron-deficiency groups treated with ferrous sulfate (FeSO4), ferrous glycinate (Fe-Gly), or REE-Fe at low-, medium-, or high-dose groups. The rats in the iron-deficiency groups were fed on an iron-deficient diet to establish iron-deficiency anemia (IDA) model. After the model established, different iron supplements were given to the rats once a day by intragastric administration for 21 days. The results showed that REE-Fe had effective restorative action returning body weight, organ coefficients, and hematological parameters in IDA rats to normal level. In addition, comparing with FeSO4 or Fe-Gly, high-dose REE-Fe was more effective on improving the levels of renal coefficient, total iron-binding capacity, and transferrin. Furthermore, the liver hepcidin messenger RNA (mRNA) expression in the high-dose group was significantly higher (p < 0.05) than that in the FeSO4 or Fe-Gly group and showed no significant difference (p > 0.05) with the normal control group. The findings suggest that REE-Fe is an effective source of iron supplement for IDA rats and might be exploited as a new iron fortifier.

Geochemistry of the suspended sediment in the estuaries of the Mandovi and Zuari rivers, central west coast of India.

PubMed

Kessarkar, Pratima M; Shynu, R; Rao, V Purnachandra; Chong, Feng; Narvekar, Tanuja; Zhang, Jing

2013-05-01

The geochemistry of the suspended particulate matter (SPM) collected during the monsoon was determined to identify the sources of SPM and to understand the physicochemical processes in the Mandovi and Zuari river estuaries. The concentrations of SPM decrease seaward in both estuaries, but are relatively high at bay stations. Kaolinite is the most dominant clay mineral in the upstream of both rivers. Smectite increases seaward in both estuaries and is abundant in the bay. Upstream stations of Mandovi, where ore deposits are stored on the shore, exhibit high Fe, Mn, total rare earth elements (∑REE), and middle REE- and heavy REE-enriched patterns. Channel stations of both estuaries exhibit middle REE- and light REE-enriched patterns, which gradually changed seaward to middle REE- and heavy REE-enriched patterns. Canal stations exhibit the highest concentrations of major and trace metals. High metal/Al ratios occur at stations in the upstream of Zuari and at the confluence of canals in the Mandovi estuary. Enrichment factors of metals indicate that Mn is significantly polluted while other metals are moderately polluted. The δ(13)C and δ(15)N of organic matter indicate that the terrigenous organic matter at the upstream is diluted seaward by marine organic matter. Organic matter at bay stations is largely marine and altered-type. The compositions of SPM are controlled by the particulates from ore dust, the geology of the drainage basins, and the physicochemical processes in the estuaries. Particulates resuspended from the bay are dominated by ore dust, which are advected into the channels of both estuaries during the lull periods of the monsoon.

Alteration geochemistry of the volcanic-hosted Dedeninyurdu, Yergen and Fındıklıyar Cu-Fe mineralization, Northern part of Gökçedoǧan Village, Çorum-Kargi Region, Turkey: Implications for the rare earth elements geochemical characteristics

NASA Astrophysics Data System (ADS)

Ozturk, Sercan; Gumus, Lokman; Abdelnasser, Amr; Yalçin, Cihan; Kumral, Mustafa; Hanilçi, Nurullah

2016-04-01

This study deals with the rare earth element (REE) geochemical behavior the alteration zonesassociated with the volcanic-hosted Cu-Femineralization at the northern part of Gökçedoǧan village, Çorum-Kargi region (N Turkey) which are Dedeninyurdu, Yergen and Fındıklıyar mineralization. The study areacomprises Bekirli Formation, Saraycık Formation, Beşpınar Formation, and Ilgaz Formation. Saraycık Formation consists ofUpper Cretaceous KargıOphiolites, pelagic limestone, siltstone, chert and spilitic volcanic rocks. Fe-Cu mineralization occurred in the spiliticvolcanic rocks of Saraycık Formation representing the host rockand is related with the silicification and sericitizationalteration zones. Dedeninyurdu and Yergen mineralization zone directed nearly N75-80oEis following structural a line but Fındıklıyar mineralization zone has nearly NW direction. The ore mineralogy in these zonesinclude pyrite, chalcopyrite, covellite, hematite with malachite, goethite and a limonite as a result of oxidation. The geochemical characteristics of REE of the least altered spiliticbasalt show flat light and heavy REE with slight positive Eu- and Sr-anomalies according to their chondrite-, N-type MORB, and primitive mantle-normalized REE patterns. While the REE geochemical features of the altered rocks collected from the different alteration zones show that there are negative Eu and Sr anomalies as a result of leaching during the alteration processes.There are positive and negative correlations between K2O index with LREE and HREE, respectively. This is due to the additions of K and La during the alteration processes referring to the pervasive sericitization alteration is the responsible for the Cu-Fe mineralization at the study area. Keywords: Cu-Fe mineralization, Spilitic volcanic rocks, alteration, Rare earth elements (REE) geochemistry.

Geochemistry of the Archean Yellowknife Supergroup

NASA Astrophysics Data System (ADS)

Jenner, G. A.; Fryer, B. J.; McLennan, S. M.

1981-07-01

The Archean Yellowknife Supergroup (Slave Structural Province. Canada) is composed of a thick sequence of supracrustal rocks, which differs from most Archean greenstone belts in that it contains a large proportion ( ~ 80%) of sedimentary rocks. Felsic volcanics of the Banting Formation are characterized by HREE depletion without Eu-anomalies, indicating an origin by small degrees of partial melting of a mafic source, with minor garnet in the residua. Granitic rocks include synkinematic granites [HREE-depleted; low ( 87Sr /86Sr ) I], post-kinematic granites [negative Eu-anomalies, high ( 87Sr /86Sr ) I] and granitic gneisses with REE patterns similar to the post-kinematic granites. Sedimentary rocks (turbidites) of the Burwash and Walsh Formations have similar chemical compositions and were derived from 20% mafic-intermediate volcanics, 55% felsic volcanics and 25% granitic rocks. Jackson Lake Formation lithic wackes can be divided into two groups with Group A derived from 50% mafic-intermediate volcanics and 50% felsic volcanics and Group B, characterized by HREE depletion, derived almost exclusively from felsic volcanics. REE patterns of Yellowknife sedimentary rocks are similar to other Archean sedimentary REE patterns, although they have higher La N/Yb N. These patterns differ significantly from typical post-Archean sedimentary REE patterns, supporting the idea that Archean exposed crust had a different composition than the present day exposed crust.

Rare earth and other elements in components of the Abee enstatite chondrite

NASA Technical Reports Server (NTRS)

Frazier, R. M.; Boynton, W. V.

1985-01-01

Radiochemical and instrumental neutron activation analyses of REEs and other elements have been conducted for Abee clast samples, a matrix sample, a dark inclusion, magnetic and nonmagnetic samples, and bulk samples. Correlations of the REEs and oldhamite abundance for both the clasts and dark inclusions indicate that the REEs chiefly occur in oldhamite. The similar REE patterns for clasts and dark inclusions, and the similar mineral composition of oldhamite in clast and dark inclusions, suggest that the oldhamite in both the clasts and dark inclusions is of a common origin.

Geochemistry of the Upper Triassic black mudstones in the Qiangtang Basin, Tibet: Implications for paleoenvironment, provenance, and tectonic setting

NASA Astrophysics Data System (ADS)

Wang, Zhongwei; Wang, Jian; Fu, Xiugen; Zhan, Wangzhong; Armstrong-Altrin, John S.; Yu, Fei; Feng, Xinglei; Song, Chunyan; Zeng, Shengqiang

2018-07-01

The Qiangtang Basin is the largest Mesozoic marine basin in the Tibetan Plateau. The Upper Triassic black mudstones are among the most significant hydrocarbon source rocks in this basin. Here, we present geochemical data for the Upper Triassic black mudstones to determine their paleoenvironment conditions, provenance, and tectonic setting. To achieve these, 30 black mudstones formed in various sedimentary environments were collected from the Zangxiahe, Zana, and Bagong formations. The results show that the total REE concentrations of mudstones from these formations range from 169 to 214 ppm, 204 to 220 ppm, and 141 to 194 ppm, respectively. All samples have chondrite-normalized REE patterns with enrichment of LREE, depletion of HREE and negative Eu and Ce anomalies. Specifically, mudstones from the Bagong Formation exhibit higher negative Eu anomalies and lower REE contents than those from the Zangxiahe and Zana formations. Mudstones from the Zangxiahe and Zana formations with low Sr/Ba and Sr/Cu ratios indicate the humid climate, whereas the high Sr/Ba and Sr/Cu ratios of rocks from the Bagong Formation suggest the arid climate. The low U/Th, (Cu + Mo)/Zn, V/Cr and Ni/Co ratios of rocks from the Zangxiahe, Zana, and Bagong formations are indicators of oxidized conditions. The bivariate diagrams (TiO2 vs. Al2O3, TiO2 vs. Zr, La/Th vs. Hf, and Co/Th vs. La/Sc) reveal that mudstones from the Zangxiahe and Zana formations were potentially derived from intermediate igneous rocks, whereas mudstones from the Bagong Formation were probably sourced from felsic igneous rocks. Their source rocks are mostly deposited in the collisional setting. REE of mudstones from the Zangxiahe, Zana, and Bagong formations were possibly originated from terrigenous detritus, with minor non-terrigenous contributions into the Zana samples. The REE contents of these mudstones are controlled mainly by terrigenous detrital minerals, rather than by the paleoclimate, paleoredox conditions, or organic matter. However, calcite minerals could dilute REE. Therefore, the REE contents of the Bagong Formation mudstones are significant lower than those of the Zangxiahe and Zana formations mudstones.

Mobility of rare earth element in hydrothermal process and weathering product: a review

NASA Astrophysics Data System (ADS)

Lintjewas, L.; Setiawan, I.

2018-02-01

The Rare Earth Element (REE), consists of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Lu, Ho, Er, Tm, Yb, are important elements to be used as raw materials of advanced technology such as semiconductors, magnets, and lasers. The research of REE in Indonesia has not been done. Several researches were conducted on granitic rocks and weathering product such as Bangka, Sibolga, West Kalimantan, West Sulawesi and Papua. REE can be formed by hydrothermal processes such as Bayan Obo, South China. The REE study on active hydrothermal system (geothermal) in this case also has the potential to produce mineral deposits. The purpose of this review paper is to know the mobility of REE on hydrothermal process and weathering products. Mobility of REE in the hydrothermal process can change the distribution patterns and REE content such as Ce, Eu, La, Lu, Nd, Sm, and Y. Another process besides the hydrothermal is weathering process. REE mobility is influenced by weathering products, where the REE will experience residual and secondary enrichment processes in heavier minerals.

Xenotime-(Y) formation from zircon dissolution-precipitation and HREE fractionation: an example from a metamorphosed phosphatic sandstone, Espinhaço fold belt (Brazil)

NASA Astrophysics Data System (ADS)

Franz, Gerhard; Morteani, Giulio; Rhede, Dieter

2015-10-01

We present an example where xenotime-(Y) together with metamorphic zircon replaces detrital zircon in a phosphatic sandstone from the Mesoproterozoic Espinhaço fold belt, Brazil, in a dissolution-precipitation reaction: {{zircon}}1 ( {{relict}} ) + {{P-}}{{bearing fluid}} = {{zircon}}2 ( {{metamorphic}} ) + {{xenotime}}. During the Brasiliano orogeny at 634 ± 19 Ma, the rocks experienced amphibolite facies metamorphism at ≥0.6 GPa/ 550 ± 37 °C (Southern Espinhaço) and ≥0.6 GPa/ 570 ± 35 °C (Northern Espinhaço), constrained by Zr-in-rutile and Ti-in-quartz thermometry and the presence of kyanite + muscovite + quartz. Many of the rocks show unusual rare earth element (REE) patterns with a hump at Gd-Tb-Dy and depletion in light REE. Detrital zircons (with relict ages between 1.5 and 3.3 Ga) show varying degrees of replacement as indicated by the presence of xenotime and associated porosity, from almost pristine to complete alteration. Textural evidence indicates local mobility of Zr and REE at the scale of the thin section. Xenotime-(Y) occurs together with other phosphates, mainly augelite, lazulite, and minerals of the svanbergite-crandallite-goyacite-florencite group. Xenotime-(Y) is very heterogeneous and reaches unusually high contents of up to 14 wt% Gd2O3, 13 wt% Dy2O3, and 3 wt% Tb2O3, corresponding to ≤0.36 REE atoms per formula unit due to the exchange Y = REE. The heavy REE patterns of xenotime-(Y) therefore show variable enrichment in individual elements, which explains the characteristic hump at Gd-Tb-Dy in the REE patterns of the whole rock. Although the rocks reached amphibolite facies conditions, textures indicate that formation of xenotime likely occurred during the early stages of diagenesis—metamorphism. Comparison with REE concentrations in xenotime-(Y) from the literature shows that selective REE incorporation into xenotime-(Y) is controlled by interaction with P-bearing hydrous fluids.

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Petrology of Ortsog-Uul peridotite-gabbro massif in Western Mongolia

NASA Astrophysics Data System (ADS)

Shapovalova, M.; Tolstykh, N.; Shelepaev, R.; Cherdantseva, M.

2017-12-01

The Ortsog-Uul mafic-ultramafic massif of Western Mongolia is located in a tectonic block with overturned bedding. The massif hosts two intrusions: a rhythmically-layered peridotite-gabbro association (Intrusion 1) and massive Bt-bearing amphibole-olivine gabbro (Intrusion 2). Intrusions 1 and 2 have different petrology features. Early Intrusion 1 (278±2.5Ma) is characterized by lower concentrations of alkalis, titanium and phosphorus than late Intrusion 2 (272±2Ma). The chondrite-normalized REE and primitive mantle-normalized rare elements patterns of Ortsog-Uul intrusions have similar curves of elements distribution. However, Intrusion 2 is characterized higher contents of REE and rare elements. High concentrations of incompatible elements are indicative of strong fractionation process. It has been suggested that Intrusions 1 and 2 derived from compositionally different parental melts. Model calculations (COMAGMAT-3.57) show that parental melts of two intrusions were close to high-Mg picrobasaltic magmas. The concentration of MgO in melt is 16.21 (Intrusion 1) and 16.17 (Intrusion 2). Isotopic data of Ortsog-Uul magmatic rocks exhibit different values of εNd (positive and negative) for Intrusion 1 and 2, respectively.

Using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to explore geochemical taphonomy of vertebrate fossils in the upper cretaceous two medicine and Judith River formations of Montana

USGS Publications Warehouse

Rogers, R.R.; Fricke, H.C.; Addona, V.; Canavan, R.R.; Dwyer, C.N.; Harwood, C.L.; Koenig, A.E.; Murray, R.; Thole, J.T.; Williams, J.

2010-01-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine rare earth element (REE) content of 76 fossil bones collected from the Upper Cretaceous (Campanian) Two Medicine (TMF) and Judith River (JRF) Formations of Montana. REE content is distinctive at the formation scale, with TMF samples exhibiting generally higher overall REE content and greater variability in REE enrichment than JRF samples. Moreover, JRF bones exhibit relative enrichment in heavy REE, whereas TMF bones span heavy and light enrichment fields in roughly equal proportions. TMF bones are also characterized by more negative Ce anomalies and greater U enrichment than JRF bones, which is consistent with more oxidizing diagenetic conditions in the TMF. Bonebeds in both formations show general consistency in REE content, with no indication of spatial or temporal mixing within sites. Previous studies, however, suggest that the bonebeds in question are attritional assemblages that accumulated over considerable time spans. The absence of geochemical evidence for mixing is consistent with diagenesis transpiring in settings that remained chemically and hydrologically stable during recrystallization. Lithology-related patterns in REE content were also compared, and TMF bones recovered from fluvial sandstones show relative enrichment in heavy REE when compared with bones recovered from fine-grained floodplain deposits. In contrast, JRF bones, regardless of lithologic context (sandstone versus mudstone), exhibit similar patterns of REE uptake. This result is consistent with previous reconstructions that suggest that channel-hosted microfossil bonebeds of the JRF developed via the reworking of preexisting concentrations embedded in the interfluve. Geochemical data further indicate that reworked elements were potentially delivered to channels in a recrystallized condition, which is consistent with rapid adsorption of REE postmortem. Copyright ?? 2010, SEPM (Society for Sedimentary Geology).

Growth Failure in Children with Intractable Epilepsy Is Not Due to Increased Resting Energy Expenditure

ERIC Educational Resources Information Center

Bergqvist, A. G. Christina; Trabulsi, Jillian; Schall, Joan I.; Stallings, Virginia A.

2008-01-01

The aim of this study was to evaluate the resting energy expenditure (REE) of children with intractable epilepsy (IE) compared with healthy children, and to determine factors that contribute to the pattern of REE. REE, growth status, and body composition were assessed in 25 prepubertal children with IE (15 males, 10 females; mean age 5y 5mo [SD 2y…

Mesosiderite clasts with the most extreme positive europium anomalies among solar system rocks

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Rubin, Alan E.; Davis, Andrew M.

1992-01-01

Pigeonite-plagioclase gabbros that occur as clasts in mesosiderites (brecciated stony-iron meteorites) show extreme fractionations of the rare-earth elements (REEs) with larger positive europium anomalies than any previously known for igneous rocks from the earth, moon, or meteorite parent bodies and greater depletions of light REEs relative to heavy REEs than known for comparable cumulate gabbros. The REE pattern for merrillite in one of these clasts is depleted in light REEs and has a large positive europium anomaly as a result of metamorphic equilibration with the silicates. The extreme REE ratios exhibited by the mesosiderite clasts demonstrate that multistage igneous processes must have occurred on some asteroids in the early solar system. Melting of the crust by large-scale impacts or electrical induction from an early T-Tauri-phase sun may be responsible for these processes.

Experimental investigation on the fracture behaviour of black shale by acoustic emission monitoring and CT image analysis during uniaxial compression

NASA Astrophysics Data System (ADS)

Wang, Y.; Li, C. H.; Hu, Y. Z.

2018-04-01

Plenty of mechanical experiments have been done to investigate the deformation and failure characteristics of shale; however, the anisotropic failure mechanism has not been well studied. Here, laboratory Uniaxial Compressive Strength tests on cylindrical shale samples obtained by drilling at different inclinations to bedding plane were performed. The failure behaviours of the shale samples were studied by real-time acoustic emission (AE) monitoring and post-test X-ray computer tomography (CT) analysis. The experimental results suggest that the pronounced bedding planes of shale have a great influence on the mechanical properties and AE patterns. The AE counts and AE cumulative energy release curves clearly demonstrate different morphology, and the `U'-shaped curve relationship between the AE counts, AE cumulative energy release and bedding inclination was first documented. The post-test CT image analysis shows the crack patterns via 2-D image reconstructions, an index of stimulated fracture density is defined to represent the anisotropic failure mode of shale. What is more, the most striking finding is that the AE monitoring results are in good agreement with the CT analysis. The structural difference in the shale sample is the controlling factor resulting in the anisotropy of AE patterns. The pronounced bedding structure in the shale formation results in an anisotropy of elasticity, strength and AE information from which the changes in strength dominate the entire failure pattern of the shale samples.

Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho

USGS Publications Warehouse

Piper, D.Z.

2001-01-01

Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.

The group separation of the rare-earth elements and yttrium from geologic materials by cation-exchange chromatography

USGS Publications Warehouse

Crock, J.G.; Lichte, F.E.; Wildeman, T.R.

1984-01-01

Demand is increasing for the determination of the rare-earth elements (REE) and yttrium in geologic materials. Due to their low natural abundance in many materials and the interferences that occur in many methods of determination, a separation procedure utilizing gradient strong-acid cation-exchange chromatography is often used to preconcentrate and isolate these elements from the host-rock matrix. Two separate gradient strong-acid cation-exchange procedures were characterized and the major elements as well as those elements thought to provide the greatest interference for the determination of the REE in geologic materials were tested for separation from the REE. Simultaneous inductively coupled argon plasma-atomic emission spectroscopy (ICAP-AES) measurements were used to construct the chromatograms for the elution studies, allowing the elution patterns of all the elements of interest to be determined in a single fraction of eluent. As a rock matrix, U.S. Geological Survey standard reference BCR-1 basalt was digested using both an acid decomposition procedure and a lithium metaborate fusion. Hydrochloric and nitric acids were tested as eluents and chromatograms were plotted using the ICAP-AES data; and we observed substantial differences in the elution patterns of the REE and as well as in the solution patterns of Ba, Ca, Fe and Sr. The nitric acid elution required substantially less eluent to elute the REE and Y as a group when compared to the hydrochloric acid elution, and provided a clearer separation of the REE from interfering and matrix elements. ?? 1984.

Geochemistry of rare earth elements in a passive treatment system built for acid mine drainage remediation.

PubMed

Prudêncio, Maria Isabel; Valente, Teresa; Marques, Rosa; Sequeira Braga, Maria Amália; Pamplona, Jorge

2015-11-01

Rare earth elements (REE) were used to assess attenuation processes in a passive system for acid mine drainage treatment (Jales, Portugal). Hydrochemical parameters and REE contents in water, soils and sediments were obtained along the treatment system, after summer and winter. A decrease of REE contents in the water resulting from the interaction with limestone after summer occurs; in the wetlands REE are significantly released by the soil particles to the water. After winter, a higher water dynamics favors the AMD treatment effectiveness and performance since REE contents decrease along the system; La and Ce are preferentially sequestered by ochre sludge but released to the water in the wetlands, influencing the REE pattern of the creek water. Thus, REE fractionation occurs in the passive treatment systems and can be used as tracer to follow up and understand the geochemical processes that promote the remediation of AMD. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of the world's largest REE deposit through protracted fluxing of carbonatite by subduction-derived fluids

PubMed Central

Ling, Ming-Xing; Liu, Yu-Long; Williams, Ian S.; Teng, Fang-Zhen; Yang, Xiao-Yong; Ding, Xing; Wei, Gang-Jian; Xie, Lu-Hua; Deng, Wen-Feng; Sun, Wei-Dong

2013-01-01

Rare Earth Elements (REE) are essential to modern society but the origins of many large REE deposits remain unclear. The U-Th-Pb ages, chemical compositions and C, O and Mg isotopic compositions of Bayan Obo, the world's largest REE deposit, indicate a protracted mineralisation history with unusual chemical and isotopic features. Coexisting calcite and dolomite are in O isotope disequilibrium; some calcitic carbonatite samples show highly varied δ26Mg which increases with increasing Si and Mg; and ankerite crystals show decreases in Fe and REE from rim to centre, with highly varied REE patterns. These and many other observations are consistent with an unusual mineralisation process not previously considered; protracted fluxing of calcitic carbonatite by subduction-released high-Si fluids during the closure of the Palaeo-Asian Ocean. The fluids leached Fe and Mg from the mantle wedge and scavenged REE, Nb and Th from carbonatite, forming the deposit through metasomatism of overlying sedimentary carbonate.

Protoliths of the high-pressure tectonic blocks from the South Carpathians basement units

NASA Astrophysics Data System (ADS)

Negulescu, Elena; Săbău, Gavril; Massonne, Hans-Joachim

2014-05-01

Several high-pressure (HP) blocks (eclogites, metagabbronorites, garnet-chloritoid-bearing schists and garnet-kyanite mylonites) hosted in medium-pressure metamorphic complexes from the Lotru Metamorphic Suite (LMS), Leaota Massif (LM), and Făgăraş Massif (FM) were investigated in order to derive the nature of their protoliths based on geochemical data and relict fabrics. The variation diagrams using Niggli values (Niggli, 1954) document a typical pelitic protolith for the HP garnet-chloritoid-bearing schists and garnet-kyanite mylonitic gneiss from the LM. Classification diagrams using major- and trace-element data show that most of the compositions of eclogite and metagabbronorite concentrate in and around the field of basalts. A few elogites from the LM and LMS have compositions similar to picrites, rich in Cr and Ni. Thus, the classification diagrams confirm the assumed basaltic character of the studied eclogites and the fact that alterations did not significantly change the original composition. However, there is one notable exception of a very-high pressure (VHP) eclogite and its metasomatic envelope (Negulescu et al., 2009) from the LM. The tholeiitic and in many instances clear MORB character of the eclogites is also illustrated in the Mullen discriminant plot (Mullen, 1983), in contrast to the VHP-eclogite, as also REE-patterns indicate. The protoliths of the studied eclogites and metagabbronorites range from N-MORB to E-MORB. The VHP-eclogite and its rind display, despite metasomatic alterations, similar REE-patterns and other trace element concentrations, comparable with that of North American shale, thereby supporting the sedimentary origin of their protoliths (Negulescu et al., 2009). The most primitive sample is a Ca, Al-rich eclogite from the FM with an overall low REE concentration, displaying a slight Eu anomaly and a tea-spoon shaped LREE depletion indicative of a cumulate origin. The same origin is also probable for a few eclogites from the LMS with a similar kind of REE-patterns. Some E-MORB type eclogites and metagabbronorites from the LM are enriched in LILE and depleted in HFSE (Nb, Zr, Ti). The consequences of the geochemical features are also supported by relict magmatic microtextures. Many eclogites contain microdomains indicating precursor phases replaced by eclogitic assemblages: (1) idiomorphic shapes of former Ti-rich clinopyroxene phenocrystals, replaced by garnet and omphacite, marked by cloudy areas containing rutile dust; (2) prismatic garnet pseudomorphs after plagioclase (3) sharply-delimited domains in composite garnet with abundant quartz inclusions outlining former plagioclase contours; and (4) omphacite replacing magmatic pyroxenes. The geochemical, petrological and thermobaric data available for the South Carpathians HP/low-medium temperature complexes document geochemical and thermobaric contrasts among adjacent lithologies, as well as ocean-derived protoliths enclosed in upper crustal rocks, in apparent structural congruence. This structural setting indicates an intricate tectonometamorphic history involving collision-associated stacking, crustal imbrications, and amalgamation of units originating from distinct continental blocks. Negulescu E. et al. (2009) Journal of Petrology 50/1, 103-125. Niggli P. (1954) Rocks and mineral Deposits. San Francisco, Freeman, 559p. Mullen E. D. (1983) Earth Planet. Sci. Lett. 62, 53-62.

Recovery and separation of rare earth elements using columns loaded with DNA-filter hybrid.

PubMed

Takahashi, Yoshio; Kondo, Kazuhiro; Miyaji, Asami; Umeo, Miyuki; Honma, Tetsuo; Asaoka, Satoshi

2012-01-01

Given that the supply of several rare earth elements (REEs) is sometimes limited, recycling REEs used in various advanced materials, such as Nd magnets, is important for realizing efficient use of REE resources. In the present work, the feasibility of using DNA for REE recovery and separation was examined, along with the identification of the binding site of REEs in DNA. In particular, a DNA-cellulose filter paper hybrid was prepared so that DNA-based materials can be used for the separation of REEs using columns loaded with DNA. N,N'-Disuccinimidyl was used as a cross-linker reagent for the fixation of DNA onto a fibrous cellulose filter. The results showed that (i) the DNA-filter hybrid has a sufficiently high affinity to adsorb REEs; (ii) the adsorption capacity was 0.182 mg/g for Nd; and (iii) the affinity of REEs for DNA was stronger for REEs with larger atomic numbers. The difference of the affinity among REEs in the third result was compared with the adsorption patterns of REEs discussed in the literature. The comparison suggests that phosphate in the DNA-filter paper hybrid was responsible for REE adsorption onto the hybrid. The results were supported by the Nd, Dy, and Lu L(III)-edge EXAFS; the REE-P shell was identified for the second neighboring atom, showing the importance of the phosphate site as REE binding sites. The difference in the affinity among REEs suggest that group separation of REEs (such as La, Ce, (Pr and Nd), (Ho, Dy, and Er), (Tb and Gd), (Sm, Eu), Tm, Yb, and Lu) is possible, although complete isolation of each REE from a solution containing all REEs may be difficult. For practical applications, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste using columns loaded with the DNA-filter hybrid.

Do patients with amyotrophic lateral sclerosis (ALS) have increased energy needs?

PubMed

Vaisman, Nachum; Lusaus, Michal; Nefussy, Beatrice; Niv, Eva; Comaneshter, Doron; Hallack, Ron; Drory, Vivian E

2009-04-15

Nutritional status is a prognostic factor for survival in amyotrophic lateral sclerosis (ALS) patients. We investigated the contribution of some of the components contributing to resting energy expenditure (REE) in order to determine whether potentially higher energy needs should be considered for these patients. Thirty three ALS patients and 33 age- and gender-matched healthy controls participated. REE was measured by an open-circuit indirect calorimeter, body composition by dual energy X-ray absorptiometry, and estimated caloric intake by 7-day food records. Patients had lower body mass indices and lower lean body mass (LBM) than healthy controls. REE values (as a percentage of predicted) was similar but increased when normalized by LBM (P<0.001). LBM and REE decreased while REE/LBM increased in ten patients who were reassessed 6 months later. A model for predicting measured REE was constructed based on the different components, with 86% prediction of its variability. ALS is associated with increased REE. Various factors, such as poor caloric intake and mechanical ventilation, may mask this tendency. All the above parameters need to be considered during nutritional intervention to prevent additional muscle loss.

Study of Geochemical System in Constructed Wetland Using Multivariate Statistical Analysis

NASA Astrophysics Data System (ADS)

Chen, V.

2015-12-01

People have recognized that the human activities lead to the degradation of the environment, and constructed wetland is one of the well-known technologies for water treatment. In constructed wetland, complicated processes should be considered such as redox reactions, acid-base reactions, adsorption-desorption between water and sediment and biochemical reactions associated with plant and microorganism. In this study, most of inorganic components were analyzed and principal component analysis (PCA) was followed for depicting the controlling biochemical reaction in the constructed wetland. The results could be a guide to operate the constructed wetland. The constructed wetland in this study is located in Taoyuan County, north Taiwan. It's a horizontal subsurface flow constructed wetland composed of ten cells. The water in wetland was pumped from Nankan River, which collects wastewater from Hwaya technology park, Linkou, Guishan and Nankan industrial zone. The water of inflow and outflow from each cell were collected for analyzing inorganic components with ICP-MS and IC. In general, the results show that water quality had dramatically changed in the first three cells and became stable in the following seven cells. In this study, PCA extracted two major factors (PCs), which can respectively explain 52.76%（PC1）and 28.32%（PC2）of variance of water quality data. PC1 separates samples of the first three cells from those of the other following cells. It is believed that there was another pollution source involved in the 4th cell because PC1 is characterized by high loadings of most of trace heavy metals. On the other hand, the hydrochemistry of water mainly evolve along PC2 axis. PC2 is composed of Fe, Mn, NH4, dissolved oxygen, pH, etc with high loadings. These chemical components are predominately controlled by redox reactions. Moreover, the deep water from the 4th cell contains high concentrations of many heavy metals, especially Cu and Ga. This confirms the previous derivation based on PCA. The rare earth elements (REEs) were also measured in this study. After normalized to North American shale, the REEs shows an uncommon pattern with Eu and Gd positive anomalies and Tm negative anomaly, which probably result from industrial contamination. However, more studies would be needed to prove it.

Analysis of Rare Earth Elements in Geologic Samples using Inductively Coupled Plasma Mass Spectrometry; US DOE Topical Report - DOE/NETL-2016/1794

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bank, Tracy L.; Roth, Elliot A.; Tinker, Phillip

2016-04-17

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is used to measure the concentrations of rare earth elements (REE) in certified standard reference materials including shale and coal. The instrument used in this study is a Perkin Elmer Nexion 300D ICP-MS. The goal of the study is to identify sample preparation and operating conditions that optimized recovery of each element of concern. Additionally, the precision and accuracy of the technique are summarized and the drawbacks and limitations of the method are outlined.

Reaction of seawater with fresh mid-ocean ridge gabbro creates ';atypical' REE pattern and high REE fluid fluxes: Experiments at 425 and 475 °C, 400 and 1000 bar

NASA Astrophysics Data System (ADS)

Beermann, O.; Garbe-Schönberg, D.; Holzheid, A. D.

2013-12-01

High-temperature MOR hydrothermalism significantly affects ocean chemistry. The Sisters Peak (SP) hydrothermal field at 5°S on the slow-spreading Mid-Atlantic Ridge (MAR) emanates fluids >400°C [1] that have high concentrations of H2, transition metals, and rare earth elements (REE) exhibiting ';atypical' REE pattern characterized by depletions of LREE and HREE relative to MREE and no Eu anomaly [2]. This is in contrast to the ';typical' LREE enrichment and strong positive Eu anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Besides temperature, the seawater-to-rock ratio (w/r ratio) has significant control on the fluid chemistry [e.g., 4, 5]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we reacted unaltered gabbro with natural bottom seawater at 425 °C and 400 bar and at 425 and 475 °C at 1000 bar at variable w/r (mass) ratios ranging from 0.5-10 by using cold seal pressure vessels (CSPV). The run durations varied from 3-72 h. Reacted fluids were analysed for major and trace elements by ICP-OES and ICP-MS. In our experiments, ';atypical' REE fluid pattern similar to those of SP fluids were obtained at high w/r ratio (5 and 10) that might be characteristic for focused fluid-flow along e.g., detachment faults at slow-spreading MOR [6]. In contrast, more ';typical'-like REE pattern with elevated LREE and slightly positive Eu anomalies have been reproduced at low w/r ratio (0.5-1). Results of numerical simulations imply that strong positive Eu anomalies of fluids and altered gabbro from high temperature MOR hydrothermal systems can be created by intense rock leaching processes at high w/r ratio (5-10). This suggests that hydrothermal circulation through the ocean crust creates ';typical' REE fluid pattern with strong positive Eu anomalies if seawater reacts with gabbroic host rock that has been already leached in REE at high fluid fluxes. Simulations of the temporal chemical evolution of high temperature MOR hydrothermal systems reveal that rock and fluid REE contents can rapidly decrease within several months particularly at high fluid fluxes. In contrast, the reaction with ';fresh', unaltered rock is evident from the high REE concentration of SP fluids. Both, fluid access to fresh rock and the fluid flux should therefore significantly control chemical fluxes to the ocean. Thus, high chemical fluxes can be expected in particular from early stage high-temperature MOR hydrothermal systems that are assumed to be not uncommon along the slow-spreading MAR. [1] Koschinsky A., Garbe-Schönberg D., Sander S., Schmidt K., Gennerich H.-H., and Strauss H. (2008) Geology 36, 615-618. [2] Schmidt K., Garbe-Schönberg D., Bau M., and Koschinsky A. (2010) Geochim. Cosmochim. Acta 74, 4058-4077. [3] Douville E., Bienvenu P., Charlou J. L., Donval J. P., Fouquet Y., Appriou P., and Gamo T. (1999). Geochim. Cosmochim. Acta 63, 627-643. [4] Seyfried [Jr.] W. E. and Bischoff J. L. (1977) Earth. Planet. Sci. Lett. 34, 71-77. [5] Hajash A. and Chandler G. W. (1981) Contrib. Mineral. Petrol. 78, 240-254. [6] McCaig A.M. and Harris M. (2012) Geology 40, 367-370.

Effect of thermal maturation on the K-Ar, Rb-Sr and REE systematics of an organic-rich New Albany Shale as determined by hydrous pyrolysis

USGS Publications Warehouse

Clauer, Norbert; Chaudhuri, Sambhudas; Lewan, M.D.; Toulkeridis, T.

2006-01-01

Hydrous-pyrolysis experiments were conducted on an organic-rich Devonian-Mississippian shale, which was also leached by dilute HCl before and after pyrolysis, to identify and quantify the induced chemical and isotopic changes in the rock. The experiments significantly affect the organic-mineral organization, which plays an important role in natural interactions during diagenetic hydrocarbon maturation in source rocks. They produce 10.5% of volatiles and the amount of HCl leachables almost doubles from about 6% to 11%. The Rb-Sr and K-Ar data are significantly modified, but not just by removal of radiogenic 40Ar and 87Sr, as described in many studies of natural samples at similar thermal and hydrous conditions. The determining reactions relate to alteration of the organic matter marked by a significant change in the heavy REEs in the HCl leachate after pyrolysis, underlining the potential effects of acidic fluids in natural environments. Pyrolysis induces also release from organics of some Sr with a very low 87Sr/86Sr ratio, as well as part of U. Both seem to have been volatilised during the experiment, whereas other metals such as Pb, Th and part of U appear to have been transferred from soluble phases into stable (silicate?) components. Increase of the K2O and radiogenic 40Ar contents of the silicate minerals after pyrolysis is explained by removal of other elements that could only be volatilised, as the system remains strictly closed during the experiment. The observed increase in radiogenic 40Ar implies that it was not preferentially released as a volatile gas phase when escaping the altered mineral phases. It had to be re-incorporated into newly-formed soluble phases, which is opposite to the general knowledge about the behavior of Ar in supergene natural environments. Because of the strictly closed-system conditions, hydrous-pyrolysis experiments allow to better identify and even quantify the geochemical aspects of organic-inorganic interactions, such as elemental exchanges, transfers and volatilisation, in potential source-rock shales during natural diagenetic hydrocarbon maturation.

Fate and Trophic Transfer of Rare Earth Elements in Temperate Lake Food Webs.

PubMed

Amyot, Marc; Clayden, Meredith G; MacMillan, Gwyneth A; Perron, Tania; Arscott-Gauvin, Alexandre

2017-06-06

Many mining projects targeting rare earth elements (REE) are in development in North America, but the background concentrations and trophic transfer of these elements in natural environments have not been well characterized. We sampled abiotic and food web components in 14 Canadian temperate lakes unaffected by mines to assess the natural ecosystem fate of REE. Individual REE and total REE concentrations (sum of individual element concentrations, ΣREE) were strongly related with each other throughout different components of lake food webs. Dissolved organic carbon and dissolved oxygen in the water column, as well as ΣREE in sediments, were identified as potential drivers of aqueous ΣREE. Log 10 of median bioaccumulation factors ranged from 1.3, 3.7, 4.0, and 4.4 L/kg (wet weight) for fish muscle, zooplankton, predatory invertebrates, and nonpredatory invertebrates, respectively. [ΣREE] in fish, benthic macroinvertebrates, and zooplankton declined as a function of their trophic position, as determined by functional feeding groups and isotopic signatures of nitrogen (δ 15 N), indicating that REE were subject to trophic dilution. Low concentrations of REE in freshwater fish muscle compared to their potential invertebrate prey suggest that fish fillet consumption is unlikely to be a significant source of REE to humans in areas unperturbed by mining activities. However, other fish predators (e.g., piscivorous birds and mammals) may accumulate REE from whole fish as they are more concentrated than muscle. Overall, this study provides key information on the baseline concentrations and trophic patterns for REE in freshwater temperate lakes in Quebec, Canada.

Hydrochemical study of an arsenic-contaminated plain in Guandu, north Taiwan

NASA Astrophysics Data System (ADS)

Hsiao, Yu-Hsiang

2015-04-01

Arsenic pollution in Guandu Plain, north Taiwan is a critical issue due to highly developed anthropogenic activities. It was considered that arsenic was carried in by surface water system. Two major rivers, Huanggang Creek and South Huang Greek, flow through Guandu Plain. Both creeks originate from Tatung Volcano Group, which is extensively active in post-volcanic activities. In this study, the hydrochemistry along the two major rivers was studied for tracing the source of arsenic pollution in Guandu Plain. The pH values in the upstream water are in the range from 6 to 8 but dramatically decrease down to 2-4.5 in the downstream area. It can be concluded that the creeks are recharged with very low pH geothermal water. In addition, arsenic shows a different spatial distribution. In Huanggang Creek, arsenic concentration is much higher, about 200 ppb to 500 ppb, in the downstream than in the upstream while arsenic concentration is extremely low, below 1 ppb, in the downstream of South Huang Greek. The geochemical results show that rare earth elements (REEs) are depleted in the upstream both in Huanggang creek and South Huang creek, and the NASC-normalized ratios of heavy to light REE (Lu/La) in the upstream are very close to 1. This demonstrates that the upstream water is geochemically dominated by the interaction between water and sedimentary rock. In the downstream, the NASC-normalized REE pattern shows a quit different type which is depleted in light REEs (much higher Lu/La ratio). It is well known that igneous rock is depleted in light REEs; therefore, arsenic is possibly volcanic origin. In this study, PHREEQC, a thermodynamic modeling program, was also utilized to calculate the saturation index (SI) of hydrous ferric oxide (HFO), which can effectively scavenge arsenic in water. The results demonstrate that SI of HFO is mainly controlled by pH in this study. When pH is greater than 3.5, HFO start to precipitate and remove arsenic from water. Therefore, it is believed that the arsenic pollution in Guandu Plain could result from HFO co-precipitation due to the increase of pH when Huanggang creek and South Huang creek flow through the land.

Accumulation of rare earth elements in human bone within the lifespan.

PubMed

Zaichick, Sofia; Zaichick, Vladimir; Karandashev, Vasilii; Nosenko, Sergey

2011-02-01

For the first time, the contents of rare earth elements (REEs) in a rib bone of a healthy human were determined. The mean value of the contents of Ce, Dy, Er, Gd, La, Nd, Pr, Sm, Tb, and Yb (10 elements out of 17 total REEs), as well as the upper limit of means for Ho, Lu, Tm, and Y (4 elements) were measured in the rib bone tissue of 38 females and 42 males (15 to 55 years old) using inductively coupled plasma mass spectrometry (ICP-MS). We found age-related accumulation of REEs in the bone tissue of healthy individuals who lived in a non-industrial region. It was calculated that during a lifespan the content of REEs in a skeleton of non-industrial region residents may increase by one to two orders of magnitude. Using our results as indicative normal values and published data we estimated relative Gd accumulation in the bone tissue of patients according to magnetic resonance imaging with contrast agent and La accumulation in the bone tissue of patients receiving hemodialysis after treatment with lanthanum carbonate as a phosphate binder. It was shown that after such procedures contents of Gd and La in the bone tissue of patients are two to three orders of magnitude higher than normal levels. In our opinion, REEs incorporation may affect bone quality and health similar to other potentially toxic trace metals. The impact of elevated REEs content on bone physiology, biochemistry and morphology requires further investigation.

Rare earth elements in intertidal sediments of Bohai Bay, China: concentration, fractionation and the influence of sediment texture.

PubMed

Zhang, Yong; Gao, Xuelu; Arthur Chen, Chen-Tung

2014-07-01

Surface sediments from intertidal Bohai Bay were assessed using a four-step sequential extraction procedure to determine their concentrations of rare earth elements (REEs) and the chemical forms in which those elements were present. The normalized ratios La/Gd and La/Yb showed that LREE contents were not significantly higher than the middle REEs or HREE contents. A negative Ce anomaly and positive Eu were observed in sand and silty sand sediments, whereas no significant Ce or Eu anomaly was found in clayey silt sediments. Residual fraction of REEs accounted for the majority of their total concentrations. Middle REEs were more easily leached than other REEs, especially in clayey silt sediment. REEs contents in the surface sediment from the intertidal Bohai Sea were consistent with data from the upper continental crust and China shallow sea sediments, indicating that they were generally unaffected by heavily anthropogenic effects from adjacent areas. Copyright © 2014 Elsevier Inc. All rights reserved.

Interactions between gastro-oesophageal reflux disease and eosinophilic oesophagitis.

PubMed

Molina-Infante, Javier; van Rhijn, Bram D

2015-10-01

Gastro-oesophageal reflux disease (GORD) is the most common oesophageal disorder, whereas eosinophilic oesophagitis (EoE) is an emerging disease unresponsive to PPI therapy. Updated guidelines in 2011 described proton pump inhibitor-responsive esophageal eosinophilia (PPI-REE), a novel phenotype in EoE patients who were responsive to PPIs. This article aims to update the complex interplay between GORD, EoE and PPIs. Oesophageal mucosal integrity is diffusely impaired in EoE and PPI-REE patients. PPI-REE might occur with either normal or pathological pH monitoring. The genetic hallmark of EoE is overlapped in PPI-REE, but not in GORD. PPIs can partially restore epithelial integrity and reverse allergic inflammation gene expression in PPI-REE. Acid hypersensitivity in EoE patients may explain symptomatic but not histological response on PPIs. Unsolved issues with PPI-REE are whether oesophageal barrier impairment is the cause or the effect of oesophageal eosinophilia and whether PPIs primarily targets barrier integrity or oesophageal inflammation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rare earth elements in core marine sediments of coastal East Malaysia by instrumental neutron activation analysis.

PubMed

Ashraf, Ahmadreza; Saion, Elias; Gharibshahi, Elham; Mohamed Kamari, Halimah; Chee Kong, Yap; Suhaimi Hamzah, Mohd; Suhaimi Elias, Md

2016-01-01

A study was carried out on the concentration of REEs (Dy, Sm, Eu,Yb, Lu, La and Ce) that are present in the core marine sediments of East Malaysia from three locations at South China Sea and one location each at Sulu Sea and Sulawesi Sea. The sediment samples were collected at a depth of between 49 and 109 m, dried, and crushed to powdery form. The entire core sediments prepared for Instrumental Neutron Activation Analysis (INAA) were weighted approximately 0.0500 g to 0.1000 g for short irradiation and 0.1500 g to 0.2000 g for long irradiation. The samples were irradiated with a thermal neutron flux of 4.0×10(12) cm(-2) s(-1) in a TRIGA Mark II research reactor operated at 750 kW. Blank samples and standard reference materials SL-1 were also irradiated for calibration and quality control purposes. It was found that the concentration of REEs varies in the range from 0.11 to 36.84 mg/kg. The chondrite-normalized REEs for different stations suggest that all the REEs are from similar origins. There was no significant REEs contamination as the enrichment factors normalized for Fe fall in the range of 0.42-2.82. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Redox Dynamics of Iron in a Seasonally Waterlogged Forest Soil (Chaux Forest, Eastern France) Traced with Rare Earth Element Distribution Patterns

NASA Astrophysics Data System (ADS)

Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.

2014-12-01

The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.

Reassessing the Formation of CK7 Northwest Africa (NWA) 8186

NASA Technical Reports Server (NTRS)

Srinivasan, P.; McCubbin, F. M.; Lapen, T. J.; Righter, M.; Agee, C. B.

2017-01-01

The classification of meteorites is commonly determined using isotopes, modal mineralogy, and bulk compositions [1]. Bulk rare earth elements (REEs) in meteorites are additionally utilized to understand parent body processes. Numerous authors have shown that chondritic groups exhibit REE patterns that may be attributable to their parent bodies [e.g. 2-4], and variations in abundances and concentrations of REEs may reflect early nebular processes, thermal metamorphism, and aqueous alteration on the parent body [5-6].

Interoceanic variation in the rare earth, major, and trace element depositional chemistry of chert: Perspectives gained from the DSDP and ODP record

USGS Publications Warehouse

Murray, R.W.; Buchholtz ten Brink, Marilyn R.; Gerlach, David C.; Russ III, G. Price; Jones, David L.

1992-01-01

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~ 11% NASC, Atlantic chert ~ 17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for ∑REE, approximations of Laex (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest Laex (85% of Latotal) and SHL chert the least (38% of Latotal). As shown by interelement associations, this Laex is most likely an adsorbed component onto aluminosilicate and phosphatic phases.Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert CeCe*⪡ 1 and LanYbn ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., LanYbn ~ 0.4), which increases the LanYbn ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and LanYbn">LanYbn ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited CeCe*~1">CeCe*~1 and inherited LanYbn">LanYbn values of ~1.2–1.4.CeCe*">~1.2–1.4.CeCe* does not vary with age, either throughout the entire data base or within a particular basin. Overall, CeCe*">CeCe* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.This and previous studies of the large-scale controlling parameters of sedimentary REEs across ocean basins collectively indicate that REE indices of depositional regime (e.g., CeCe*">CeCe*, LanYbn">LanYbn, Laex) are reproducible in a variety of sediment and rock lithologies, ages, and ocean basins, and present a coherent tool for paleoceanographic and tectonic basin reconstructions.

Mineralogical and geochemical features of alluvial sediments from the Lobo watershed (Southern Cameroon): Implications for rutile exploration

NASA Astrophysics Data System (ADS)

Nyobe, Jules Mbanga; Sababa, Elisé; Bayiga, Elie Constantin; Ndjigui, Paul-Désiré

2018-03-01

This paper is focused on the morphological, mineralogical, and geochemical features of alluvial sediments from the Neoproterozoic Pan-African belt to explore rutile. The fine-grained sediments, which contain a large proportion of rutile, are made up of quartz, rutile, zircon, brookite, tourmaline, andalusite, and kyanite. The high SiO2 and TiO2 contents highlight the predominance of silica minerals in the alluvia from the humid tropical zone. La/Sc, La/Co, Th/Sc and Zr/Cr ratios reflect the contribution of felsic and mafic sources. The highest Ti contents, which occur at the outlet of the Lobo watershed, indicate the resistance of rutile. The REE distribution could be linked to the heavy mineral sorting. The low (La/Yb)N ratios and high Zr contents are attributed to the high proportion of zircon. Chondrite-normalized REE patterns indicate high felsic sources, which are the regional rocks. Ultimately, the Yaoundé Group constitutes a favorable potential target for further rutile exploration.

Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

NASA Technical Reports Server (NTRS)

Fahey, A. J.; Mckeegan, K. D.; Zinner, E.; Goswami, J. N.

1987-01-01

Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

Spatial variability and geochemistry of rare earth elements in soils from the largest uranium-phosphate deposit of Brazil.

PubMed

Cunha, Cleyton Saialy Medeiros; da Silva, Ygor Jacques Agra Bezerra; Escobar, Maria Eugenia Ortiz; do Nascimento, Clístenes Williams Araújo

2018-02-22

The Itataia uranium-phosphate deposit is the largest uranium reserve in Brazil. Rare earth elements (REEs) are commonly associated with phosphate deposits; however, there are no studies on the concentrations of REEs in soils of the Itataia deposit region. Thus, the objective of the research was to evaluate the concentration and spatial variability of REEs in topsoils of Itataia phosphate deposit region. In addition, the influence of soil properties on the geochemistry of REEs was investigated. Results showed that relatively high mean concentrations (mg kg -1 ) of heavy REEs (Gd 6.01; Tb 1.25; Ho 1.15; Er 4.05; Tm 0.64; Yb 4.61; Lu 0.65) were found in surface soils samples. Soil properties showed weak influence on the geochemical behavior of REEs in soils, except for the clay content. On the other hand, parent material characteristics, such as P and U, had strong influence on REEs concentrations. Spatial distribution patterns of REEs in soils are clearly associated with P and U contents. Therefore, geochemical surveys aiming at the delineation of ore-bearing zones in the region can benefit from our data. The results of this work reinforce the perspective for co-mining of P, U and REEs in this important P-U reserve.

The Chicxulub impact at the K-Pg boundary - search for traces of the projectile

NASA Astrophysics Data System (ADS)

Deutsch, A.

2012-04-01

One of the most interesting problems in the context of the end-Cretaceous Chicxulub impact is the question after the whererabouts of the main mass of the projectile. The nature of this >10 km-sized Chicxulub projectile was constrained by an anomaly in the chromium isotope 54 in the K-Pg deposit at Stevens Klint, Denmark, to a carbonaceous chondrite of type CM2 [1]. About 1.5 % of the estimated mass of the projectile has been detected world-wide in the K-Pg boundary layer; mainly in the form of platinum group elements (PGE) as well as other siderophile elements (Ni, Co ... ). A contamination by or even a major contribution of other "projectile" elements to the K-Pg event bed was rarely proposed. The few examples in the literature (cf. compilation in [2, 3]) used rare earth elements (REE) distribution patterns that are slightly inconsistent with REE patterns typical for the upper continental crust (UCC). Ejecta consisting of UCC target rocks is expected to form the overwhelming mass of the ejecta. In most K-Pg layers, however, the ejecta is diluted or even totally masked by a component of more local origin and with features of high-energy deposition mechanisms. Numerical models [4] indicate a deposition of >500km3 projectile material, corresponding to >2 x 10exp9 tons of mainly silica, iron, and magnesium in the K-Pg event bed. Detecting the "meteoritic" origin of these major elements, however, in a matrix of siliceous detritus, is practically impossible. Recent LA-ICP-MS analyses show that siliceous impact spherules - hydrated glass or altered to chlorite - in the Chicxulub event bed at various locations (e.g., Shell Creek, La Lajilla, La Popa) have REE patterns that are flat and un-fractionated, corresponding quite well to a typical CI-pattern. The REE abundances are chondritic to sub-chondritic. Mixing calculations indicate that the maximum REE contribution of UCC material to the REE budget of these spherules is on the order of 2 %, but usually much less. These flat REE patterns cannot originate from any known alteration process; they truly reflect a "meteoritic" component in the spherules. Accepting this fact, a certain amount of the siliceous host material (i.e., the spherules) must consist also of projectile material. Depending on the sampling site, the spherules with the flat REE distribution patterns amount to between 10 and ~70 vol% of the Chicxulub event bed. The widespread occurrence of this projectile matter in the K-Pg event bed reconciles observations with impact models [4]. Ref. [1] Trinquier A. et al. (2006) EPSL 241, 780-788. [2] Smit J. (1999) Ann. Rev. Earth Planet. Sci. 27, 75-113. [3] Schulte P. et al. (2010) Science 327, 1214-1218. [4] Artemieva N. and Morgan J. (2009) Icarus 201, 768-780.

Geochemical constraints on provenance of the mid-Pleistocene red earth sediments in subtropical China

NASA Astrophysics Data System (ADS)

Hong, Hanlie; Wang, Chaowen; Zeng, Kefeng; Gu, Yansheng; Wu, Yuanbao; Yin, Ke; Li, Zhaohui

2013-05-01

The source of mid-Pleistocene red earth sediments in the middle to lower reaches of the Yangtze (Changjiang) River was investigated based on their geochemical characteristics. The Xuancheng and Jiujiang red earth sediments have similar major and trace element distribution patterns. Compared to the loess and paleosol deposits of the Chinese Loess Plateau, the upper continental crust (UCC), and the post-Archean Australian average shale (PAAS), the sediments display notable depletion of CaO, MgO, Na2O, and accumulation of TiO2, Al2O3, and Fe2O3(t). The trace element distribution patterns of the red earth sediments are also different from those of loess and the PAAS, but are similar to those of the loess deposits, except for lower values of mobile trace elements Sr, Ba, and Ni, and higher values of Zr and Y. The red earth samples have uniform La/Th ratios of ~ 2.8, compatible with those of the UCC, loess, and paleosol. They also have similar chondrite-normalized REE patterns, characterized by enriched LREE and relatively flat HREE profiles, and consistent negative Eu anomalies, similar to those of the UCC, the loess and paleosol, and the Yangtze deposits. These results suggest that the red earth sediments have been subject to considerable mixing prior to deposition and strong subsequent chemical weathering. The sediments have very uniform 143Nd/144Nd and 147Sm/144Nd ratios, this points to well-mixed and multi-recycled sediments. The 143Nd/144Nd and 87Sr/86Sr values of the red earth sediments match well with those of the deposits in the middle to lower reaches of the Yangtze River, but are different from those of the loess and paleosols. This suggests that the red earth sediments are derived from the drainage basins of the middle to lower Yangtze River and might have experienced more intense chemical weathering relative to the Yangtze deposits, as reflected by their higher Rb/Sr ratios, intense depletion of mobile elements and accumulation of immobile elements, as well as their well-developed net-like structure.

The Mineralogical Record of Oxygen Fugacity Variation and Alteration in Northwest Africa 8159: Evidence for Interaction Between a Mantle Derived Martian Basalt and a Crustal Component(s)

NASA Technical Reports Server (NTRS)

Shearer, Charles K.; Burger, Paul V.; Bell, Aaron S.; McCubbin, Francis M.; Agee, Carl; Simon, Justin I.; Papike, James J.

2015-01-01

A prominent geochemical feature of basaltic magmatism on Mars is the large range in initial Sr isotopic ratios (approx. 0.702 - 0.724) and initial epsilon-Nd values (approx. -10 to greater than +50). Within this range, the shergottites fall into three discreet subgroups. These subgroups have distinct bulk rock REE patterns, mineral chemistries (i.e. phosphate REE patterns, Ni, Co, V in olivine), oxygen fugacity of crystallization, and stable isotopes, such as O. In contrast, nakhlites and chassignites have depleted epsilon-Nd values (greater than or equal to +15), have REE patterns that are light REE enriched, and appear to have crystallized near the FMQ buffer. The characteristics of these various martian basalts have been linked to different reservoirs in the martian crust and mantle, and their interactions during the petrogenesis of these magmas. These observations pose interesting interpretive challenges to our understanding of the conditions of the martian mantle (e.g. oxygen fugacity) and the interaction of mantle derived magmas with the martian crust and surface. Martian meteorite NWA 8159 is a unique fine-grained augite basalt derived from a highly depleted mantle source as reflected in its initial epsilon-Nd value, contains a pronounced light REE depleted pattern, and crystallized presumably under very oxidizing conditions. Although considerably older than both shergottites and nahklites, it has been petrogenetically linked to both styles of martian magmatism. These unique characteristics of NWA 8159 may provide an additional perspective for deciphering the petrogenesis of martian basalts and the nature of the crust of Mars.

Water Content in the SW USA Mantle Lithosphere: FTIR Analysis of Dish Hill and Kilbourne Hole Pyroxenites

NASA Technical Reports Server (NTRS)

Gibler, Robert; Peslier, Anne H.; Schaffer, Lillian Aurora; Brandon, Alan D.

2014-01-01

Kilbourne Hole (NM, USA) and Dish Hill (CA, USA) mantle xenoliths sample continental mantle in two different tectonic settings. Kilbourne Hole (KH) is located in the Rio Grande rift. Dish Hill (DH) is located in the southern Mojave province, an area potentially affected by subduction of the Farallon plate beneath North America. FTIR analyses were obtained on well characterized pyroxenite, dunite and wehrlite xenoliths, thought to represent crystallized melts at mantle depths. PUM normalized REE patterns of the KH bulk-rocks are slightly LREE enriched and consistent with those of liquids generated by < 5% melting of a spinel peridotite source. Clinopyroxenes contain from 272 to 313 ppm weight H2O similar to the lower limit of KH peridotite clinopyroxenes (250-530 ppm H2O). This is unexpected as crystallized melts like pyroxenites should concentrate water more than residual mantle-like peridotites, given that H is incompatible. PUM normalized bulk REE of the DH pyroxenites are characterized by flat to LREE depleted REE profiles consistent with > 6% melting of a spinel peridotite source. Pyroxenite pyroxenes have no detectable water but one DH wehrlite, which bulk-rock is LREE enriched, has 4 ppm H2O in orthopyroxene and <1ppm in clinopyroxene. The DH pyroxenites may thus come from a dry mantle source, potentially unaffected by the subduction of the Farallon plate. These water-poor melts either originated from shallow oceanic lithosphere overlaying the Farallon slab or from continental mantle formed > 2 Ga. The Farallon subduction appears to have enriched in water the southwestern United States lithospheric mantle further east than DH, beneath the Colorado plateau.

Geochemical characteristics of aluminum depleted and undepleted komatiites and HREE-enriched low-Ti tholeiites, western Abitibi greenstone belt: A heterogeneous mantle plume-convergent margin environment

NASA Astrophysics Data System (ADS)

Fan, J.; Kerrich, R.

1997-11-01

A compositionally diverse suite of komatiites, komatiitic basalts, and basalts coexist in the Tisdale volcanic assemblage of the late-Archean (˜2.7 Ga) Abitibi greenstone belt. The komatiites are characterized by a spectrum of REE patterns, from low total REE contents (9 ppm) and pronounced convex-up patterns to greater total REE (18 ppm) and approximately flat-distributions. Thorium and niobium are codepleted with LREE. Komatiites with the most convex-up patterns have low Al 2O 3 (4.7 wt%) contents and Al 2O 3/TiO 2(12) ratios; they are interpreted to be the Al-depleted variety of komatiite derived from a depleted mantle source. Those komatiites and komatiitic basalts with flatter REE patterns are characterized by greater Al 2O 3 (7.0 wt%) and near chondritic Al 2O 3/TiO 2 (20) ratios; they are interpreted to be Al-undepleted komatiites generated from trace element undepleted mantle. For the komatiites and komatiitic basalts collectively, Gd/Ybn ratios are negatively correlated with La/Smn, but positively with MgO and Ni. The spectrum of patterns is interpreted as mixing between Al, HREE, Y-depleted, and Sc-depleted komatiites and Al-undepleted komatiites in a heterogeneous mantle plume. Auminum-depleted komatiites are characterized by negative Zr and Hf anomalies, consistent with majorite garnet-liquid D's for HFSE and REEs, signifying melt segregation at depths of >400 km. Tisdale Al-undepleted komatiites and komatiitic basalts have small negative to zero Zr(Hf)/MREE fractionation, signifying melt segregation in or above the garnet stability field. Collectively, the komatiites have correlations of Zr/Zr∗ and Hf/Hf ∗ with Gd/Ybn, and hence the Zr(Hf)/MREE fractionations are unlikely to have stemmed from alteration or crustal contamination. Two types of basalts are present. Type I basalts are Mg-tholeiites with near flat REE and primitive mantle normalized patterns, compositionally similar to abundant Mg-tholeiites associated with both Al-undepleted and Al-depleted komatiites in the Abitibi belt. They have absolute concentrations and ratios of most moderately and highly compatible elements comparable to N- MORB (Zr ˜79 vs. 74, Y ˜30 vs. 28, and Zr/Y = 2.4-2.9 vs. 2.6 ), but are relatively less depleted in highly incompatible elements and lack positive Nb or P anomalies. Type II basalts are relatively aluminous (Al 2O 3 ˜ 16 wt%), with high Al 2O 3/TiO 2 (24-28) ratios. They are characterized by low Th, Nb, and LREE contents at eight to ten times chondrite, with slightly convex-up LREE patterns ( La/Smn = 0.86-0.99 ), but strongly fractionated and enriched HREEs, Y, and Sc, where Gd/Ybn = 0.50-0.55 and consistently positive Zr(Hf)/MREEs anomalies. These basalts are tentatively interpreted as low-Ti tholeiites formed in a convergent margin setting with second stage melting, induced by fluids and melts enriched in incompatible elements and Zr(Hf) relative to MREEs, of a mantle source depleted during first stage melting. They are analogous to the Phanerozoic low-Ti tholeiite - boninite association. Accordingly the Tisdale volcanic sequence records a plume-convergent margin interaction. New analyses of Al-undepleted komatiites from the classical locality at Pyke Hill in Munro Township confirm the presence of small positive anomalies of P, Zr, and Hf, with Zr/Hf ratios generally < 36. These signatures are similar in spinifex and cumulate zones signifying that they are unlikely to have resulted from alteration. The data were generated by INAA and ICP-MS using both HFHNO 3 dissolution and Na 2O 2 sinter. The lack of LREE enrichment with negative Nb, Ta, P, and Ti anomalies in any of the Tisdale or Munro komatiites confirms an intraoceanic setting for the volcanic stage of the Western Abitibi greenstone belt.

Rare earth element mobility in vesicular lava during low-grade metamorphism

NASA Astrophysics Data System (ADS)

Nyström, Jan Olov

1984-12-01

A geochemical comparison of basaltic relicts and spilitic domains from two burial metamorphosed flows in central Chile, of similar original composition and rich and poor in amygdules, respectively, demonstrates a relationship between initial vesicularity and rare earth element (REE) mobility. During spilitization the REE were partly leached from permeable parts of the flows and precipitated in voids, now amygdules and veinlets. The REE (excluding Eu) moved coherently in the highly amygdaloidal flow: spilitic domains and amygdules inherited the basaltic REE pattern. Besides being characterized by a positive Eu anomaly, epidotes separated from amygdules have a REE distribution which mimics that of the basalt; the absolute contents range widely, suggesting local and/or temporal REE variations in the metamorphic fluids. Pumpellyite differs by being strongly enriched in heavy REE. Similar ratios of Th, Hf and Ta in samples as contrasting as relict basalt and a geode are consistent with coherent leaching. Coherent mobility, when established for a rock system, can be used to elucidate, for example, whether minerals in cross-cutting veins were formed by local redistribution or from introduced material.

Preliminary study of extraction of heavy metals in sediments under pH-controlled conditions

NASA Astrophysics Data System (ADS)

Kao, M.

2012-12-01

The arsenic ingestion not only increases the risk of developing cancer of the skin, internal organs and lungs but also causes a peripheral vascular gangrene disease known as black-foot disease. It is crucial to determine the arsenic source for managing groundwater resources properly. The study area, Tsengwen Creek watershed, is in the middle of Chianan Plain, which has been identified with problems of high arsenic content in groundwater. According to the results of BCR extraction procedure conducting on core sediments, it is interesting that arsenic content extracted by deionized water is significantly higher than that extracted with the first step of BCR, which is 0.11 mol/L acetic acid. It is believed that deionized water can only extract metals adsorbing on mineral surface without strong chemical bonding and acetic acid can extract those in the forms both of adsorption and carbonate. Even though arsenic is scarcely associated with carbonates, the deionized water can obviously extract much more arsenic than acid solution. Therefore, desorption of arsenic is possible to be controlled by a strong pH-dependent reaction. For the preliminary analysis, a laboratory experiment was performed to evaluated desorption of metals with pH control in this study. The solutions with different values of pH are simply adjusted with sodium hydroxide (NaOH). Ten sediment samples were collected from aquifers in Tsengwen Creek watershed. To simulate an isolated system like groundwater in aquifer, these sediments were extracted with solutions of pH=7, 8, 9 and 10 in a container purged by nitrogen gas. The results demonstrate that arsenic does show significant enrichment in solution of pH=10 and vanadium shares the similar property with arsenic. On the contrary, the other selected metals of cadmium, copper, nickel and cobalt have no similar enrichment in high-pH extraction solution; especially, nickel and cobalt are highly enriched in deionized water. These are possibly caused by the variation of ionic potential. Rare earth elements (REE) are an excellent tracer in geochemical reaction system and were also measured in this study. The NASC-normalized results demonstrate a middle-REE-enriched pattern; i.e. terbium is the most abundant NASC-normalized REE. Some previous studies reported that a middle-REE-enriched pattern indicates a source of organic matter in soil. It is also known that humic substances prefer to be dissolved in higher pH solution. This is consistence with the results in this study.

Rare earth element carriers in the Shergotty meteorite and implications for its chronology

NASA Technical Reports Server (NTRS)

Lundberg, Laura L.; Crozaz, Ghislaine; Zinner, Ernst; Mckay, Gordon

1988-01-01

This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).

Rare earth elements minimal harvest year variation facilitates robust geographical origin discrimination: The case of PDO "Fava Santorinis".

PubMed

Drivelos, Spiros A; Danezis, Georgios P; Haroutounian, Serkos A; Georgiou, Constantinos A

2016-12-15

This study examines the trace and rare earth elemental (REE) fingerprint variations of PDO (Protected Designation of Origin) "Fava Santorinis" over three consecutive harvesting years (2011-2013). Classification of samples in harvesting years was studied by performing discriminant analysis (DA), k nearest neighbours (κ-NN), partial least squares (PLS) analysis and probabilistic neural networks (PNN) using rare earth elements and trace metals determined using ICP-MS. DA performed better than κ-NN, producing 100% discrimination using trace elements and 79% using REEs. PLS was found to be superior to PNN, achieving 99% and 90% classification for trace and REEs, respectively, while PNN achieved 96% and 71% classification for trace and REEs, respectively. The information obtained using REEs did not enhance classification, indicating that REEs vary minimally per harvesting year, providing robust geographical origin discrimination. The results show that seasonal patterns can occur in the elemental composition of "Fava Santorinis", probably reflecting seasonality of climate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mineralogical Features and REE Distribution in Ortho- and Clinopyroxenes of the HaH 317 Enstatite Chondrite

NASA Astrophysics Data System (ADS)

Moggi-Cecchi, V.; Pratesi, G.

2004-03-01

SEM, EMPA and LA-ICP-MS analyses have been performed on HaH 317, an EL4 enstatite chondrite. Phases detected are En, Kam, Tro, Dio, Pla, Nin, Old. Diopside and enstatite grains display similar REEs patterns with marked Ce and LREE enrichments.

Trace element studies of silicate-rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

NASA Astrophysics Data System (ADS)

Kurat, Gero; Zinner, Ernst; Varela, Maria Eugenia

2007-08-01

A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO2, Al2O3, and Na2O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (˜80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low-Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10-50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co-existing glass is poor in REEs (˜0.1-1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO2, Al2O3, Na2O, and K2O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass-only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca-Al-rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene-rich liquids) and vapor-solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe2+ metasomatism, metasomatic loss of REEs from glass).

a Dual Proxy of Oceanic Weathering Inputs: Rare Earth Element Patterns and nd Isotopes from Metalliferous Sediment Cores

NASA Astrophysics Data System (ADS)

Sherrell, R. M.; Wright, J. D.; Hamelin, B.; Michard, A.

2002-12-01

Recent interest in reconstructing Nd isotopic distributions in the past ocean using Fe-Mn crusts, oxide coatings on sediment particles, foraminifera shells and fish teeth has raised questions about relative influence of water mass mixing vs. variations in weathering input. We have explored the utility of hydrothermal metalliferous sediments for generating high-resolution records of both Nd isotopes and rare earth element (REE) patterns in deepwater. We present a 135kyr record of high precision REE data, preliminary Nd isotope ratios, and δ18O from a 2.3 m core collected at 3180m at 11S on the East Pacific Rise (EPR). REEs are dominated (\\>96%) by seawater REEs adsorbed to Fe particles in these metalliferous carbonates; the hydrothermal REE source itself is negligible. Downcore variations in Nd/Er (proxy for light/heavy pattern fractionation) are not large (10%) but are easily quantified by our ICP-MS method (precision 1%), and reproducibly correspond to δ18O shifts. The largest Nd/Er excusions occur during deglaciations, e.g. Nd/Er=5.1 to 4.4 mol/mol between glacial MIS 6 and interglacial MIS 5e. If these variations reflect composition of ambient deepwater, then the results are opposite those expected by reduced influence of Atlantic component water (high Nd/Er) during glacials. Prelimininary ɛNd values for samples taken at Nd/Er extrema in MIS 1, 2, 5e and 6 are nearly invarient at -3.5+/-0.4, in excellent agreement with modern water column ɛNd for Pacific deepwater at this depth. Thus, while paleo-ɛNd shows virtually no change over 135kyr, REE pattern does carry information, but not, we believe, about water mass mixing changes. We suggest instead that Nd/Er reflects climatically-influenced weathering inputs to the Pacific REE pool. We propose a sea-level-driven mechanism: glacial low sea-stand reduces the extent of estuarine environments in which the light-REE-depleted seawater pattern is imparted, causing 1) more direct input of unfractionated crustal REE sources, and 2) release of REEs during erosion of high Nd/Er shelf sediments. This mechanism, unlike tectonically-driven shifts in weathering sources, can occur on glacial/interglacial timescales, and is expected to result in negligible change in Nd isotopic input, consistent with observations. Alternative mechanisms could involve temporal variations in the flux and composition of water column particles. In a first application to longer timescales, a low-resolution Cenozoic record from DSDP Leg 92, shows much larger but smooth variation of 50% in Nd/Er between 28 and 1.5 Ma, with high values from 28 to 20 Ma, decreasing during the mid-Miocene to values similar to modern at <8 Ma. ɛNd varies from -3 (near present deepwater value) to ~-6, but does not co-vary simply with Nd/Er. The combination of Nd/Er and ɛNd constitutes a new tandem proxy that may reveal changes in the style and/or source of weathering inputs to the past ocean, not interpretable from ɛNd alone. The results may have implications for climate-linked changes in the oceanic supply of biogeochemically important elements such as Fe and P.

A New Dual Proxy of Oceanic Weathering Inputs: Rare Earth Element Patterns and Nd Isotopes From Metalliferous Sediment Cores

NASA Astrophysics Data System (ADS)

Sherrell, R.; Wright, J.; Michard, A.; Hamelin, B.

Recent interest in reconstructing Nd isotopic distributions in the past ocean using Fe- Mn crusts, oxide coatings on sediment particles, foraminifera shells and fish teeth has raised questions about relative influence of water mass mixing vs. variations in weath- ering input. We have explored the utility of hydrothermal metalliferous sediments for generating high-resolution records of both Nd isotopes and rare earth element (REE) patterns in deepwater. We present a 135kyr record of high precision REE data, pre- liminary Nd isotope ratios, and 18O from a 2.3 m core collected at 3180m at 11S on the East Pacific Rise (EPR). REEs are dominated ( 96%) by seawater REEs adsorbed to Fe particles in these metalliferous carbonates; the hydrothermal REE source itself is negligible. Downcore variations in Nd/Er (proxy for light/heavy pattern fractiona- tion) are not large (10%) but are easily quantified by our ICP-MS method (precision 1%), and reproducibly correspond to 18O shifts. The largest Nd/Er excusions occur during deglaciations, e.g. Nd/Er=5.1 to 4.4 mol/mol between glacial MIS 6 and inter- glacial MIS 5e. If these variations reflect composition of ambient deepwater, then the results are opposite those expected by reduced influence of Atlantic component water (high Nd/Er) during glacials. Prelimininary Nd values for samples taken at Nd/Er ex- trema in MIS 1, 2, 5e and 6 are nearly invarient at -3.5+/-0.4, in excellent agreement with modern water column Nd for Pacific deepwater at this depth. Thus, while paleo- Nd shows virtually no change over 135kyr, REE pattern does carry information, but not, we believe, about water mass mixing changes. We suggest instead that Nd/Er re- flects climatically-influenced weathering inputs to the Pacific REE pool. We propose a sea-level-driven mechanism: glacial low sea-stand reduces the extent of estuarine environments in which the light-REE-depleted seawater pattern is imparted, causing 1) more direct input of unfractionated crustal REE sources, and 2) release of REEs during erosion of high Nd/Er shelf sediments. This mechanism, unlike tectonically- driven shifts in weathering sources, can occur on glacial/interglacial timescales, and is expected to result in negligible change in Nd isotopic input, consistent with ob- servations. Alternative mechanisms could involve temporal variations in the flux and composition of water column particles. In a first application to longer timescales, a low-resolution Cenozoic record from DSDP Leg 92, shows much larger but smooth variation of 50% in Nd/Er between 28 and 1.5 Ma, with high values from 28 to 20 Ma, decreasing during the mid-Miocene to values similar to modern at <8 Ma. Nd varies from -3 (near present deepwater value) to -6, but does not co-vary simply with Nd/Er. The combination of Nd/Er and Nd constitutes a new tandem proxy that may reveal changes in the style and/or source of weathering inputs to the past ocean, not interpretable from Nd alone. The results may have implications for climate-linked changes in the oceanic supply of biogeochemically important elements such as Fe and P.

Rare-earth abundances in chondritic meteorites

NASA Technical Reports Server (NTRS)

Evensen, N. M.; Hamilton, P. J.; Onions, R. K.

1978-01-01

Fifteen chondrites, including eight carbonaceous chondrites, were analyzed for rare earth element abundances by isotope dilution. Examination of REE for a large number of individual chondrites shows that only a small proportion of the analyses have flat unfractionated REE patterns within experimental error. While some of the remaining analyses are consistent with magmatic fractionation, many patterns, in particular those with positive Ce anomalies, can not be explained by known magmatic processes. Elemental abundance anomalies are found in all major chondrite classes. The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibrium or were introduced at a late stage of chondrite formation. Large-scale segregation of gas and condensate is implied, and bulk variations in REE abundances between planetary bodies is possible.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis

NASA Astrophysics Data System (ADS)

Zaharescu, Dragos G.; Burghelea, Carmen I.; Dontsova, Katerina; Presler, Jennifer K.; Maier, Raina M.; Huxman, Travis; Domanik, Kenneth J.; Hunt, Edward A.; Amistadi, Mary K.; Gaddis, Emily E.; Palacios-Menendez, Maria A.; Vaquera-Ibarra, Maria O.; Chorover, Jon

2017-02-01

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis

PubMed Central

Zaharescu, Dragos G.; Burghelea, Carmen I.; Dontsova, Katerina; Presler, Jennifer K.; Maier, Raina M.; Huxman, Travis; Domanik, Kenneth J.; Hunt, Edward A.; Amistadi, Mary K.; Gaddis, Emily E.; Palacios-Menendez, Maria A.; Vaquera-Ibarra, Maria O.; Chorover, Jon

2017-01-01

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake. PMID:28230202

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications

DOE PAGES

Balboni, Enrica; Jones, Nina; Spano, Tyler; ...

2016-08-31

This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO 2+x) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relativemore » to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic 87Sr/ 86Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. Lastly, this result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.« less

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Jones, Nina; Spano, Tyler

This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO 2+x) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relativemore » to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic 87Sr/ 86Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. Lastly, this result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.« less

Petrology and geochemistry of komatiites and tholeiites from Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Aitken, Bruce G.; Echeverría, Lina M.

1984-04-01

Komatiitic rocks from Gorgona Island, Colombia, in contrast to their Archaean counterparts, occur as rather structureless flows. In addition, textural and mineralogical features indicate that the Gorgona komatiites may have crystallized from superheated liquids. Komatiitic rocks have MgO contents which range from 24 to 11 wt.% and plot on well-defined olivine (Fo90) control lines. Calculations show that potential evolved liquids (MgO<11 wt%) will be SiO2-poor. Komatiites, in this case, cannot be regarded as parental to the associated tholeiitic basalt sequence. On the basis of REE concentrations and Sr, Nd isotopic compositions, the associated basalts are found to be of two types. One type (K-tholeiite) is characterized by noticeably fractionated REE patterns and relatively primitive isotopic compositions similar to those of the komatiites. K-tholeiites, together with komatiites, are regarded as comprising a distinctive komatiitic suite. REE patterns within this suite show progressive depletion in the LREE from K-tholeiites to komatiites, and represent increasingly higher degrees of melting of the same mantle source region. The other type (T-tholeiite), representative of the bulk of the exposed basalt sequence, has flat REE patterns and relatively evolved isotopic compositions. This tholeiitic suite is clearly genetically unrelated to the komatiitic suite.

Compositional heterogeneity of the Sugarloaf melilite nephelinite flow, Honolulu Volcanics, Hawai'i

NASA Astrophysics Data System (ADS)

Clague, David A.; Frey, Frederick A.; Garcia, Michael O.; Huang, Shichun; McWilliams, Michael; Beeson, Melvin H.

2016-07-01

The Sugarloaf flow is a melilite nephelinite erupted from the Tantalus rift during rejuvenated-stage volcanism on O'ahu, the Honolulu Volcanics. The flow ponded in Mānoa Valley forming a ∼15 m thick flow which was cored and sampled in a quarry. Nepheline from a pegmatoid segregation in the flow yielded a 40Ar-39Ar age of 76 ka. This age, combined with others, indicates that the Tantalus rift eruptions are some of the youngest on O'ahu. Honolulu Volcanics erupt on average about every 35-40 ka indicating that future eruptions are possible. We evaluated the compositional variability of 19 samples from the flow, including 14 from the core. Twelve samples are representative of the bulk flow, four are dark- or light-colored variants, one is a heavy rare earth element (REE)-enriched pegmatoid, and two visually resemble the bulk flow, but have chemical characteristics of the dark and light variants. Our objective was to determine intraflow heterogeneity in mineralogy and composition. Variable abundances of Na2O, K2O, Sr, Ba, Rb, Pb and U in the flow were caused by post-eruptive mobility in a vapor phase, most likely during or soon after flow emplacement, and heterogeneous deposition of secondary calcite and zeolites. Relative to fine-grained samples, a pegmatoid vein that crosscuts the flow is enriched in incompatible trace elements except Sr and TiO2. Element mobility after eruption introduced scatter in trace element ratios including light-REE/heavy-REE, and all ratios involving mobile elements K, Rb, Ba, Sr, Pb, and U. Lavas from some of the 37 Honolulu Volcanics vents have crosscutting REE patterns in a primitive mantle-normalized plot. Such patterns have been interpreted to reflect variable amounts of residual garnet during partial melting. Previous studies of lavas from different vents concluded that garnet, phlogopite, amphibole, and Fe-Ti oxides were residual phases of the partial melting processes that created the Honolulu Volcanics (Clague and Frey, 1982; Yang et al., 2003). However post-eruptive processes in the Sugarloaf flow also produced crossing REE patterns. Eruptions on the Tantalus rift, including the Sugarloaf flow, produced volatile- and crystal-rich ash with interstitial glass and melt inclusions in olivine containing 4.2-6.4 wt% MgO compared to the flow average of 11.8 wt%. This flow erupted as a partially crystallized viscous magma at least 100 °C below its liquidus. The slow advance and cooling of the 15-m thick 'a' ā low promoted the segregation of pegmatoids, formation of light and dark bands with differing proportions of melilite and clinopyroxene, and induced volatile-enhanced mobility of incompatible elements.

Evaluation of rare earth elements in groundwater of Lagos and Ogun States, Southwest Nigeria.

PubMed

Ayedun, H; Arowolo, T A; Gbadebo, A M; Idowu, O A

2017-06-01

Rare earth elements in our environment are becoming important because of their utilization in permanent magnets, lamp phosphors, superconductors, rechargeable batteries, catalyst, ceramics and other applications. This study was conducted to evaluate the level of rare earth elements (REE) and the variability of their anomalous behavior in groundwater samples collected from Lagos and Ogun States, Southwest, Nigeria. REE concentrations were determined in 170 groundwater samples using inductively coupled plasma-mass spectrometry, while the physicochemical parameters were determined using standard methods. Lagos State groundwater is enriched with REE [sum REEs range (mean ± SD)]; [0.365-488 (69.5 ± 117)] µg L -1 than Ogun State groundwater [sum REEs range (mean ± SD)]; [1.14-232 (22.6 ± 41.1)] µg L -1 . Boreholes are more enriched with REEs than wells. Significant (P < 0.05) positive correlation (R = Pearson) was recorded in Lagos State groundwater between sum REEs and Fe (R = 0.55). However, there were no significant correlations between sum REEs, pH (R = 0.073) and HCO 3 2- (R = 0.157) in Ogun State groundwater. Chondrite-normalized plot shows that Lagos groundwater exhibits positive Ce anomaly, while Ogun State groundwater does not. The source of REE in Lagos State may be from the ocean and leaching from wastes dumpsites, while the source in Ogun State groundwater may be from the rocks.

Ion-adsorption REEs in regolith of the Liberty Hill pluton, South Carolina, USA: An effect of hydrothermal alteration

USGS Publications Warehouse

Bern, Carleton R.; Yesavage, Tiffany; Foley, Nora K.

2017-01-01

Ion-adsorbed rare earth element (REE) deposits supply the majority of world heavy REE production and substantial light REE production, but relatively little is known of their occurrence outside Southeast Asia. We examined the distribution and forms of REEs on a North American pluton located in the highly weathered and slowly eroding South Carolina Piedmont. The Hercynian Liberty Hill pluton experiences a modern climate that includes ~ 1500 mm annual rainfall and a mean annual temperature of 17 °C. The pluton is medium- to coarse-grained biotite-amphibole granite with minor biotite granite facies. REE-bearing phases are diverse and include monazite, zircon, titanite, allanite, apatite and bastnäsite. Weathered profiles were sampled up to 7 m-deep across the ~ 400 km2 pluton. In one profile, ion-adsorbed REEs plus yttrium (REE + Y) ranged up to 581 mg/kg and accounted for up to 77% of total REE + Y in saprolite. In other profiles, ion-adsorbed REE + Y ranged 12–194 mg/kg and only accounted for 3–37% of totals. The profile most enriched in ion-adsorbed REEs was located along the mapped boundary of two granite facies and contained trioctahedral smectite in the saprolite, evidence suggestive of hydrothermal alteration of biotite at that location. Post-emplacement deuteric alteration can generate easily weathered REE phases, particularly fluorocarbonates. In the case of Liberty Hill, hydrothermal alteration may have converted less soluble to more soluble REE minerals. Additionally, regolith P content was inversely correlated with the fraction ion-adsorbed REEs, and weathering related secondary REE-phosphates were found in some regolith profiles. Both patterns illustrate how low P content aids in the accumulation of ion-adsorbed REEs. The localized occurrence at Liberty Hill sheds light on conditions and processes that generate ion-adsorbed REEs.

An investigation into heterogeneity in a single vein-type uranium ore deposit: Implications for nuclear forensics.

PubMed

Keatley, A C; Scott, T B; Davis, S; Jones, C P; Turner, P

2015-12-01

Minor element composition and rare earth element (REE) concentrations in nuclear materials are important as they are used within the field of nuclear forensics as an indicator of sample origin. However recent studies into uranium ores and uranium ore concentrates (UOCs) have shown significant elemental and isotopic heterogeneity from a single mine site such that some sites have shown higher variation within the mine site than that seen between multiple sites. The elemental composition of both uranium and gangue minerals within ore samples taken along a single mineral vein in South West England have been measured and reported here. The analysis of the samples was undertaken to determine the extent of the localised variation in key elements. Energy Dispersive X-ray spectroscopy (EDS) was used to analyse the gangue mineralogy and measure major element composition. Minor element composition and rare earth element (REE) concentrations were measured by Electron Probe Microanalysis (EPMA). The results confirm that a number of key elements, REE concentrations and patterns used for origin location do show significant variation within mine. Furthermore significant variation is also visible on a meter scale. In addition three separate uranium phases were identified within the vein which indicates multiple uranium mineralisation events. In light of these localised elemental variations it is recommended that representative sampling for an area is undertaken prior to establishing the REE pattern that may be used to identify the originating mine for an unknown ore sample and prior to investigating impact of ore processing on any arising REE patterns. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tectonic Origin of Serpentinites on Syros, Greece: Geochemical Signatures of Seafloor Serpentinization Preserved in the HP/LT Subduction Complex

NASA Astrophysics Data System (ADS)

Raia, N. H.; Cooperdock, E. H. G.; Barnes, J.; Stockli, D. F.; Schwarzenbach, E. M.

2016-12-01

Serpentinized ultramafic rocks are commonly found in exhumed HP/LT subduction complexes, but their tectonic origins (i.e., setting of serpentinization) are difficult to decipher due to extensive alteration. Growing literature and geochemical datasets demonstrate that immobile elements (REE, HFSE) in serpentinites can retain magmatic signatures indicative of the tectonic setting of parent peridotite, while fluid-mobile elements and stable isotopic signatures shed light on the fluids causing serpentinization. This study combines whole-rock trace and major element geochemistry, stable isotope (δD and δO) analyses with petrographic observation to determine the tectonic origin of ultramafic rocks in the HP/LT Aegean subduction complex. The best-preserved HP rocks of the Cycladic Blueschist Unit (CBU) are found on Syros, Greece, where serpentinized ultramafic rocks within the CBU are closely associated with metamorphosed remnants of subducted oceanic crust. All samples are completely serpentinized, lacking relict pyroxene or spinel grains, with typical assemblages consisting of serpentine, talc, chlorite, magnetite, and minor carbonate. The serpentinizing fluid was characterized using stable isotopes. δD and δO values of bulk-rock serpentinite powders and chips, respectively, suggest seafloor serpentinites hydrated by seawater at low T, typical of alteration at mid-ocean ridges and hyper-extended margins (δD = -64 to -33‰ and δO = 5.2 to 9.0‰). To fingerprint a tectonic origin, whole rock serpentinite REE patterns are compared to a global database of whole rock serpentinite analyses from fore-arc mantle wedge, mid-ocean ridge, and hyper-extended margin tectonic settings. Whole rock major element, trace element, and REE analyses are consistent with limited melt extraction, flat REE patterns (LaN/SmN = 0.2-2.6, SmN/YbN = 0.3-3.5; N= C1 normalized), and do not show pronounced Eu anomalies. These data are consistent with abyssal peridotites derived from hyper-extended margin settings, although some overlap with mid-ocean ridge serpentinites makes it difficult to rule out. In any case, the geochemical signatures retained in these serpentinites indicate they are unlikely sourced from the mantle wedge, as has been historically speculated.

The prediction of resting energy expenditure in type 2 diabetes mellitus is improved by factoring for glycemia.

PubMed

Gougeon, R; Lamarche, M; Yale, J-F; Venuta, T

2002-12-01

Predictive equations have been reported to overestimate resting energy expenditure (REE) for obese persons. The presence of hyperglycemia results in elevated REE in obese persons with type 2 diabetes, and its effect on the validity of these equations is unknown. We tested whether (1) indicators of diabetes control were independent associates of REE in type 2 diabetes and (2) their inclusion would improve predictive equations. A cross-sectional study of 65 (25 men, 40 women) obese type 2 diabetic subjects. Variables measured were: REE by ventilated-hood indirect calorimetry, body composition by bioimpedance analysis, body circumferences, fasting plasma glucose (FPG) and hemoglobin A(1c). Data were analyzed using stepwise multiple linear regression. REE, corrected for weight, fat-free mass, age and gender, was significantly greater with FPG>10 mmol/l (P=0.017) and correlated with FPG (P=0.013) and hemoglobin A(1c) as percentage upper limit of normal (P=0.02). Weight was the main determinant of REE. Together with hip circumference and FPG, it explained 81% of the variation. FPG improved the predictability of the equation by >3%. With poor glycemic control, it can represent an increase in REE of up to 8%. Our data indicate that in a population of obese subjects with type 2 diabetes mellitus, REE is better predicted when fasting plasma glucose is included as a variable.

Tectonomagmatic evolution of the proto Andean Margin: Geochemical characterization and zircon U-Pb geochronologic constraints from the Ecuadorian Eastern Cordilleran granitoids

NASA Astrophysics Data System (ADS)

Buchwaldt, R.; Toulkeridis, T.

2013-05-01

The timing of pan-Pacific Gondwanide Orogeny in the proto-Andes, and its driving mechanisms are still highly debated and relies predominantly upon whole-rock Rb-Sr and K-Ar chronology and rudimentary mineralogy and geochemistry. In order to decipher these uncertainties we have studied the composition, age and provenance of granitoids along the strike of the Eastern Cordillera of Ecuador and related these deep-seated and surface tectonic processes attending the Late Cretaceous-Palaeogene history of the northern Andes. The plutonic rocks constitute a metaluminous to peraluminous (A/CNK ~ 0.8-1.2), calc-alkaline suite. A unimodal and wide compositional range of the intrusives (49-78 wt. % SiO2) is characteristic of this I-type orogenic suites. Mantle-normalized trace element patterns reveal typical subduction-related signature. Chondrite-normalized REE patterns do not show significant HREE fractionation suggesting the absence of high-pressure residual mineralogy in the source and formation in a "normal thickness", garnet-free crust. Slight Eu anomalies, lowering Sr contents, and concave-up REE patterns of samples dioritic in composition indicate a model involving fractionation of plagioclase, amphibole and pyroxene from a basaltic parent. The analyzed zircon crystals are colorless - transparent ranging in size from 50 to 250 μm. In CL images, 95% of the zircons exhibit oscillatory zonation, characteristic of a magmatic origin. This observation is consistent with the REE zircon composition showing a are characteristic steep positive slope from La to Lu with a significantly positive Ce-anomaly and slight negative Eu-anomaly. There is very little variation in Hf isotopic composition with most of the crust maintains near chondritic Zr/Hf ratios of around 35-40. Our results indicate the development of two tectonic episodes; with the first varying between 210-250 Ma and the second approximate 170-180 Ma. These results are consistent with similar events observed throughout the northern Andes from Peru to Columbia. The occurrence of numerous granite intrusions during Triassic times along the South American margin indicates that western South America underwent a widespread thermal anomaly between 250 and 210 Ma, which produced large amounts of granitoids. We argue that this occurrence is associated with the closure of the Panthalassan Gondwana sutur between 200 and 300 Ma and the correlated magmatism is related to the development of strike-slip tectonics subparallel to the proto-Andean margin. Contrasting to the older episode the younger magmatics appears to be the ultimate dispersal of Gondwana in the Cretaceous, which has been followed by the establishment of a continental arc that has intermittently characterized the modern Andean orogeny for the past 180 Ma.

Cryogenian cap carbonates - what do laminar scale investigations reveal about formation?

NASA Astrophysics Data System (ADS)

Miller, N. R.; Maupin, C. R.; Partin, J. W.; Quinn, T.; Giddings, J.

2009-12-01

Mid- to Late-Neoproterozoic “Cryogenian” cap carbonates are generally regarded as marine chemical sediments rapidly deposited during climatic recoveries from some of Earth’s most extreme glacial intervals, but there is little consensus regarding formation. Many cap successions initiate abruptly above glacigenic strata as finely laminated carbonate (typically dolostone), even in otherwise siliciclastic dominated marine continua, suggesting water mass control and widespread deposition below storm wave base. Cap carbonate units often culminate intervals of ongoing negative δ13C, transitioning to positive δ13C in the higher succession. Considering that fine lamination is a common characteristic among many cap carbonate units in space and time, laminar scale chemostratigraphic investigations may offer insights to modes of formation. Toward this end, we integrate bedding-normal LA-ICP-MS scans and high-resolution C and O isotope stratigraphy, for an array of cap carbonate units spanning “Kaigas”, “Sturtian”, and “Marinoan” post-glacial intervals; namely: Assem Limestone, N. Ethiopia (Nubia); Beck Spring Dolomite and Noonday Dolomite, Death Valley Area (W. Laurentia); Scout Mountain Member of the Pocatello Formation, S. Idaho (W. Laurentia); Tindelpina Shale Member, S. Australia (Adelaide Geosyncline); Rasthof and Keilberg Formations, N. Namibia (Congo Craton); and Mirrasol O’est, Brazil (Sao Francisco Craton). Whole-rock assessments for basal cap samples have δ13C between -4.8 to -1.4‰ and δ18O between -15.5 to -3.1‰. Corresponding PASS-normalized REE patterns show moderate LREE depletion, minor MREE enrichment, and slight HREE depletion. Cap samples from the higher positive δ13C succession (Noonday/Rasthof) display flatter patterns. Laser ablation scans for the Rasthof Fm (basal rhythmite and middle sublittoral microbialite) and Noonday Dolomite show that lamina couplets consist of alternations of comparatively darker organic/terrigenous (Si, Al, Ba, Rb) and lighter carbonate (Ca, Mg, Sr, Ce) end-members. For the middle Rasthof Formation, alternating dark-light couplets show sympathetic patterns of enrichment and depletion in both δ13C and δ18O, not easily reconciled by meteoric diagenetic processes. The presence of roll-up structures and internal cements (Rasthof) argues that the locus of carbonatogenesis was at or below the sediment-water interface. Within couplet δ18O variation is ~1‰, analogous to ~5°C temperature variation in modern oceans. Distinct alternation of δ18O between couplets may thus indicate moderate changes in bottom water temperatures or that carbonatogenesis was linked to contrasting water masses.

Comparison of five equations for estimating resting energy expenditure in Chinese young, normal weight healthy adults

PubMed Central

2012-01-01

Background Most resting energy expenditure (REE) predictive equations for adults were derived from research conducted in western populations; whether they can also be used in Chinese young people is still unclear. Therefore, we conducted this study to determine the best REE predictive equation in Chinese normal weight young adults. Methods Forty-three (21 male, 22 female) healthy college students between the age of 18 and 25 years were recruited. REE was measured by the indirect calorimetry (IC) method. Harris-Benedict, World Health Organization (WHO), Owen, Mifflin and Liu’s equations were used to predictREE (REEe). REEe that was within 10% of measured REE (REEm) was defined as accurate. Student’s t test, Wilcoxon Signed Ranks Test, McNemar Test and the Bland-Altman method were used for data analysis. Results REEm was significantly lower (P < 0.05 or P < 0.01) than REEe from equations, except for Liu’s, Liu’s-s, Owen, Owen-s and Mifflin in men and Liu’s and Owen in women. REEe calculated by ideal body weight was significantly higher than REEe calculated by current body weight ( P < 0.01), the only exception being Harris-Benedict equation in men. Bland-Altman analysis showed that the Owen equation with current body weight generated the least bias. The biases of REEe from Owen with ideal body weight and Mifflin with both current and ideal weights were also lower. Conclusions Liu’s, Owen, and Mifflin equations are appropriate for the prediction of REE in young Chinese adults. However, the use of ideal body weight did not increase the accuracy of REEe. PMID:22937737

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe-oxide (Fe-P-REE) systems

NASA Astrophysics Data System (ADS)

Gleason, James D.; Marikos, Mark A.; Barton, Mark D.; Johnson, David A.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium isotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, ɛ Nd for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age (ɛ Nd = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, ɛ Nd for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks (-1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks (ɛ Nd = -2.0 to -4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar ɛ Nd (-1.7 to -2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with ɛ Nd = -2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe oxide (Fe-P-REE) systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gleason, J.D.; Marikos, M.A.; Barton, M.D.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium iosotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, {epsilon}{sub Nd} for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of themore » same age ({epsilon}{sub Nd} = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, {epsilon}{sub Nd} for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks ({minus}1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks ({epsilon}{sub Nd} = {minus}2.0 to {minus}4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar {epsilon}{sub Nd}({minus}1.7 to {minus}2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with {epsilon}{sub Nd} = {minus}2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.« less

Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

NASA Technical Reports Server (NTRS)

McIntosh, E. C.; Rapp, J. F.; Draper, D. S.

2016-01-01

The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

USGS Publications Warehouse

Kim, Ji-Hoon; Torres, Marta E.; Haley, Brian A.; Kastner, Miriam; Pohlman, John W.; Riedel, Michael; Lee, Young-Joo

2012-01-01

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Relative contribution of organs other than brain to resting energy expenditure is consistent among male power athletes.

PubMed

Oshima, Satomi; Miyauchi, Sakiho; Asaka, Meiko; Kawano, Hiroshi; Taguchi, Motoko; Torii, Suguru; Higuchi, Mitsuru

2013-01-01

We have previously shown that resting energy expenditure (REE) adjusted by fat-free mass (FFM) in male college athletes remains consistent regardless of FFM. The FFM comprises internal organs with high metabolic activity, such as liver and brain, which account for 60 to 80% of REE in adults. The purpose of the present study is to examine the contribution of internal organs to the REE of the FFM fraction among male power athletes. The study included 37 American male college football players. REE was measured by indirect calorimetry and body composition was measured by dual energy X-ray absorptiometry (DXA). Mass of brain, liver, and kidneys was measured by MRI and mass of heart was estimated by echocardiography. Normal levels of thyroid hormone (triiodothyronine: T3) were confirmed in all subjects prior to the analysis. Multiple regression analysis was used to assess the influence of FFM, fat mass (FM), T3, and mass of organs on variance of REE. Average body weight and FFM were 81.2±11.3 kg and 67.7±7.4 kg, respectively. The relative contributions of liver, kidneys, and heart to REE were consistent regardless of FFM, while the REE of brain was negatively correlated with FFM (r=-0.672, p<0.001). Only FFM and T3 were found to be independent factors influencing REE. These results suggest that a steady contribution of internal organs other than the brain is the major reason for the consistency of the REE/FFM ratio in male power athletes.

Using rare earth elements for the identification of the geographic origin of food

NASA Astrophysics Data System (ADS)

Meisel, T.; Bandoniene, D.; Joebstl, D.

2009-04-01

The European Union defined regimes within the Protected Geographical Status (PGS) framework to protect names of regional food specialities. Thus only food produced in a specific geographical area with a specific way of production or quality can be protected by a protected geographical indication (PGI) label. As such Styrian Pumpkin Seed Oil has been approved with this label, but as with many other high priced regional specialities, fraud cannot be excluded or nor identified. Thus the aim of this work is, to develop an analytical method for the control of the geographic origin of pumpkin seed oil and also to test the method for other protected products. The development of such a method is not only of interest for scientists, but also of importance for the consumer wanting to know the origin of the food products and the assurance of the purity and quality. The group of rare earth elements (REE) in plants also have a characteristic distribution pattern similar to upper crustal REE distributions. Since the REE concentrations are extremely low in pumpkin seed oil (ppt to low ppb), ICP-MS was the only sensitive tool able to produce validated results. The carrier of the REE are most likely small particles distributed within the pumpkin seed oil. Unlike, e.g., olive oil, pumpkin seed oil is bottled and sold unfiltered, which makes this Styrian speciality an interesting sampling target. As pumpkin seed oils from different geographic origin show variable trace element and rare earth distribution patterns, is should possible to trace the origin of these oils. In the current project pumpkin seeds from different regions in Austria and from abroad were sampled. The trace element patterns in the extracted oil of these seeds were determined and a preliminary classification with discriminate analysis was successfully done on a statistical basis. In addition to the study of the geographic origin it was demonstrated that REE distribution patterns can also be used for the identification of adulteration of high priced pumpkin seed oil with cheap neutral tasting refined oils. Interestingly enough, the variations of the REE patterns between oils from different regions are much more pronounced than their host soils. Thus we assume that microbiological processes in the rhizosphere are in control of the REE uptake into the plant. Regional variations of the microbiological composition of the soils and probably not only a priori the bulk soil composition of the minerals in the soil are the cause of the regional variations making it possible to identify the geographic origin of pumpkin seeds and as a consequence the pumpkin seed oil.

Sediment provenance and paleoenvironmental changes in the northwestern shelf mud area of the South China Sea since the mid-Holocene

NASA Astrophysics Data System (ADS)

Xu, Fangjian; Hu, Bangqi; Dou, Yanguang; Liu, Xiting; Wan, Shiming; Xu, Zhaokai; Tian, Xu; Liu, Zhaoqing; Yin, Xuebo; Li, Anchun

2017-07-01

The late Quaternary paleoceanography and paleoenvironment of the South China Sea (SCS) have been well reconstructed over the last decade. In contrast, the provenance of the terrigenous sediments that have accumulated in the northwestern continental shelf mud area remains enigmatic. This study investigated the provenance of these sediments and the paleoenvironmental changes archived in Core X2 via the analysis of geochemical elements, grain size, and accelerator mass spectrometry (AMS) 14C ages. Based on the upper continental crust (UCC)-normalized REE patterns and REE fractionation parameters, southwestern and western Taiwanese rivers and the Pearl River were identified as the main sources of the fine-grained sediment deposited in the northwestern shelf mud area off Hainan Island. This finding further confirms the long-distance transport (> 1000 km) of fine-grained sediment from Taiwanese rivers to the northern SCS shelf and slope. Obvious changes in the grain size and Chemical Index of Alteration (CIA) record occurred at approximately 4.0 cal kyr BP and were likely caused by increased Hainan Island inputs due to sea level changes.

Reconstruction of the Paleoproterozoic deeper ocean environment: Preliminary Report of the Ghana Birimian Greenstone Belt Drilling Project (GHB)

NASA Astrophysics Data System (ADS)

Kiyokawa, S.; Yoshimaru, S.; Miki, T.; Sakai, S.; Ikehara, M.; Yamaguchi, K. E.; Ito, T.; Onoue, T.; Takehara, M.; Tetteh, G. M.; Nyame, F. K.

2016-12-01

The Paleoproterozoic Era are one of the most rapid environmental change when the earth surface environment was affected by formation of continents and increasing atmospheric oxygen levels. Major oxidation of Great Oxidation Event (GOE) are reported this ages (eg. Holland, 2006; Condie, 2001; Lyons et al., 2014). The nature of deep sea environments at this time have not been clearly identified and oceanic sediments are mostly involved in subduction. The Paleoproterozoic Birimian Greenstone Belt is an ophiolitic volcaniclastic sequence in Ghana, with depositional age of over 2.3-2.2 Ga (Petersson et al., 2016). Detail research was conducted of the Ashanti (Axim-Konongo) Belt of the Birimian Greenstone Belt along the coast near Cape Three Points area. Very thick volcaniclastic and organic-rich sedimentary rocks, which we now refer to as the Cape Three Points Group, crop out in the lower part of the Birimian Greenstone Belt. Stratigraphically, three unit identified; the lower portion contains thick vesicular volcaniclastic rocks, the middle portion is made up of laminated volcaniclastics and black shale, and the upper portion dominated by fine laminated volcaniclastics with more black shale sequence. Continuous core drilling from Dec 3-12th 2015 of the upper part of the sequence intersected saprolite to a depth of 30m and fresh, well preserved stratigraphy with graded bedding and lamination to a depth of 195m. Half cut cores show well laminated organic rich black shale and relative carbonate rich layers with very fine pyrite grains. SHRIMP age data from a porphyry intrusion into this sequence indicate an age of 2250 Ma. Carbon isotope analysis shows δ13C = -43 to -37‰ for black shale with the very light isotope values for cyanobacterial signature.The fining-upward sequences, well laminated bed and black shales and REE data suggest this sequence situated partly silent stagnant with volcanic activity ocean floor environment around an oceanic island arc condition.

Prediction equation of resting energy expenditure in an adult Spanish population of obese adult population.

PubMed

de Luis, D A; Aller, R; Izaola, O; Romero, E

2006-01-01

The aim of our study was to evaluate the accuracy of the equations to estimate REE in obese patents and develop a new equation in our obese population. A population of 200 obesity outpatients was analyzed in a prospective way. The following variables were specifically recorded: age, weight, body mass index (BMI), waist circumference, and waist-to-hip ratio. Basal glucose, insulin, and TSH (thyroid-stimulating hormone) were measured. An indirect calorimetry and a tetrapolar electrical bioimpedance were performed. REE measured by indirect calorimetry was compared with REE obtained by prediction equations to obese or nonobese patients. The mean age was 44.8 +/- 16.81 years and the mean BMI 34.4 +/- 5.3. Indirect calorimetry showed that, as compared to women, men had higher resting energy expenditure (REE) (1,998.1 +/- 432 vs. 1,663.9 +/- 349 kcal/day; p < 0.05) and oxygen consumption (284.6 +/- 67.7 vs. 238.6 +/- 54.3 ml/min; p < 0.05). Correlation analysis among REE obtained by indirect calorimetry and REE predicted by prediction equations showed the next data; Berstein's equation (r = 0.65; p < 0.05), Harris Benedict's equation (r = 0.58; p < 0.05), Owen's equation (r = 0.56; p < 0.05), Ireton's equation (r = 0.58; p < 0.05) and WHO's equation (r = 0.57; p < 0.05). Both the Berstein's and the Ireton's equations overpredicted REE and showed nonsignificant mean differences form measured REE. The Owen's, WHO's, and Harris Benedict's equations underpredicted REE. Our male prediction equation was REE = 58.6 + (6.1 x weight (kg)) + (1,023.7 x height (m)) - (9.5 x age). The female model was REE = 1,272.5 + (9.8 x weight (kg)) - (61.6 x height (m)) - (8.2 x age). Our prediction equations showed a nonsignificant difference with REE measured (-3.7 kcal/day) with a significant correlation coefficient (r = 0.67; p < 0.05). Previously developed prediction equations overestimated and underestimated REE measured. WHO equation developed in normal weight individuals provided the closest values. The two new equations (male and female equations) developed in our study had a good accuracy. Copyright 2006 S. Karger AG, Basel.

Genesis of post-collisional calc-alkaline and alkaline granitoids in Qiman Tagh, East Kunlun, China

NASA Astrophysics Data System (ADS)

Yu, Miao; Feng, Chengyou; Zhao, Yiming; Li, Daxin

2015-12-01

The post-collisional magmatism of Qiman Tagh is characterized by the intrusion of voluminous intermediate to felsic granitoids, including syenogranite, monzogranite, granodiorite, tonalite and diorite. The granitoids can be divided into two magmatic suites: Calc-alkaline (CA) and alkaline (Alk), which were emplaced from ~ 236 Ma to ~ 204 Ma. The CA suite contains metaluminous granodiorites and monzogranites. Typical Qiman Tagh CA granodiorites show moderately fractionated REE patterns ((La/Yb)N = 4.35-25.11) with significant negative Eu anomalies (Eu/Eu* = 0.54-1.34), and the primitive mantle-normalized spidergrams show strong depletion of Nb and Sr. The Qiman Tagh CA monzogranites show similar fractionated REE patterns ((La/Yb)N = 2.70-13.5) with less prominent negative Eu anomalies, and the chondrite-normalized spidergrams show strongly depleted Ba, Nb and Sr. The Alk suite, including syenogranite, is highly potassic (K2O/Na2O = 1.09-3.56) and peraluminous (A/CNK = 0.91-1.06). Compared to typical Qiman Tagh CA granodiorites, the Qiman Tagh Alk granitoids can be distinguished by their higher Rb, Nb, Ga/Al, FeO*/MgO, Y/Sr and Rb/Sr, as well as their lower Mg#, MgO, CaO, Al2O3, Sr, Co, V, Eu/Eu*, Ba/Nb, La/Nb, Ba/La and Ce/Nb. The Qiman Tagh CA rocks were most likely to be derived from the partial melting of garnet-amphibolite-facies rocks in the lower crust, leaving behind anhydrous granulite-facies rocks with plagioclase and garnet in the residue. The Alk rocks may have formed by the continued partial melting of granulite-facies rocks at elevated temperatures (> 830 °C).

Rare earth element distributions in the West Pacific: Trace element sources and conservative vs. non-conservative behavior

NASA Astrophysics Data System (ADS)

Behrens, Melanie K.; Pahnke, Katharina; Paffrath, Ronja; Schnetger, Bernhard; Brumsack, Hans-Jürgen

2018-03-01

Recent studies suggest that transport and water mass mixing may play a dominant role in controlling the distribution of dissolved rare earth element concentrations ([REE]) at least in parts of the North and South Atlantic and the Pacific Southern Ocean. Here we report vertically and spatially high-resolution profiles of dissolved REE concentrations ([REE]) along a NW-SE transect in the West Pacific and examine the processes affecting the [REE] distributions in this area. Surface water REE patterns reveal sources of trace element (TE) input near South Korea and in the tropical equatorial West Pacific. Positive europium anomalies and middle REE enrichments in surface and subsurface waters are indicative of TE input from volcanic islands and fingerprint in detail small-scale equatorial zonal eastward transport of TEs to the iron-limited tropical East Pacific. The low [REE] of North and South Pacific Tropical Waters and Antarctic Intermediate Water are a long-range (i.e., preformed) laterally advected signal, whereas increasing [REE] with depth within North Pacific Intermediate Water result from release from particles. Optimum multiparameter analysis of deep to bottom waters indicates a dominant control of lateral transport and mixing on [REE] at the depth of Lower Circumpolar Deep Water (≥3000 m water depth; ∼75-100% explained by water mass mixing), allowing the northward tracing of LCDW to ∼28°N in the Northwest Pacific. In contrast, scavenging in the hydrothermal plumes of the Lau Basin and Tonga-Fiji area at 1500-2000 m water depth leads to [REE] deficits (∼40-60% removal) and marked REE fractionation in the tropical West Pacific. Overall, our data provide evidence for active trace element input both near South Korea and Papua New Guinea, and for a strong lateral transport component in the distribution of dissolved REEs in large parts of the West Pacific.

Prediction of shale prospectivity from seismically-derived reservoir and completion qualities: Application to a shale-gas field, Horn River Basin, Canada

NASA Astrophysics Data System (ADS)

Mo, Cheol Hoon; Lee, Gwang H.; Jeoung, Taek Ju; Ko, Kyung Nam; Kim, Ki Soo; Park, Kyung-sick; Shin, Chang Hoon

2018-04-01

Prospective shale plays require a combination of good reservoir and completion qualities. Total organic carbon (TOC) is an important reservoir quality and brittleness is the most critical condition for completion quality. We analyzed seismically-derived brittleness and TOC to investigate the prospectivity of the Horn River Group shale (the Muskwa, Otter Park, Evie shales) of a shale-gas field in the western Horn River Basin, British Columbia, Canada. We used the λρ-μρ brittleness template, constructed from the mineralogy-based brittleness index (MBI) and elastic logs from two wells, to convert the λρ and μρ volumes from prestack seismic inversion to the volume for the brittleness petrotypes (most brittle, intermediate, and least brittle). The probability maps of the most brittle petrotype for the three shales were generated from Bayesian classification, based on the λρ-μρ template. The relationship between TOC and P-wave and S-wave velocity ratio (VP/VS) at the wells allowed the conversion of the VP/VS volume from prestack inversion to the TOC volume, which in turn was used to construct the TOC maps for the three shales. Increased TOC is correlated with high brittleness, contrasting with the commonly-held understanding. Therefore, the prospectivity of the shales in the study area can be represented by high brittleness and increased TOC. We propose a shale prospectivity index (SPI), computed by the arithmetic average of the normalized probability of the most brittle petrotype and the normalized TOC. The higher SPI corresponds to higher production rates in the Muskwa and Evie shales. The areas of the highest SPI have not been fully tested. The future drilling should be focused on these areas to increase the economic viability of the field.

Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

2016-04-01

The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous rocks, calcite invariably has higher REE and LILE levels than dolomite. Hydrothermal reworking of carbonatites does not produce a unique geochemical fingerprint, leading instead to a variety of evolutionary trends that range from light-REE and LILE enrichment (Turiy Mys, Russia) to heavy-REE enrichment and LILE depletion (Bear Lodge, USA). These differences clearly attest to variations in the chemistry of carbonatitic fluids and, consequently, their ability to mobilize specific trace elements from earlier-crystallized minerals. An important telltale indicator of hydrothermal reworking is deviation from the primary, chondrite-like REE ratios (in particular, Y/Ho and Eu/Eu*), accompanied by a variety of other compositional changes depending on the redox state of the fluid (e.g., depletion of carbonates in Mn owing to its oxidation and sequestration by secondary oxides). The effect of supergene processes was studied on a single sample from Bear Lodge, which shows extreme depletion in Mn and Ce (both due to oxidation), coupled with enrichment in Pb and U, possibly reflecting an increased availability of Pb2+ and (UO2)2+ species in the system. On the basis of these findings, several avenues for future research can be outlined: (1) structural mechanisms of REE uptake by carbonates; (2) partitioning of REE and LILE between cogenetic calcite and dolomite; (3) the effects of fluorapatite, phlogopite and pyrochlore fractionation on the LILE budget of magmatic carbonates; (4) the cause(s) of coupled Mn-Ce depletion in some primary calcite; and (5) relations between fluid chemistry and compositional changes in hydrothermal carbonates.

Residual levels of rare earth elements in freshwater and marine fish and their health risk assessment from Shandong, China.

PubMed

Yang, Luping; Wang, Xining; Nie, Hongqian; Shao, Lijun; Wang, Guoling; Liu, Yongjun

2016-06-15

The total concentrations of rare earth elements (ΣREE) were quantified in 251 samples from 10 common species of freshwater and marine fish in seventeen cities of Shandong, China. ΣREE obtained from the freshwater fish ranged from 34.0 to 37.9ngg(-1) (wet weight) and marine fish from 12.7 to 37.6ngg(-1). The ratio of LREE to HREE was 13.7:1 and 10:1 for freshwater and marine fish, respectively. This suggests that freshwater fish exhibit greater REE concentrations than marine fish and the biological effects of LREE are higher than HREE. Results revealed a similar REE distribution pattern between those fish and coastal sediments, abiding the "abundance law". The health risk assessment demonstrated the EDIs of REEs in fish were significantly lower than the ADI, indicating that the consumption of these fish presents little risk to human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemistry and mineralogy of sediments from the Ventersdorp and Transvaal Supergroups, South Africa: Cratonic evolution during the early Proterozoic

NASA Astrophysics Data System (ADS)

Wronkiewicz, David J.; Condie, Kent C.

1990-02-01

Approximately 100 pelite and 12 quartzite samples from the Ventersdorp (~2.7 Ga) and Transvaal Supergroups (~2.6-2.1 Ga) have been analyzed to monitor the early Proterozoic evolution of the Kaapvaal Craton, southern Africa. From oldest to youngest, pelites were sampled from the Ventersdorp-Bothaville (BOT), Transvaal-Selati (SEL), Black Reef (BR), Timeball Hill (TH), Strubenkop (STR), and Silverton (SIL) Formations. Paleocurrent measurements in Transvaal quartzites indicate sources lying predominantly to the north and east. Relative to the BOT-SEL-BR, pelites from the TH-STR-SIL are enriched in heavy-REE, LILE, Zr, Hf, Nb, and Ta, depleted in K 2O, MgO, Ni, and Cr, and have lower Cr/Zr, Sc/Th, K 2O/Na 2O, and K/ Rb ratios. Compared to SEL-BR, BOT-TH-STR-SIL pelites have higher light-REE contents and La/Yb ratios, and lower Eu/Eu∗ ratios (0.61-0.66). Relative to NASC (North American Shale Composite), THSTR-SIL pelites are enriched in light-REE, Th, U, Ta, Nb, Sc, Cs, have higher La/Yb ratios, and are depleted in K 2O and MgO. BOT-SEL-BR pelites are enriched in K 2O, MgO, Cr, and Ni, have higher K 2O/Na 2O, Sc/Th, and Eu/Eu∗ ratios, and are depleted in Th, U, heavy-REE, and High Field Strength Elements (HFSE) relative to NASC. Compositions of TH-STR-SIL pelites suggest a provenance similar to average Phanerozoic uppercontinental crust. This source is more evolved than that of BOT-SEL-BR pelites, indicating a transformation from primitive (mafic-rich) to evolved (felsic-rich) upper-crust at 2.2 Ga. This transition follows earlier primitive to evolved trends in Moodies-Pongola (3.3-3.0 Ga) and Witwatersrand (~2.8 Ga) successions. These data suggest that several cycles of changing upper-continental crust occurred in the Kaapvaal craton between 3.3-2.1 Ga.

Chemical Evidence for Episodic Growth of a Fibrous Antitaxial Calcite Vein From Externally Derived Fluid

NASA Astrophysics Data System (ADS)

Barker, S. L.; Cox, S. F.; Eggins, S. M.; Gagan, M. K.

2005-12-01

Fibrous, massive and crustiform textured quartz and calcite veins occur within a deformed limestone-shale sequence at Taemas, in the Lachlan Fold Belt, eastern New South Wales, Australia. Stable isotope analyses of veins and host rock indicate that these veins formed from upwardly migrating, externally derived fluids. High spatial resolution (100 μm) analyses reveal per mil scale variations of stable C and O isotope ratios, and radiogenic Sr isotope ratios in a 1.5 cm thick, fibrous, antitaxial-growth calcite vein. LA-ICP-MS analyses (30 μm resolution) demonstrate significant variations in Fe, Mn, Sr, REE and Eu/Eu* parallel to the long axes of fibres. Stable and radiogenic isotopic ratio variations, and trace and REE concentration changes correlate with different cathodoluminesence zones, and slight changes in fibre orientation and thickness. The covariance of calcite textures and chemistry indicate that this fibrous vein grew episodically. Moreover, calcite in this vein was precipitated from externally derived fluid, which underwent variable fluid-rock interaction, and had a fluctuating oxidation state. This fibrous, antitaxial growth vein likely formed from fluid that migrated along fracture-controlled flow pathways.

Geochemical Study on an Abandoned Copper Smelting Plant Using Rare Earth Elements

NASA Astrophysics Data System (ADS)

Sun, S. H.

2017-12-01

The Shuei Nan Dong Copper Smelting Plant smelting is located on the northern coast of New Taipei City, Taiwan. The plant built in 1906 for but has been shut down since 1987. However, the watershed is continuing to discharge acid mine water into the sea; and, the acid mine drainage releases high amounts of sulfate, heavy metals without any treatment. In this study, the water samples were sequentially collected along the main channel and its tributaries in the watershed. The results of hydrochemical analysis show that the untreated inflow water can be characterized with low pH value of <3 and enriched sulfate, copper and arsenic. However, the water is much less contaminated in the upstream area until a major tributary converge. The results of principal component analysis (PCA) demonstrate that the first principal component (PC) can explain >80% of the total variance and almost all chemical components have high loadings in the PC. Therefore, the hydrochemical properties in the watershed are mainly dominated by the mixing process between main channel and the major tributary but the geochemical reactions during flow down the channel is insignificant. Rare earth elements (REE) are an excellent tracer, which can indicate sources of chemical components and geochemical reactions in water. The analysis results demonstrate two distinct REE patterns. The water with low REE can be characterized by prominent Eu positive anomaly and Ce negative anomaly, which may result from the alteration of Na-plagioclase in sandstone and oxidation reaction when contact with air, respectively. On the contrary, the water with high REE shows only minor Ce negative anomaly and insignificant Eu positive anomaly. In addition, there is an enrichment of middle REE in high-REE water, which is quite different with the REE pattern of pyrite. According to the Grawunder's study (2014), it corresponds to the complexation to sulphite during pyrite oxidation. It is worth noting that REE show no considerable fractionation along the channel and confirms the results from PCA. It can be derived that the water may not reached equilibrium condition. A simple aerated retention pool could dramatically reduce the pollutants due to coprecipitation of iron oxide and aluminum oxide.

Mineralogy and geochemistry of the Lower Cretaceous siliciclastic rocks of the Morita Formation, Sierra San José section, Sonora, Mexico

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Pacheco-Olivas, S. A.; González-León, Carlos M.; Espinoza-Maldonado, Inocente G.; Sanchez-Medrano, P. A.; Villanueva-Amadoz, U.; Monreal, Rogelio; Pi-Puig, T.; Ramírez-Montoya, Erik; Grijalva-Noriega, Francisco J.

2017-07-01

Clay mineralogy and geochemical studies were carried out on sandstone and shale samples collected from the Sierra San José section of the Morita Formation to infer the paleoclimate and paleoweathering conditions that prevailed in the source region during the deposition of these sediments. The clay mineral assemblages (fraction < 2 μm) of the Sierra San José section are composed of chlorite and illite. The abundance of illite and chlorite in the studied samples suggest that the physical weathering conditions were dominant over chemical weathering. Additionally, the illite and chlorite assemblages reflect arid or semi-arid climatic conditions in the source regions. K2O/Al2O3 ratio of shales vary between 0.15 and 0.26, which lie in the range of values for clay minerals, particularly illite composition. Likewise, sandstones vary between 0.06 and 0.13, suggesting that the clay minerals are mostly kaolinte and illite types. On the chondrite-normalized diagrams, sandstone and shale samples show enriched light rare earth elements (LREE), flat heavy rare earth elements (HREE) patterns and negative Eu anomalies. The CIA and PIA values and A-CN-K plot of shales indicate low to moderate degree of weathering in the source regions. However, the sandstones have moderate to high values of CIA and PIA suggesting a moderate to intense weathering in the source regions. The SiO2/Al2O3 ratios, bivariate and ternary plots, discriminant function diagram and elemental ratios indicate the felsic source rocks for sandstone and shale of the Morita Formation.

Dissolved rare earth elements in the central-western sector of the Ross Sea, Southern Ocean: Geochemical tracing of seawater masses.

PubMed

Turetta, Clara; Barbaro, Elena; Capodaglio, Gabriele; Barbante, Carlo

2017-09-01

The present essay contributes to the existing literature on rare earth elements (REEs) in the southern hemisphere by presenting the first data, to our knowledge, on the vertical profiles of dissolved REEs in 71 samples collected in the central-western sector of the Ross Sea (Southern Ocean-SO). The REEs were measured in the water samples collected during the 2002-2003 and 2005-2006 austral summers. 4 samples were collected and analysed in the framework of a test experiment, as part of the WISSARD Project (Whillans Ice Stream Subglacial Access Research Drilling). Our results show significant differences between the REE patterns of the main water masses present in the SO: we could observe specific signature in the High Salinity Shelf Water (HSSW), Ice Shelf Water (ISW) and Low Salinity Shelf Water (LSSW). A significant increase in Terbium (Tb) concentration was observed in the HSSW and ISW, the two principal water masses contributing to the formation of Antarctic Bottom Water (AABW) in the Ross Sea area, and in LSSW. Some of the HSSW samples show enrichment in Neodymium (Nd). Dissolved REE could therefore be used as tracers to understand the deep circulation of the SO (Pacific sector). We hypothesize that: (I) the characteristic dissolved REE pattern may derive from the composition of source area and from the hydrothermal activity of the central-western area of the Ross Sea; (II) the Tb anomaly observed in the AABW on the South Australian platform could be partially explained by the contribution of AABW generated in the Ross Sea region. Copyright © 2017 Elsevier Ltd. All rights reserved.

"Normal" to adakite-like arc magmatism associated with the El Abra porphyry copper deposit, Central Andes, Northern Chile

NASA Astrophysics Data System (ADS)

Rabbia, Osvaldo M.; Correa, Karen J.; Hernández, Laura B.; Ulrich, Thomas

2017-03-01

The El Abra porphyry copper deposit belongs to the Late Eocene—Early Oligocene metallogenic belt of northern Chile, which host several world-class porphyry copper deposits. Our previous geochronological work done on this deposit provides the temporal framework for petrological data interpretation. The magmatic history of the El Abra deposit lasts for 8.6 Ma and can be divided into two stages. An early period, from about 45 to 38.7 Ma, dominated by diorites and quartz monzodiorites with "normal" (non-adakite) arc geochemistry and a late period, with rocks younger than 38.7 Ma that developed adakite-like geochemistry, where equigranular granodiorites are the volumetrically dominant rock type (e.g., Clara granodiorite 38 Ma). These granodiorites are then intruded by leucocratic porphyry dikes and aplites. Most copper mineralization is associated with multiple intrusions of these younger porphyritic rocks, described as the El Abra porphyry unit, and emplaced over a 1.4 Ma period, from 37.5 to 36.1 Ma. The adakite-like geochemistry of the younger rock units (<38.7 Ma) is attested by a significant depletion in REE contents, particularly MREE and HREE (concave MREE distribution patterns), high La/Yb and Sr/Y ratios, and Na2O and Al2O3 contents, along with the absence of the Eu anomaly in normalized REE distribution patterns. The evolution of this large, long-lived magmatic system from "normal" to adakite-like arc magmatism is discussed in a tectonic context of crust overthickening due to a major orogenic episode (Incaic compressive phase). This tectonic setting may have promoted higher pressure conditions at the lower crust "hot zone" and increased the crustal residence time of derivative melts favoring extensive differentiation leading to water-rich (and oxidized?) felsic melts, where amphibole fractionation played an important role. Strontium, Nd, and Pb isotope data suggest a common mantle source for both the non-adakite and adakite-like rocks. This implies that these two groups of rocks from the El Abra porphyry copper deposit may have largely resulted from the different crustal conditions under which they have evolved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sablock, J.

A trace element signature, a characteristic pattern of enrichment and depletion of trace elements, was determined for a group of siliciclastic-carbonate Oxfordian and Kimmeridgian sedimentary strata, collected from outcrops in western Montana, southeastern British Columbia and southern Alberta. The average values, by petrofacies, of 10 major and 18 trace elements were measured for 40 samples. These data were normalized to Upper Continental Crust (UCC), and plotted against averaged published values of graywackes from the same facies. The rare earth elements (REEs), as well as Ti, Zr, Nb and Y are considered immobile even through diagenesis, and at least low levelmore » metamorphism. So these elements should form a reliable part of the geochemical signature. Compared to UCC and average graywacke, Jurassic samples are very depleted in Zr, Nb and Y. Oxfordian samples have slightly higher rare earth element values, i.e. La, Ce and Nd, than either other Jurassic samples or average graywacke. The most likely source of REE values are garnets and tourmaline which occur as inclusions in monocrystalline quartz grains. This pattern, and petrological study, point to a sedimentary source area, deficient in feldspar, heavy minerals and rock fragments. The consistency of the signature throughout this time may indicate slow uplift of a widespread sedimentary source area, or could be an effect of greater mixing and shorter residence time of dissolved materials in an epeiric sea.« less

Depositional setting and geochemistry of phosphorites and metalliferous black shales in the Carboniferous-Permian Lisburne Group, Northern Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; Slack, John F.; Whalen, Michael T.; Harris, Anita G.

2011-01-01

Phosphatic rocks are distributed widely in the Lisburne Group, a mainly Carboniferous carbonate succession that occurs throughout northern Alaska. New sedimentologic, paleontologic, and geochemical data presented here constrain the geographic and stratigraphic extent of these strata and their depositional and paleogeographic settings. Our findings support models that propose very high oxygen contents of the Permo-Carboniferous atmosphere and oceans, and those that suggest enhanced phosphogenesis in iron-limited sediments; our data also have implications for Carboniferous paleogeography of the Arctic. Lisburne Group phosphorites range from granular to nodular, are interbedded with black shale and lime mudstone rich in radiolarians and sponge spicules, and accumulated primarily in suboxic outer- to middle-ramp environments. Age constraints from conodonts, foraminifers, and goniatite cephalopods indicate that most are middle Late Mississippian (early Chesterian; early late Visean). Phosphorites form 2- to 40-cm-thick beds of sand- to pebble-sized phosphatic peloids, coated grains, and (or) bioclasts cemented by carbonate, silica, or phosphate that occur through an interval =12 m thick. High gamma-ray response through this interval suggests strongly condensed facies related to sediment starvation and development of phosphatic hardgrounds. Phosphorite textures, such as unconformity-bounded coated grains, record multiple episodes of phosphogenesis and sedimentary reworking. Sharp bed bases and local grading indicate considerable redeposition of phosphatic material into deeper water by storms and (or) gravity flows. Lisburne Group phosphorites contain up to 37 weight percent P2O5, 7.6 weight percent F, 1,030 ppm Y, 517 ppm La, and 166 ppm U. Shale-normalized rare earth element (REE) plots show uniformly large negative Ce anomalies Ce/Ce*=0.11 + or - 0.03) that are interpreted to reflect phosphate deposition in seawater that was greatly depleted in Ce due to increased oxygenation of the atmosphere and oceans during the Carboniferous evolution of large vascular land plants. Black shales within the phosphorite sections have up to 20.2 weight percent Corg and are potential petroleum source rocks. Locally, these strata also are metalliferous, with up to 1,690 ppm Cr, 2,831 ppm V, 551 ppm Ni, 4,670 ppm Zn, 312 ppm Cu, 43.5 ppm Ag, and 12.3 ppm Tl; concentrations of these metals covary broadly with Corg, suggesting coupled redox variations. Calculated marine fractions (MF) of Cr, V, and Mo, used to evaluate the paleoredox state of the bottom waters, show generally high CrMF/MoMF and VMF/MoMF ratios that indicate deposition of the black shales under suboxic denitrifying conditions; Re/Mo ratios also plot mainly within the suboxic field and support this interpretation. Predominantly seawater and biogenic sources are indicated for Cr, V, Mo, Zn, Cd, Ni, and Cu in the black shales, with an additional hydrothermal contribution inferred for Zn, Cd, Ag, and Tl in some samples. Lisburne Group phosphorites formed in the Ikpikpuk Basin and along both sides of the mud- and chert-rich Kuna Basin, which hosts giant massive sulfide and barite deposits of the Red Dog district. Lisburne Group phosphatic strata are coeval with these deposits and formed in response to a nutrient-rich upwelling regime. Phosphate deposition occurred mainly in suboxic bottom waters based on data for paleoredox proxies (Cr, V, Mo, Re) within contemporaneous black shales. Recent global reconstructions are consistent with Carboniferous upwelling in northern Alaska, but differ in the type of upwelling expected (zonal versus meridional). Paleoenvironmental data suggest that meridional upwelling may better explain phosphorite deposition in the Lisburne Group.

Transport and transformation of riverine neodymium isotope and rare earth element signatures in high latitude estuaries: A case study from the Laptev Sea

NASA Astrophysics Data System (ADS)

Laukert, Georgi; Frank, Martin; Bauch, Dorothea; Hathorne, Ed C.; Gutjahr, Marcus; Janout, Markus; Hölemann, Jens

2017-11-01

Marine neodymium (Nd) isotope and rare earth element (REE) compositions are valuable tracers for present and past ocean circulation and continental inputs. Yet their supply via high latitude estuaries is largely unknown. Here we present a comprehensive dissolved Nd isotope (expressed as εNd values) and REE data set together with seawater stable oxygen isotope (δ18O) compositions of samples from the Laptev Sea recovered in two Arctic summers and one winter. The Laptev Sea is a shallow Siberian Shelf sea characterized by extensive river-runoff, sea-ice production and ice transport into the Arctic Ocean. The large variability in εNd (-6 to -17), REE concentrations (16 to 600 pmol/kg for Nd) and REE patterns is controlled by freshwater supply from distinct riverine sources and open ocean Arctic Atlantic Water. Strikingly and contrary to expectations, except for cerium no evidence for significant release of REEs from particulate phases is found, which is attributed to low amounts of suspended particulate matter and high dissolved organic carbon concentrations present in the contributing rivers. Essentially all shelf waters are depleted in light (L)REEs, while the distribution of the heavy REEs shows a deficiency at the surface and a pronounced excess in the bottom layer. This distribution is consistent with REE removal through coagulation of riverine nanoparticles and colloids starting at salinities near 10 and resulting in a drop of all REE concentrations by ∼30%. With increasing salinity preferential LREE removal is observable reaching ∼75% for Nd at a salinity of 34. Although the delayed onset of dissolved REE removal contrasts with most previous observations from other estuarine environments, it agrees remarkably well with results from recent experiments simulating estuarine mixing of seawater with organic-rich river waters. In addition, melting and formation of sea ice leads to further REE depletion at the surface and strong REE enrichment near the shelf bottom as a function of ice melting and brine transfer, respectively. The ice-related processes significantly affect the distribution of dissolved REEs in high-latitude estuaries and likely also similarly contribute to the redistribution of other dissolved seawater constituents.

Possible impact-induced refractory-lithophile fractionations in EL chondrites

NASA Astrophysics Data System (ADS)

Rubin, Alan E.; Huber, Heinz; Wasson, John T.

2009-03-01

Literature data show that refractory-lithophile elements in most chondrite groups are unfractionated relative to CI chondrites; the principal exception is the EL-chondrite group whose observed falls (all of which are type 6) are depleted in Ca and light REE. In contrast, literature data and our new INAA data on EL3 PCA 91020, EL3 MAC 88136 and EL4 Grein 002 show that some replicates of these samples have nearly flat REE patterns (unlike those of EL6 chondrites); other replicates exhibit fractionated REE patterns similar to those of EL6 chondrites. Petrographic examination shows that many EL6 (and some EL3 and EL4) chondrites are impact-melt breccias or contain impact-melted portions. We suggest that the same impact processes that formed these breccias and produced melt are responsible for the observed bulk compositional fractionations in refractory-lithophile elements, i.e., EL6 chondrites were produced from initially unequilibrated EL3 material. When large amounts of impact heat were deposited, plagioclase and/or oldhamite (CaS) (the major REE carriers in enstatite chondrites) may have been melted and then transported appreciable (>10 cm) distances. EL6 chondrites represent the residuum that is depleted in REE (particularly in LREE) and Ca. Unlike the case for EL chondrites, our new INAA data on ALH 84170, EET 87746 and SAH 97096 (all EH3) show some scatter but are consistent with the EH group having uniform refractory-lithophile abundances.

The elemental geochemistry of Lower Triassic shallow-marine carbonates from central Saudi Arabia: Implications for redox conditions in the immediate aftermath of the latest Permian mass extinction

NASA Astrophysics Data System (ADS)

Eltom, Hassan A.; Abdullatif, Osman M.; Babalola, Lamidi O.

2018-03-01

The southern margin of the Tethys Ocean was occupied by a broad, shallow continental shelf during the Permian-Triassic boundary interval, with the area of present-day Saudi Arabia located from 10° to 30° south of the paleo-equator. The strata deposited in modern Saudi Arabia in the aftermath of the latest Permian mass extinction (LPME) are dominated by oolitic microbialite limestone (OML), which are overlain by skeletal oolitic limestones (SOL) capped by dolostones and dolomitic limestones (DDL). This succession reflects changes in depositional setting, which can be potentially tied to redox conditions using redox sensitive trace elements and rare earth elements (REEs). Statistical analyses reveals that trace elements and REEs are associated with detrital material, and possibly with diagenetic minerals as well. Proxies such as the Y/Ho, Pr/Pr*, Smn/Ybn, Lan/Smn and Lan/Ybn ratios indicate that REEs do not record a seawater-like pattern, and cannot be used as redox indicator. The presence of a normal marine fauna implies oxic conditions during deposition of the DDL and SOL units. However, the OML unit, which represents the immediate aftermath of LPME, lacks both a normal marine fauna and reliable geochemical signals, making it difficult to infer redox conditions in the depositional environment. Similar to published data from sections that reflect shallow marine condition in the LPME of the Tethys Ocean, chemical index of alteration values are consistently high throughout the study succession, suggesting globally intense chemical weathering in the aftermath of the LPME. As a result, geochemical redox proxies in shallow marine carbonates of the Tethys Ocean are likely to be contaminated by detrital material that have been generated by chemical weathering, and thus, other methods are required to determine depositional redox conditions.

Water content in the SW USA mantle lithosphere: FTIR analysis of Dish Hill and Kilbourne Hole pyroxenites

NASA Astrophysics Data System (ADS)

Gibler, R.; Peslier, A. H.; Schaffer, L. A.; Brandon, A. D.

2014-12-01

Kilbourne Hole (NM, USA) and Dish Hill (CA, USA) mantle xenoliths sample continental mantle in two different tectonic settings. Kilbourne Hole (KH) is located in the Rio Grande rift. Dish Hill (DH) is located in the southern Mojave province, an area potentially affected by subduction of the Farallon plate beneath North America [1]. FTIR analyses were obtained on well characterized pyroxenite, dunite and wehrlite xenoliths, thought to represent crystallized melts at mantle depths. PUM normalized REE patterns of the KH bulk-rocks are slightly LREE enriched and consistent with those of liquids generated by < 5% melting of a spinel peridotite source [2]. Clinopyroxenes contain from 272 to 313 ppm weight H2O similar to the lower limit of KH peridotite clinopyroxenes (250-530 ppm H2O, [3]). This is unexpected as crystallized melts like pyroxenites should concentrate water more than residual mantle-like peridotites, given that H is incompatible. PUM normalized bulk REE of the DH pyroxenites are characterized by flat to LREE depleted REE profiles consistent with > 6% melting of a spinel peridotite source. Pyroxenite pyroxenes have no detectable water but one DH wehrlite, which bulk-rock is LREE enriched, has 4 ppm H2O in orthopyroxene and <1ppm in clinopyroxene. The DH pyroxenites may thus come from a dry mantle source, potentially unaffected by the subduction of the Farallon plate. These water-poor melts either originated from shallow oceanic lithosphere overlaying the Farallon slab [4] or from continental mantle formed > 2 Ga [5]. The Farallon subduction appears to have enriched in water the southwestern United States lithospheric mantle further east than DH, beneath the Colorado plateau [6]. [1] Atwater, 1970 Tectonophysics 31, 145-165. [2] Shaw, 2000 CM 38, 1041-1064. [3] Schaffer et al, 2013 AGU Fall Meeting. [4] Luffi et al, 2009 JGR 114, 1-36. [5] Armytage et al, 2013 GCA 137, 113-133. [6] Li et al, 2008 JGR 113, 1-22.

The chemistry of rare earth elements in the solar nebula

NASA Technical Reports Server (NTRS)

Larimer, J. W.; Bartholomay, H. A.; Fegley, B.

1984-01-01

The high concentration of rare earth elements (REE) in primitive CaS suggests that the REE along with the other normally lithophile elements form stable sulfides under the unusual conditions which existed during the formation of enstatite chrondites. In order to acquire a more quantitative framework in which to interpret these data, the behavior of the REE in systems with solar, or slightly fractionated solar, composition is being studied. These new data introduce modest changes in the behavior of some of the REE when compared to previous studies. For example, the largest differences are in the stabilities of the gaseous monoxides of Ce, Eu, Tb, Ho, and Tm, all of which now appear to be less stable than previously thought, and YbO(g) which is somewhat more stable. Much more significant are the changes in REE distribution in the gas phase in fractionated systems, especially those made more reducing by changing the C/O ratio from the solar value of 0.6 to about 1.0. In almost all cases, the exceptions being Eu, Tm and Yb whose elemental gaseous species dominate, the monosulfides become more abundant. Moreover, the solid oxides of Eu, Tm and Yb become less stable under more reducing conditions which, in effect, should reduce the condensation temperature of all REE in more reduced systems.

Rare earth element abundances in presolar SiC

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Ávila, J. N.; Lugaro, M.; Cristallo, S.; Holden, P.; Lanc, P.; Nittler, L.; Alexander, C. M. O'D.; Gyngard, F.; Amari, S.

2018-01-01

Individual isotope abundances of Ba, lanthanides of the rare earth element (REE) group, and Hf have been determined in bulk samples of fine-grained silicon carbide (SiC) from the Murchison CM2 chondrite. The analytical protocol involved secondary ion mass spectrometry with combined high mass resolution and energy filtering to exclude REE oxide isobars and Si-C-O clusters from the peaks of interest. Relative sensitivity factors were determined through analysis of NIST SRM reference glasses (610 and 612) as well as a trace-element enriched SiC ceramic. When normalised to chondrite abundances, the presolar SiC REE pattern shows significant deficits at Eu and Yb, which are the most volatile of the REE. The pattern is very similar to that observed for Group III refractory inclusions. The SiC abundances were also normalised to s-process model predictions for the envelope compositions of low-mass (1.5-3 M⊙) AGB stars with close-to-solar metallicities (Z = 0.014 and 0.02). The overall trace element abundances (excluding Eu and Yb) appear consistent with the predicted s-process patterns. The depletions of Eu and Yb suggest that these elements remained in the gas phase during the condensation of SiC. The lack of depletion in some other moderately refractory elements (like Ba), and the presence of volatile elements (e.g. Xe) indicates that these elements were incorporated into SiC by other mechanisms, most likely ion implantation.

Relationships between slope erosion processes and aggregate stability of Ultisols from subtropical China during rainstorms

NASA Astrophysics Data System (ADS)

Liu, Gang; Xiao, Hai; Liu, Puling

2017-04-01

Soil aggregates, being a key soil structural unit, influence several soil physical properties such as water infiltration, runoff and erosion. The relationship between soil aggregate stability and interrill and rill erodibility is unclear but critical to process-based erosion prediction models. One obvious reason is that it is hard to distinguish between interrill and rill-eroded sediment during the erosion process. This study was designed to partition interrill and rill erosion rates and relates them to the aggregate stability of Ultisols in subtropical China. Six kinds of rare earth element (REE) were applied as tracers mixed with two cultivated soils derived from the Quaternary red clay soil and the shale soil at six slope positions. Soil aggregate stability was determined by the Le Bissonnais (LB)-method. Simulated rainfall with three intensities (60, 90 and 120 mm/h) were applied to a soil plot (2.25 m long, 0.5 m wide, 0.2 m deep) at three slope gradients (10°, 20° and 30°) with duration of 30 min after runoff initiation. The results indicated that interrill and rill erosion increased with increasing rainfall intensity and slope gradient for both types of soil. Rill and interrill erosion rates of the shale soil were much higher than those of the Quaternary red clay soil. Rill erosion contribution enhanced with increasing rainfall intensity and slope gradient for both soils. Percentage of the downslope area erosion to total erosion was the largest, followed by the mid-slope area and then upslope area. Equations using an aggregate stability index As to replace the erodibility factor of interrill and rill erosion in the Water Erosion Prediction Project (WEPP) model were constructed after analyzing the relationships between estimated and measured rill and interrill erosion data. It was shown that these equations based on the stability index, As, have the potential to improve methods for assessing interrill and rill erosion erodibility synchronously for the subtropical Ultisols by using REE tracing method.

The Pasamonte unequilibrated eucrite: Pyroxene REE systematic and major-, minor-, and trace-element zoning. [Abstract only

NASA Technical Reports Server (NTRS)

Pun, A.; Papike, J. J.

1994-01-01

We are evaluating the trace-element concentrations in the pyroxenes of Pasamonte. Pasamonte is a characteristic member of the main group eucrites, and has recently been redescribed as a polymict eucrite. Our Pasamonte sample contained eucritic clasts with textures ranging from subophitic to moderately coarse-grained. This study concentrates on pyroxenes from an unequilibrated, coarse-grained eucrite clast. Major-, minor-, and trace-element analyses were measured for zoned pyroxenes in the eucritic clast of Pasamonte. The major- and minor-element zoning traverses were measured using the JEOL 733 electron probe with an Oxford-Link imaging/analysis system. Complemenatry trace elements were then measured for the core and rim of each of the grains by SIMS. The trace elements analyzed consisted of eight REE, Sr, Y, and Zr. These analyses were performed on a Cameca 4f ion probe. The results of the CI chondrite normalized (average CI trace-element analyses for several grains and the major- and minor-element zoning patterns from a single pyroxene grain are given. The Eu abundance in the cores of the pyroxenes represents the detection limit and therefore the (-Eu) anomaly is a minimum. Major- and minor-element patterns are typical for igneous zoning. Pyroxene cores are Mg enriched, whereas the rims are enriched in Fe and Ca. Also, Ti and Mn are found to increase, while Cr and Al generally decrease in core-to-rim traverses. The cores of the pyroxenes are more depleted in the Rare Earth Elements (REE) than the rims. Using the minor- and trace-element concentrations of bulk Pasamonte and the minor- and trace-element concentrations from the cores of the pyroxenes in Pasamonte measured in this study, we calculated partition coefficients between pyroxene and melt. This calculation assumes that bulk Pasamonte is representative of a melt composition.

Rare earth elements in minerals of the ALHA77005 shergottite and implications for its parent magma and crystallization history

NASA Technical Reports Server (NTRS)

Lundberg, Laura L.; Crozaz, Ghislaine; Mcsween, Harry Y., Jr.

1990-01-01

Analyses of mineral REE and selected minor and trace elements were carried out on individual grains of pyroxenes, whitlockite, maskelynite, and olivine of the Antarctic shergottite ALHA77005, and the results are used to interpret its parent magma and crystallization history. The results of mineral compositions and textural observations suggest that ALHA77005 is a cumulate with about half cumulus material (olivine + chromite) and half postcumulus phases. Most of the REEs in ALHA77005 reside in whitlockite whose modal concentration is about 1 percent. Mineral REE data support previous suggestions that plagioclase and whitlockite crystallized late, and that low-Ca pyroxene initiated crystallization before high-Ca pyroxene. The REE patterns for the intercumulus liquid, calculated from distribution coefficients for ALHA77005 pyroxene, plagioclase, and whitlockite, are in very good agreement and are similar to that of Shergotty.

Geochemistry and microprobe investigations of Abu Tartur REE-bearing phosphorite, Western Desert, Egypt

NASA Astrophysics Data System (ADS)

Awadalla, Gamal S.

2010-07-01

Phosphorites in Egypt occur in the Eastern Desert, the Nile Valley and the Western Desert at Abu Tartur area and present in Duwi Formation as a part of the Middle Eastern to North African phosphogenic province of Late Cretaceous to Paleogene age (Campanian-Maastrichtian). The Maghrabi-Liffiya phosphorite sector is considered as the most important phosphorite deposits in the Abu Tartur area due to its large reserve thickness and high-grade of lower phosphorite bed beside high content of REE. Back scattered electron (BSE) images show framboidal pyrite filling the pores of the phosphatic grains, suggesting diagenetic reducing conditions during phosphorites formation. Electron Probe Micro Analyzer (EPMA) chemical mapping was conducted to examine the variation and distributions of selected elements (P, F, La, Fe, Yb, Si, Ce, W, Eu, S, Ca, Y and Er) within the shark teeth, coprolites and bone fragments. In the teeth W, S, Fe are concentrated along the axis of the teeth, the bone fragments show high concentration of W, Yb, Er and Eu, whereas coprolites are nearly homogenous in composition contains S, Er with some Si as micro-inclusions. Fluorapatite is considered as main phosphate mineral whereas pyrite occurs as pore-filling within the phosphatic grains and cement materials. Maghrabi-Liffiya samples show a wide range in the P 2O 5 content, between 19.8 wt.% and 29.8 wt.% with an average of 24.6 wt.% and shows low U content ranging from 15 ppm to 34 ppm with an average of 22 ppm. The total REE content in nine samples representing the Maghrabi-Liffiya ranges from 519 to 1139 ppm with an average of about 879 ppm. The calculation of LREE (La-Gd) show indeed a marked enrichment relative to the HREE (Tb-Lu) where LREE/HREE ratio attains 8.4 indicating a strong fractionation between the LREE and HREE. Chondrite-normalized REE patterns of the studied phosphorite samples show a negative Eu anomaly.

Influence of Normal and Shear Stress on the Hydraulic Transmissivity of Thin Cracks in a Tight Quartz Sandstone, a Granite, and a Shale

NASA Astrophysics Data System (ADS)

Rutter, Ernest H.; Mecklenburgh, Julian

2018-02-01

Transmissivity of fluids along fractures in rocks is reduced by increasing normal stress acting across them, demonstrated here through gas flow experiments on Bowland shale, and oil flow experiments on Pennant sandstone and Westerly granite. Additionally, the effect of imposing shear stress at constant normal stress was determined, until frictional sliding started. In all cases, increasing shear stress causes an accelerating reduction of transmissivity by 1 to 3 orders of magnitude as slip initiated, as a result of the formation of wear products that block fluid pathways. Only in the case of granite, and to a lesser extent in the sandstone, was there a minor amount of initial increase of transmissivity prior to the onset of slip. These results cast into doubt the commonly applied presumption that cracks with high resolved shear stresses are the most conductive. In the shale, crack transmissivity is commensurate with matrix permeability, such that shales are expected always to be good seals. For the sandstone and granite, unsheared crack transmissivity was respectively 2 and 2.5 orders of magnitude greater than matrix permeability. For these rocks crack transmissivity can dominate fluid flow in the upper crust, potentially enough to permit maintenance of a hydrostatic fluid pressure gradient in a normal (extensional) faulting regime.

An assessment of exposure to rare earth elements among patients receiving long-term parenteral nutrition.

PubMed

Galusha, Aubrey L; Kruger, Pamela C; Howard, Lyn J; Parsons, Patrick J

2018-05-01

Patients receiving long-term parenteral nutrition (PN) are exposed to potentially toxic elements, which may accumulate in bone. Bone samples collected from seven PN patients (average = 14 years) and eighteen hip/knee samples were analyzed for Al as part of a previous investigation. Yttrium was serendipitously detected in the PN bone samples, leading to the present investigation of rare earth elements (REEs). A method for quantitating fifteen REEs in digested bone was developed based on tandem ICP-MS (ICP-MS/MS) to resolve spectral interferences. The method was validated against nine biological reference materials (RMs) for which assigned values were available for most REEs. Values found in two NIST bone SRMs (1400 Bone Ash and 1486 Bone Meal) compared favorably to those reported elsewhere. Method detection limits ranged from 0.9 ng g -1 (Tm) to 5.8 ng g -1 (Y). Median REE values in the PN patient group were at least fifteen times higher than the "control" group, and exceeded all previously reported data for eleven REEs in human bones. REE content in PN bones normalized to the Earth's upper crust revealed anomalies for Gd in two patients, likely from exposure to Gd-containing contrast agents used in MRI studies. A retrospective review of the medical record for one patient revealed an almost certain case of nephrogenic systemic fibrosis, associated with Gd exposure. Analysis of two current PN formulations showed traces of REEs with relative abundances similar to those found in the PN bones, providing convincing evidence that PN solutions were the primary source of REEs in this population. Copyright © 2018 Elsevier GmbH. All rights reserved.

Mathematical model for the contribution of individual organs to non-zero y-intercepts in single and multi-compartment linear models of whole-body energy expenditure.

PubMed

Kaiyala, Karl J

2014-01-01

Mathematical models for the dependence of energy expenditure (EE) on body mass and composition are essential tools in metabolic phenotyping. EE scales over broad ranges of body mass as a non-linear allometric function. When considered within restricted ranges of body mass, however, allometric EE curves exhibit 'local linearity.' Indeed, modern EE analysis makes extensive use of linear models. Such models typically involve one or two body mass compartments (e.g., fat free mass and fat mass). Importantly, linear EE models typically involve a non-zero (usually positive) y-intercept term of uncertain origin, a recurring theme in discussions of EE analysis and a source of confounding in traditional ratio-based EE normalization. Emerging linear model approaches quantify whole-body resting EE (REE) in terms of individual organ masses (e.g., liver, kidneys, heart, brain). Proponents of individual organ REE modeling hypothesize that multi-organ linear models may eliminate non-zero y-intercepts. This could have advantages in adjusting REE for body mass and composition. Studies reveal that individual organ REE is an allometric function of total body mass. I exploit first-order Taylor linearization of individual organ REEs to model the manner in which individual organs contribute to whole-body REE and to the non-zero y-intercept in linear REE models. The model predicts that REE analysis at the individual organ-tissue level will not eliminate intercept terms. I demonstrate that the parameters of a linear EE equation can be transformed into the parameters of the underlying 'latent' allometric equation. This permits estimates of the allometric scaling of EE in a diverse variety of physiological states that are not represented in the allometric EE literature but are well represented by published linear EE analyses.

Rare earth elements in weathering profiles and sediments of Minnesota: Implications for provenance studies

USGS Publications Warehouse

Morey, G.B.; Setterholm, D.R.

1997-01-01

The relative abundance of rare earth elements in sediments has been suggested as a tool for determining their source rocks. This correlation requires that weathering, erosion, and sedimentation do not alter the REE abundances, or do so in a predictable manner. We find that the rare earth elements are mobilized and fractionated by weathering, and that sediments derived from the weathered materials can display modifications of the original pattern of rare earth elements of some due to grain-size sorting of the weathered material. However, the REE distribution pattern of the provenance terrane can be recognized in the sediments.

Continuous TDEM for monitoring shale hydraulic fracturing

NASA Astrophysics Data System (ADS)

Yan, Liang-Jun; Chen, Xiao-Xiong; Tang, Hao; Xie, Xing-Bing; Zhou, Lei; Hu, Wen-Bao; Wang, Zhong-Xin

2018-03-01

Monitoring and delineating the spatial distribution of shale fracturing is fundamentally important to shale gas production. Standard monitoring methods, such as time-lapse seismic, cross-well seismic and micro-seismic methods, are expensive, timeconsuming, and do not show the changes in the formation with time. The resistivities of hydraulic fracturing fluid and reservoir rocks were measured. The results suggest that the injection fluid and consequently the injected reservoir are characterized by very low resistivity and high chargeability. This allows using of the controlled-source electromagnetic method (CSEM) to monitor shale gas hydraulic fracturing. Based on the geoelectrical model which was proposed according to the well-log and seismic data in the test area the change rule of the reacted electrical field was studied to account for the change of shale resistivity, and then the normalized residual resistivity method for time lapse processing was given. The time-domain electromagnetic method (TDEM) was used to continuously monitor the shale gas fracturing at the Fulin shale gas field in southern China. A high-power transmitter and multi-channel transient electromagnetic receiver array were adopted. 9 h time series of Ex component of 224 sites which were laid out on the surface and over three fracturing stages of a horizontal well at 2800 m depth was recorded. After data processing and calculation of the normalized resistivity residuals, the changes in the Ex signal were determined and a dynamic 3D image of the change in resistivity was constructed. This allows modeling the spatial distribution of the fracturing fluid. The model results suggest that TDEM is promising for monitoring hydraulic fracturing of shale.

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE PAGES

Balboni, Enrica; Spano, T; Cook, N; ...

2017-10-20

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Spano, T; Cook, N

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Proton pump inhibitor-responsive esophageal eosinophilia: a historical perspective on a novel and evolving entity.

PubMed

Molina-Infante, Javier; Katzka, David A; Dellon, Evan S

2015-01-01

Eosinophilic esophagitis (EoE) is an emerging chronic esophageal disease, first described in 1993, with a steadily increasing incidence and prevalence in western countries. Over the 80's and early 90's, dense esophageal eosinophilia was mostly associated gastroesophageal reflux disease (GERD). For the next 15 years, EoE and GERD were rigidly considered separate entities: Esophageal eosinophilia with pathological acid exposure on pH monitoring or response to proton pump inhibitor (PPI) therapy was GERD, whereas normal pH monitoring or absence of response to PPIs was EoE. Updated guidelines in 2011 described a novel phenotype, proton pump inhibitor-responsive esophageal eosinophilia (PPI-REE), referring to patients who appear to have EoE clinically, but who achieve complete remission after PPI therapy. Currently, PPI-REE must be formally excluded before diagnosing EoE, since 30-40% of patients with suspected EoE are eventually diagnosed with PPI-REE.Interestingly, PPI-REE and EoE remain undistinguishable based on clinical, endoscopic, and histological findings, pH monitoring, and measurement of tissue markers and cytokines related to eosinophilic inflammation.This review article aims to revisit the relatively novel concept of PPI-REE from a historical perspective, given the strong belief that only GERD, as an acid peptic disorder, could respond to the acid suppressing ability of PPI therapy, is becoming outdated. Evolving evidence suggests that PPI-REE is genetically and phenotypically undistinguishable from EoE and PPI therapy alone can almost completely reverse allergic inflammation. As such, PPI-REE might constitute a subphenotype of EoE and PPI therapy may be the first therapeutic step and diet/ steroids may represent step up therapy. Possibly, the term PPI-REE will be soon replaced by PPI-responsive EoE. The mechanism as to why some patients respond to PPI therapy (PPI-REE) while others do not (EoE), remains to be elucidated.

The rare earth element geochemistry on surface sediments, shallow cores and lithological units of Lake Acıgöl basin, Denizli, Turkey

NASA Astrophysics Data System (ADS)

Budakoglu, Murat; Abdelnasser, Amr; Karaman, Muhittin; Kumral, Mustafa

2015-11-01

The sediments in Lake Acıgöl, located in SW Anatolia, Turkey, were formed under tectono-sedimentary events. REE geochemical investigations of the Lake Acıgöl sediments, from surface and shallow core sediments at different depths (0-10 cm, 10-20 cm and 20-30 cm) are presented to clarify the characteristics of REE and the nature of source rocks in the lake sediments' and to deduce their paleoenvironmental proxies. The chondrite-normalized REE patterns of these sediments are shown as light enrichment in LREE and flat HREE with a negative Eu anomaly that is close to the continental collision basin (CCB) in its profile; this is not comparable with PAAS and UCC. Inorganic detrital materials control the REE characteristics of the Lake Acıgöl sediments and these sediments were accumulated in oxic and dysoxic depositional conditions and/or at passive margins derived from oceanic island arc rocks. They were affected by low chemical weathering, either at the original source or during transport, before deposition under arid or subtropical humid climatic conditions. In addition, we used GIS techniques (such as Inverse Distance Weighted (IDW) and Geographically Weighted Regression (GWR)) to investigate the spatial interpolation and spatial correlation of the REEs from the lake surface sediments in Lake Acıgöl and its surrounding lithological units. GIS techniques showed that the lithological units (e.g., Hayrettin Formation) north of Lake Acıgöl have high REE contents; however, Eu/Eu∗ values were higher in some lake surface sediments than in lithological units, and that refers to a negative Eu-anomaly. Therefore, Lake Acıgöl sediments are derived from the weathered products, mainly from local, highly basic bedrock around the lake from the Archean crust. The chronology of Lake Acıgöl sediment was conducted using the Constant Rate of Supply (CRS) model. Using the CRS methods for the calculation of sedimentation rate, we obtained a 0.012 g/cm2/year value which is an average value for the first 20 cm depth of this lake. The core activity profiles of 210Pb and 137Cs were measured to estimate the age of the sediments; we observed activities of 8.08 ± 5.5 Bq/kg for 210Pb and 0.86 ± 0.6 Bq/kg for 137Cs.

Bacterial physiological diversity in the rhizosphere of range plants in response to retorted shale stress. [Agropyron smithii Rydb; Atriplex canescens (Pursh) Nutt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Metzger, W.C.; Klein, D.A.; Redente, E.F.

1986-10-01

Bacterial populations were isolated from the soil-root interface and root-free regions of Agropyron smithii Rydb. and Atriplex canescens (Pursh) Nutt. grown in soil, retorted shale, or soil over shale. Bacteria isolated from retorted shale exhibited a wider range of tolerance to alkalinity and salinity and decreased growth on amino acid substrates compared with bacteria from soil and soil-over-shale environments. Exoenzyme production was only slightly affected by growth medium treatment. Viable bacterial populations were higher in the rhizosphere and rhizoplane of plants grown in retorted shale than in plants grown in soil or soil over shale. In addition, a greater numbermore » of physiological groups of rhizosphere bacteria was observed in retorted shale, compared with soil alone. Two patterns of community similarity were observed in comparisons of bacteria from soil over shale with those from soil and retorted-shale environments. Root-associated populations from soil over shale had a higher proportion of physiological groups in common with those from the soil control than those from the retorted-shale treatment. However, in non-rhizosphere populations, bacterial groups from soil over shale more closely resembled the physiological groups from retorted shale.« less

Trace Element Abundances in Refractory Inclusions from Antarctic Micrometeorites

NASA Astrophysics Data System (ADS)

Greshake, A.; Hoppe, P.; Bischoff, A.

1995-09-01

Refractory inclusions are charcteristic components in carbonaceous chondrites. Therefore, refractory inclusions found in micrometeorites can give important hints about the relationship between micrometeorites and carbonaceous chondrites. So far, only a few inclusions were found in micrometeorites [1-4]. In this study we report the first trace element analysis of perovskite and fassaite found in micrometeorites. We studied two Antarctic micrometeorites by ASEM, EMP, and SIMS. The first particle is 120 micrometers in size mainly consisting of a fine-grained matrix of dehydrated former phyllosilikates that enclose a 5 micrometers sized perovskite [5]. The perovskite is surrounded by a 1 micrometers thick rim of ilmenite and contains up to 1.3 wt% FeO as determined by EMP. The trace element abundances were determined by SIMS following the procedure described by [6]. The REE pattern of the perovskite is shown in Fig. 1. The pattern is closely related to the Group II pattern with its typical depletion of the more refractory REEs [7]. It is also very similar to the REE abundances of perovskite from Murchison (CM) [8] and CH-chondrites [9]. This may indicate a relationship between this micrometeorite and components in carbonaceous chondrites. The second micrometeorite is 100 micrometers in size consisting of a fine-grained (20 micrometers across) and a coarse-grained (80 micrometers across) area. Both areas contain fassaite with different chemical compositions. The particle was previously analyzed by Lindstrom and Kloeck [1] without knowing the mineralogy. We carried out SIMS analysis of each area of the micrometeorite separately. The TEE patterns of these two areas are similar and show in general a Group III pattern (20-30x CI) in which the more refractory REEs are not fractionated. The negative Eu anomaly is much more apparent in the coarse-grained area and no Yb anomaly is apparent in one of the areas. This is the first CAI of a micrometeorite showing a Group III REE pattern. References: [1] Lindstrom D. J. and Kloeck W. (1992) Meteoritics, 27, 250. [2] Kurat G. et al. (1994) Meteoritics, 29, 487-488. [3] Kurat G. et al. (1995) LPS XXV, 763-764. [4] Hoppe P. et al. (1995) LPS XXVI, 623-624. [5] Beckerling W. et al. (1992) Meteoritics, 27, 200-201. [6] Zinner E. and Crozaz G. (1986) Int. J. Mass. Spectr. Ion Processes, 69, 17-38. [7] Martin P. and Mason B. (1974) Nature, 249, 333-334. [8] Ireland T. et al. (1988) GCA, 52, 2841-2854. [9] Weber et al. (1995) GCA, 59, 803-823.

Properties of Silurian shales from the Barrandian Basin, Czech Republic

NASA Astrophysics Data System (ADS)

Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

2017-04-01

Although shale gas-bearing deposits have a markedly lower gas content than coal deposits, great attention has recently been paid to shale gas as a new potential source of fossil energy. Shale gas extraction is considered to be quite economical, despite the lower sorption capacity of shales, which is only about 10% of coal sorption capacities The selection of a suitable locality for extracting shale gas requires the sorption capacity of the shale to be determined. The sorption capacity is determined in the laboratory by measuring the amount of methane absorbed in a shale specimen at a pressure and a temperature corresponding to in situ conditions, using high pressure sorption. According to the principles of reversibility of adsorption/desorption, this amount should be roughly related to the amount of gas released by forced degassing. High pressure methane sorption isotherms were measured on seven representative samples of Silurian shales from the Barrandian Basin, Czech Republic. Excess sorption measurements were performed at a temperature of 45oC and at pressures up to 15 MPa on dry samples, using a manometric method. Experimental methane high-pressure isotherms were fitted to a modified Langmuir equation. The maximum measured excess sorption parameter and the Langmuir sorption capacity parameter were used to study the effect of TOC content, organic maturity, inorganic components and porosity on the methane sorption capacity. The studied shale samples with random reflectance of graptolite 0.56 to 1.76% had a very low TOC content and dominant mineral fractions. Illite was the prevailing clay mineral. The sample porosity ranged from 4.6 to 18.8%. In most samples, the micropore volumes were markedly lower than the meso- and macropore volumes. In the Silurian black shales, the occurrence of fractures parallel with the original sedimentary bending was highly significant. A greater proportion of fragments of carbonaceous particles of graptolites and bitumens in the Barrandian Silurian shales had a smooth surface without pores. No relation has been proven between TOC-normalized excess sorption capacities or the TOC-normalized Langmuir sorption capacities and thermal maturation of the shales. The methane sorption capacities of shale samples show a positive correlation with TOC and a positive correlation with the clay content. The highest sorption capacity was observed in shale samples with the highest percentage of micropores, indicating that the micropore volume in the organic matter and clay minerals is a principal factor affecting the sorption capacity of the shale samples.

Petrogenesis of Late Cretaceous lava flows from a Ceno-Tethyan island arc: The Raskoh arc, Balochistan, Pakistan

NASA Astrophysics Data System (ADS)

Siddiqui, Rehanul Haq; Qasim Jan, M.; Asif Khan, M.

2012-10-01

The Raskoh arc is about 250 km long, 40 km wide and trends in an ENE direction. The oldest rock unit in the Raskoh arc is an accretionary complex (Early to Late Jurassic), which is followed in age by Kuchakki Volcanic Group, the most wide spread unit of the Raskoh arc. The Volcanic Group is mainly composed of basaltic to andesitic lava flows and volcaniclastics, including agglomerate, volcanic conglomerate, breccia and tuff, with subordinate shale, sandstone, limestone and chert. The flows generally form 3-15 m thick lenticular bodies but rarely reach up to 300 m. They are mainly basaltic-andesites with minor basalts and andesites. The main textures exhibited by these rocks are hypocrystalline porphyritic, subcumulophyric and intergranular. The phenocrysts comprise mainly plagioclase (An30-54 in Nok Chah and An56-64 in Bunap). They are embedded in a micro-cryptocrystalline groundmass having the same minerals. Apatite, magnetite, titanomagnetite and hematite occur as accessory minerals. Major, trace and rare earth elements suggest that the volcanics are oceanic island arc tholeiites. Their low Mg # (42-56) and higher FeO (total)/MgO (1.24-2.67) ratios indicate that the parent magma of these rocks was not directly derived from a mantle source but fractionated in an upper level magma chamber. The trace element patterns show enrichment in LILE and depletion in HFSE relative to N-MORB. Their primordial mantle-normalized trace element patterns show marked negative Nb anomalies with positive spikes on K, Ba and Sr which confirm their island arc signatures. Slightly depleted LREE to flat chondrite normalized REE patterns further support this interpretation. The Zr versus Zr/Y and Cr versus Y studies show that their parent magma was generated by 20-30% melting of a depleted mantle source. The trace elements ratios including Zr/Y (1.73-3.10), Ti/Zr (81.59-101.83), Ti/V (12.39-30.34), La/YbN (0.74-2.69), Ta/Yb (0.02-0.05) and Th/Yb (0.11-0.75) of the volcanics are more consistent with oceanic island arcs rather than continental margin arcs. It is suggested that the Raskoh arc is an oceanic island arc which formed due to the intra-oceanic convergence in the Ceno-Tethys during the Late Cretaceous rather than constructed on the southern continental margin of the Afghan block, as claimed by previous workers. It is further suggested that the Semail, Zagros, Chagai-Raskoh, Muslim Bagh, and Waziristan island arcs were developed in a single but segmented Cretaceous Ceno-Tethyan convergence zone.

The Middle Triassic evolution of the Bangong-Nujiang Tethyan Ocean: evidence from analyses of OIB-type basalts and OIB-derived phonolites in northern Tibet

NASA Astrophysics Data System (ADS)

Fan, Jian-Jun; Li, Cai; Liu, Jin-Heng; Wang, Ming; Liu, Yi-Ming; Xie, Chao-Ming

2017-12-01

In this paper, we present new major and trace element chemical data for the basalts and phonolites of the Nare ocean island fragment (NaOI), as well as zircon U-Pb age data and Hf isotope compositions for the NaOI phonolites in the middle segment of the Bangong-Nujiang Suture Zone, northern Tibet. Our aim is to assess the genesis of these rocks and to reconstruct the Middle Triassic evolution of the Bangong-Nujiang Tethyan Ocean (BNTO). The NaOI retains an ocean island-type double-layered structure comprising a basaltic basement and an oceanic sedimentary cover sequence (conglomerate and limestone, the latter accompanied by layers of erupted phonolite near the top of the sequence). The basalts in the NaOI are enriched in light rare earth elements and high field strength elements (Nb, Ta, Zr, Hf, and Ti), and they exhibit chondrite-normalized REE patterns and primitive mantle-normalized trace element patterns similar to those of ocean island basalts. Taking into consideration their high Dy/Yb, Sm/Yb, and La/Sm ratios, we conclude that the NaOI basalts were derived from the partial melting of garnet peridotite in the mantle. The NaOI phonolites have LREE-enriched chondrite-normalized REE patterns with negative Eu anomalies (Eu/Eu* = 0.41-0.43) and primitive mantle-normalized trace element patterns with enrichments in Nb, Ta, Zr, and Hf, and depletions in Ba, U, Sr, P, and Ti. Given the high contents of Nb (172-256 ppm), Ta (11.8-16.0 ppm), Zr (927-1117 ppm), and Hf (20.8-26.9 ppm), and the very low contents of MgO (0.11-0.25 wt%), the very low Mg# values (5-10), and the near-zero contents of Cr (1.27-7.59 ppm), Ni (0.43-7.19 ppm), and Co (0.11-0.38 ppm), and the small and homogeneously positive ɛ Hf(t) values (+ 4.9 to + 9.5), we infer that the NaOI phonolites were formed by the fractional crystallization of an OIB-derived mafic parent magma. The phonolites of the NaOI contain zircons that yielded U-Pb ages of 239 and 242 Ma, indicating that the NaOI formed during the Middle Triassic. These data, combined with data from modern ocean islands (e.g., Canary Islands, Cape Verde, Fernando de Noronha, Tristan da Cunha, and Gough in the Atlantic Ocean, and Society and Austral-Cook in the Pacific Ocean), lead us to infer that the BNTO was open for a long time before the Middle Triassic, and that the ocean had already developed into a mature ocean with a thick oceanic lithosphere by at least the Middle Triassic.

Does sediment geochemistry (based on selective extractions of Al and Fe and REE) provide a record of soil evolution?

NASA Astrophysics Data System (ADS)

Mourier, B.; Poulenard, J.; Blarquez, O.; Williamson, D.; Arnaud, F.; Carcaillet, C.

2009-04-01

Soil is a natural body occurring at the interface between the lithosphere, atmosphere and biosphere. As a result, the physical and chemical properties of soils evolve with time, and the reconstruction of their history represents a key to understand past environmental changes. Palaeolimnological techniques such as sediment geochemistry can be used to investigate changes in catchment history by providing information about soil development. However, due to the lack of conservative pedosignatures (soil proxies), only few paleoecological studies have attempted to reconstruct the history of soil genesis using geochemical analyses of lacustrine sediments. Here we present a multidisciplinary study which aims to use pedosignatures, defined by a previous soil study, in order to characterize the history of soil genesis, podzolization and chemical weathering processes in two sediment sequences. Moreover, we aim to compare the timing of soil evolution with other paleoenvironmental markers (macroremains, charcoals…) in order to infer the role of climate, vegetation and possible human activities as forcing factors. In a first step, the geochemical investigation of eight subalpine soil profiles from the inner Alps allowed to define relevant proxies of two major soil processes. Parent material normalized REE patterns provide a precise tracer of chemical weathering whereas the proportions of secondary Al- and Fe-bearing phases provide a tracer of the podzolisation process. Then, the same tracers were assessed on two lacustrine and peat sediment sequences (Loup and Thyl lakes) from the subalpine domain. The proxy records, spanning ca. 4.500 yr at the Thyl lake and ca. 13.500 yr at the Loup lake, indicate that both progressive and regressive pedogenesis occurred after the deglaciation. The Thyl record is highly contrasted: the progressive setting of the mixed cembra pine ecosystem is associated to the podzolisation process (secondary Al- and Fe-bearing phases are maximal) and the increase of chemical weathering (enrichments of specific REE's fractions) that lasted totally ca. 1500 to 2000 years. Then, these progressive pathways are followed by abrupt and rapid secondary processes that could result from drastic transformation of the plant cover. The flat normalized REE patterns associated with low secondary Al and Fe values suggest a decrease of chemical weathering and podzolization. Moreover, the higher variability in cembra pine and the enrichment in sedge and other herbs remains in the lake suggest the setting of semi-open vegetation associated to the evidence of regressive soil processes. On the other hand, Loup environment and soil history are characterized by a progressive and stable evolution leading to present day old growing forests and Podzol soil type. Whereas the major sedimentological changes are sensitive to climate, the soil proxy records may be more triggered by the natural dynamic of the plant cover. At this site, human disturbances seem to have lower importance than at the Thyl site.

Role of upper-most crustal composition in the evolution of the Precambrian ocean-atmosphere system

NASA Astrophysics Data System (ADS)

Large, R. R.; Mukherjee, I.; Zhukova, I.; Corkrey, R.; Stepanov, A.; Danyushevsky, L. V.

2018-04-01

Recent research has emphasized the potential relationships between supercontinent cycles, mountain building, nutrient flux, ocean-atmosphere chemistry and the origin of life. The composition of the Upper-Most Continental Crust (UMCC) also figures prominently in these relationships, and yet little detailed data on each component of this complex relationship has been available for assessment. Here we provide a new set of data on the trace element concentrations, including the Rare Earth Elements (REE), in the matrix of 52 marine black shale formations spread globally through the Archean and Proterozoic. The data support previous studies on the temporal geochemistry of shales, but with some important differences. Results indicate a change in provenance of the black shales (upper-most crustal composition), from more mafic in the Archean prior to 2700 Ma, to more felsic from 2700 to 2200 Ma, followed by a return to mafic compositions from 2200 to 1850 Ma. Around 1850 to 1800 Ma there is a rapid change to uniform felsic compositions, which remained for a billion years to 800 Ma. The shale matrix geochemistry supports the assertion that the average upper-most continental source rocks for the shales changed from a mix of felsic, mafic and ultramafic prior to 2700 Ma to more felsic after 1850 Ma, with an extended transition period between. The return to more mafic UMCC from 2200 to 1850 Ma is supported by the frequency of Large Igneous Provinces (LIPs) and banded iron formations, which suggest a peak in major mantle-connected plume events and associated Fe-rich hydrothermal activity over this period. Support for the change to felsic UMCC around 1850 Ma is provided by previous geological data which shows that felsic magmas, including, A-type granites and K-Th-U-rich granites intruded vast areas of the continental crust, peaking around 1850 Ma and declining to 1000 Ma. The implications of this change in UMCC are far reaching and may go some way to explain the distinct features of the Boring Billion (1800-800 Ma). Firstly, because mafic-ultramafic rocks contain significantly higher levels of the bio-essential nutrient elements (e.g. Fe, P, Ni, Cr, Co, Cu, Se, Mn, Zn) compared with felsic rocks, the flux of macro- and micro-nutrients to the ocean would have decreased significantly post 1850 Ma. This would have contributed to a drop in productivity and a drop in atmosphere O2 as suggested by the marine pyrite proxy. In addition, a change from mafic to felsic dominant composition of the UMCC post 1850 Ma, would have led to a decrease in the erosive flux of Ca and Mg to the ocean, affecting the oceanic carbonate equilibrium and likely contributing to a rise in atmosphere CO2. On this basis, we speculate that the commencement of the middle Proterozoic, commonly known as the Boring Billion period from 1800 to 800 Ma, marks the start of an extended time in Earth's evolution when the UMCC became dominated by felsic rocks, particularly K-U-Th-anorogenic granites. This led to a period of anomalously low concentrations of bio-essential trace elements, but elevated REE, U, Th, Pb, Tl, Rb/Al and K/Na in the oceans.

Rare earth element evidence for the petrogenesis of the banded series of the Stillwater Complex, Montana, and its anorthosites

USGS Publications Warehouse

Loferski, P.J.; Arculus, R.J.; Czamanske, G.K.

1994-01-01

A rare earth element (REE) study was made by isotope-dilution mass spectrometry of plagioclase separates from a variety of cumulates stratigraphically spanning the Banded series of the Stillwater Complex, Montana. Evaluation of parent liquid REE patterns, calculated on the basis of published plagioclase-liquid partition coefficients, shows that the range of REE ratios is too large to be attributable to fractionation of a single magma type. At least two different parental melts were present throughout the Banded series. This finding supports hypotheses of previous workers that the Stillwater Complex formed from two different parent magma types, designated the anorthosite- or A-type liquid and the ultramafic- or U-type liquid. -from Authors

African Dust Transport Captured by Rare Earth Elemental Concentrations in Coral Microatolls

NASA Astrophysics Data System (ADS)

Ouellette, G., Jr.; DeLong, K.; Herrmann, A.; Huang, C. Y.; Shen, C. C.

2017-12-01

Winds are integral components of the climate system; unfortunately, windsare also among the climate variables that are most difficult to study prior to the instrumentalrecord. Paleoclimatologists use sedimentary dust records (e.g., lake and ocean cores) tounderstand past wind circulation conditions; however, these types of records typically are notamenable to sub-annual interpretation due to their limited temporal resolution. Here wedeveloped a coral-based dust-wind proxy to overcome these temporal limitations by usingtrace (nmol/mol) rare earth elemental concentrations recorded in the skeletons of coralmicroatolls. The rare earth elements (REE; the lanthanides as well as scandium and yttrium)behave similarly in geologic and geochemical systems, and have served as useful proxies ofgeological processes in both deep and shallow time. Corals incorporate REE as they deposittheir exoskeletons that extend incrementally with time forming annual density band couplets.Coral microatolls grow at or near the sea surface, where coral REE concentrations are mostsensitive to dust deposition. Our study site off the west coast of Haiti is down stream of light-REE depleted bedrock whereas REE in African dust, transported by the easterly trade winds,reflect average crustal abundances. This unique "upstream" source signature allows forterrestrial contamination of the dust-wind signal to be ruled out. Light REE concentrations (esp.Nd and Pr) demonstrate an order of magnitude increase within coral aragonite coincident withmajor African dust plume events throughout the past decade, with Nd/Ca and Pr/Ca increasingfrom an average of 27 nmol/mol to an average 144 nmol/mol and an average of 5 nmol/mol toan average of 37 nmol/mol, respectively, during major African dust plume events. Monthly-resolved REE analysis shows these REE peaks coincide with the summer dust season rather thanHaiti's two wet seasons in spring and autumn. Regression of our coral REE dust proxy tosatellite records of African dust aerosol optical depth (AOD) provides a significant transferfunction [(REE)=3.00(AOD)-3.11, R 2 = 0.72, p ≤ 0.0005, df= 24]. Our results suggest coral REErecords have the potential to robustly reconstruct past African dust plume transport, thusproviding insight into the regional easterly trade wind patterns driving them.

Aqueous Rare Earth Element Patterns and Concentration in Thermal Brines Associated With Oil and Gas Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nye, Charles; Quillinan, Scott Austin; Neupane, Ghanashyam

This study is part of a joint effort by the University of Wyoming (UW) School of Energy Resources (SER), the UW Engineering Department, Idaho National Laboratories (INL), and the United States Geological Survey (USGS) to describe rare earth element concentrations in oil and gas produced waters and in coal-fired power station ash ponds. In this work we present rare earth element (REE) and trace metal behavior in produced water from four Wyoming oil and gas fields and surface ash pond water from two coal-fired power stations. The concentration of REEs in oil and gas produced waters is largely unknown. Formore » example, of the 150,000 entries in the USGS National Produced Waters Geochemical Database less than 5 include data for REEs. Part of the reason for this scarcity is the analytical challenge of measuring REEs in high salinity, hydrocarbon-bearing waters. The industry standard for water analysis struggles to detect REEs in natural waters under ideal conditions. The detection of REEs in oil and gas field samples becomes all but impossible with the background noise and interferences caused by high concentrations of non-REE ions and residual hydrocarbons. The INL team members have overcome many of these challenges (e.g. McLing, 2014), and continue to develop their methods. Using the methods of the INL team members we measured REEs in high salinity oil and gas produced waters. Our results show that REEs exist as a dissolved species in all waters measured for this project, typically within the parts per trillion range. The samples may be grouped into two broad categories analytically, and these categories match their genesis: Wyoming oil and gas brines contain elevated levels of Europium, and Wyoming industrial pond waters show elevation in heavy REEs (HREEs). While broadly true, important variations exist within both groups. In the same field Europium can vary by more than an order of magnitude, and likewise HREEs in industrial ponds at the same site can vary by more than an order of magnitude. Future work will investigate the reasons for these variations.« less

Petrography, geochemistry and U-Pb zircon age of the Matongo carbonatite Massif (Burundi): Implication for the Neoproterozoic geodynamic evolution of Central Africa

NASA Astrophysics Data System (ADS)

Midende, Gilbert; Boulvais, Philippe; Tack, Luc; Melcher, Frank; Gerdes, Axel; Dewaele, Stijn; Demaiffe, Daniel; Decrée, Sophie

2014-12-01

The Matongo carbonatite intrusion belongs to the Neoproterozoic Upper Ruvubu alkaline plutonic complex (URAPC), that is located in Burundi along the western branch of the East African Rift. Beside the Matongo carbonatite, the URAPC alkaline complex comprises feldspathoidal syenites, diorites, quartz-bearing syenites and granites. Three main facies have been recognized in the Matongo carbonatite: (1) Sövites represent the dominant facies. Two varieties have been recognized. A scarce coarse-grained sövite (sövite I), which is altered and poorly enriched in REE (4 < ΣREE < 8 ppm), is encountered in highly fractured zones. A fine-grained sövite (sövite II), which is made of saccharoidal calcite, commonly associated with apatite, aegirine and amphibole, is abundant in the intrusion. Sövite II is enriched in LREE (442 < ΣREE < 1550 ppm, 49 < LaN/YbN < 175). (2) Ferrocarbonatites, that form decimeter-wide veins crosscutting the sövites, are characterized by a LREE enriched patterns (225 < ΣREE < 1048 ppm, 17 < LaN/YbN < 64). (3) K-feldspar and biotite-rich fenite facies (silicocarbonatites) have been recognized at the contact between the carbonatites and the country rock. They are likewise LREE-enriched (134 < ΣREE < 681 ppm, 25 < LaN/YbN < 46). Additionaly, "late" hydrothermal MREE-rich carbonatite veinlets can be found in sövite I. They are characterized by moderate enrichment in REE (ΣREE = 397 ppm), with a MREE-humped pattern (LaN/YbN = 3.7). The different facies represent the typical magmatic evolution of a carbonatite, while the silicocarbonatites are interpreted as resulting from the fenitisation of the country host-rocks. In addition, the most REE-depleted and fractionated facies, i.e. the coarse-grained sövite facies and the "late" calcite veinlets testify for hydrothermal processes that occurred after carbonatite emplacement and result from REE mobilization and redistribution. Large idiomorphic zircon crystals (megacrysts), found in the vicinity of the carbonatite can directly be related to the carbonatite evolution. They have been dated at 705.5 ± 4.5 Ma (U-Pb concordant age, LA-ICP-MS). Similar zircon megacrysts of the Lueshe carbonatite (DRCongo) have been dated and give a concordant age at 798.5 ± 4.9 Ma (U-Pb, LA-ICP-MS). Considering that an extensional tectonic regime occured at that time in Central Africa - what remains debated - both ages could relate to different stages of Rodinia breakup, with uprise of mantle-derived magmas along Palaeoproterozoic lithospheric zones of weakness.

Shale across Scales from the Depths of Sedimentary Basins to Soil and Water at Earth's Surface

NASA Astrophysics Data System (ADS)

Brantley, S. L.; Gu, X.

2017-12-01

Shale has become highly important on the world stage because it can host natural gas. In addition, shale is now targeted as a formation that can host repositories for disposal of radioactive waste. This newly recognized importance of shale has driven increased research into the nature of this unusual material. Much of this research incorporates characterization tools that probe shale at scales from nanometers to millimeters. Many of the talks in this Union session discuss these techniques and how scientists use them to understand how they impact the flow of fluids at larger scales. Another research avenue targets how material properties affect soil formation on this lithology and how water quality is affected in sedimentary basins where shale gas resources are under development. For example, minerals in shale are dominated by clays aligned along bedding. As the shales are exhumed and exposed at the surface during weathering, bedding planes open and fractures and microfractures form, allowing outfluxes or influxes of fluids. These phenomena result in specific patterns of fluid flow and, eventually, soil formation and landscape development. Specifically, in the Marcellus Formation gas play - the largest shale gas play in the U.S.A. - exposures of the shale at the surface result in deep oxidation of pyrite and organic matter, deep dissolution of carbonates, and relatively shallow alteration of clays. Micron-sized particles are also lost from all depths above the oxidation front. These characteristics result in deeply weathered and quickly eroded landscapes, and may also be related to patterns in water quality in shale gas plays. For example, across the entire Marcellus shale gas play in Pennsylvania, the single most common water quality issue is contamination by natural gas. This contamination is rare and is observed to be more prevalent in certain areas. These areas are likely related to shale material properties and geological structure. Specifically, natural gas moves along opening bedding planes as well as through faults and other larger scale geologic structures within basins. Understanding how shale acts as a material at all depths from that of fracking to that of the forest will enhance our ability to power our societal needs, dispose of our wastes, and sustain our water and soil resources.

Eclogites and garnet pyroxenites from Kimberley, Kaapvaal craton, South Africa: their diverse origins and complex metasomatic signatures

NASA Astrophysics Data System (ADS)

Shu, Qiao; Brey, Gerhard P.; Pearson, D. Graham

2018-06-01

We describe the petrography and mineral chemistry of sixteen eclogite and garnet pyroxenite xenoliths from the reworked Boshof road dump (Kimberley) and define three groups that stem from different depths. Group A, the shallowest derived, has low HREE (heavy rare earth element) abundances, flat middle to heavy REE patterns and high Mg# [= 100·Mg/(Mg + Fe)]. Their protoliths probably were higher pressure cumulates ( 0.7 GPa) of mainly clinopyroxene (cpx) and subordinate orthopyroxene (opx) and olivine (ol). Group B1 xenoliths, derived from the graphite/diamond boundary and below show similarities to present-day N-MORB that were modified by partial melting (higher Mg# and positively inclined MREE (middle REE) and HREE (heavy REE) patterns of calculated bulk rocks). Group B2 samples from greatest depth are unique amongst eclogites reported so far worldwide. The calculated bulk rocks have humped REE patterns with very low La and Lu and prominent maxima at Sm or Eu and anomalously high Na2O (up to 5 wt%) which makes protolith identification difficult. The complex trace element signatures of the full spectrum of Kimberley eclogites belie a multi-stage history of melt depletion and metasomatism with the introduction of new phases especially of phlogopite (phlog). Phlogopite appears to be characteristic for Kimberley eclogites and garnet peridotites. Modelling the metasomatic overprint indicates that groups A and B1 were overprinted by volatile- and potassium-rich melts probably by a process of chromatographic fractionation. Using constraints from other metasomatized Kimberley mantle rocks suggest that much of the metasomatic phlogopite in the eclogites formed during an intense episode of metasomatism that affected the mantle beneath this region 1.1 Gyr ago.

Geochemistry and structure of the Hawley Formation: Northwestern Massachusetts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, J.; Jacobi, R.

1993-03-01

The Hawley Formation in northwestern Massachusetts is composed of mafic and felsic, (trondhjemitic) igneous units and black sulfidic schists and quartzites. The dominant lithology is a thinly foliated hbd-plag.-chi-qtz.-Fe carbonate schist with or without hornblende fasicules. Locally, this schist has alternating folia of chl/hbd and plag. and probably has a volcaniclastic protolith. Distinct pillows and tuffs are observed locally. In general, these schists have flat REE patterns at 10X chondrite and plot as IABs on discrimination diagrams. In the eastern part of the Hawley, some amphibolites show concave upward REE patterns, plot in the IAT or boninite field on discriminationmore » diagrams, and appear to have boninitic affinities. The felsic lithologies are trondhjemitic and are intrusive into the IAT/boninite amphibolites. The intrusive nature is based on the presence of mafic xenoliths and intruded rafts of country rock in the trondhjemite as well as the occurrence of thin tabular trondhjemite bodies in sharp contact with the surrounding amphibolite. The trondhjemite varies from coarse-grained weakly foliated qtz-plag.-biotite gneiss with probable relict igneous zoned plagioclases to finer-grained well foliated qtz-plag.-garnet-hbd gneiss. REE patterns for the trondhjemites are weakly U-shaped with moderate to pronounced negative Eu anomalies. The trondhjemites, surrounding amphibolites, and black sulfidic schists and quartzites of the eastern part of the Hawley are intruded by massive, granular, medium grained, plagioclase phenocryst amphibolites with chilled margins. These intrusive sills predate or are coeval with the dominant foliation in the Hawley. Both sills and country rock contain a contact-parallel foliation as well as a later foliation at a low angle to the earlier foliation. The sill amphibolites are high TiO2 high Zr varieties that plot as MORBs to WPBs on discrimination diagrams and exhibit slightly LREE enriched MORB-like to T-MORB REE patterns.« less

Eastern Devonian shales: Organic geochemical studies, past and present

USGS Publications Warehouse

Breger, I.A.; Hatcher, P.G.; Romankiw, L.A.; Miknis, F.P.

1983-01-01

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Ilinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of the fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales will be reviewed. Recent solid state 13C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a "coaly" nature and hence more prone to producing natural gas.

Eastern Devonian shales: Organic geochemical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berger, I.A.; Hatchner, P.G.; Miknis, F.P.

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Illinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of themore » fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales are reviewed. Recent solid state /sup 13/C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a ''coaly'' nature and hence more prone to producing natural gas.« less

Mathematical Model for the Contribution of Individual Organs to Non-Zero Y-Intercepts in Single and Multi-Compartment Linear Models of Whole-Body Energy Expenditure

PubMed Central

Kaiyala, Karl J.

2014-01-01

Mathematical models for the dependence of energy expenditure (EE) on body mass and composition are essential tools in metabolic phenotyping. EE scales over broad ranges of body mass as a non-linear allometric function. When considered within restricted ranges of body mass, however, allometric EE curves exhibit ‘local linearity.’ Indeed, modern EE analysis makes extensive use of linear models. Such models typically involve one or two body mass compartments (e.g., fat free mass and fat mass). Importantly, linear EE models typically involve a non-zero (usually positive) y-intercept term of uncertain origin, a recurring theme in discussions of EE analysis and a source of confounding in traditional ratio-based EE normalization. Emerging linear model approaches quantify whole-body resting EE (REE) in terms of individual organ masses (e.g., liver, kidneys, heart, brain). Proponents of individual organ REE modeling hypothesize that multi-organ linear models may eliminate non-zero y-intercepts. This could have advantages in adjusting REE for body mass and composition. Studies reveal that individual organ REE is an allometric function of total body mass. I exploit first-order Taylor linearization of individual organ REEs to model the manner in which individual organs contribute to whole-body REE and to the non-zero y-intercept in linear REE models. The model predicts that REE analysis at the individual organ-tissue level will not eliminate intercept terms. I demonstrate that the parameters of a linear EE equation can be transformed into the parameters of the underlying ‘latent’ allometric equation. This permits estimates of the allometric scaling of EE in a diverse variety of physiological states that are not represented in the allometric EE literature but are well represented by published linear EE analyses. PMID:25068692

Mineralogy and geochemistry of the Lokoundje alluvial clays from the Kribi deposits, Cameroonian Atlantic coast: Implications for their origin and depositional environment

NASA Astrophysics Data System (ADS)

Ndjigui, Paul-Désiré; Onana, Vincent Laurent; Sababa, Elisé; Bayiga, Elie Constantin

2018-07-01

The Lokoundje alluvial clay deposits are located at the left floodplain of the Lokoundje River, towards the estuary in the Kribi region. The mineralogical and geochemical features of the Lokoundje River fine-grained sediments have been reported using XRD, XRF, ICP-MS, and IR instruments in order to understand their provenance and depositional history. The Lokoundje watershed covers a surface area of about 5381 km2. The basement of this watershed is made up of gneisses, amphibolites, migmatites, charnockites, and pyroxenites from the Nyong and Ntem units, in the NW border of the Congo craton. The alluvial materials are about 100 cm thick and cover a total area of 1.4 km2. They are mainly plastic clays with silty-clayey texture and four colors (yellow, red yellow, white, and light grey). The mineral assemblage is composed of kaolinite, quartz, illite, gibbsite, goethite, rutile, and interstratified illite-vermiculite. The infra-red data associated with those of XRD portray the disordering of kaolinite. These materials are mostly constituted by SiO2 (44.33-69.19 wt%, av. = 51.17 wt% with n = 18) and Al2O3 (20.69-30.26 wt%, av. = 26.07 wt%) with very low Fe2O3 contents (1-7.71 wt%, av. = 3.35 wt%). The SiO2/Al2O3 ratio range between 1.46 and 4.1 (av. = 2.06). The alkali contents (Na2O + K2O) are below 5 wt%. ICV, CIA, PIA, and SiO2/Al2O3 portray high degree of chemical weathering in the source area as well as the maturity of sediments. The trace element behavior is quite different probably due to the mixed source rocks; Ba, Sr, Zn have high contents while several elements such as Th and U show low contents. The REE contents are also variable; their concentrations vary between 92 and 1065 ppm (av. = 307 ppm). The mineral assemblage associated with the geochemical data reveal that REE are mainly housed in clay minerals. The behavior of REE is also marked by the abundance of LREE (LREE/HREE = 19.69-34.62). The REE chondrite-normalized spectra confirm the LREE-abundance and exhibit negative Eu anomalies. The PAAS-normalized patterns reveal slight positive Eu anomalies and negative Ce anomalies. The (La/Yb)N values (3.30-8.43, av. = 5.71) display low degree of REE-fractionation in the Lokoundje watershed. The morphological, mineralogical, and geochemical features reveal that the fine-grained sediments derive from the intense weathering of mixed source. The disordering of kaolinite confirms that sediments were sorted during a long transportation before their deposition under oxic conditions (U/Th < 1.25; V/Cr < 2) in the floodplains near the Atlantic coast.

Anoxic deep-sea microbial dolomite as a paleoceanographic archive - new insights from old "bugs"

NASA Astrophysics Data System (ADS)

Miller, N. R.; Leybourne, M. I.

2010-12-01

Earth’s history of biogenic carbonate production is dominated by pre-skeletal (late Ediacaran) microbe-catalyzed carbonate, including low T/P microbial (aka organogenic) dolomite, but paleoceanographic contexts are unclear due to the lack of proxy control provided by skeletal analogs and/or diagenesis. Microbial communities affiliated with dolomite generation (chiefly sulfate reducers and methanogens) are now known to persist in a diversity of Recent anoxic environments, but only deep-sea settings are sufficiently insulated from eustatic-meteoric diagenesis to preserve long-term records of possible paleoceanographic significance. The Miocene Monterey Formation contains episodic-to-cyclic microbial dolomite intervals interstratified with microfossil calcite, and thereby offers an excellent test the paleoceoanographic archive potential of microbial dolomite. Accordingly, we established a detailed dolomite chemostratigraphic profile (δ18O, δ13C, TOC, trace elements/REEs) from a continuous, thermally immature, Monterey core (offshore Santa Barbara-Ventura Basin), preserving >100 distinct early diagenetic (pre significant compaction, pre-diatom dissolution, post-pyrite) microbial dolomite intervals. Despite dolomite horizons being physically separate from one stratum to the next, they exhibit regular core-wide variations in δ13C and δ18O. Dolomite within the main Monterey depositional interval has entirely negative δ13C values (-2 to -16‰) consistent with generation in the zone of microbial sulfate reduction, whereas positive δ13C values (+2 to +9‰) consistent with generation from methanogenic pore-waters occur in lithologic transitions with bounding formations. Dolomites within the main Monterey depositional interval mirror microfossil calcite δ18O variations, notably pronounced global mid-Miocene enrichment after ~14 Ma linked to cooling and significant expansion of Antarctic ice. Dolomite δ13C mirrors sediment accumulation rate, with lightest values associated with both slowest sedimentation rates and highest TOC contents. Interestingly, lightest δ13C dolomite intervals correspond in time to distinct δ13C enrichment (~16-13.5 Ma, CM6-CM3) observed globally in marine benthic foraminifera records, potentially directly linking organic matter burial to open ocean δ13C enrichment, prior to cooling and Antarctic ice expansion (Monterey Hypothesis). The persistent negative δ13C values of Monterey dolomites suggest formation within the zone of sulfate reduction, tied to slow sediment accumulation rates or increases in the flux of marine sulfate. Fe, Mn, Al, and Ba all follow δ13C variation, being less enriched where dolomites are more negative. Associated shale-normalized REE patterns also follow δ13C, being most like modern seawater (most negative Ce/Ce*, greatest HREE enrichment) where sediment accumulation rates were lowest. Monterey organogenic dolomites formed under steady state anoxic conditions thus appear to proxy several paleoceanographic processes.

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

USGS Publications Warehouse

Birdwell, Justin E.

2012-01-01

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Geochemical and mineralogical constraints on the distribution and enrichment of the rare earth elements during pedogenesis and tropical weathering

NASA Astrophysics Data System (ADS)

Hardy, Liam; Smith, Martin; Moles, Norman; Marsellos, Antonios

2015-04-01

Current European manufacturing relies heavily on imports from the USA & China for unprocessed rare earth elements (REEs) and rare earth oxides (REOs). It has been suggested that the EU holds viable reserves of REEs that, with adequate research, could satisfy 10% of EU industrial demand, by the recycling of mine waste from bauxite production (red muds) alone (Deady, E. (BGS), 2014). Focus has been turned to the potential for Mount Weld type laterite deposits being exploited in the EU, but limited exploration and understanding of EU laterite (& paleo laterite) formations currently makes them unattractive to investment. Although previously researched, the full range of factors influencing the transition of rare earth (primarily lanthanide series, Y & Sc) elements between mineral and clay phases in allochthonous soils, saprolites and laterites is not fully understood, especially in present and Paleo-European environments (Herrington, Boni, Skarpelis, & Large, 2007) (Deady, E. (BGS), 2014) but several deposits globally are suggested to have formed at economically viable concentrations due to this secondary remobilisation & transition from mineral to clay phase and subsequent seasonal leaching and evaporation system, to form depositional buffer zones other than the soil base. (Hoatson, Jaireth, & Miezitis, 2011) (Berger, Janots, Gnos, Frei, & Bernier, 2014). This project intends to use new techniques in sequential extractions, ICP-MS, Quantitative XRD & SEM analysis to expand current knowledge around lateritic & allochtonous ore forming, & weathering processes. Heavy REE content and mineralogical variations in clays will be examined, with examples from a selection of profiles across Southern Europe (and potentially paleo soils from Scandinavia) to define the main influencing factors on REE concentration. Are the specific sites enriched simply by the nature of their source rock (protolith), by the soil formation (pedogenesis), or by biogenic & meteorological factors? These results will then be applied in targeted, environmentally focused exploration projects, and perhaps enhance techniques used industrially for the extraction of HREEs, for less environmentally damaging production in sensitive areas (with current research sites within national parks in Italy and Portugal; and in areas where it is believed more attention should be paid to environmental preservation, including Central Turkey and Southern China). It is hypothesised that: HREE content in tropical laterite formations is due primarily to the source rock's mineralogy, although it's distribution is a result of slower genesis and leaching as opposed to more common biogenetic pedogenesis. It is suggested this distribution initially forms banded horizontal enrichment zones according to protolith, but eventual separation of heavy and light REEs is controlled by clay-surface (the protolith's weathering style), solvent type, fluctuation and availability. It may be found, as in Fe-Ni laterite resources globally (Herrington, Boni, Skarpelis, & Large, 2007) (Eliopoulos, 2000), that high initial bedrock concentrations of REEs are not necessarily required if prolonged weathering continues to concentrate these elements/minerals over longer periods (although this has been found inversely in certain Turkish bauxites (Karadag˘, Peli, Ary, & Ayhan, 2008)). Regardless of eventual concentrations, identifying the argillic phase and the time scales required for clay REE hosting clay formation may broaden the European search for supergene enrichments to REE hosting marine shales, mineral sands and other sedimentary formations that have been long-term- weathered without major displacement.

Non-CI refractory lithophile abundances in bulk planetary materials

NASA Astrophysics Data System (ADS)

Dauphas, N.

2015-12-01

Refractory inclusions in meteorites show evidence for fractionation of refractory lithophile elements relative to one another. For bulk planetary materials, it is most often assumed that refractory lithophile elements (e.g., Ca, Al, Ti, REEs) are in proportions similar to CI carbonaceous chondrites, which is taken to be a proxy for solar composition. A diagnostic feature of REE patterns in refractory inclusions in meteorites is the presence of thulium anomalies, arising from the fact that this heavy REE is more volatile than the highly refractory HREEs surrounding it (Tm/Tm* is defined relative to either Er-Yb or Er-Lu). Tm anomalies thus represent an excellent diagnostic tool to test the assumption that refractory lithophile elements have uniform relative abundances at a bulk planetary scale. Prior to this work, high precision Tm measurements were lacking because it is mono-isotopic and as such is not amenable to high-precision single spike measurements. We have developed a multi-collector REE abundance measurement technique to measure all REEs at high precision, including the mono-isotopic ones. This technique was used to revise the abundance of CI and PAAS REE abundances (Pourmand et al. 2012) and the CI composition agrees well with an independent study (Barrat et al. 2012). The same technique was applied to measure REE patterns in 41 chondrites as well as terrestrial rocks (Dauphas and Pourmand, 2015). Our results reveal the presence of Tm anomalies of about -4.5 % in terrestrial rocks, enstatite and ordinary chondrites, relative to carbonaceous chondrites including CIs. This demonstrates that the assumption that refractory lithophile elements are in constant proportions among planetary bodies is unwarranted. It also shows that carbonaceous chondrites cannot be a major constituent of the Earth. The presence of Tm anomalies in meteorites and terrestrial rocks suggests that either (i) the material in the inner part of the solar system was formed from a gas reservoir that had been depleted in refractory dust or (ii) CI are enriched in refractory dust and are not representative of solar composition for refractory elements. Barrat J.A. et al. (2012) GCA 83, 79-92. Dauphas N., Pourmand A. (2015) GCA 163, 234-261. Pourmand et al. (2012) Chem. Geol. 291, 38-54.

Geochemical associations between fluorite mineralization and A-type shoshonitic magmatism in the Keban-Elazig area, East Anatolia, Turkey

NASA Astrophysics Data System (ADS)

Akgul, Bunyamin

2015-11-01

Keban fluorite mineralizations are closely related Coniacian-Campanian subvolcanics intruded into Permian-Triassic Keban metamorphites; this event caused pyrometasomatic, porphyry, and vein-type Pb-Zn-Ag, Cu, W, and Pb-Zn-Ag-Mo-F mineralizations. These rocks are syenitic and syenomonzonitic in composition and have high Al2O3, alkali (Na2O + K2O), FeO*/MgO, Zr, Nb, Ta, Ga, Rb, Y, and rare earth element (REE) contents. They are A-type, metaluminous, and all fall in the shoshonitic series field in K2O vs SiO2 and Th/Yb vs Ta/Yb diagrams. The trace element contents and discriminations indicate that the Keban syenitoids were derived from lithospheric mantle metasomatized by oceanic-crust/sediment fluids. The metal and halogen contents of the Keban mineralizations apparently originated from metasomatized mantle and were transported to the crust by syenitoid magmas. Clear resemblances in chondrite-normalized REE patterns, LREE-HREE partionation, and high LILE contents of the magmatics and fluorites indicate a close kinship between the syenitoids and fluorite mineralizations. The HFSE contents of the fluorites are lower than those of the magmatics, as HFSEs are not soluble in aqueous fluids. The fluorites are products of early-phase alkali magmatism (LREE > HREE). The high contents of Rb, Sr, and Ba of fluorites are inherited from the magma, which also has very high contents of these elements. In Sc-∑REE, (La/Yb)n-(Eu/Eu*)n and (Tb/La)n-(Tb/Ca)n diagrams, Keban fluorites fall into distinct areas from Akcakisla-Akdagmadeni and Celikhan-Adiyaman fluorites.

Generation of felsic rocks of bimodal volcanic suites from thinned and rifted continental margins: Geochemical and Nd, Sr, Pb-isotopic evidence from Haida Gwaii, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Dostal, Jaroslav; Hamilton, Tark S.; Shellnutt, J. Gregory

2017-11-01

The compositionally bimodal volcanic rocks of the Eocene-Miocene Masset Formation from Queen Charlotte basin, Haida Gwaii, British Columbia, Canada, underlie an area greater than 5000 km2 where their exposed sections are up to 1.6 km thick. The suite of mafic and felsic rocks (dacites and rhyolites) that erupted closely spaced in time, in both submarine and subaerial conditions, was associated with significant crustal extension and thin continental crust ( 19-24 km thick), with volcanism persisting for 35 Ma (from 46 to 11 Ma). Predominant mafic types (mafic:felsic 2:1) are moderately enriched mid-ocean-ridge-like basalts that were derived by a partial melting of a heterogeneous spinel peridotite source. Felsic rocks are plagioclase-phyric, two pyroxene-bearing, mainly peraluminous types which have Nd, Pb and Sr isotopic compositions overlapping those of basalts including high positive ƐNd(t) values (up to >+6). The chondrite-normalized REE patterns show light REE enrichment but flat heavy REE along with a variable negative Eu anomaly. Mineralogy, major and trace elements, Nd-Sr-Pb isotopic data and model calculations using MELTS are consistent with a derivation of felsic rocks from the basalts by fractional crystallization. The intercalation of basaltic and felsic rocks suggests the existence of separate, simultaneously active plumbing and feeder systems and relatively stable magma chamber(s) to generate large volumes of differentiated felsic magmas by fractional crystallization. The Masset rocks provide an example for the generation of felsic magmas of bimodal volcanic suites during rifting along a thinned continental margin. Appendix 1b Representative analyses of minerals of the Masset Formation felsic rocks

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

NASA Astrophysics Data System (ADS)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

Audre's daughter: Black lesbian steganography in Dee Rees' Pariah and Audre Lorde's Zami: A New Spelling of My Name.

PubMed

Kang, Nancy

2016-01-01

This article argues that African-American director Dee Rees' critically acclaimed debut Pariah (2011) is a rewriting of lesbian poet-activist Audre Lorde's iconic "bio-mythography" Zami: A New Spelling of My Name (1982). The article examines how Rees' work creatively and subtly re-envisions Lorde's Zami by way of deeply rooted and often cleverly camouflaged patterns, resonances, and contrasts. Shared topics include naming, mother-daughter bonds, the role of clothing in identity formation, domestic abuse, queer time, and lesbian, gay, bisexual, and transgender legacy discourse construction. What emerges between the visual and written texts is a hidden language of connection--what may be termed Black lesbian steganography--which proves thought-provoking to viewers and readers alike.

The effect of the water-to-rock ratio on REE distribution in hydrothermal fluids: An experimental study

NASA Astrophysics Data System (ADS)

Beermann, Oliver; Garbe-Schönberg, Dieter; Holzheid, Astrid

2013-04-01

High-temperature submarine MOR hydrothermalism creates high elemental fluxes into, and out of, oceanic lithosphere significantly affecting ocean chemistry. The Turtle Pits hydrothermal system discovered at 5° S on the slow-spreading Mid-Atlantic Ridge (MAR) in water depths of ~3000 m (~300 bar) emanates 'ultrahot' fluids > 400 ° C [1] with high concentrations of dissolved gases (e.g., H2), transition metals, and rare earth elements (REE). The normalised REE patterns of these 'ultrahot' fluids are uncommon as they exhibit depletions of LREE and no Eu-anomaly ('special' REE-signature in [2]), which is in contrast to the "typical" LREE enrichment and pronounced positive Eu-anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Although hydrothermal fluid REE-signatures may play a key role in understanding processes during water-rock interaction, only few experimental data have been published on REE distribution in seawater-like fluids reacted with rocks from the ocean crust [e.g., 4, 5]. Besides temperature, the seawater-to-rock ratio (w/r ratio) strongly affects water-rock reaction processes and, thus, has significant control on the fluid chemistry [e.g., 6, 7]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we designed a series of experiments reacting different fluid types with mineral assemblages from fresh, unaltered gabbro at 425 ° C and 400 bar using cold seal pressure vessels (CSPV). Mixtures of 125-500 μm-sized hand-picked plagioclase and clinopyroxene grains separated from unaltered gabbro reacted in gold capsules with 3.2 wt.% NaCl(aq) fluid (similar to seawater salinity), or with natural seawater. The w/r (mass) ratio ranged from 1 to 100 and the run durations were varied from 3 to 30 d in the NaCl(aq) experiments, and was 3 d in the seawater experiments. The reacted fluids were extracted after quenching and analysed by ICP-OES and ICP-MS. Only in the seawater experiments, the gabbro reacted considerably with the liquid resulting in a strong REE enrichment relative to the original seawater. Increasing w/r ratios gave rise to decreasing pH of the quench fluid and enforced the enrichment of HREE in the fluid with relative depletion of LREE and no Eu-anomaly. The 'special' REE-signatures observed in Turtle Pits vent fluids at 5° S MAR could be reproduced in our experiments at a w/r ratio of 5 (pH = ~6), whereas at a w/r ratio of 1 (pH = ~7) the fluid exhibited the "typical" REE pattern with a positive Eu-anomaly. Fluids from experiments with w/r ratios ×10 (pH ~6 to ~2) showed higher HREE enrichment than observed in natural MOR vent fluids so far. Concluding, elevated REE concentrations in hydrothermal fluids exhibiting the 'special' REE pattern with relative enrichment of HREE and no Eu anomaly are indicative for leaching processes under high w/r ratios (~5-10) that might be more common in slow-spreading oceanic crust with focused hydrothermal fluid-flow along e.g., detachment faults [8]. References: [1] Koschinsky A., Garbe-Schönberg D., Sander S., Schmidt K., Gennerich H.-H., and Strauss H. (2008) Geology 36, 615-618. [2] Schmidt K., Garbe-Schönberg D., Bau M., and Koschinsky A. (2010) GCA 74, 4058-4077. [3] Douville E., Bienvenu P., Charlou J. L., Donval J. P., Fouquet Y., Appriou P., and Gamo T. (1999). GCA 63, 627-643. [4] You C.-F., Castillo P. R., Gieskes J. M., Chan L. H., and Spivak A. J. (1996) EPSL 140, 41-52. [5] Allen D. E. and Seyfried [Jr.] W. E.(2005) GCA 69, 675-683. [6] Seyfried [Jr.] W. E. and Bischoff J. L. (1977) EPSL 34, 71-77. [7] Hajash A. and Chandler G. W. (1981) Contrib Mineral Petrol 78, 240-254. [8] McCaig A.M. and Harris M. (2012) Geology 40, 367-370.

North-South Gradients in Carbon Isotopic Compositions of Atlantic Ocean Black Shales: Evidence for Paleohydrologic Influences on Mid-Cretaceous Black Shale Deposition

NASA Astrophysics Data System (ADS)

Meyers, P. A.

2013-12-01

Organic del13C values of organic-carbon-rich Albian-Cenomanian-Turonian black shales from a north-south transect of the Atlantic Ocean have been compiled to explore for possible existence of latitudinal patterns. Black shales at equatorial sites have mean del13C values of -28 per mil, whereas black shales at mid-latitude sites have mean del13C values around -25 per mil. The mid-Cretaceous del13C values are routinely lower than those of modern marine sediments. The more negative Cretaceous del13C values generally reflect concentrations of atmospheric CO2 that were four to six times higher than today, but the geographic differences imply a regional overprint on this global feature. Latitudinal differences in oceanic temperature might be a factor, but a low thermal gradient from the poles to the equator during the mid-Cretaceous makes this factor not likely to be significant. Instead, a correspondence between the geographic differences in the organic del13C values of black shales with the modern latitudinal precipitation pattern suggests that differences in precipitation are a more likely factor. Establishment of a strongly salinity-stratified near-surface ocean and magnified delivery of land-derived phosphorus by continental runoff during this time of a magnified hydrologic cycle were evidently significant to deposition of marine black shales. A likely scenario is that the stratification resulted in blooms of nitrogen-fixing bacteria that become the dominant photoautotrophs and thereby stimulated primary production of organic matter. Regional differences in precipitation resulted in different amounts of runoff, consequent stratification, enhancement of primary production, and therefore the different carbon isotopic compositions of the black shales.

Correlation of resource plays and biodiversity patterns: accumulation of organic-rich shale tracks taxonomic turnover

USGS Publications Warehouse

Eoff, Jennifer D.

2012-01-01

Similar paleogeographic and paleotectonic settings characterize most self-sourced shale hydrocarbon plays. Their deposition occurred within similar orders of magnitude of eustatic events and during geologic periods characterized by “warm” (or transitional) climates and calcitic seas. In addition, the stratigraphic occurrence of shale plays parallels certain historical patterns of marine metazoan biodiversity. Such strong agreement among several correlation tools elucidates why these resources may be limited to discrete intervals of geological time. Correlation of self-sourced shale with biodiversity trends indicates that the factors controlling the deposition of marine organic matter may not be independent of those that induced taxonomic turnover. Paleoecological changes promoted accumulation and preservation of Type II kerogen. Deposition of self-sourced shale appears to correspond to reductions in absolute biodiversity and declining percentages of bioturbating taxa, with concomitant increases in proportions of pelagic taxa relative to infaunal and epifaunal organisms. Whereas upwelling and anoxia may have contributed to the deposition of kerogen in source rocks throughout much of the sedimentary record, diminished consumption of biomass by benthic metazoans likely augmented the preservation of organic carbon during deposition of this shale type. Rapid tectonic-plate reconfiguration induced coeval events, creating basins with sufficiently high rates of accommodation creation necessary to preserve additional organic material accumulating as the heterotrophic benthos suffered in response to rapidly changing environments. Combining sea-level curves, paleogeography, climate, and seawater chemistry provides a first-order approximation of the distribution of potential self-sourced shale in the geologic record. A model that predicts the stratigraphic distribution of self-sourced-shale deposition can aid in exploration of continuous hydrocarbon accumulations in self-sourced reservoirs globally.

REE concentration processes in ion adsorption deposits: Evidence from Madagascar and China.

NASA Astrophysics Data System (ADS)

Smith, Martin; Estrade, Guillaume; Marquis, Eva; Goodenough, Kathryn; Nasun, Peter; Cheng, Xu; Kynicky, Jindrich

2017-04-01

Lateritic clay deposits, where the rare earth elements (REE) occur adsorbed to clay mineral surfaces, are the world's dominant supply of heavy REE (Gd-Lu). These deposits are currently only mined in China where there is a reported heavy REE enrichment, but other deposits are currently under exploration in Brazil, the Philippines and Madagascar. Concentration of REE within IADs has been proposed to be a dominantly supergene process, where easily degradable REE-minerals (e.g. REE-fluorcarbonates) break down and release REE that are then adsorbed to clay minerals resulting in HREE enrichment. Here we present data from the Ambohimirahavavy Complex, Madagascar, and compare them to data from mineralised profiles in China, with the aim of further constraining the formation and REE enrichment processes in ion adsorption deposits. Bulk rock total REE contents from Madagascar vary from 400-5000ppm, with the HREE varying from 10 to 20% of the TREE. Ammonium Sulphate leaches (designed to remove clay-adsorbed REE) of laterite show leachable TREE from 130-500ppm, with no preferential HREE adsorption. Within the sequential extraction procedure the reducible fraction (hydroxylammonium chloride leach) showed the highest REE, but this is largely attributable to Ce4+ in oxide layers. Analysis of laterite profiles show that the REE distribution is heterogeneous, with control from both bedrock heterogeneity, and the hydrological variation between pedolith and saprolith. Similar patterns are seen in Chinese profiles from Jiangxi province. X-ray diffraction shows the clay fraction in all sites is dominated by kaolinite and halloysite. These data are consistent with experimental data which show that kaolinite is only HREE selective in high ionic strength solutions (Coppin et al., 2002), and suggest that HREE enrichment in lateritic deposits may be a function of exceptional bed rock conditions. Petrographic investigation of the Zhaibei granite, immediately underlying HREE enriched weathering profiles in Jiangxi province has identified the presence of HREE-enriched secondary phases associated with carbonate-rich areas (Xu et al., In press). Neodymium isotope data from primary granitic minerals (ɛNd(t)=-11.5±0.5) contrasts dramatically with data from HREE-enriched minerals (ɛNd(t)=0.9±0.8) indicating that pre-weathering metasomatism from fluids derived from outside the granite system may be critical in the HREE enrichment process of mineralised laterites. This may be important in determining the viability of ion adsorption deposits as HREE resources. Coppin et al. (2002) Sorption of lanthanides on smectite and kaolinite. Chem. Geol. 182, 57-68 Xu et al., (In press) Origin of heavy rare earth mineralization in South China. Nature Comms.

Method of rubblization for in-situ oil shale processing

NASA Technical Reports Server (NTRS)

Yang, Lien C. (Inventor)

1985-01-01

A method that produces a uniformly rubblized oil shale bed of desirable porosity for underground, in-situ heat extraction of oil. Rubblization is the generation of rubble of various sized fragments. The method uses explosive loadings lying at different levels in adjacent holes and detonation of the explosives at different levels in sequence to achieve the fracturing and the subsequent expansion of the fractured oil shale into excavated rooms both above and below the hole pattern.

The nature of Mesoarchaean seawater and continental weathering in 2.85 Ga banded iron formation, Slave craton, NW Canada

NASA Astrophysics Data System (ADS)

Haugaard, Rasmus; Ootes, Luke; Creaser, Robert A.; Konhauser, Kurt O.

2016-12-01

Banded iron formations (BIF) have been extensively used as proxies to infer the chemical composition of ancient bulk seawater. However, their proximity to ancient crust suggests that they might also be used to reveal the composition of emergent continental landmass at the time of their deposition. Here we use the combination of geochemistry and Sm-Nd isotopes on a layer-by-layer basis to interpret the relative contributions of hydrothermal, hydrogenous and terrestrial input to one of the oldest documented Superior-type BIF in the world. The ∼2.85 Ga Central Slave Cover Group BIF is deposited within a rift basin related to a continental margin and is found associated with basement gneisses, as well as shoreline and shallow-shelf type facies, such as fuchsitic quartzite and pebble-to-cobble conglomerate, that confirm a near-shore depositional setting for the BIF. The BIF ranges from a pure chemical oxide (magnetite)-silicate (grunerite + actinolite) sediment with low Al2O3 (<1 wt.%) into a mixture of chemical and clastic sediment characterized by higher Al2O3 (⩽10 wt.%) and the occurrence of ferro-hornblende, biotite and garnet. The silica bands have low trace metal content (e.g., Ni), low ∑REE (average of 6 ppm) and a shale-normalized rare earth and yttrium (REY) pattern that is HREE-to-LREE enriched with (Pr/Yb)SN values reaching <0.2. The iron bands are more enriched, with average ∑REE of 26 and with a more uniform and less fractionated REY pattern (average (Pr/Yb)SN of 0.5). During active rifting of the basement, excess of Eu2+ impacted the basin yielding seawater with Eu anomalies [(Eu/Eu∗)SN] as high as 3.85 (average 2.75), larger than similarly-aged BIF. High-resolution geochemistry shows that there is more silica (19.4 wt.% SiO2) in the iron bands than iron (8.7 wt.% Fe2O3) in the silica bands, implying that dissolved Fe2+ came to the BIF site in pulses and that silica likely represents background deposition. Consistently radiogenic εNd(t) values for the iron bands (average +1.7) show that the dissolved REY in the source water during ferric iron precipitation was provided by submarine hydrothermal fluids with relatively uniform 143Nd/144Nd. The silica bands, by contrast, reveal high variation in seawater 143Nd/144Nd as evident from the bimodal εNd(t) distribution with one segment exhibiting negative εNd(t) values averaging -1.1 and another with positive εNd(t) values averaging +2.5. This suggests input of dissolved REY into the upper seawater from weathering of isotopically different crustal components in the source region. Collectively, we speculate that the low REY in the upper seawater and the overall low Ni content implies a highly weathered crustal surface that was unable to contribute a significant dissolved load to the shelf environment.

Sodium Inverse Relationships During Melting in Ultraslow Spreading Regions: Insights from SWIR-Smoothseafloor Peridotites

NASA Astrophysics Data System (ADS)

Cannat, M.; Brunelli, D.; Paquet, M.; Sforna, M. C.; Seyler, M.

2015-12-01

Ultraslow spreading ridges are key regions to unravel mantle processes. Low potential temperatures and reduced melting allow decrypting early melting processes and shad lights on the source short-scale heterogeneities and their interactions with transient melts. Mantle-derived peridotites from the Smoothseafloor region of the eastern Southwest Indian Ridge reveal countertrending Na-Ti relationships. Na apparently behaves as a compatible element during partial melting similarly to light REEs. Heavy REEs, however, follow a normal relationship with the other melting indicators (e.g. Cr#), a behaviour that results in pattern rotation around a pivot element when looking to REE systematic. These relationships can be explained by percolation of relatively enriched, grt-field derived, melts in the spinel-field melting mantle 1. A feature that also explains the inverse Na-Cr# correlation, frequently observed in abyssal mantle rocks. Experimental relationships constraint the grt-field derived melts to be produced by low-melting paragenesis that experience a garnet to spinel phase transition shallower than mantle peridotites for a given temperature. Based on potential mantle temperatures estimated by Cannat et al., 19992, the grt-sp transition can be set at ca. 2.0 and 1.5 GPa for mantle peridotites and Mg pyroxenites respectively with the onset of mantle melting at 1.2 GPa. Mass balance calculations based on the amount of produced melt constrains the pyroxenitic fraction < 10% by mass of the mantle source. The contemporaneous presence of lithologies too depleted with respect to the described process suggests that some portions of the mantle source are inherited from more sustained ancient depletion events not related to present-day processes beneath this ridge portion. PNRA funding : PdR 2013/B1.02 1. Brunelli, D., et al., 2104. Percolation of enriched melts during incremental open-system melting in the spinel field : A REE approach to abyssal peridotites from the Southwest Indian Ridge. Geochim. Cosmochim. Acta 127,190-203. 2. Cannat, M., et al., 1999. Formation of the axial relief at the very slow spreading Southwest Indian Ridge (49° to 69°E). J. Geophys. Res. 104, 22825-22843.

Aegirine-melt element partitioning and implications for the formation of nepheline syenite REE deposits

NASA Astrophysics Data System (ADS)

Beard, Charles; van Hinsberg, Vincent; Stix, John; Wilke, Max

2017-04-01

Sodic clinopyroxene is a key fractionating phase in alkaline magmatic systems but its impact on metal enrichment processes, and the formation of REE + HFSE mineralizations in particular, is not fully understood. Sodic pyroxenes appear to more readily incorporate REE than their calcic equivalents1. Despite this, melts in evolved alkaline systems can attain high REE contents, even up to economic levels (e.g. the Nechalacho layered suite in Canada2). To constrain the control of pyroxene on REE + HFSE behaviour in alkaline magmas, a series of internally heated pressure vessel experiments was performed to determine pyroxene-melt element partitioning systematics. Synthetic trachy-andesite to phonolite compositions were run water saturated at 650-825°C with fO2 buffered by ca. 1 bar of H2 (QFM + 1) or by Hm-Mt (QFM +5). Fluorine was added to selected experiments (0.3 to 2.5 wt %) to ascertain its effect on element partitioning. Run products were analysed by EMP for major elements and LA-ICP-MS for trace elements. Mineral and glass compositions bracket the compositions of natural alkaline systems, allowing for direct application of our experimental results to nature. Our results indicate that REE partitioning systematics vary strongly with pyroxene composition: Diopside-rich pyroxenes (Aeg5-25) prefer the MREE, medium aegirine pyroxenes (Aeg25-50) preferentially incorporate the LREE, whereas high aegirine pyroxenes (Aeg55-95) strongly prefer HREE. REE partitioning coefficients are 0.3-40, typically 2-6, with minima for high aegirine pyroxenes. Melt composition (e.g. (Na+K)/Al) also impacts partitioning although to a lesser extent, except for the F-content, which shows no impact at all. The composition of fractionating pyroxene has a major impact on the REE pattern of the residual melt, and thus on the ability of a system to develop economic concentrations of the REE. Element partitioning systematics suggest that late-crystallising aegirine-rich cumulates would be HREE-rich, in accord with the composition of mineralised intrusions, such as Nechalacho2. 1 - Marks, M., Halama, R., Wenzel, T. & Markl, G., 2004. Chem. Geol. 211, 185-215. 2 - Möller, V. & Williams-Jones, A. E., 2016. J. Petrology 57, 229-276.

Analysis of rare earth elements in coal fly ash using laser ablation inductively coupled plasma mass spectrometry and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Thompson, Robert L.; Bank, Tracy; Montross, Scott; Roth, Elliot; Howard, Bret; Verba, Circe; Granite, Evan

2018-05-01

Reference standard NIST SRM 1633b and FA 345, a fly ash sample from an eastern U.S. coal power plant, were analyzed to determine and quantify the mineralogical association of rare earth elements (REE). These analyses were completed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer (SEM-EDS). Internal standardization was avoided by quantifying elemental concentrations by normalizing to 100% oxides. Mineral grains containing elevated REE concentrations were found in diverse chemical environments, but were most commonly found in regions where Al and Si were predominant. Dividing the spot analyses into time segments yielded plots that showed the REE content changing over time as individual mineral grains were being ablated. SEM-EDS images of FA 345 confirmed the trends that were found in the LA-ICP-MS results. Small grains of apatite, monazite, or zircon were frequently observed as free mineral grains or embedded in amorphous aluminosilicate glass and were not associated with ferrous particles. This finding is consistent with previous reports that magnetic enrichment may be an effective way of concentrating non-magnetic REE phases. Furthermore, aggressive mechanical and chemical-based separation schemes will be required to separate and recover REE from aluminosilicate glass.

[Geochemical characteristics and sources of atmospheric particulates in Shanghai during dust storm event].

PubMed

Qian, Peng; Zheng, Xiang-min; Zhou, Li-min

2013-05-01

Atmospheric particulates were sampled from three sampling sites of Putuo, Minhang and Qingpu Districts in Shanghai between Oct. , 2009 and Oct. , 2010. In addition, particulate samples were also collected from Nantong, Zhengzhou, Xi'an, and Beijing city where dust storm dust transported along during spring. Element compositions of atmospheric particulates were determined by XRF and ICP-MS. The concentrations of major and trace elements in atmospheric particulates from Putuo, Minhang and Qingpu Districts were similar, indicating their common source. The UCC standardization distribution map showed that the major element composition of dust storm samples was similar to that of loess in northwestern China, indicating that the dust storm dust was mainly derived from Western desert and partly from local area. The REE partition patterns of dust storm dusts among different cities along dust transport route were similar to each other, as well as to those of northern loess, which indicates that the dust storm samples may have the same material source as loess, which mainly comes from crust material. However, the REE partition patterns of non-dust storm particulates were different among the studied cities, and different from those of loess, which suggests that the non-dust storm samples may be mixed with non-crust source material, which is different from dust storm dust and loess. The major element composition and REE partition pattern are effective indicators for source tracing of dust storm dust.

Sequence stratigraphy in the middle Ordovician shale successions, mid-east Korea: Stratigraphic variations and preservation potential of organic matter within a sequence stratigraphic framework

NASA Astrophysics Data System (ADS)

Byun, Uk Hwan; Lee, Hyun Suk; Kwon, Yi Kyun

2018-02-01

The Jigunsan Formation is the middle Ordovician shale-dominated transgressive succession in the Taebaeksan Basin, located in the eastern margin of the North China platform. The total organic carbon (TOC) content and some geochemical properties of the succession exhibit a stratigraphically distinct distribution pattern. The pattern was closely associated with the redox conditions related to decomposition, bulk sedimentation rate (dilution), and productivity. To explain the distinct distribution pattern, this study attempted to construct a high-resolution sequence stratigraphic framework for the Jigunsan Formation. The shale-dominated Jigunsan Formation comprises a lower layer of dark gray shale, deposited during transgression, and an upper layer of greenish gray siltstone, deposited during highstand and falling stage systems tracts. The concept of a back-stepped carbonate platform is adopted to distinguish early and late transgressive systems tracts (early and late TST) in this study, whereas the highstand systems tracts and falling stage systems tracts can be divided by changes in stacking patterns from aggradation to progradation. The late TST would be initiated on a rapidly back-stepping surface of sediments and, just above the surface, exhibits a high peak in TOC content, followed by a gradually upward decrease. This trend of TOC distribution in the late TST continues to the maximum flooding surface (MFS). The perplexing TOC distribution pattern within the late TST most likely resulted from both a gradual reduction in productivity during the late TST and a gradual increase in dilution effect near the MFS interval. The reduced production of organic matter primarily incurred decreasing TOC content toward the MFS when the productivity was mainly governed by benthic biota because planktonic organisms were not widespread in the Ordovician. Results of this study will help improve the understanding of the source rock distribution in mixed carbonate-siliciclastic successions within a stratigraphic framework, particularly for unconventional shale reservoirs.

Geochemical indications and Detrital Zircon U-Pb ages of net-like laterite from Youjiang terrace, Bose Basin, southwestern China: new evidence of proximal provenance for laterite sediments

NASA Astrophysics Data System (ADS)

Cheng, F.; Hong, H.; Li, C.; Ye, H.; Yang, H.

2015-12-01

The net-like laterite sediments is widely spread over the terraces and high lands of the river valley in southern China during mid-Pleistocene, although whose origin is still debated. The Xiaomei laterite sediments on the terraces of Youjiang River, Guangxi Zhuang Autonomous Region, southern China, was dominated by the intermittently uplift of the Tibetan Plateau for the mechanism during the Quaternary times. Compared to the loess-paleosol deposits in Chinese Loess Plateau (CLP), the upper continental crust (UCC) and the post-Archean Australian average shale (PAAS), the sediments show notable depletion of the relative mobile compositions like CaO, MgO, Na2O, K2O, Sr, Ba and the accumulation of TiO2, Al2O3, Fe2O3(t), Zr, but similar with other laterite sediments (the Xuancheng and Jiujiang laterite profiles) in the middle to lower reaches of Yangtze River, southern China. The relatively uniform La/Th ratio, U/Pb vs. Th/Pb ratio and chondrite-normalized REE distribution pattern of Xiaomei samples are similar with the loess-paleosol deposits and UCC values, which suggesting the sediments have experienced well-mixing prior to deposition and intense superficial weathering. The low ɛNd(t) values and uniform 147Sm/144Nd ratios with the 87Sr/86Sr vs. Rb/Sr ratios show the notable differences with loess-paleosol deposits and the recycling function of the old fluvial sediments which are similar with the Pearl River sediments. The stable zircon age distribution pattern with three age groups of 240-300Ma, 420-480Ma and 900-1000Ma for Xiaomei laterite samples are different with the loess-paleosol deposits and its source regions. The zircons are mainly derived from a source of the Upper Permian to Middle Triassic clastic rocks in Youjiang Basin, superordinate tectonic unit of Bose Basin, and their potential source areas like the Emeishan Large Igneous Province (Emeishan LIP) and the southeastern area of south China Craton (SCC). For the basis of these data, we suggest that that the aeolian dusts may have not started to accumulate in southern China during these times, and the laterite sediments in southern China may dominate by the proximal supplementation.

Petrogenesis and magmatic evolution of ∼130 Ma A-type granites in Southeast China

NASA Astrophysics Data System (ADS)

Sun, Fajun; Xu, Xisheng; Zou, Haibo; Xia, Yan

2015-02-01

A number of Late Mesozoic (∼130 Ma) A-type granitic plutons have been identified in Southeast China. Here we investigate the petrogenesis of one of these granitic plutons in Southeast China, the Sanqingshan-Damaoshan (SD) granites in northeastern Jiangxi Province, using zircon U-Pb geochronology, Hf isotopic analyses, and major and trace element analyses. The SD granites are metaluminous to weakly peraluminous and show typical A-type affinity, which is characterized by high SiO2, Na2O + K2O, rare earth element (REE), high field strength element (HFSE) contents, Ga/Al and Fe# [FeOt/(FeOt + MgO)] values. Zircon grains from the SD granites and some other ∼130 Ma A-type granites commonly contain oscillatory zoning ;cores; surrounded by unzoned to weakly zoned ;rims;. Detailed studies of zircons from the SD granites show that ;rims; are enriched in LREE, Th and U compared with ;cores;. Chondrite-normalized REE patterns of the ;cores; increase steeply from La to Lu and show pronounced Ce and Eu anomalies, while REE patterns of the ;rims; display higher REE abundances with flatter LREE patterns and moderate Ce anomalies. Nevertheless, Lu-Hf isotopic analyses and Ti-in zircon thermometer show similar characteristics between ;rims; and ;cores;, indicating that the ;rims; may crystallize under the effect of internal magmatic hydrothermal fluids. U-rich ;rims; are more susceptible to Pb loss caused by self-irradiation, which may lead to significant younger U-Pb ages. As a result, U-Pb ages of zircon ;cores; (∼130 Ma) represent crystallization ages of the SD granites. εHf(t) values of zircon grains from the SD granites are between -6.4 and -0.4 with Mesoproterozoic model ages (T2DM) ranging from 1.22 to 1.59 Ga, suggesting that the granites may be formed by partial melting of Proterozoic basement. Compared with other adjacent ∼130 Ma A-type granitic plutons in SE China, the SD granites have similar geochemical characteristics and Hf isotopic compositions to those of Xiangshan, Daqiaowu, Yangmeiwan, and Tongshan granites, but different from the Baijuhuajian granite. εHf(t) values of the Baijuhuajian granites are higher than other granites, indicating significant participation of juvenile materials. These ∼130 Ma A-type granites indicate a back-arc extension setting due to the roll-back of paleo-Pacific plate, where the crust and lithospheric mantle became progressively thinned. The upwelling of asthenosphere triggered the partial melting of crustal rocks and generated the Sanqingshan-Damaoshan, Tongshan, Daqiaowu and Yangmeiwan granitic plutons. With ongoing back-arc extension and increased subduction angle during the roll-back of subducted paleo-Pacific slab, the back-arc extension gradually intensified, resulting in significant additions of mantle juvenile materials to the crustal magma and the formation of the Baijuhuajian granite.

Major, trace and REE geochemistry of recent sediments from lower Catumbela River (Angola)

NASA Astrophysics Data System (ADS)

Vinha, Manuela; Silva, M. G.; Cabral Pinto, Marina M. S.; Carvalho, Paula Cristina S.

2016-03-01

The mineralogy, texture, major, trace and rare earth elements, from recent sediment samples collected in the lower Catumbela River, were analysed in this study to characterize and discuss the factors controlling its geochemistry and provide data that can be used as tracers of Catumbela River inputs to the Angolan continental shelf. The sediments are mainly sands and silty-sands, but sandy-silt also occurs and the mineralogy is composed of quartz, feldspar, phyllosilicates, magnetite, ilmenite and also carbonates when the river crosses limestones and marls in the downstream sector. The hydraulic sorting originates magnetite-ilmenite and REE-enriched minerals placers. The mineralogy of the sediments is controlled by the source rocks and the degree of chemical weathering is lower than erosion. The texture is mainly controlled by location. There is enrichment in all the analysed trace elements in the fine grained, clay minerals and Fe-oxy-hydroxides rich sediments, compared to the coarse grained and quartz plus feldspar rich ones. The coarse grained sediments (without the placers) are impoverished in ΣREE when compared with UCC and NASC compositions, while the fine grained sediments have ΣREE contents similar to UCC and NASC. The placers have ΣREE contents up to 959.59 mg/kg. The source composition is the dominant factor controlling the REE geochemistry of the analysed sediments as there is no difference in the (La/Yb)N, (La/Sm)N and (Gd/Yb)N ratios in coarse and fine grained sediments. The sorting of magnetite, ilmenite, zircon, throrite, thorianite, rutile and titanite explain the HREE/LREE enriched patterns of the coarse grained sediments.

Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent Boulder Creek, Colorado

USGS Publications Warehouse

Verplanck, P.L.; Taylor, Howard E.; Nordstrom, D. Kirk; Barber, L.B.

2005-01-01

In many surface waters, sewage treatment plant (STP) effluent is a substantial source of both regulated and unregulated contaminants, including a suite of complex organic compounds derived from household chemicals, pharmaceutical, and industrial and medical byproducts. In addition, STP effluents in some urban areas have also been shown to have a positive gadolinium (Gd) anomaly in the rare earth element (REE) pattern, with the Gd derived from its use in medical facilities. REE concentrations are relatively easy to measure compared to many organic wastewater compounds and may provide a more widely utilized tracer of STP effluents. To evaluate whether sewage treatment plant-associated Gd is a useful tracer of treatment plant effluent, an investigation of the occurrence, fate, and transport of rare earth elements was undertaken. The rare earth element patterns of four of five STP effluents sampled display positive Gd anomalies. The one site that did not have a Gd anomaly serves a small community, population 1200, with no medical facilities. Biosolids from a large metropolitan STP are not enriched in Gd even though the effluent is, suggesting that a substantial fraction of Gd remains in the aqueous phase through routine treatment plant operation. To evaluate whether STP-derived Gd persists in the fluvial environment, a 14-km study reach downstream of an STP was sampled. Gadolinium anomalies were present at all five downstream sites, but the magnitude of the anomaly decreased. Effluent from STPs is a complex mixture of organic and inorganic constituents, and to better understand the chemical interactions and their effect on REEs, the aqueous speciation was modeled using comprehensive chemical analyses of water samples collected downstream of STP input. These calculations suggest that the REEs will likely remain dissolved because phosphate and carbonate complexes dominate over free REE ions. This study supports the application of Gd anomalies as a useful tracer of urban wastewater.

Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent, Boulder Creek, Colorado.

PubMed

Verplanck, Philip L; Taylor, Howard E; Nordstrom, D Kirk; Barber, Larry B

2005-09-15

In many surface waters, sewage treatment plant (STP) effluent is a substantial source of both regulated and unregulated contaminants, including a suite of complex organic compounds derived from household chemicals, pharmaceuticals, and industrial and medical byproducts. In addition, STP effluents in some urban areas have also been shown to have a positive gadolinium (Gd) anomaly in the rare earth element (REE) pattern, with the Gd derived from its use in medical facilities. REE concentrations are relatively easy to measure compared to many organic wastewater compounds and may provide a more widely utilized tracer of STP effluents. To evaluate whether sewage treatment plant-associated Gd is a useful tracer of treatment plant effluent, an investigation of the occurrence, fate, and transport of rare earth elements was undertaken. The rare earth element patterns of four of five STP effluents sampled display positive Gd anomalies. The one site that did not have a Gd anomaly serves a small community, population 1200, with no medical facilities. Biosolids from a large metropolitan STP are not enriched in Gd even though the effluent is, suggesting that a substantial fraction of Gd remains in the aqueous phase through routine treatment plant operation. To evaluate whether STP-derived Gd persists in the fluvial environment, a 14-km study reach downstream of an STP was sampled. Gadolinium anomalies were present at all five downstream sites, but the magnitude of the anomaly decreased. Effluent from STPs is a complex mixture of organic and inorganic constituents, and to better understand the chemical interactions and their effect on REEs, the aqueous speciation was modeled using comprehensive chemical analyses of water samples collected downstream of STP input. These calculations suggest that the REEs will likely remain dissolved because phosphate and carbonate complexes dominate over free REE ions. This study supports the application of Gd anomalies as a useful tracer of urban wastewater.

The use of decision tree induction and artificial neural networks for recognizing the geochemical distribution patterns of LREE in the Choghart deposit, Central Iran

NASA Astrophysics Data System (ADS)

Zaremotlagh, S.; Hezarkhani, A.

2017-04-01

Some evidences of rare earth elements (REE) concentrations are found in iron oxide-apatite (IOA) deposits which are located in Central Iranian microcontinent. There are many unsolved problems about the origin and metallogenesis of IOA deposits in this district. Although it is considered that felsic magmatism and mineralization were simultaneous in the district, interaction of multi-stage hydrothermal-magmatic processes within the Early Cambrian volcano-sedimentary sequence probably caused some epigenetic mineralizations. Secondary geological processes (e.g., multi-stage mineralization, alteration, and weathering) have affected on variations of major elements and possible redistribution of REE in IOA deposits. Hence, the geochemical behaviors and distribution patterns of REE are expected to be complicated in different zones of these deposits. The aim of this paper is recognizing LREE distribution patterns based on whole-rock chemical compositions and automatic discovery of their geochemical rules. For this purpose, the pattern recognition techniques including decision tree and neural network were applied on a high-dimensional geochemical dataset from Choghart IOA deposit. Because some data features were irrelevant or redundant in recognizing the distribution patterns of each LREE, a greedy attribute subset selection technique was employed to select the best subset of predictors used in classification tasks. The decision trees (CART algorithm) were pruned optimally to more accurately categorize independent test data than unpruned ones. The most effective classification rules were extracted from the pruned tree to describe the meaningful relationships between the predictors and different concentrations of LREE. A feed-forward artificial neural network was also applied to reliably predict the influence of various rock compositions on the spatial distribution patterns of LREE with a better performance than the decision tree induction. The findings of this study could be effectively used to visualize the LREE distribution patterns as geochemical maps.

Cytokines and metabolic patterns in pediatric patients with critical illness.

PubMed

Briassoulis, George; Venkataraman, Shekhar; Thompson, Ann

2010-01-01

It is not known if cytokines, which are cell-derived mediators released during the host immune response to stress, affect metabolic response to stress during critical illness. The aim of this prospective study was to determine whether the metabolic response to stress is related to the inflammatory interleukin-6 (IL-6), 10 (IL-10), and other stress mediators' responses and to assess their relationships with different feeding patterns, nutritional markers, the severity of illness as assessed by the Multiple Organ System Failure (MOSF), the Pediatric Risk of Mortality Score (PRISM), systemic inflammatory response syndrome (SIRS), and mortality in critically ill children. Patients were classified as hypermetabolic, normometabolic, and hypometabolic when the measured resting energy expenditures (REE) were >110%, 90-110% and, <90% of the predicted basal metabolic rate, respectively. The initial predominance of the hypometabolic pattern (48.6%) declined within 1 week of acute stress (20%), and the hypermetabolic patterns dominated only after 2 weeks (60%). Only oxygen consumption (VO(2)) and carbon dioxide production (VCO(2)) (P < .0001) but none of the cytokines and nutritional markers, were independently associated with a hypometabolic pattern. REE correlated with the IL-10 but not PRISM. In the presence of SIRS or sepsis, CRP, IL-6, IL-10, Prognostic Inflammatory and Nutritional Index (NI), and triglycerides--but not glucose, VO(2), or VCO(2) increased significantly. High IL-10 levels (P = .0000) and low measured REE (P = .0000) were independently associated with mortality (11.7%), which was higher in the hypometabolic compared to other metabolic patterns (P < .005). Our results showed that only VO(2) and VCO(2), but not IL-6 or IL-10, were associated with a hypometabolic pattern which predominated the acute phase of stress, and was associated with increased mortality. Although in SIRS or sepsis, the cytokine response was reliably reflected by increases in NI and triglycerides, it was different from the metabolic (VO(2), VCO(2)) or glucose response.

Cytokines and Metabolic Patterns in Pediatric Patients with Critical Illness

PubMed Central

Briassoulis, George; Venkataraman, Shekhar; Thompson, Ann

2010-01-01

It is not known if cytokines, which are cell-derived mediators released during the host immune response to stress, affect metabolic response to stress during critical illness. The aim of this prospective study was to determine whether the metabolic response to stress is related to the inflammatory interleukin-6 (IL-6), 10 (IL-10), and other stress mediators' responses and to assess their relationships with different feeding patterns, nutritional markers, the severity of illness as assessed by the Multiple Organ System Failure (MOSF), the Pediatric Risk of Mortality Score (PRISM), systemic inflammatory response syndrome (SIRS), and mortality in critically ill children. Patients were classified as hypermetabolic, normometabolic, and hypometabolic when the measured resting energy expenditures (REE) were >110%, 90–110% and, <90% of the predicted basal metabolic rate, respectively. The initial predominance of the hypometabolic pattern (48.6%) declined within 1 week of acute stress (20%), and the hypermetabolic patterns dominated only after 2 weeks (60%). Only oxygen consumption (VO2) and carbon dioxide production (VCO2) (P < .0001) but none of the cytokines and nutritional markers, were independently associated with a hypometabolic pattern. REE correlated with the IL-10 but not PRISM. In the presence of SIRS or sepsis, CRP, IL-6, IL-10, Prognostic Inflammatory and Nutritional Index (NI), and triglycerides—but not glucose, VO2, or VCO2 increased significantly. High IL-10 levels (P = .0000) and low measured REE (P = .0000) were independently associated with mortality (11.7%), which was higher in the hypometabolic compared to other metabolic patterns (P < .005). Our results showed that only VO2 and VCO2, but not IL-6 or IL-10, were associated with a hypometabolic pattern which predominated the acute phase of stress, and was associated with increased mortality. Although in SIRS or sepsis, the cytokine response was reliably reflected by increases in NI and triglycerides, it was different from the metabolic (VO2, VCO2) or glucose response. PMID:20490277

Borehole petrophysical chemostratigraphy of Pennsylvanian black shales in the Kansas subsurface

USGS Publications Warehouse

Doveton, J.H.; Merriam, D.F.

2004-01-01

Pennsylvanian black shales in Kansas have been studied on outcrop for decades as the core unit of the classic Midcontinent cyclothem. These shales appear to be highstand condensed sections in the sequence stratigraphic paradigm. Nuclear log suites provide several petrophysical measurements of rock chemistry that are a useful data source for chemostratigraphic studies of Pennsylvanian black shales in the subsurface. Spectral gamma-ray logs partition natural radioactivity between contributions by U, Th, and K sources. Elevated U contents in black shales can be related to reducing depositional environments, whereas the K and Th contents are indicators of clay-mineral abundance and composition. The photoelectric factor log measurement is a direct function of aggregate atomic number and so is affected by clay-mineral volume, clay-mineral iron content, and other black shale compositional elements. Neutron porosity curves are primarily a response to hydrogen content. Although good quality logs are available for many black shales, borehole washout features invalidate readings from the nuclear contact devices, whereas black shales thinner than tool resolution will be averaged with adjacent beds. Statistical analysis of nuclear log data between black shales in successive cyclothems allows systematic patterns of their chemical and petrophysical properties to be discriminated in both space and time. ?? 2004 Elsevier B.V. All rights reserved.

Physical and chemical characterization of Devonian gas shale. Quarterly status report, October 1-December 31, 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zielinski, R.E.; Nance, S.W.

On shale samples from the WV-6 (Monongalia County, West Virginia) well, mean total gas yield was 80.4 ft/sup 3//ton. Mean hydrocarbon gas yield was 5.7 ft/sup 3//ton, 7% of total yield. Methane was the major hydrocarbon component and carbon dioxide the major nonhydrocarbon component. Oil yield was negligible. Clay minerals and organic matter were the dominant phases of the shale. Illite averages 76% of the total clay mineral content. This is detrital illite. Permeation of methane, parallel to the bedding direction for select samples from WV-5 (Mason County, West Virginia) well ranges from 10/sup -4/ to 10/sup -12/ darcys. Themore » permeability of these shales is affected by orgaic carbon content, density, particle orientation, depositional facies, etc. Preliminary studies of Devonian shale methane sorption rates suggest that these rates may be affected by shale porosity, as well as absorption and adsorption processes. An experimental system was designed to effectively simulate sorption of methane at natural reservoir conditions. The bulk density and color of select shales from Illinois, Appalachian and Michigan Basins suggest a general trend of decreasing density with increasing organic content. Black and grayish black shales have organic contents which normally exceed 1.0 wt %. Medium dark gray and gray shales generally have organic contents less than 1.0 wt %.« less

Titanium isotopes and rare earth patterns in CAIs: Evidence for thermal processing and gas-dust decoupling in the protoplanetary disk

NASA Astrophysics Data System (ADS)

Davis, Andrew M.; Zhang, Junjun; Greber, Nicolas D.; Hu, Jingya; Tissot, François L. H.; Dauphas, Nicolas

2018-01-01

Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to 49Ti/47Ti, we found that ε50Ti values are somewhat variable among CAIs, and that ε46Ti is highly correlated with ε50Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between ε46Ti and ε50Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ‧49Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ‧49Ti is from ∼-4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

Baseflow recession analysis across the Eagle Ford shale play (Texas, USA)

NASA Astrophysics Data System (ADS)

Arciniega, Saul; Brena-Naranjo, Agustin; Hernandez-Espriu, Jose Antonio; Pedrozo-Acuña, Adrian

2016-04-01

Baseflow is an important process of the hydrological cycle as it can be related to aquatic ecosystem health and groundwater recharge. The temporal and spatial dynamics of baseflow are typically governed by fluctuations in the water table of shallow aquifers hence groundwater pumping and return flow can greatly modify baseflow patterns. More recently, in some regions of the world the exploitation of gas trapped in shale formations by means of hydraulic fracturing (fracking) has raised major concerns on the quantitative and qualitative groundwater impacts. Although fracking implies massive amounts of groundwater withdrawals, its contribution on baseflow decline has not yet been fully investigated. Furthermore, its impact with respect to other human activities or climate extremes such as irrigation or extreme droughts, respectively, remain largely unknown. This work analyzes baseflow recession time-space patterns for a set of watersheds located across the largest shale producer in the world, the Eagle Ford shale play in Texas (USA). The period of study (1985-2014) includes a pre-development and post-development period. The dataset includes 56 hydrometric time series located inside and outside the shale play. Results show that during the development and expansion of the Eagle Ford play, around 70 % of the time series displayed a significant decline wheras no decline was observed during the pre-development)

Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

NASA Astrophysics Data System (ADS)

Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.

2016-03-01

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

Structure, Mechanics and Flow Properties of Fractured Shale: Core-Scale Experimentation and In-situ Imaging

NASA Astrophysics Data System (ADS)

Abdelmalek, B. F.; Karpyn, Z.; Liu, S.

2014-12-01

Over the last several years, hydrocarbon exploitation and development in North America has been heavily centered on shale gas plays. However, the physical attributes of shales and their manifestation on transport properties and storage capacity remain poorly understood. Therefore, more experimentally based data are needed to fill the gaps in understanding both transport and storage of fluids in shale. The proposed work includes installation and testing of an experimental system which is capable of monitoring the dynamic evolution of shale core permeability under variable loading conditions and in coordination with X-ray microCT imaging. The goal of this study is to better understand and quantify fluid flow patterns and associated transport dynamics of fractured shale samples. The independent variables considered in this study are: mechanical loading and pore pressure. The mechanical response of shale core is captured for different loading paths. To best replicate the in-situ production scenario, the pore pressure is progressively depleted to mimic pressure decline. During the course of experimentation, permeability is estimated using the pulse-decay method under tri-axial stress boundary conditions. Simultaneously, X-ray microCT imaging is used with a tracer gas that is allowed to flow through the sample as an illuminating agent. In the presence of an illuminating agent, either Xenon or Krypton, the X-ray CT scanner can image fractures, global pathways and diffusional fronts in the matrix, as well as sorption sites that reflect heterogeneities in the sample and localized deformation. Anticipated results from these experiments will help quantify permeability evolution as a function of different loading conditions and pore pressure depletion. Also, the X-ray images will help visualize the change of flow patterns and the intensity of sorption as a function of mechanical loading and pore pressure.

Sphene (Titanite) as Both Monitor and Driver of Evolution of Felsic Magma: Miocene Volcanic Plutonic and Rocks of the Colorado River Region, NV-AZ, USA

NASA Astrophysics Data System (ADS)

Miller, C. F.; Colombini, L. L.; Wooden, J. L.; Mazdab, F. K.; Gualda, G. A.; Claiborne, L. E.; Ayers, J. C.

2009-05-01

Sphene is commonly the most abundant accessory mineral in metaluminous to weakly peraluminous igneous rocks. Its relatively large crystals preserve a wide array of zoning patterns and inclusions - notably, abundant other accessories and melt inclusions - and it is a major host for REE, U, Th, and HFSE. Thus it is a valuable repository of information about the history of the magmas from which it forms. Recent development of a Zr-in- sphene thermometer (Hayden et al CMP 155:529 2008) and of sensitive and precise in situ trace element analysis by SHRIMP-RG (Mazdab et al GSA abst 39:6:406 2007) permit more powerful exploitation of this repository. We have initiated a study of sphene in Miocene intrusive and extrusive rocks of the Colorado River extensional corridor for which extensive field, geochemical, and geochronological data provide context. Sphene is present as a late interstitial phase in some gabbros and diorites and common in quartz monzonites and granites. Among extrusive rocks, it occurs as phenocrysts in rhyolite lavas and tuffs that are products of small to giant eruptions (Peach Spring Tuff, >600 km3). Glasses that host sphene in the rhyolites are highly evolved (>76 wt% SiO2). Applying the Zr-in-sphene thermometer (TZr), SHRIMP-RG analyses indicate crystallization T between 730 and 810 C in both plutonic and volcanic rocks. This range is narrower than T estimates for zircon growth (Ti thermometry) for the same suite, which extend to somewhat lower and considerably higher values; zircons also tend to record more events and, evidently, longer histories. Ranges of REE patterns are variable and to some extent sample-specific, but all reveal common characteristics: (1) extremely high concentrations, especially for middle REE (maximum Sm in interiors 10-40x103 x chondrite); (2) deep negative Eu anomalies (Eu/Eu* ca. 0.1-0.2); (3) TZr and REE dropping toward rims - especially pronounced for MREE. Estimated Kds for REE from sphene rims and rhyolite glass or phenocryst- poor whole rocks are very high, especially for middle REE: LREE Kds ca. 50-100, MREE ~500-600 (Eu ca. 300- 400), HREE ca. 100. Late REE fractionation trends that are evident in both plutonic and volcanic sequences are clearly controlled for the most part by sphene: aplites, some leucogranites, and high-Si rhyolite whole rocks and glasses reveal extreme MREE depletion and suppressed development of Eu anomalies, a trend that is also expressed in core-to-rim REE depletion patterns in sphene crystals. Results suggest that sphene saturation in these magmas occurred in melts that were already evolved but that it had a dramatic effect on final stages of fractionation. The sphene 'fingerprint' is similar to that proposed by Glazner et al. (Geology 36:183 2008) for Sierra Nevada aplites and as they suggest it marks a late-stage process, but in contrast to their inference we demonstrate that it is evident in volcanic as well as comagmatic plutonic rocks. A better understanding of the controls of sphene saturation will lead to refined interpretation of its presence (or absence), onset of growth, and geochemical fingerprint with respect to magmatic-tectonic environments (cf. Bachmann & Bergantz JPet 49:2277 2008). We intend to address these issues further with saturation experiments and tomographic and geochemical studies of sphene and its inclusions and associated phases.

Geochemical signature of provenance, tectonics and chemical weathering in the Quaternary flood plain sediments of the Hindon River, Gangetic plain, India

NASA Astrophysics Data System (ADS)

Mondal, M. E. A.; Wani, H.; Mondal, Bulbul

2012-09-01

The Ganga basin in the Himalayan foreland is a part of the world's largest area of modern alluvial sedimentation. Flood plain sediments of the Hindon River of the Gangetic plain have been analyzed for sediment texture, major and trace elements including rare earth elements (REEs). The results have been used to characterize the source rock composition and to understand the intensity of chemical weathering, tectonics and their interplay in the Hindon flood plain. The sediments of the Hindon flood plain dominantly consist of sand sized particles with little silt and clay. The geochemistry of the Hindon sediments has been compared to the Siwalik mudstone of the Siwalik Group (Siwaliks). The Siwalik sedimentary rocks like sandstones, mudstones and conglomerates are the known source rocks for the Hindon flood plain sediments. Mudstone geochemistry has been considered best to represent the source rock characteristics. The UCC (Upper Continental Crust) normalized major and trace elements of the Hindon flood plain sediments are very similar to the Siwalik mudstone except for Th and Cr. Furthermore, the average chondrite normalized REE pattern of the Hindon flood plain sediments is similar to the Siwalik mudstone. Textural immaturity, K/Rb ratios and the average CIA (Chemical Index of Alteration) and PIA (Plagioclase Index of Alteration) values of the Hindon flood plain sediments indicate that the sediments have not been affected by chemical weathering. Our study suggests that the active tectonics of the Himalayas and monsoon climate enhances only physical erosion of the source rocks (Siwaliks) rather than the chemical alteration. These factors help the Hindon sediments to retain their parental and tectonic signature even after recycling.

Lanthanide, yttrium, and zirconium anomalies in the Fire Clay coal bed, Eastern Kentucky

USGS Publications Warehouse

Hower, J.C.; Ruppert, L.F.; Eble, C.F.

1999-01-01

The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, thhat constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y + ??REE): total Y + ??REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y + ??REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, that constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y+???REE): total Y+???REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y+???REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.

Rare earth element fingerprints in Korean coastal bay sediments: Association with provenance discrimination

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Woo, Han Jun; Jang, Seok; Jeong, Kap-Sik; Jung, Hoi-Soo; Hwang, Ha Gi; Lee, Jun-Ho; Cho, Jin Hyung

2016-09-01

Rare earth elements (REEs: La-Lu) in surface sediments collected from the mouth and middle tidal flats of Gomso Bay, South Korea, in August 2011 and May 2012 were analyzed to investigate the fine-grained sediment provenance. The upper continental crust (UCC)-normalized light REEs (LREEs: La to Nd) were more enriched than the middle REEs (MREEs: Sm to Dy) and heavy REEs (HREEs: Ho to Lu), resulting in large (La/Yb)UCC (1.9 ± 0.4) to (Gd/Yb)UCC (1.4 ± 0.2) ratios. The monthly (La/Yb)UCC values differed between the mouth and middle tidal flats due to deposition of fine-grained sediments that originated from distant rivers (the Geum and Yeongsan) and the Jujin Stream, located on the southern shore of the inner bay. We observed relative reductions in the (La/Yb)UCC value and REE content in the sediments from the mouth of the bay compared with those from Jujin Stream sediments. Confined to the middle tidal flat around the KH Line of Jujin Stream, the sediments, most enriched in LREEs but depleted in Eu, were distributed in August as strong Jujin Stream runs. Here, we suggest that an increase in LREE/HREE and decrease in MREE/LREE ratios can be used as a proxy to identify the Jujin Stream provenance in mixed riverine sediments and to trace Jujin Stream sediments within the Gomso Bay tidal flat, especially in the summer rainy season.

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau, East Sea

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Jeong, Kap-Sik; Cho, Jin Hyung; Lee, Jun Ho; Jang, Seok; Kim, Seong Ryul

2014-03-01

We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.

Direct determination of europium valence state by XANES in extraterrestrial merrillite: Implications for REE crystal chemistry and martian magmatism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shearer, C.K.; Papike, J.J.; Burger, P.V.

2012-03-15

The relative proportion of divalent and trivalent Eu has proven to be a useful tool for estimating f{sub O{sub 2}} in various magmatic systems. However, in most cases, direct determination of the Eu valence state has not been made. In this study, direct determination of Eu valence by XANES and REE abundance in merrillite provide insights into the crystal chemistry of these phosphates and their ability to record conditions of magmatism. Merrillite strongly prefers Eu{sup 3+} to Eu{sup 2+}, with the average valence state of Eu ranging between 2.9 and 3 over approximately six orders of magnitude in f{sub O{submore » 2}}. The dramatic shift in the REE patterns of merrillite in martian basaltic magmas, from highly LREE-depleted to LREE-enriched, parallels many other trace element and isotopic variations and reflects the sources for these magmas. The behavior of REE in the merrillite directly reflects the relationship between the eightfold-coordinated Ca1 site and adjacent sixfold Na and tetrahedral P sites that enables charge balancing through coupled substitutions.« less

Peering Through a Martian Veil: ALHA84001 Sm-Nd Age Revisited

NASA Technical Reports Server (NTRS)

Nyquist, Laurence E.; Shih, Chi-Yu

2013-01-01

The ancient Martian orthopyroxenite ALH84001experienced a complex history of impact and aqueous alteration events. Here we summarize Sm-147-Nd-143 and Sm-146-Nd-142 analyses performed at JSC. Further, using REE data, we model the REE abundance pattern of the basaltic magma parental to ALH84001 cumulus orthopyroxene. We find the Sm-146-Nd-142 isotopic data to be consistent with isotopic evolution in material having the modeled Sm/Nd ratio from a time very close to the planet's formation to igneous crystallization of ALH84001 as inferred from the Sm-Nd studies.

Stability constants for mono- and dioxalato-complexes of Y and the REE, potentially important species in groundwaters and surface freshwaters

NASA Astrophysics Data System (ADS)

Schijf, J.; Byrne, R. H.

2001-04-01

We present the first measured set of stability constants for mono- and dioxalato-complexes of yttrium and all rare earths except Pm (Y+REE), Oxβ n = [MOx n3-2n] [M 3+] -1 [Ox 2-] -n(where [ ] ≡ concentrations, M ≡ Y+REE, and Ox 2- ≡ C 2O 42-). Aqueous solutions of Y+REE were titrated with oxalic acid in the presence of a cation-exchange resin, and Y+REE concentrations in the solution phase were measured by ICP-MS. This method allows investigation of all Y+REE simultaneously under identical conditions and is thus very sensitive to subtle inter-element variations in log Oxβ n. Experiments were performed at a single ionic strength ( I = 0.05 M), but at two values of pH. Patterns of log Oxβ 1 and log Oxβ 2, determined from our experiments, are similar in shape and reminiscent of those for carbonato-complexes. The average ratio of stepwise stability constants K 2/K 1 = Oxβ 2/( Oxβ 1) 2 is 0.05 ± 0.02 for Y+REE excluding La and Ce. Literature values of Oxβ 1(Eu) for 0.03 mol/L ≤ I ≤ 1 mol/L were used to derive the relation log Oxβ 1(Eu) = log Oxβ 10(Eu) - 6.132√ I/(1 + 1.47√ I) + 0.902 I, where log Oxβ 10(Eu) is the stability constant at infinite dilution. Applying this relation to all Y+REE, the following values of log Oxβ 10 (at zero ionic strength) were found: 6.66 (Y), 5.87 (La), 5.97 (Ce), 6.25 (Pr), 6.31 (Nd), 6.43 (Sm), 6.52 (Eu), 6.53 (Gd), 6.63 (Tb), 6.74 (Dy), 6.77 (Ho), 6.83 (Er), 6.89 (Tm), 6.95 (Yb), 6.96 (Lu). These values, which are based on direct measurements for each individual Y+REE, agree quite well with published extrapolations that are mostly based on linear free-energy relationships. Total oxalate concentrations of 10 -5-10 -3 M have been reported for soil solutions. Free oxalate ions persist at much lower pH than free carbonate ions and a simple speciation model demonstrates that oxalato-complexes can dominate Y+REE speciation in mildly acidic groundwaters of low-to-moderate alkalinity.

Timing and duration of Variscan high-pressure metamorphism in the French Massif Central: A multimethod geochronological study from the Najac Massif

NASA Astrophysics Data System (ADS)

Lotout, Caroline; Pitra, Pavel; Poujol, Marc; Anczkiewicz, Robert; Van Den Driessche, Jean

2018-05-01

Accurate dating of eclogite-facies metamorphism is of paramount importance in order to understand the tectonic evolution of an orogen. An eclogite sample from the Najac Massif (French Massif Central, Variscan belt) displays a zircon-bearing garnet-omphacite-amphibole-rutile-quartz peak assemblage. Pseudosection modeling suggests peak pressure conditions of 15-20 kbar, 560-630 °C. Eclogite-facies garnet displays Lu-enriched cores and Sm-rich rims and yields a Lu-Hf age of 382.8 ± 1.0 Ma and a Sm-Nd age of 376.7 ± 3.3 Ma. The ages are interpreted as marking the beginning of the prograde garnet growth during the initial stages of the eclogite-facies metamorphism, and the high-pressure (and temperature) peak reached by the rock, respectively. Zircon grains display chondrite-normalized REE spectra with variably negative, positive or no Eu anomalies and are characterized by either enriched or flat HREE patterns. However, they yield a well constrained in situ LA-ICP-MS U-Pb age of 385.5 ± 2.3 Ma, despite this REE pattern variability. Zr zonation in garnet, Y content in zircon and the diversity of zircon HREE spectra may suggest that zircon crystallized prior to and during incipient garnet growth on the prograde P-T path, recording the initial stages of the eclogite-facies conditions. Consequently, the zircon age of 385.5 ± 2.3 Ma, comparable within error with the Lu-Hf age obtained on garnet, is interpreted as dating the beginning of the eclogite-facies metamorphism. Accordingly, the duration of the prograde part of the eclogite-facies event is estimated at 6.1 ± 4.3 Myr. Subsequent exhumation is constrained by an apatite U-Pb age at 369 ± 13 Ma.

On the past climate of the Dobrogea (Romania) during the late Quaternary as reflected by loess geochemistry

NASA Astrophysics Data System (ADS)

Duliu, Octavian G.; Tugulan, Liviu C.; Bojar, Ana-Voica; Dumitras, Delia; Zincovskaya, Inga; Culicov, Otilia A.; Frontasyeva, Marina V.

2015-04-01

Ten samples of loess and paleosoil collected from the Costinesti - Dobrogea (Romania) loess deposit that are covering a time span of about 690 ± 90 ky were analyzed by X-ray diffraction (XRD) , Instrumental Neutron Activation Analysis (INAA) and X-ray Fluorescence (XRF) in order to evidentiate the origin as well as the climatic conditions during the formation of loess material. The presence of illite and calcite, suggests reduced weathering. This was confirmed by further climate proxies as Chemical Index of Alteration (CIA) whose values are between 54.6 and 64.0, Chemical Index of Weathering (CIW) between 65.7 and 71.7 as well as Rb/Sr ratio between 0.26 and 0.47, lower than the neighboring Hungarian loess, but closer to the average Chinese and European loess. No statistical significant differences were observed between average values of loess and palaeosol samples regarding these proxies. The content of 27 trace elements, including 10 REE were, excepting Cr, Ni, Zr and Hf,very close to average rocks composition as Upper Continental Crust (UCC), North America Shale Composite (NASC) and Post-Archean Average Australian Shale (PAAS). Both mineralogical and geochemical data from Costinesti loess and palaeosol samples support a continental origin of loess material deposited in a rather arid and cold climate during the past 690 ± 90 ky.

Multistage hydrothermal silicification and Fe-Tl-As-Sb-Ge-REE enrichment in the Red Dog Zn-Pb-Ag district, northern Alaska: Geochemistry, origin, and exploration applications

USGS Publications Warehouse

Slack, J.F.; Kelley, K.D.; Anderson, V.M.; Clark, J.L.; Ayuso, R.A.

2004-01-01

Geochemical analyses of major, trace, and rare earth elements (REE) in more than 200 samples of variably silicified and altered wall rocks, massive and banded sulfide, silica rock, and sulfide-rich and unmineralized barite were obtained from the Main, Aqqaluk, and Anarraaq deposits in the Red Dog Zn-Pb-Ag district of northern Alaska. Detailed lithogeochemical profiles for two drill cores at Aqqaluk display an antithetic relationship between SiO2/Al2O3 and TiO2/Zr which, together with textural information, suggest preferential silicification of carbonate-bearing sediments. Data for both drill cores also show generally high Tl, Sb, As, and Ge and uniformly positive Eu anomalies (Eu/Eu* > 1.0). Similar high Tl, Sb, As, Ge, and Eu/Eu* values are present in the footwall and shallow hanging wall of Zn-Pb-Ag sulfide intervals at Anarraaq but are not as widely dispersed. Net chemical changes for altered wall rocks in the district, on the basis of average Al-normalized data relative to unaltered black shales of the host Kuna Formation, include large enrichments (>50%) of Fe, Ba, Eu, V, S, Co, Zn, Pb, Tl, As, Sb, and Ge at both Red Dog and Anarraaq, Si at Red Dog, and Sr, U, and Se at Anarraaq. Large depletions (>50%) are evident for Ca at both Red Dog and Anarraaq, for Mg, P, and Y at Red Dog, and for Na at Anarraaq. At both Red Dog and Anarraaq, wall-rock alteration removed calcite and minor dolomite during hydrothermal decarbonation reactions and introduced Si, Eu, and Ge during silicification. Sulfidation reactions deposited Fe, S, Co, Zn, Pb, Tl, As, and Sb; barite mineralization introduced Ba, S, and Sr. Light REE and U were mobilized locally. This alteration and mineralization occurred during Mississippi an hydrothermal events that predated the Middle Jurassic-Cretaceous Brookian orogeny. Early hydrothermal silicification at Red Dog took place prior to or during massive sulfide mineralization, on the basis of the dominantly planar nature of Zn-Pb veins, which suggests filling of fractures that developed in previously lithified rock. Uniformly low Ca and Mg and uniformly negative Ce anomalies in highly siliceous Red Dog wall rocks reflect hydrothermal decarbonation reactions and pervasive silicification owing to conductive cooling of oxidized metalliferous fluids. Similar Ca and Mg depletions are evident at Anarraaq but generally lack associated silicification, possibly because temperatures of the hydrothermal fluids were too low (<180??C) or because the thermal contrast between the fluids and wall rocks was smaller owing to the greater depth of alteration and mineralization there, compared with Red Dog. Chalcophile element anomalies (Fe, Zn, Pb, Tl, As, Sb) in wall rocks at both Red Dog and Anarraq are attributed to sulfidation reactions, coeval with subsurface Zn-Pb-Ag mineralization, during the mixing of oxidized metalliferous fluids with H2S-rich fluids derived locally within the Kuna Formation. Sedimentary wall rocks in the Red Dog district are characterized by a distinctive suite of geochemical anomalies, especially for Zn, Pb, Tl, As, Sb, Ge, and Eu/Eu*. At the Aqqaluk deposit, wall rocks without visible sphalerite or galena (<300 ppm Zn + Pb) have anomalous Eu/Eu*, Tl, Sb, and As for up to ???100 m stratigraphically below Zn-rich silica rock. At Anarraaq, the Tl anomaly is most extensively developed, and enrichment relative to unaltered black shale of the Kuna Formation is present up to 62 m above the highest Zn-Pb sulfide zones. The magnitude of the enrichment and systematic behavior of Tl in the district make Tl a promising geochemical exploration guide for Red Dog-type Zn-Pb-Ag deposits elsewhere. ?? 2004 by Economic Geology.

An integrated study of geochemistry and mineralogy of the Upper Tukau Formation, Borneo Island (East Malaysia): Sediment provenance, depositional setting and tectonic implications

NASA Astrophysics Data System (ADS)

Nagarajan, Ramasamy; Roy, Priyadarsi D.; Kessler, Franz L.; Jong, John; Dayong, Vivian; Jonathan, M. P.

2017-08-01

An integrated study using bulk chemical composition, mineralogy and mineral chemistry of sedimentary rocks from the Tukau Formation of Borneo Island (Sarawak, Malaysia) is presented in order to understand the depositional and tectonic settings during the Neogene. Sedimentary rocks are chemically classified as shale, wacke, arkose, litharenite and quartz arenite and consist of quartz, illite, feldspar, rutile and anatase, zircon, tourmaline, chromite and monazite. All of them are highly matured and were derived from a moderate to intensively weathered source. Bulk and mineral chemistries suggest that these rocks were recycled from sedimentary to metasedimentary source regions with some input from granitoids and mafic-ultramafic rocks. The chondrite normalized REE signature indicates the presence of felsic rocks in the source region. Zircon geochronology shows that the samples were of Cretaceous and Triassic age. Comparable ages of zircon from the Tukau Formation sedimentary rocks, granitoids of the Schwaner Mountains (southern Borneo) and Tin Belt of the Malaysia Peninsular suggest that the principal provenance for the Rajang Group were further uplifted and eroded during the Neogene. Additionally, presence of chromian spinels and their chemistry indicate a minor influence of mafic and ultramafic rocks present in the Rajang Group. From a tectonic standpoint, the Tukau Formation sedimentary rocks were deposited in a passive margin with passive collisional and rift settings. Our key geochemical observation on tectonic setting is comparable to the regional geological setting of northwestern Borneo as described in the literature.

Compositional variation in minerals of the chevkinite group

USGS Publications Warehouse

Macdonald, R.; Belkin, H.E.

2002-01-01

The composition of chevkinite and perrierite, the most common members of the chevkinite group, is closely expressed by the formula A4BC2D2Si4O22, where A = (La,Ce,Ca,Sr,Th), B = Fe2+, C = (Fe2+,Fe3+,Ti,Al,Zr,Nb) and D = Ti. The A site is dominated by a strong negative correlation between (Ca+Sr) and the REE. Chondrite-normalized REE patterns are very variable, e.g. in LREE/HREE and Eu/Eu*. The C site is dominated by Ti, Al and Fe2+, in very variable proportions. Most chevkinites and perrierites are close to stoichiometric, with cation sums between 12.9 and 13.5, compared to the theoretical 13. There is no single, generally applicable charge balancing substitution scheme in the group; however, the general relationship (Ca+Sr)A + TiC + REEA + M3C+2+ defines a linear array with r2 = 0.91. Chevkinite and perrierite are shown to be compositionally distinct on the basis of CaO, FeO* Al2O3 and Ce2O3 abundances. Chevkinite forms mainly in chemically evolved parageneses, such as syenites, rhyolites and fenites associated with carbonatite complexes. Perrierite is more commonly recorded from igneous rocks of mafic to intermediate composition. The compositional characteristics and possible structural formulae of other members of the chevkinite group are reviewed briefly.

Serpentinite-driven Exhumation of the UHP Lago di Cignana Unit in the Fossil Alpine Plate Interface

NASA Astrophysics Data System (ADS)

Scambelluri, M.; Gilio, M.; Angiboust, S.; Godard, M.; Pettke, T.

2015-12-01

The Lago di Cignana Unit (LCU) is a coesite- [1] and diamond-bearing [2] slice of oceanic-derived eclogites and metasediments recording Alpine UHP metamorphism at 600 °C-3.2 GPa (~110 km depth) [3]. The LCU is tectonically sandwiched between the eclogitic Zermatt-Saas Zone (ZSZ; 540 °C-3.2 GPa) [4] and the blueschist Combin Zone (400 °C-0.9 GPa) [5] along a tectonic structure joining HP units recording a ~1.2 GPa (40 km) pressure difference. So far, the ZSZ has been attributed to normal HP conditions and the mechanism driving exhumation and accretion of the LCU in its present structural position is not fully understood.We performed petrography and bulk-rock trace element analyses of rocks from LCU and ZSZ serpentinites. We observed that, while serpentinites in the core of the ZSZ show normal subduction zone trace elements and REE's patterns, the Ol+Ti-chu+Chl veins and host serpentinites enveloping the LCU are strongly enriched in sediment-derived fluid-mobile elements (U, Th, Nb, Ta, Ce, Y, As, Sb) and REE's: their patterns well match those of the closely associated LCU-UHP rocks.The presence of extremely enriched Ol+Ti-chu+Chl veins in the serpentinites at direct contact with the UHP Lago di Cignana Unit suggests that fluid exchange between serpentinite and LCU crustal rocks occurred at peak metamorphic conditions. Their coupling therefore occurred during subduction burial and/or peak UHP conditions. As such, the buoyancy force originating from the relatively light serpentinites fuelled the exhumation of the Lago di Cignana Unit. In this contest, the tectonic contact between the Zermatt-Saas Zone and the Combin Zone evolved into a true tectonic plate interface surface.1. Reinecke (1998). Lithos 42(3), 147-189; 2. Frezzotti et al. (2011). Nat. Geosci. 4(10), 703-706; 3. Groppo et al. (2009). J. Metam. Geol. 27(3), 207-231; 4. Angiboust et al. (2009). Terra Nova 21(3), 171-180; 5. Reddy et al. (1999). J. Metam. Geol. 17, 573-590.

Cerium anomaly at microscale in fossils.

PubMed

Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

2015-09-01

Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

Synthesis and analysis of jet fuel from shale oil and coal syncrudes

NASA Technical Reports Server (NTRS)

Gallagher, J. P.; Collins, T. A.; Nelson, T. J.; Pedersen, M. J.; Robison, M. G.; Wisinski, L. J.

1976-01-01

Thirty-two jet fuel samples of varying properties were produced from shale oil and coal syncrudes, and analyzed to assess their suitability for use. TOSCO II shale oil and H-COAL and COED syncrudes were used as starting materials. The processes used were among those commonly in use in petroleum processing-distillation, hydrogenation and catalytic hydrocracking. The processing conditions required to meet two levels of specifications regarding aromatic, hydrogen, sulfur and nitrogen contents at two yield levels were determined and found to be more demanding than normally required in petroleum processing. Analysis of the samples produced indicated that if the more stringent specifications of 13.5% hydrogen (min.) and 0.02% nitrogen (max.) were met, products similar in properties to conventional jet fuels were obtained. In general, shale oil was easier to process (catalyst deactivation was seen when processing coal syncrudes), consumed less hydrogen and yielded superior products. Based on these considerations, shale oil appears to be preferred to coal as a petroleum substitute for jet fuel production.

Mixed integer simulation optimization for optimal hydraulic fracturing and production of shale gas fields

NASA Astrophysics Data System (ADS)

Li, J. C.; Gong, B.; Wang, H. G.

2016-08-01

Optimal development of shale gas fields involves designing a most productive fracturing network for hydraulic stimulation processes and operating wells appropriately throughout the production time. A hydraulic fracturing network design-determining well placement, number of fracturing stages, and fracture lengths-is defined by specifying a set of integer ordered blocks to drill wells and create fractures in a discrete shale gas reservoir model. The well control variables such as bottom hole pressures or production rates for well operations are real valued. Shale gas development problems, therefore, can be mathematically formulated with mixed-integer optimization models. A shale gas reservoir simulator is used to evaluate the production performance for a hydraulic fracturing and well control plan. To find the optimal fracturing design and well operation is challenging because the problem is a mixed integer optimization problem and entails computationally expensive reservoir simulation. A dynamic simplex interpolation-based alternate subspace (DSIAS) search method is applied for mixed integer optimization problems associated with shale gas development projects. The optimization performance is demonstrated with the example case of the development of the Barnett Shale field. The optimization results of DSIAS are compared with those of a pattern search algorithm.

Effects of spatial heterogeneity and material anisotropy on the fracture pattern and macroscopic effective toughness of Mancos Shale in Brazilian tests

NASA Astrophysics Data System (ADS)

Na, SeonHong; Sun, WaiChing; Ingraham, Mathew D.; Yoon, Hongkyu

2017-08-01

For assessing energy-related activities in the subsurface, it is important to investigate the impact of the spatial variability and anisotropy on the geomechanical behavior of shale. The Brazilian test, an indirect tensile-splitting method, is performed in this work, and the evolution of strain field is obtained using digital image correlation. Experimental results show the significant impact of local heterogeneity and lamination on the crack pattern characteristics. For numerical simulations, a phase field method is used to simulate the brittle fracture behavior under various Brazilian test conditions. In this study, shale is assumed to consist of two constituents including the stiff and soft layers to which the same toughness but different elastic moduli are assigned. Microstructural heterogeneity is simplified to represent mesoscale (e.g., millimeter scale) features such as layer orientation, thickness, volume fraction, and defects. The effect of these structural attributes on the onset, propagation, and coalescence of cracks is explored. The simulation results show that spatial heterogeneity and material anisotropy highly affect crack patterns and effective fracture toughness, and the elastic contrast of two constituents significantly alters the effective toughness. However, the complex crack patterns observed in the experiments cannot completely be accounted for by either an isotropic or transversely isotropic effective medium approach. This implies that cracks developed in the layered system may coalesce in complicated ways depending on the local heterogeneity, and the interaction mechanisms between the cracks using two-constituent systems may explain the wide range of effective toughness of shale reported in the literature.

Effects of spatial heterogeneity and material anisotropy on the fracture pattern and macroscopic effective toughness of Mancos Shale in Brazilian tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Na, SeonHong; Sun, WaiChing; Ingraham, Mathew D.

For assessing energy-related activities in the subsurface, it is important to investigate the impact of the spatial variability and anisotropy on the geomechanical behavior of shale. The Brazilian test, an indirect tensile-splitting method, is performed in this work, and the evolution of strain field is obtained using digital image correlation. Experimental results show the significant impact of local heterogeneity and lamination on the crack pattern characteristics. For numerical simulations, a phase field method is used to simulate the brittle fracture behavior under various Brazilian test conditions. In this study, shale is assumed to consist of two constituents including the stiffmore » and soft layers to which the same toughness but different elastic moduli are assigned. Microstructural heterogeneity is simplified to represent mesoscale (e.g., millimeter scale) features such as layer orientation, thickness, volume fraction, and defects. The effect of these structural attributes on the onset, propagation, and coalescence of cracks is explored. The simulation results show that spatial heterogeneity and material anisotropy highly affect crack patterns and effective fracture toughness, and the elastic contrast of two constituents significantly alters the effective toughness. However, the complex crack patterns observed in the experiments cannot completely be accounted for by either an isotropic or transversely isotropic effective medium approach. In conclusion, this implies that cracks developed in the layered system may coalesce in complicated ways depending on the local heterogeneity, and the interaction mechanisms between the cracks using two-constituent systems may explain the wide range of effective toughness of shale reported in the literature.« less

Effects of spatial heterogeneity and material anisotropy on the fracture pattern and macroscopic effective toughness of Mancos Shale in Brazilian tests

DOE PAGES

Na, SeonHong; Sun, WaiChing; Ingraham, Mathew D.; ...

2017-07-31

For assessing energy-related activities in the subsurface, it is important to investigate the impact of the spatial variability and anisotropy on the geomechanical behavior of shale. The Brazilian test, an indirect tensile-splitting method, is performed in this work, and the evolution of strain field is obtained using digital image correlation. Experimental results show the significant impact of local heterogeneity and lamination on the crack pattern characteristics. For numerical simulations, a phase field method is used to simulate the brittle fracture behavior under various Brazilian test conditions. In this study, shale is assumed to consist of two constituents including the stiffmore » and soft layers to which the same toughness but different elastic moduli are assigned. Microstructural heterogeneity is simplified to represent mesoscale (e.g., millimeter scale) features such as layer orientation, thickness, volume fraction, and defects. The effect of these structural attributes on the onset, propagation, and coalescence of cracks is explored. The simulation results show that spatial heterogeneity and material anisotropy highly affect crack patterns and effective fracture toughness, and the elastic contrast of two constituents significantly alters the effective toughness. However, the complex crack patterns observed in the experiments cannot completely be accounted for by either an isotropic or transversely isotropic effective medium approach. In conclusion, this implies that cracks developed in the layered system may coalesce in complicated ways depending on the local heterogeneity, and the interaction mechanisms between the cracks using two-constituent systems may explain the wide range of effective toughness of shale reported in the literature.« less

Thermal maturity patterns (conodont color alteration index and vitrinite reflectance) in Upper Ordovician and Devonian rocks of the Appalachian basin: a major revision of USGS Map I-917-E using new subsurface collections: Chapter F.1 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Repetski, John E.; Ryder, Robert T.; Weary, David J.; Harris, Anita G.; Trippi, Michael H.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

The conodont color alteration index (CAI) introduced by Epstein and others (1977) and Harris and others (1978) is an important criterion for estimating the thermal maturity of Ordovician to Mississippian rocks in the Appalachian basin. Consequently, the CAI isograd maps of Harris and others (1978) are commonly used by geologists to characterize the thermal and burial history of the Appalachian basin and to better understand the origin and distribution of oil and gas resources in the basin. The main objectives of this report are to present revised CAI isograd maps for Ordovician and Devonian rocks in the Appalachian basin and to interpret the geologic and petroleum resource implications of these maps. The CAI isograd maps presented herein complement, and in some areas replace, the CAI-based isograd maps of Harris and others (1978) for the Appalachian basin. The CAI data presented in this report were derived almost entirely from subsurface samples, whereas the CAI data used by Harris and others (1978) were derived almost entirely from outcrop samples. Because of the different sampling methods, there is little geographic overlap of the two data sets. The new data set is mostly from the Allegheny Plateau structural province and most of the data set of Harris and others (1978) is from the Valley and Ridge structural province, east of the Allegheny structural front (fig. 1). Vitrinite reflectance, based on dispersed vitrinite in Devonian black shale, is another important parameter for estimating the thermal maturity in pre-Pennsylvanian-age rocks of the Appalachian basin (Streib, 1981; Cole and others, 1987; Gerlach and Cercone, 1993; Rimmer and others, 1993; Curtis and Faure, 1997). This chapter also presents a revised percent vitrinite reflectance (%R0) isograd map based on dispersed vitrinite recovered from selected Devonian black shales. The Devonian black shales used for the vitrinite studies reported herein also were analyzed by RockEval pyrolysis and total organic carbon (TOC) content in weight percent. Although the RockEval and TOC data are included in this chapter (table 1), they are not shown on the maps. The revised CAI isograd and percent vitrinite reflectance isograd maps cover all or parts of Kentucky, New York, Ohio, Pennsylvania, Virginia, and West Virginia (fig. 1), and the following three stratigraphic intervals: Upper Ordovician carbonate rocks, Lower and Middle Devonian carbonate rocks, and Middle and Upper Devonian black shales. These stratigraphic intervals were chosen for the following reasons: (1) they represent target reservoirs for much of the oil and gas exploration in the Appalachian basin; (2) they are stratigraphically near probable source rocks for most of the oil and gas; (3) they include geologic formations that are nearly continuous across the basin; (4) they contain abundant carbonate grainstone-packstone intervals, which give a reasonable to good probability of recovery of conodont elements from small samples of drill cuttings; and (5) the Middle and Upper Devonian black shale contains large amounts of organic matter for RockEval, TOC, and dispersed vitrinite analyses. Thermal maturity patterns of the Upper Ordovician Trenton Limestone are of particular interest here, because they closely approximate the thermal maturity patterns in the overlying Upper Ordovician Utica Shale, which is the probable source rock for oil and gas in the Upper Cambrian Rose Run Sandstone (sandstone), Upper Cambrian and Lower Ordovician Knox Group (Dolomite), Lower and Middle Ordovician Beekmantown Group (dolomite or Dolomite), Upper Ordovician Trenton and Black River Limestones, and Lower Silurian Clinton/Medina sandstone (Cole and others, 1987; Jenden and others, 1993; Laughrey and Baldassare, 1998; Ryder and others, 1998; Ryder and Zagorski, 2003). The thermal maturity patterns of the Lower Devonian Helderberg Limestone (Group), Middle Devonian Onondaga Limestone, and Middle Devonian Marcellus Shale-Upper Devonian Rhine street Shale Member-Upper Devonian Ohio Shale are of interest, because they closely approximate the thermal maturity patterns in the Marcellus Shale, Upper Devonian Rhinestreet Shale Member, and Upper Devonian Huron Member of the Ohio Shale, which are the most important source rocks for oil and gas in the Appalachian basin (de Witt and Milici, 1989; Klemme and Ulmishek, 1991). The Marcellus, Rhinestreet, and Huron units are black-shale source rocks for oil and (or) gas in the Lower Devonian Oriskany Sandstone, the Upper Devonian sandstones, the Middle and Upper Devonian black shales, and the Upper Devonian-Lower Mississippian(?) Berea Sandstone (Patchen and others, 1992; Roen and Kepferle, 1993; Laughrey and Baldassare, 1998).

Age and duration of eclogite-facies metamorphism, North Qaidam HP/UHP terrane, Western China

USGS Publications Warehouse

Mattinson, C.G.; Wooden, J.L.; Liou, J.G.; Bird, D.K.; Wu, C.L.

2006-01-01

Amphibolite-facies para-and orthogneisses near Dulan, at the southeast end of the North Qaidam terrane, enclose minor eclogite and peridotite which record ultra-high pressure (UHP) metamorphism associated with the Early Paleozoic continental collision of the Qilian and Qaidam microplates. Field relations and coesite inclusions in zircons from paragneiss suggest that felsic, mafic, and ultramafic rocks all experienced UHP metamorphism and a common amphibolite-facies retrogression. SHRIMP-RG U-Pb and REE analyses of zircons from four eclogites yield weighted mean ages of 449 to 422 Ma, and REE patterns (flat HREE, no Eu anomaly) and inclusions of garnet, omphacite, and rutile indicate these ages record eclogite-facies metamorphism. The coherent field relations of these samples, and the similar range of individual ages in each sample suggests that the ???25 m.y. age range reflects the duration of eclogite-facies conditions in the studied samples. Analyses from zircon cores in one sample yield scattered 433 to 474 Ma ages, reflecting partial overlap on rims, and constrain the minimum age of eclogite protolith crystallization. Inclusions of Th + REE-rich epidote, and zircon REE patterns are consistent with prograde metamorphic growth. In the Lu??liang Shan, approximately 350 km northwest in the North Qaidam terrane, ages interpreted to record eclogite-facies metamorphism of eclogite and garnet peridotite are as old as 495 Ma and as young as 414 Ma, which suggests that processes responsible for extended high-pressure residence are not restricted to the Dulan region. Evidence of prolonged eclogite-facies metamorphism in HP/UHP localities in the Northeast Greenland eclogite province, the Western Gneiss Region of Norway, and the western Alps suggests that long eclogite-facies residence may be globally significant in continental subduction/collision zones.

Determining the Sensitivity of the Hf-Nd Proxy to Glacial Weathering

NASA Astrophysics Data System (ADS)

Namsinh, A.; Scher, H.; Piotrowski, A. M.

2017-12-01

The history of polar ice sheets through the Cenozoic is incompletely known. Estimates of the onset of northern hemisphere glaciation range from the Pliocene to mid-Eocene and precursor Antarctic glaciations are believed to have commenced in the middle Eocene. Uncertainty surrounding the history of ice sheets has resulted in debates about the sensitivity of ice sheets to changes in atmospheric CO2 through the Cenozoic. Geochemical proxies for continental weathering — particularly those that are sensitive to mechanical breakdown of the upper continental crust by ice sheets — could improve the fidelity of paleoclimate reconstructions of ice sheet history. Coupled hafnium (Hf) and neodymium (Nd) isotopes in seawater and authigenic sediment phases show a strong correlation with mechanical weathering rates, however the proxy has not been systematically tested on Pleistocene time scales. We measured the Hf and Nd isotope ratios of authigenic and detrital phases of sediment cores from 1150 m to 4045 m depth on the Rockall Plateau in the NE Atlantic Ocean. Our study is limited to the LGM, deglaciation and Holocene intervals. The authigenic fraction was extracted from bulk sediments by leaching with dilute hydroxylamine hydrochloride and EDTA to prevent readsorption of Hf. A stronger leach solution was then used to isolate the terrigenous detrital fraction. The fidelity of the seawater signal obtained by leaching is assessed by comparison of leachate eNd values to previously published eNd values from uncleaned forams from the same depth intervals. Initial tests with Holocene and deglacial samples verify that leachate eNd values are statistically indistinguishable from uncleaned forams. Shale-normalized REE patterns for leachates reveal negative Ce anomalies and a MREE enrichment typical of Fe-Mn oxydydroxide phases. Coupled Hf-Nd isotopes from authigenic leachates from our initial tests fall along the Seawater Array when plotted on a Hf-Nd isotope diagram, confirming that a primary seawater Hf isotope signal can also be extracted from authigenic leachates. Further isotopic analysis of these cores, including the LGM intervals, will reveal if changes in weathering style through the deglaciation resulted in decoupling of Hf and Nd isotopes, which may be expressed as a deviation from the Seawater Array.

Determining the locus of a processing zone in an in situ oil shale retort by sound monitoring

DOEpatents

Elkington, W. Brice

1978-01-01

The locus of a processing zone advancing through a fragmented permeable mass of particles in an in situ oil shale retort in a subterranean formation containing oil shale is determined by monitoring for sound produced in the retort, preferably by monitoring for sound at at least two locations in a plane substantially normal to the direction of advancement of the processing zone. Monitoring can be effected by placing a sound transducer in a well extending through the formation adjacent the retort and/or in the fragmented mass such as in a well extending into the fragmented mass.

The effect of temperature and surface area on Sr, Ba and REE fractionation during low temperature serpentinization

NASA Astrophysics Data System (ADS)

Frisby, C. P.; Bizimis, M.; Foustoukos, D.

2013-12-01

Peridotite hosted hydrothermal vent systems are a direct link between the hydrosphere and the Earth's mantle. They promote elemental mass exchange between these two regimes, driven by hydrothermal alteration of peridotite by seawater. Most experimental, theoretical and field studies of peridotite alteration have focused on high temperature (>1800C) conditions where serpentinization is readily observed, but less is known for low-temperature alteration that likely resembles near seafloor processes. Furthermore, while major element exchange during serpentinization has been studied extensively, the behavior of trace elements remains unclear, especially at low temperatures (<1000C). Here we report data from time-series experiments designed to constrain the reaction of Sr, Ba and REE between synthetic seawater and olivine as a function of both temperature (15-900C) and mineral grain size (geometric surface area). Our experimental data shows a clear decoupling of REE from Sr-Ba under all experimental conditions. While Sr and Ba remain quantitatively in solution, the REE are being removed from the solution at rates that increase with increasing temperature and GSA (i.e. decreasing particle size). We also observe the HREE are removed from solution faster than the LREE. The REE removal can be described as a two-stage process, with a fast initial rate followed by a slower rate as the reaction approaches equilibrium. For instance at 900C and GSA of 57.57cm2/g (average grain diameter of 258.7μm), 50% of Nd is removed in 8 hours but only 80% at 120 hours. We quantify the initial reaction rate constant of each element as a function of temperature and grain size, in order to understand the mechanisms of REE removal. The experimentally determined surface-normalized reaction rate constants (0.29-1.84 s-1m-2), constrain the temperature dependence and activation energy for the scavenging of REE driven by olivine hydrolysis. For example, LREE reaction rates have a higher temperature dependency than the HREE, i.e. higher activation energy for Nd than Yb. This activation energy does not correlate well with ionic radius, but correlates well with the third ionization potential of REE. This indicates a 3+ charge speciation for the REE upon removal to the olivine substrate. Recent experimental data had shown the formation of secondary phases (i.e. Fe(III)-(hydr)oxides, Fe bearing-talc and Fe(II)-brucite) with olivine, facilitated by the presence of spinel [1], that may contribute to the REE scavenging observed here. Our experiments however are pure olivine (>99.9%) and spinel-free. We also observed limited dissolution (<0.001%) of olivine at up to 21 days of reaction, and no evidence for the formation of Fe-oxyhydroxides, using ICPMS, XRD, Mossbauer and SEM methods. It therefore seems unlikely that Fe(III)-(hydr)oxides are responsible for the REE fractionations. This new information will enhance our limited understanding of the cycling of REE in seawater hydrothermal circulation and abyssal peridotite alteration. 1. Mayhew et al (2013) Nat Geo. 6, 478-484

Geochemistry, Nd-Pb Isotopes, and Pb-Pb Ages of the Mesoproterozoic Pea Ridge Iron Oxide-Apatite–Rare Earth Element Deposit, Southeast Missouri

USGS Publications Warehouse

Ayuso, Robert A.; Slack, John F.; Day, Warren C.; McCafferty, Anne E.

2016-01-01

Iron oxide-apatite and iron oxide-copper-gold deposits occur within ~1.48 to 1.47 Ga volcanic rocks of the St. Francois Mountains terrane near a regional boundary separating crustal blocks having contrasting depleted-mantle Sm-Nd model ages (TDM). Major and trace element analyses and Nd and Pb isotope data were obtained to characterize the Pea Ridge deposit, improve identification of exploration targets, and better understand the regional distribution of mineralization with respect to crustal blocks. The Pea Ridge deposit is spatially associated with felsic volcanic rocks and plutons. Mafic to intermediate-composition rocks are volumetrically minor. Data for major element variations are commonly scattered and strongly suggest element mobility. Ratios of relatively immobile elements indicate that the felsic rocks are evolved subalkaline dacite and rhyolite; the mafic rocks are basalt to basaltic andesite. Granites and rhyolites display geochemical features typical of rocks produced by subduction. Rare earth element (REE) variations for the rhyolites are diagnostic of rocks affected by hydrothermal alteration and associated REE mineralization. The magnetite-rich rocks and REE-rich breccias show similar REE and mantle-normalized trace element patterns.Nd isotope compositions (age corrected) show that: (1) host rhyolites have ɛNd from 3.44 to 4.25 and TDM from 1.51 to 1.59 Ga; (2) magnetite ore and specular hematite rocks display ɛNd from 3.04 to 4.21 and TDM from 1.6 to 1.51 Ga, and ɛNd from 2.23 to 2.81, respectively; (3) REE-rich breccias have ɛNd from 3.04 to 4.11 and TDM from 1.6 to 1.51 Ga; and (4) mafic to intermediate-composition rocks range in ɛNd from 2.35 to 3.66 and in TDM from 1.66 to 1.56. The ɛNd values of the magnetite and specular hematite samples show that the REE mineralization is magmatic; no evidence exists for major overprinting by younger, crustal meteoric fluids, or by externally derived Nd. Host rocks, breccias, and magnetite ore shared a common origin from a similar source.Lead isotope ratios are diverse: (1) host rhyolite has 206Pb/204Pb from 24.261 to 50.091; (2) Pea Ridge and regional galenas have 206Pb/204Pb from 16.030 to 33.548; (3) REE-rich breccia, magnetite ore, and specular hematite rock are more radiogenic than galena; (4) REE-rich breccias have high 206Pb/204Pb (38.122–1277.61) compared to host rhyolites; and (5) REE-rich breccias are more radiogenic than magnetite ore and specular-hematite rock, having 206Pb/204Pb up to 230.65. Radiogenic 207Pb/206Pb age estimates suggest the following: (1) rhyolitic host rocks have ages of ~1.50 Ga, (2) magnetite ore is ~1.44 Ga, and (3) REE-rich breccias are ~1.48 Ga. These estimates are broadly consistent and genetically link the host rhyolite, REE-rich breccia, and magnetite ore as being contemporaneous.Alteration style and mineralogical or textural distinctions among the magnetite-rich rocks and REE-rich breccias do not correlate with different isotopic sources. In our model, magmatic fluids leached metals from the coeval felsic rocks (rhyolites), which provided the metal source reflected in the compositions of the REE-rich breccias and mineralized rocks. This model allows for the likelihood of contributions from other genetically related felsic and intermediate to more mafic rocks stored deeper in the crust. The deposit thus records an origin as a magmatic-hydrothermal system that was not affected by Nd and Pb remobilization processes, particularly if these processes also triggered mixing with externally sourced metal-bearing fluids. The Pea Ridge deposit was part of a single, widespread, homogeneous mixing system that produced a uniform isotopic composition, thus representing an excellent example of an igneous-dominated system that generated coeval magmatism and REE mineralization. Geochemical features suggest that components in the Pea Ridge deposit originated from sources in an orogenic margin. Basaltic magmatism produced by mantle decompression melting provided heat for extracting melts from the middle or lower crust. Continual addition of mafic magmas to the base of the subcontinental lithosphere, in a back-arc setting, remelted calc-alkaline rocks enriched in metals that were stored in the crust.The St. Francois Mountains terrane is adjacent to the regional TDM line (defined at a value of 1.55 Ga) that separates ~1600 Ma basement to the west, from younger basements to the east. Data for Pea Ridge straddle the TDM values proposed for the line. The Sm-Nd isotope system has been closed since formation of the deposit and the original igneous signatures have not been affected by cycles of alteration or superimposed mineralizing events. No evidence exists for externally derived Nd or Sm. The source region for metals within the Pea Ridge deposit had a moderate compositional variation and the REE-rich breccias and mineralized rocks are generally isotopically homogeneous. The Pea Ridge deposit thus constitutes a distinctive isotopic target for use as a model in identifying other mineralized systems that may share the same metal source in the St. Francois Mountains terrane and elsewhere in the eastern Granite-Rhyolite province.

Spectroscopic geochemical study of vanadiferous marine sediments of the Gibellini claims, southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.

1981-01-01

Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.

A Gradient in Cooling Rate Beneath the Moho at the Oman Ophiolite: Fresh Insights into Cooling Processes at Mid-Ocean Ridges from REE-Based Thermometry

NASA Astrophysics Data System (ADS)

Dygert, N. J.; Kelemen, P. B.; Liang, Y.

2015-12-01

The Wadi Tayin massif in the southern Oman ophiolite has a more than 10 km thick mantle section and is believed to have formed in a mid-ocean ridge like environment with an intermediate to fast spreading rate. Previously, [1] used major element geothermometers to investigate spatial variations in temperatures recorded in mantle peridotites and observed that samples near the paleo-Moho have higher closure temperatures than samples at the base of the mantle section. Motivated by these observations, we measured major and trace elements in orthopyroxene and clinopyroxene in peridotites from depths of ~1-8km beneath the Moho to determine closure temperatures of REE in the samples using the REE-in-two-pyroxene thermometer [2]. Clinopyroxene are depleted in LREE and have REE concentrations that vary depending on distance from the Moho. Samples nearer the Moho have lower REE concentrations than those deeper in the section (e.g., chondrite normalized Yb ranges from ~1.5 at the Moho to 4 at 8km depth), consistent with near fractional melting along a mantle adiabat. Orthopyroxene are highly depleted in LREE but measurements of middle to heavy REE have good reproducibility. We find that REE-in-two-pyroxene temperatures decrease with increasing distance from the Moho, ranging from 1325±10°C near the Moho to 1063±24°C near the base of the mantle section. Using methods from [3], we calculate cooling rates of >1000°C/Myr near the Moho, dropping to rates of <10°C/Myr at the bottom of the section. The faster cooling rate is inconsistent with conductive cooling models. Fast cooling of the mantle lithosphere could be facilitated by infiltration of seawater to or beneath the petrologic Moho. This can explain why abyssal peridotites from ultra-slow spreading centers (which lack a crustal section) have cooling rates comparable to those of Oman peridotites [3]. [1] Hanghøj et al. (2010), JPet 51(1-2), 201-227. [2] Liang et al. (2013), GCA 102, 246-260. [3] Dygert & Liang (2015), EPSL 420, 151-161.

Trace Elements and Oxygen Isotope Zoning of the Sidewinder Skarn

NASA Astrophysics Data System (ADS)

Draper, C.; Gevedon, M. L.; Barnes, J.; Lackey, J. S.; Jiang, H.; Lee, C. T.

2016-12-01

Skarns of the Verde Antique Quarry and White Horse Mountain areas of the Sidewinder Range give insight into the paleohydrothermal systems operating in the California's Jurassic arc in the Southwestern Mojave Desert. Garnet from these skarns is iron rich: Xand= 55-100. Laser fluorination measurements show oxygen isotope (δ18O) compositions of garnet crystals and crystals domains have large ranges: -3.1‰ to +4.4‰ and -8.9‰ to +3.4‰, respectively. In general, the garnet cores have more negative δ18O values than rims, although oscillations are present. Negative values have been interpreted as influx of meteoric fluid and positive values as increased magmatic input. Here we report major and trace element concentrations for 17 core to rim Sidewinder garnet transects. REEs concentrations are low in all crystals, with total REE concentrations ranging from 0.710 ppm to 33.7 ppm, values that are lower than Cretaceous skarn garnets in the Sierra Nevada in the White Chief and Empire Mt skarns. Such low concentrations are likely due to the higher fraction of meteoric fluids during formation of the Sidewinder skarns. REE concentrations decrease from core to rim (REE core average=12.2ppm, REE rim average=7.21ppm). This is slightly more pronounced in the LREEs than in the HREEs (LaN/YbN core average= 10.9; rim average= 9.73, normalized to Chondrite). X­and tends to decrease core to rim in the Verde Antique skarn, whereas, Xand of the White Horse skarn does not correlate with distance from core. A large positive Eu anomaly (Eu/Eu* = 3­-30) in garnet from both skarns suggests oxidizing fluid conditions. Oxygen isotope data from garnet in these same skarns show periods of time with increased proportion of magmatic derived fluids in the total fluid budget. However, there is no corresponding widespread increase in total REE concentrations. Other studies of skarns from the western Sierra Nevadan arc (White Chief and Empire Mountain) observe complete decoupling of d18O values and trace element compositions. Future modeling should consider modal abundance of fluid soluble minerals in cooling and altering plutons to probe the REE budget.

Micro/Nano-pore Network Analysis of Gas Flow in Shale Matrix

PubMed Central

Zhang, Pengwei; Hu, Liming; Meegoda, Jay N.; Gao, Shengyan

2015-01-01

The gas flow in shale matrix is of great research interests for optimized shale gas extraction. The gas flow in the nano-scale pore may fall in flow regimes such as viscous flow, slip flow and Knudsen diffusion. A 3-dimensional nano-scale pore network model was developed to simulate dynamic gas flow, and to describe the transient properties of flow regimes. The proposed pore network model accounts for the various size distributions and low connectivity of shale pores. The pore size, pore throat size and coordination number obey normal distribution, and the average values can be obtained from shale reservoir data. The gas flow regimes were simulated using an extracted pore network backbone. The numerical results show that apparent permeability is strongly dependent on pore pressure in the reservoir and pore throat size, which is overestimated by low-pressure laboratory tests. With the decrease of reservoir pressure, viscous flow is weakening, then slip flow and Knudsen diffusion are gradually becoming dominant flow regimes. The fingering phenomenon can be predicted by micro/nano-pore network for gas flow, which provides an effective way to capture heterogeneity of shale gas reservoir. PMID:26310236

Micro/Nano-pore Network Analysis of Gas Flow in Shale Matrix.

PubMed

Zhang, Pengwei; Hu, Liming; Meegoda, Jay N; Gao, Shengyan

2015-08-27

The gas flow in shale matrix is of great research interests for optimized shale gas extraction. The gas flow in the nano-scale pore may fall in flow regimes such as viscous flow, slip flow and Knudsen diffusion. A 3-dimensional nano-scale pore network model was developed to simulate dynamic gas flow, and to describe the transient properties of flow regimes. The proposed pore network model accounts for the various size distributions and low connectivity of shale pores. The pore size, pore throat size and coordination number obey normal distribution, and the average values can be obtained from shale reservoir data. The gas flow regimes were simulated using an extracted pore network backbone. The numerical results show that apparent permeability is strongly dependent on pore pressure in the reservoir and pore throat size, which is overestimated by low-pressure laboratory tests. With the decrease of reservoir pressure, viscous flow is weakening, then slip flow and Knudsen diffusion are gradually becoming dominant flow regimes. The fingering phenomenon can be predicted by micro/nano-pore network for gas flow, which provides an effective way to capture heterogeneity of shale gas reservoir.

Detachments in Shale: Controlling Characteristics on Fold-Thrust Belt Style

NASA Astrophysics Data System (ADS)

Hansberry, Rowan; King, Ros; Collins, Alan; Morley, Chris

2013-04-01

Fold-thrust belts occur across multiple tectonic settings where thin-skinned deformation is accommodated by one or more detachment zones, both basal and within the fold-thrust belt. These fold-thrust belts exhibit considerable variation in structural style and vergence depending on the characteristics (e.g. strength, thickness, and lithology) and number of detachment zones. Shale as a detachment lithology is intrinsically weaker than more competent silts and sands; however, it can be further weakened by high pore pressures, reducing resistance to sliding and; high temperatures, altering the rheology of the detachment. Despite the implications for petroleum exploration and natural hazard assessment the precise nature by which detachments in shale control and are involved in deformation in fold-thrust belts is poorly understood. Present-day active basal detachment zones are usually located in inaccessible submarine regions. Therefore, this project employs field observations and sample analysis of ancient, exhumed analogues to document the nature of shale detachments (e.g. thickness, lithology, dip and dip direction, deformational temperature and thrust propagation rates) at field sites in Thailand, Norway and New Zealand. X-ray diffraction analysis of illite crystallinity and oxygen stable isotopes analysis are used as a proxy for deformational temperature whilst electron-backscatter diffraction analysis is used to constrain microstructural deformational patterns. K-Ar dating of synkinematic clay fault gouges is being applied to date the final stages of activity on individual faults with a view to constraining thrust activation sequences. It is not possible to directly measure palaeo-data for some key detachment parameters, such as pore pressure and coefficients of friction. However, the use of critical taper wedge theory has been used to successfully infer internal and basal coefficients of friction and depth-normalized pore pressure within a wedge and at its base (e.g. Platt, 1986; Bilotti and Shaw, 2005; Morley, 2007). Therefore, through a mixture of field observations, sample analysis and theoretical analysis it will be possible to determine a full range of shale detachment parameters and their impact on the structural style of fold-thrust belts across a variety of settings. Recent work in Muak Lek, central Thailand has focused on a structural investigation of fold-thrust belt deformation of a passive margin sequence as a result of continent-continent collision during the Triassic Indosinian Orogeny. Exceptional outcropping of the detachment lithology is accessible in the Siam City Cement quarry allowing construction of sections detailing the deformational style across the detachment itself. The detachment forms complex, 3-dimensional duplex-like structures creating egg-carton geometries enveloping foliation surfaces in the zones of most intense strain. Up section strain decreases to discrete thrust imbricates of decametre scale. Samples of limestone and secondary calcite were collected through the sections for oxygen stable isotopes analysis which show a distinct pattern of isotopic fractionation across the main thrust and into the detachment. Results from this study give insights into the nature of shale detachments and the control on fold-thrust belt development.

Application of unsupervised pattern recognition approaches for exploration of rare earth elements in Se-Chahun iron ore, central Iran

NASA Astrophysics Data System (ADS)

Sarparandeh, Mohammadali; Hezarkhani, Ardeshir

2017-12-01

The use of efficient methods for data processing has always been of interest to researchers in the field of earth sciences. Pattern recognition techniques are appropriate methods for high-dimensional data such as geochemical data. Evaluation of the geochemical distribution of rare earth elements (REEs) requires the use of such methods. In particular, the multivariate nature of REE data makes them a good target for numerical analysis. The main subject of this paper is application of unsupervised pattern recognition approaches in evaluating geochemical distribution of REEs in the Kiruna type magnetite-apatite deposit of Se-Chahun. For this purpose, 42 bulk lithology samples were collected from the Se-Chahun iron ore deposit. In this study, 14 rare earth elements were measured with inductively coupled plasma mass spectrometry (ICP-MS). Pattern recognition makes it possible to evaluate the relations between the samples based on all these 14 features, simultaneously. In addition to providing easy solutions, discovery of the hidden information and relations of data samples is the advantage of these methods. Therefore, four clustering methods (unsupervised pattern recognition) - including a modified basic sequential algorithmic scheme (MBSAS), hierarchical (agglomerative) clustering, k-means clustering and self-organizing map (SOM) - were applied and results were evaluated using the silhouette criterion. Samples were clustered in four types. Finally, the results of this study were validated with geological facts and analysis results from, for example, scanning electron microscopy (SEM), X-ray diffraction (XRD), ICP-MS and optical mineralogy. The results of the k-means clustering and SOM methods have the best matches with reality, with experimental studies of samples and with field surveys. Since only the rare earth elements are used in this division, a good agreement of the results with lithology is considerable. It is concluded that the combination of the proposed methods and geological studies leads to finding some hidden information, and this approach has the best results compared to using only one of them.

Shale Gas Exploration and Exploitation Induced Risks - SHEER

NASA Astrophysics Data System (ADS)

Capuano, Paolo; Orlecka-Sikora, Beata; Lasocki, Stanislaw; Cesca, Simone; Gunning, Andrew; jaroslawsky, Janusz; Garcia-Aristizabal, Alexander; Westwood, Rachel; Gasparini, Paolo

2017-04-01

Shale gas operations may affect the quality of air, water and landscapes; furthermore, it can induce seismic activity, with the possible impacts on the surrounding infrastructure. The SHEER project aims at setting up a probabilistic methodology to assess and mitigate the short and the long term environmental risks connected to the exploration and exploitation of shale gas. In particular we are investigating risks associated with groundwater contamination, air pollution and induced seismicity. A shale gas test site located in Poland (Wysin) has been monitored before, during and after the fracking operations with the aim of assessing environmental risks connected with groundwater contamination, air pollution and earthquakes induced by fracking and injection of waste water. The severity of each of these hazards depends strongly on the unexpected enhanced permeability pattern, which may develop as an unwanted by-product of the fracking processes and may become pathway for gas and fluid migration towards underground water reservoirs or the surface. The project is devoted to monitor and understand how far this enhanced permeability pattern develops both in space and time. The considered hazards may be at least partially inter-related as they all depend on this enhanced permeability pattern. Therefore they are being approached from a multi-hazard, multi parameter perspective. We expect to develop methodologies and procedures to track and model fracture evolution around shale gas exploitation sites and a robust statistically based, multi-parameter methodology to assess environmental impacts and risks across the operational lifecycle of shale gas. The developed methodologies are going to be applied and tested on a comprehensive database consisting of seismicity, changes of the quality of ground-waters and air, ground deformations, and operational data collected from the ongoing monitoring episode (Wysin) and past episodes: Lubocino (Poland), Preese Hall (UK), Oklahoma (USA), Groningen Field (Netherlands), Gross Schönebeck (Germany), The Geysers (USA), Cooper Basin(Australia). Best practices to be applied in Europe to monitor and minimize any environmental impacts will be worked out with the involvement of governmental decisional bodies, private industries and experts This work was supported under SHEER: "Shale Gas Exploration and Exploitation Induced Risks" project n.640896, funded from Horizon 2020 - R&I Framework Programme, call H2020-LCE-2014-1

Partial melting under conditions of filter pressing: field and geochemical evidence from the migmatites of NE Minnesota

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheehan, T.J.; Bauer, R.L.; Nabelek, P.I.

1985-01-01

Amphibolite-grade Archean migmatites in the southern Vermilion Granitic Complex with well-defined paleosome-melanosome and melanosome-leucosome boundaries and with exceptionally wide melanosomes (on the order of centimeters) were studied to elucidate granite-forming processes during high-grade metamorphism. Metagreywacke paleosomes containing 50% plag, 28% qtz, 20% biot and minor hbld, and apat, have (Ce/Yb)/sub N/ = 13.5 to 21 with 650-960 ppm Ba, 42-110 ppm Rb, and 982-1159 ppm Sr. Melanosomes containing 45% plag, 35% biot, 20% hbld and minor qtz and apat, have (Ce/Yb)/sub N/ = 6.8 to 9.3 and have 950-1750 ppm Ba, 41-194 ppm Rb, and 1020-1926 ppm Sr. Leucosomes containingmore » 82% plag, 13% qtz, 5% biot and minor hbld and apat, have overall depleted REE patterns with positive Eu anomalies and 460-750 ppm Ba, 41-43 ppm Rb, and 1876-2106 ppm Sr, suggesting cumulate plagioclase. Mass balance calculations preclude formation of the melanosome from mixing the paleosomes and leucosomes. However, major and trace element modeling suggest that the leucosome formed by in situ partial melting followed by fractional crystallization and filter pressing which resulted in the removal of the residual liquid. Model REE patterns for the melt drive off by this process are REE enriched with a negative Eu anomaly. Such patterns which have been found in some low Sr granites are difficult to produce by simple belting models. Partial melting under conditions of tectonic stress may thus provide an explanation for such granites.« less

High-Mg subduction-related Tertiary basalts in Sardinia, Italy

NASA Astrophysics Data System (ADS)

Morra, V.; Secchi, F. A. G.; Melluso, L.; Franciosi, L.

1997-03-01

The Oligo-Miocene volcanics (32-15 Ma), which occur in the Oligo-Miocene Sardinian Rift, were interpreted in the literature as an intracontinental volcanic arc built upon continental crust about 30 km thick. They are characterized by a close field association of dominantly andesites and acid ignimbrites, with subordinate basalts. In this paper we deal with the origin and evolution of recently discovered high-magnesia basalts aged ca. 18 Ma occurring in the Montresta area, northern Sardinia, relevant to the petrogenesis of the Cenozoic volcanics of Sardinia. The igneous rocks of the Montresta area form a tholeiitic, subduction-related suite. Major-element variation from the high-magnesia basalts (HMB) to high-alumina basalts (HAB) are consistent with crystal/liquid fractionation dominated by olivine and clinopyroxene. Proportions of plagioclase and titanomagnetite increase from HAB to andesites. Initial {87Sr }/{86Sr } ratios increase with differentiation from 0.70398 for the HMB to 0.70592 for the andesites. This suggests concomitant crustal contamination. The geochemical characteristics of the high-magnesia basalts are typical of subduction-related magmas, with negative Nb, Zr and Ti spikes in mantle-normalized diagrams. It is proposed that these high-magnesia basalts were produced by partial melting of a mantle source characterized by large-ion lithophile elements (LILE) enrichment related principally to dehydration of subducted oceanic crust. Chondrite-normalized rare earth elements (REE) patterns indicate that the lavas are somewhat enriched in light rare earth elements (LREE), with flat heavy rare earth elements (HREE) patterns. This evidence is consistent with a spinel-bearing mantle source. The sub-parallel chondrite-normalized patterns show enrichment with differentiation, with a greater increase of LREE than HREE. The occurrence of high-magnesia basalts at 18 Ma in Sardinia appears to be correlated with and favoured by pronounced extensional tectonics at that time.

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

NASA Astrophysics Data System (ADS)

Thomas, J. B.; Bodnar, R. J.; Shimizu, N.; Sinha, A. K.

2002-09-01

Partition coefficients ( zircon/meltD M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques. D REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce 4+ in the melt results in elevated D Ce compared to neighboring REE due to the similar valence and size of Ce 4+ and Zr 4+. Predicted zircon/meltD values for Ce 4+ and Ce 3+ indicate that the Ce 4+/Ce 3+ ratios of the melt ranged from about 10 -3 to 10 -2. Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D M < 1.0), and Ti, Y and Nb showing compatible behavior (D M > 1.0). The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D Yb from this study. Using D Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.

Rare Mineralogy in Alkaline Ultramafic Rocks, Western Kentucky Fluorspar District

NASA Astrophysics Data System (ADS)

Anderson, W.

2017-12-01

The alkaline ultramafic intrusive dike complex in the Western Kentucky Fluorspar District contains unusual mineralogy that was derived from mantle magma sources. Lamprophyre and peridotite petrologic types occur in the district where altered fractionated peridotites are enriched in Rare Earth Elements (REE) and some lamprophyre facies are depleted in incompatible elements. Unusual minerals in dikes, determined by petrography and X-ray diffraction, include schorlomite and andradite titanium garnets, astrophyllite, spodumene, niobium rutile, wüstite, fluoro-tetraferriphlogopite, villiaumite, molybdenite, and fluocerite, a REE-bearing fluoride fluorescent mineral. Mixing of MVT sphalerite ore fluids accompanies a mid-stage igneous alteration and intrusion event consistent with paragenetic studies. The presence of lithium in the spodumene and fluoro-tetraferriphlogopite suggests a lithium phase in the mineral fluids, and the presence of enriched REE in dikes and fluorite mineralization suggest a metasomatic event. Several of these rare minerals have never been described in the fluorspar district, and their occurrence suggests deep mantle metasomatism. Several REE-bearing fluoride minerals occur in the dikes and in other worldwide occurrences, they are usually associated with nepheline syenite and carbonatite differentiates. There is an early and late stage fluoride mineralization, which accompanied dike intrusion and was also analyzed for REE content. One fluorite group is enriched in LREE and another in MREE, which suggests a bimodal or periodic fluorite emplacement. Whole-rock elemental analysis was chondrite normalized and indicates that some of the dikes are slightly enriched in light REE and show a classic fractionation enrichment. Variations in major-element content; high titanium, niobium, and zirconium values; and high La/Yb, Zr/Y, Zr/Hf, and Nb/Ta ratios suggest metasomatized lithospheric-asthenospheric mantle-sourced intrusions. The high La/Yb ratios in some dikes in the titanium garnet facies suggest a magma melt trend toward the carbonation phase of a fractionated peridotite parent magma.

Hydraulic fracturing offers view of microbial life in the deep terrestrial subsurface.

PubMed

Mouser, Paula J; Borton, Mikayla; Darrah, Thomas H; Hartsock, Angela; Wrighton, Kelly C

2016-11-01

Horizontal drilling and hydraulic fracturing are increasingly used for recovering energy resources in black shales across the globe. Although newly drilled wells are providing access to rocks and fluids from kilometer depths to study the deep biosphere, we have much to learn about microbial ecology of shales before and after 'fracking'. Recent studies provide a framework for considering how engineering activities alter this rock-hosted ecosystem. We first provide data on the geochemical environment and microbial habitability in pristine shales. Next, we summarize data showing the same pattern across fractured shales: diverse assemblages of microbes are introduced into the subsurface, eventually converging to a low diversity, halotolerant, bacterial and archaeal community. Data we synthesized show that the shale microbial community predictably shifts in response to temporal changes in geochemistry, favoring conservation of key microorganisms regardless of inputs, shale location or operators. We identified factors that constrain diversity in the shale and inhibit biodegradation at the surface, including salinity, biocides, substrates and redox. Continued research in this engineered ecosystem is required to assess additive biodegradability, quantify infrastructure biocorrosion, treat wastewaters that return to the surface and potentially enhance energy production through in situ methanogenesis. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Conservatism of Late Pennsylvanian vegetational patterns during short-term cyclic and long-term directional environmental change, western equatorial Pangea.

PubMed

Tabor, Neil J; Romanchock, Charles M; Looy, Cynthia V; Hotton, Carol L; Dimichele, William A; Chaney, Dan S

2013-09-19

Patterns of plant distribution by palaeoenvironment were examined across the Pennsylvanian-Permian transition in North-Central Texas. Stratigraphically recurrent packages of distinct lithofacies, representing different habitats, contain qualitatively and quantitatively different macrofloras and microfloras. The species pools demonstrate niche conservatism, remaining closely tied to specific habitats, during both short-term cyclic environmental change and a long-term trend of increasing aridity. The deposits examined principally comprise the terrestrial Markley and its approximate marine equivalent, the Harpersville Formation and parts of lower Archer City Formation. Fossiliferous deposits are lens-like, likely representing fill sequences of channels formed during abandonment phases. Palaeosols, represented by blocky mudstones, comprise a large fraction of the deposits. They suggest progressive climate change from minimally seasonal humid to seasonal subhumid to seasonal dry subhumid. Five lithofacies yielded plants: kaolinite-dominated siltstone, organic shale, mudstone beds within organic shale, coarsening upward mudstone-sandstone interbeds and channel sandstone. Both macro- and microflora were examined. Lithofacies proved compositionally distinct, with different patterns of dominance diversity. Organic shales (swamp deposits), mudstone partings (swamp drainages) and coarsening upward mudstone-sandstone interbeds (floodplains) typically contain Pennsylvanian wetland vegetation. Kaolinite-dominated siltstones and (to the extent known) sandstones contain taxa indicative of seasonally dry substrates. Some kaolinite-dominated siltstones and organic shales/coals yielded palynomorphs. Microfloras are more diverse, with greater wetland-dryland overlap than macrofloras. It appears that these two floras were coexistent at times on the regional landscape.

Conservatism of Late Pennsylvanian vegetational patterns during short-term cyclic and long-term directional environmental change, western equatorial Pangea

PubMed Central

TABOR, NEIL J.; ROMANCHOCK, CHARLES M.; LOOY, CYNTHIA V.; HOTTON, CAROL L.; DIMICHELE, WILLIAM A.; CHANEY, DAN S.

2014-01-01

Patterns of plant distribution by palaeoenvironment were examined across the Pennsylvanian–Permian transition in North–Central Texas. Stratigraphically recurrent packages of distinct lithofacies, representing different habitats, contain qualitatively and quantitatively different macrofloras and microfloras. The species pools demonstrate niche conservatism, remaining closely tied to specific habitats, during both short-term cyclic environmental change and a long-term trend of increasing aridity. The deposits examined principally comprise the terrestrial Markley and its approximate marine equivalent, the Harpersville Formation and parts of lower Archer City Formation. Fossiliferous deposits are lens-like, likely representing fill sequences of channels formed during abandonment phases. Palaeosols, represented by blocky mudstones, comprise a large fraction of the deposits. They suggest progressive climate change from minimally seasonal humid to seasonal subhumid to seasonal dry subhumid. Five lithofacies yielded plants: kaolinite-dominated siltstone, organic shale, mudstone beds within organic shale, coarsening upward mudstone–sandstone interbeds and channel sandstone. Both macro- and microflora were examined. Lithofacies proved compositionally distinct, with different patterns of dominance diversity. Organic shales (swamp deposits), mudstone partings (swamp drainages) and coarsening upward mudstone–sandstone interbeds (floodplains) typically contain Pennsylvanian wetland vegetation. Kaolinite-dominated siltstones and (to the extent known) sandstones contain taxa indicative of seasonally dry substrates. Some kaolinite-dominated siltstones and organic shales/coals yielded palynomorphs. Microfloras are more diverse, with greater wetland–dryland overlap than macrofloras. It appears that these two floras were coexistent at times on the regional landscape. PMID:25339793

High-resolution seismic reflection to delineate shallow gas in Eastern Kansas

USGS Publications Warehouse

Miller, R.D.; Watney, W.L.; Begay, D.K.; Xia, J.

2000-01-01

Unique amplitude characteristics of shallow gas sands within Pennsylvanian clastic-carbonate dominated sequences are discernible on high-resolution seismic reflection data in eastern Kansas. Upward grading sequences of sand into shale represent a potential gas reservoir with a low-impedence acoustic contrast at the base of the encasing layer. The gas sand and encasing shale, which define the gas reservoir studied here, are part of an erosional incised valley where about 30 m of carbonates and shale have been replaced by sandstone and shale confined to the incised valley. These consolidated geologic settings would normally possess high impedence gas sand reservoirs as defined by abrupt contacts between the gas sand and encasing shale. Based orr core and borehole logs, the gas sand studied here grades from sand into shale in a fashion analogous to that observed in classic low-impedance environments. Amplitude and phase characteristics of high-resolution seismic data across this approximately 400-m wide gas sand are indicative of a low-impedance reservoir. Shot gathers possess classic amplitude with offsett-dependent characteristics which are manifeted on the stacked section as "bright spots." Dominant Frequencies of around 120 Hz allow detection of several reflectors within the 30+ meters of sand/shale that make up this localized gas-rich incised valley fill. The gradational nature of the trapping mechanism observed in this gas reservoir would make detection with conventional seismic reflection methods unlikely.

Dissolved Rare Earth Elements in the US GEOTRACES North Atlantic Section

NASA Astrophysics Data System (ADS)

Shiller, A. M.

2016-12-01

The rare earth elements (REEs) are a unique chemical set wherein there are systematic changes in geochemical behavior across the series. Furthermore, while most REEs are in the +III oxidation state, Ce and Eu can be in other oxidation states leading to distinct characteristics of those elements. Thus, the geochemical properties of the REEs make them particularly useful tools for inquiring into various geochemical processes. As part of the US GEOTRACES effort, we determined dissolved REEs and Y at 32 stations across the North Atlantic during US cruises GT10 and GT11 along a meridional transect from Lisbon to the Cape Verde Islands and a zonal transect from Cape Cod to the Mauritanian coast. While profiles are similar to previous reports, the high spatial resolution of the section allows for better elucidation of processes. Light rare earths (LREEs) show removal in the upper water column with a minimum at the chlorophyll maximum. LREE concentrations then increase into the oxygen minimum followed by a slight decrease and fairly constant concentrations in the mid-water column followed by an increase into the deep and bottom waters. Heavy rare earths (HREEs) show a more monotonic increase with depth. We also take advantage of a previously published water mass analysis for the section to estimate that most of the deep water changes can be explained by conservative mixing of waters with different pre-formed REE concentrations. Nonetheless, the pattern of LREE shallow water removal followed by regeneration, possible re-scavenging, and then deep water input is still preserved. Other features of note include an increase in LREEs in the strong oxygen minimum zone off Mauritania, consistent with an association of REE cycling with the redox cycles of Fe and Mn. Also along the eastern margin, but below the oxygen minimum, a small but distinct increase in the cerium and europium anomalies is observed, consistent with terrigenous input. In hydrothermally influenced waters along the mid-Atlantic Ridge, there are increases in Ce/Ce*, Eu/Eu*, and Y/Ho but a decrease in Nd/Yb and in REE concentrations. Surface water distributions are more consistent with elements influenced by margin inputs than with atmospheric input.

The obesity of patients with Laron Syndrome is not associated with excessive nutritional intake.

PubMed

Ginsberg, Shira; Laron, Zvi; Bed, Mira Arbiv; Vaisman, Nachum

2009-03-01

To study the metabolic parameters which may affect the excessive weight of treated and untreated patients with Laron Syndrome. Body composition, daily caloric intake and resting energy expenditure (REE), when possible, were measured for each patient. Caloric intake was calculated based on 7-day food records, REE was measured by indirect calorimetry and body composition was determined by dual energy X-ray absorptiometry (DEXA). Nine untreated adult subjects with Laron Syndrome (6 female subjects, 3 male subjects) aged 28-53 years and 4 girls with Laron Syndrome treated by insulin-like growth factor-I (IGF-I) 120-150 μg/kg/d were included in the study. Patients with Laron Syndrome have an abnormally high body fat (BF) mass (54 ± 10% of body weight) and a relatively low lean body mass (LBM) compared to a healthy normal population. Energy intake varied but in most of the patients was not significantly higher than the measured REE. The REE corrected for LBM was higher than expected, based on our norms for healthy adults. The mean distribution of energy sources in the food was 47% carbohydrates, 17% protein and 36% fat. The severe obesity of patients with Laron Syndrome is not due to hyperphagia or hypometabolism. © 2009 Asian Oceanian Association for the Study of Obesity . Published by Elsevier Ltd. All rights reserved.

Heterogeneity in a room-temperature ionic liquid: persistent local environments and the red-edge effect.

PubMed

Hu, Zhonghan; Margulis, Claudio J

2006-01-24

In this work, we investigate the slow dynamics of 1-butyl-3-methylimidazolium hexafluorophosphate, a very popular room-temperature ionic solvent. Our study predicts the existence of heterogeneity in the liquid and shows that this heterogeneity is the underlying microscopic cause for the recently reported "red-edge effect" (REE) observed in the study of fluorescence of the organic probe 2-amino-7-nitrofluorene. This theoretical work explains in microscopic terms the relation between REE and dynamic heterogeneity in a room-temperature ionic liquid (IL). The REE is typical of micellar or colloidal systems, which are characterized by microscopic environments that are structurally very different. In contrast, in the case of this room-temperature IL, the REE occurs because of the long period during which molecules are trapped in quasistatic local solvent cages. This trapping time, which is longer than the lifetime of the excited-state probe, together with the inability of the surroundings to adiabatically relax, induces a set of site-specific spectroscopic responses. Subensembles of fluorescent molecules associated with particular local environments absorb and emit at different frequencies. We describe in detail the absorption wavelength-dependent emission spectra of 2-amino-7-nitrofluorene and show that this dependence on lambda(ex) is characteristic of the IL and, as is to be expected, is absent in the case of a normal solvent such as methanol.

Accumulation and fractionation of rare earth elements (REEs) in the naturally grown Phytolacca americana L. in southern China.

PubMed

Yuan, Ming; Liu, Chang; Liu, Wen-Shen; Guo, Mei-Na; Morel, Jean Louis; Huot, Hermine; Yu, Hong-Jie; Tang, Ye-Tao; Qiu, Rong-Liang

2018-04-16

The widespread use of rare earth elements (REEs) has resulted in problems for soil and human health. Phytolacca americana L. is a herbaceous plant widely distributed in Dingnan county of Jiangxi province, China, which is a REE mining region (ion absorption rare earth mine) and the soil has high levels of REEs. An investigation of REE content of P. americana growing naturally in Dingnan county was conducted. REE concentrations in the roots, stems, and leaves of P. americana and in their rhizospheric soils were determined. Results showed that plant REEs concentrations varied among the sampling sites and can reach 1040 mg/kg in the leaves. Plant REEs concentrations decreased in the order of leaf > root > stem and all tissues were characterized by a light REE enrichment and a heavy REE depletion. However, P. americana exhibited preferential accumulation of light REEs during the absorption process (from soil to root) and preferential accumulation of heavy REEs during the translocation process (from stem to leaf). The ability of P. americana to accumulate high REEs in the shoot makes it a potential candidate for understanding the absorption mechanisms of REEs and for the phytoremediation of REEs contaminated soil.

Experimental evidence for mobility of Zr and other trace elements in soils

NASA Astrophysics Data System (ADS)

Hodson, Mark E.

2002-03-01

A Soxhlet extraction was carried out over a period of 27 d on a column comprising 3 cm of quartz overlain by 4 cm of soil from the B horizon and then 1 cm of soil from the A horizon of a granitic podzol. Major and trace elements were leached from the column and accumulated in a reservoir at the base of the column. Total loss of elements from the soil over the course of the experiment ranged from 0.002 to 1 wt% with major elements and the light and heavy rare earth elements (REE) showing the largest percentage losses. Zirconium (0.002%) and then Al (0.008%) showed the lowest percentage loss. The light REE were leached out of the soil preferentially to the mid REE. All elements showed accumulation, by a factor of 2 to 11, in the quartz layers at the base of the column, particularly in the upper first 1 cm of the quartz. Major elements were leached from the column at a rate of 0.02 to 0.59 μmol h-1 whereas Zr, Nd, Sm, Gd, Dy, Rb, and Sr were leached at the rate of 0.5 to 30 × 10-6 μmol h-1. Concentrations of other REE in the reservoir increased over the duration of the experiment, but they were poorly correlated with time, so leaching rates were not calculated. Normalization of the major element leaching rates to take into account the constant flushing of water through the column, the average annual rainfall in the Allt a'Mharcaidh catchment in Scotland from where the soil was sampled, and the cross-sectional area of the soil in the column, together with the temperature of the soil in the column (70°C) compared with the average annual temperature of the Allt a'Mharcaidh catchment (5.7°C), gave major element release rates from the soil of 0.002 to 0.97 mEq m-2 yr-1 (depending on the choice of Ea, the dissolution activation energy), which are generally less than those measured in the field of 0.1 to 40.9 mEq m-2 yr-1. Calculations showed that despite the redistribution and loss of Zr from the column, assumptions of Zr mobility would have had a negligible effect on calculated element release rates of Na, Ca, Fe, and Mg. However, significant underestimates of the release of K (5%), Ti (57%), Al (5%), and Si (10%) as well as some trace elements (e.g., Nd, 23%; Rb, 54%; Sr, 24%) would have occurred. Concentrations of Ca and Sr leached from the column correlated well (RSQ = 0.93, p < 0.01), supporting the idea of the use of Sr release as a proxy for Ca release in weathering rate calculations. The release rates and percentage loss of REE from the soil varied between elements indicating that REE distribution patterns of rocks and soils may not be preserved in drainage waters.

Fracture-permeability behavior of shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carey, J. William; Lei, Zhou; Rougier, Esteban

The fracture-permeability behavior of Utica shale, an important play for shale gas and oil, was investigated using a triaxial coreflood device and X-ray tomography in combination with finite-discrete element modeling (FDEM). Fractures generated in both compression and in a direct-shear configuration allowed permeability to be measured across the faces of cylindrical core. Shale with bedding planes perpendicular to direct-shear loading developed complex fracture networks and peak permeability of 30 mD that fell to 5 mD under hydrostatic conditions. Shale with bedding planes parallel to shear loading developed simple fractures with peak permeability as high as 900 mD. In addition tomore » the large anisotropy in fracture permeability, the amount of deformation required to initiate fractures was greater for perpendicular layering (about 1% versus 0.4%), and in both cases activation of existing fractures are more likely sources of permeability in shale gas plays or damaged caprock in CO₂ sequestration because of the significant deformation required to form new fracture networks. FDEM numerical simulations were able to replicate the main features of the fracturing processes while showing the importance of fluid penetration into fractures as well as layering in determining fracture patterns.« less

Fracture-permeability behavior of shale

DOE PAGES

Carey, J. William; Lei, Zhou; Rougier, Esteban; ...

2015-05-08

The fracture-permeability behavior of Utica shale, an important play for shale gas and oil, was investigated using a triaxial coreflood device and X-ray tomography in combination with finite-discrete element modeling (FDEM). Fractures generated in both compression and in a direct-shear configuration allowed permeability to be measured across the faces of cylindrical core. Shale with bedding planes perpendicular to direct-shear loading developed complex fracture networks and peak permeability of 30 mD that fell to 5 mD under hydrostatic conditions. Shale with bedding planes parallel to shear loading developed simple fractures with peak permeability as high as 900 mD. In addition tomore » the large anisotropy in fracture permeability, the amount of deformation required to initiate fractures was greater for perpendicular layering (about 1% versus 0.4%), and in both cases activation of existing fractures are more likely sources of permeability in shale gas plays or damaged caprock in CO₂ sequestration because of the significant deformation required to form new fracture networks. FDEM numerical simulations were able to replicate the main features of the fracturing processes while showing the importance of fluid penetration into fractures as well as layering in determining fracture patterns.« less

Zircon Trace Element Contents and Refined U-Pb Crystallization Ages for the Tatoosh Pluton, Mount Rainier National Park, Washington Cascades

NASA Astrophysics Data System (ADS)

Bacon, C. R.; Du Bray, E. A.; John, D. A.; Mazdab, F. K.; Wooden, J. L.

2008-12-01

The 7x12 km Tatoosh pluton south of Mount Rainier consists of 4 petrographic/compositional phases, here termed Nisqually, Reflection, Pyramid, and Stevens, that intrude Tertiary volcanic and sedimentary wall and roof rocks; contacts between the 4 intrusive units are rarely exposed. We used the USGS-Stanford SHRIMP- RG to analyze, in a continuous session, zircons from each of 6 quartz monzodiorite (qmd), quartz monzonite (qm), or granodiorite (grd) samples for 206Pb/238U ages and, concurrently, U, Th, Hf, and REE concentrations. A round-robin procedure yielded statistically robust geochronological results. Ages that we reported previously (FM07) were compromised by instrument instability and by calibration differences between analytical sessions. Between 11 and 31 new analyses of zircons from each sample were evaluated using the TuffZirc and Umix Ages routines of Isoplot 3.41 (Ludwig, 2003). TuffZirc solidification ages for the intrusions are: Nisqually grd (Paradise Valley; 65.4% SiO2) 17.29 +0.37/-0.24 Ma, Nisqually grd (Christine Falls; 66.4%) 17.70 +0.30/-0.16 Ma, Reflection qm (Pinnacle Peak trail; 66.6%) 18.38 +0.45/-0.28 Ma, Pyramid qmd (58.5%) 18.58 +0.20/-0.15 Ma, Stevens grd (Stevens Canyon; 67.8%) 19.15 +0.15/-0.12 Ma, and Stevens grd (south of Louise Lake; 69.3%) 19.20 +0.31/-0.26 Ma (U-Th initial-disequilibrium corrected, ±2σ). Precision of the U-Pb data limits rigorous identification of antecrysts to those with ages ~1 Myr > solidification ages. Antecryst ages that produce subsidiary modes in relative probability diagrams for the two Stevens samples give weighted mean values of 20.18 ±0.26 Ma and 20.07 ±0.18 Ma. Wide ranges in trace element concentrations and ratios indicate that many analyzed zircons grew in highly fractionated residual liquids in high-crystallinity environments. Concentrations of Th and U in Tatoosh zircons vary by two orders of magnitude, cores tend to have higher Th, U, and Th/U than rims, and overgrowths that fill reentrants have high U contents and low Th/U ratios. Chondrite-normalized REE patterns have familiar convex-up shapes with positive Ce and negative Eu anomalies: LaN = 0.03-6 (10 values >6 may reflect inclusions), YbN = 380-33,900, Ce/Ce* = 0.7-505, and Eu/Eu* = 0.06-1.25. Slopes of REE patterns increase subtly in the order Reflection < Pyramid ≤ Nisqually < Stevens. Fractionation of plagioclase + pyroxene and(or) amphibole + Fe-Ti oxide + apatite + zircon should produce relative-LREE- enriched successive liquids. Observed marginally steeper REE patterns (greater positive slopes) for rims, lower REE concentrations, and lower Th/U ratios may reflect co-precipitation of allanite ± thorite. Two parallel arrays in Eu/Eu* versus Hf, in which Eu/Eu* decreases as Hf increases, are consistent with growth of higher-Hf, lower-Eu/Eu* zircon from more evolved melts; separate arrays imply Nisqually and Pyramid + Reflection intrusions. Zircon Eu/Eu* and Hf in the Stevens granodiorite define one high-Eu/Eu* field and another similar to that for Pyramid and Reflection samples that imply more than one parental magma. The zircon ages indicate solidification in three episodes: Stevens ~19.2 Ma, Pyramid + Reflection ~18.5 Ma, and Nisqually ~17.5 Ma. An ~20.1 Ma stage is represented by antecrysts in Stevens samples. The source(s) of the pluton were active for at least ~2.7 Myr and major crystallization episodes were separated by intervals of 0.7-1.0 Myr.

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

NASA Technical Reports Server (NTRS)

Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

2016-01-01

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately -5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

Petrophysical Properties of Cody, Mowry, Shell Creek, and Thermopolis Shales, Bighorn Basin, Wyoming

NASA Astrophysics Data System (ADS)

Nelson, P. H.

2013-12-01

The petrophysical properties of four shale formations are documented from well-log responses in 23 wells in the Bighorn Basin in Wyoming. Depths of the examined shales range from 4,771 to 20,594 ft. The four formations are the Thermopolis Shale (T), the Shell Creek Shale (SC), the Mowry Shale (M), and the lower part of the Cody Shale (C), all of Cretaceous age. These four shales lie within a 4,000-ft, moderately overpressured, gas-rich vertical interval in which the sonic velocity of most rocks is less than that of an interpolated trendline representing a normal increase of velocity with depth. Sonic velocity, resistivity, neutron, caliper, and gamma-ray values were determined from well logs at discrete intervals in each of the four shales in 23 wells. Sonic velocity in all four shales increases with depth to a present-day depth of about 10,000 ft; below this depth, sonic velocity remains relatively unchanged. Velocity (V), resistivity (R), neutron porosity (N), and hole diameter (D) in the four shales vary such that: VM > VC > VSC > VT, RM > RC > RSC > RT, NT > NSC ≈ NC > NM, and DT > DC ≈ DSC > DM. These orderings can be partially understood on the basis of rock compositions. The Mowry Shale is highly siliceous and by inference comparatively low in clay content, resulting in high sonic velocity, high resistivity, low neutron porosity, and minimal borehole enlargement. The Thermopolis Shale, by contrast, is a black fissile shale with very little silt--its high clay content causes low velocity, low resistivity, high neutron response, and results in the greatest borehole enlargement. The properties of the Shell Creek and lower Cody Shales are intermediate to the Mowry and Thermopolis Shales. The sonic velocities of all four shales are less than that of an interpolated trendline that is tied to velocities in shales above and below the interval of moderate overpressure. The reduction in velocity varies among the four shales, such that the amount of offset (O) from the trendline is OT > OSC > OC > OM, that is, the velocity in the Mowry Shale is reduced the least and the velocity in the Thermopolis Shale is reduced the most. Velocity reductions are attributed to increases in pore pressure during burial, caused by the generation and retention of gas, with lithology playing a key role in the amount of reduction. Sonic velocity in the four shale units remains low to the present day, after uplift and erosion of as much as 6,500 ft in the deeper part of the basin and consequent possible reduction from maximum pore pressures reached when strata were more deeply buried. A model combining burial history, the decrease of effective stress with increasing pore pressure, and Bower's model for the dependence of sonic velocity on effective stress is proposed to explain the persistence of low velocity in shale units. Interruptions to compaction gradients associated with gas occurrences and overpressure are observed in correlative strata in other basins in Wyoming, so the general results for shales in the Bighorn Basin established in this paper should be applicable elsewhere.

Fluid driven fracture mechanics in highly anisotropic shale: a laboratory study with application to hydraulic fracturing

NASA Astrophysics Data System (ADS)

Gehne, Stephan; Benson, Philip; Koor, Nick; Enfield, Mark

2017-04-01

The finding of considerable volumes of hydrocarbon resources within tight sedimentary rock formations in the UK led to focused attention on the fundamental fracture properties of low permeability rock types and hydraulic fracturing. Despite much research in these fields, there remains a scarcity of available experimental data concerning the fracture mechanics of fluid driven fracturing and the fracture properties of anisotropic, low permeability rock types. In this study, hydraulic fracturing is simulated in a controlled laboratory environment to track fracture nucleation (location) and propagation (velocity) in space and time and assess how environmental factors and rock properties influence the fracture process and the developing fracture network. Here we report data on employing fluid overpressure to generate a permeable network of micro tensile fractures in a highly anisotropic shale ( 50% P-wave velocity anisotropy). Experiments are carried out in a triaxial deformation apparatus using cylindrical samples. The bedding planes are orientated either parallel or normal to the major principal stress direction (σ1). A newly developed technique, using a steel guide arrangement to direct pressurised fluid into a sealed section of an axially drilled conduit, allows the pore fluid to contact the rock directly and to initiate tensile fractures from the pre-defined zone inside the sample. Acoustic Emission location is used to record and map the nucleation and development of the micro-fracture network. Indirect tensile strength measurements at atmospheric pressure show a high tensile strength anisotropy ( 60%) of the shale. Depending on the relative bedding orientation within the stress field, we find that fluid induced fractures in the sample propagate in two of the three principal fracture orientations: Divider and Short-Transverse. The fracture progresses parallel to the bedding plane (Short-Transverse orientation) if the bedding plane is aligned (parallel) with the direction of σ1. Conversely, the crack plane develops perpendicular to the bedding plane, if the bedding plane is orientated normal to σ1. Fracture initiation pressures are higher in the Divider orientation ( 24MPa) than in the Short-Transverse orientation ( 14MPa) showing a tensile strength anisotropy ( 42%) comparable to ambient tensile strength results. We then use X-Ray Computed Tomography (CT) 3D-images to evaluate the evolved fracture network in terms of fracture pattern, aperture and post-test water permeability. For both fracture orientations, very fine, axial fractures evolve over the entire length of the sample. For the fracturing in the Divider orientation, it has been observed, that in some cases, secondary fractures are branching of the main fracture. Test data from fluid driven fracturing experiments suggest that fracture pattern, fracture propagation trajectories and fracturing fluid pressure (initiation and propagation pressure) are predominantly controlled by the interaction between the anisotropic mechanical properties of the shale and the anisotropic stress environment. The orientation of inherent rock anisotropy relative to the principal stress directions seems to be the main control on fracture orientation and required fracturing pressure.

Geochemistry, environmental and provenance study of the Middle Miocene Leitha limestones (Central Paratethys)

NASA Astrophysics Data System (ADS)

Ali, Ahmed; Wagreich, Michael

2017-06-01

Mineralogical, major, minor, REE and trace element analyses of rock samples were performed on Middle Miocene limestones (Leitha limestones, Badenian) collected from four localities from Austria (Mannersdorf, Wöllersdorf, Kummer and Rosenberg quarries) and the Fertőrákos quarry in Hungary. Impure to pure limestones (i.e. limited by Al2O3 contents above or below 0.43 wt. %) were tested to evaluate the applicability of various geochemical proxies and indices in regard to provenance and palaeoenvironmental interpretations. Pure and impure limestones from Mannersdorf and Wöllersdorf (southern Vienna Basin) show signs of detrital input (REEs = 27.6 ± 9.8 ppm, Ce anomaly = 0.95 ± 0.1 and the presence of quartz, muscovite and clay minerals in impure limestones) and diagenetic influence (low contents of, e.g., Sr = 221 ± 49 ppm, Na is not detected, Ba = 15.6 ± 8.8 ppm in pure limestones). Thus, in both limestones the reconstruction of original sedimentary palaeoenvironments by geochemistry is hampered. The Kummer and Fertőrákos (Eisenstadt-Sopron Basin) comprise pure limestones (e.g., averages Sr = 571 ± 139 ppm, Na = 213 ± 56 ppm, Ba = 21 ± 4 ppm, REEs = 16 ± 3 ppm and Ce anomaly = 0.62 ± 0.05 and composed predominantly of calcite) exhibiting negligible diagenesis. Deposition under a shallow-water, well oxygenated to intermittent dysoxic marine environment can be reconstructed. Pure to impure limestones at Rosenberg-Retznei (Styrian Basin) are affected to some extent by detrital input and volcano-siliciclastic admixture. The Leitha limestones at Rosenberg have the least diagenetic influence among the studied localities (i.e. averages Sr = 1271 ± 261 ppm, Na = 315 ± 195 ppm, Ba = 32 ± 15 ppm, REEs = 9.8 ± 4.2 ppm and Ce anomaly = 0.77 ± 0.1 and consist of calcite, minor dolomite and quartz). The siliciclastic sources are characterized by immobile elemental ratios (i.e. La/Sc and Th/Co) which apply not only for the siliciclastics, but also for marls and impure limestones. At Mannersdorf the detrital input source varies between intermediate to silicic igneous rocks, while in Kummer and Rosenberg the source is solely silicic igneous rocks. The Chemical Index of Alteration (CIA) is only applicable in the shale-contaminated impure limestones. CIA values of the Leitha limestones from Mannersdorf indicate a gradual transition from warm to temperate palaeoclimate within the limestone succession of the Badenian.

Shale gas activity and increased rates of sexually transmitted infections in Ohio, 2000-2016.

PubMed

Deziel, Nicole C; Humeau, Zoe; Elliott, Elise G; Warren, Joshua L; Niccolai, Linda M

2018-01-01

The growing shale gas ("fracking") industry depends on a mobile workforce, whose influx could have social impacts on host communities. Sexually transmitted infections (STIs) can increase through sexual mixing patterns associated with labor migration. No prior studies have quantified the relationship between shale gas activity and rates of three reportable STIs: chlamydia, gonorrhea, and syphilis. We conducted a longitudinal, ecologic study from 2000-2016 in Ohio, situated in a prolific shale gas region in the United States (US). Data on reported cases of chlamydia, gonorrhea, and syphilis by county and year were obtained from the Ohio Department of Health. All 88 counties were classified as none, low, and high shale gas activity in each year, using data from the Ohio Department of Natural Resources. Annual rate ratios (RR) and 95% confidence intervals (95% CIs) were calculated from mixed-effects Poisson regression models evaluating the relationship between shale gas activity and reported annual STI rates while adjusting for secular trends and potential confounders obtained from the US Census. Compared to counties with no shale gas activity, counties with high activity had 21% (RR = 1.21; 95%CI = 1.08-1.36) increased rates of chlamydia and 19% (RR = 1.27; 95%CI 0.98-1.44) increased rates of gonorrhea, respectively. No association was observed for syphilis. This first report of a link between shale gas activity and increased rates of both chlamydia and gonorrhea may inform local policies and community health efforts.

Factor Structure of the Air Force Officer Qualifying Test Form S: Analysis and Comparison with Previous Forms

DTIC Science & Technology

2008-10-01

training grades, and class rank (Carretta, in press; Carretta & Ree, 2003; Olea & Ree, 1994), and several non-aviation officer jobs (Arth, 1986...series of papers, Ree and colleagues ( Olea & Ree, 1994; Ree, Carretta, & Teachout, 1996; Ree, & Earles, 1991; Ree, Earles, & Teachout, 1994) showed...Report No. 4. Washington, DC: U.S. Government Printing Office. Olea , M. M., Ree, M. J. (1994). Predicting pilot and navigator criteria: Not much

Petrography and geochemistry of Jurassic sandstones from the Jhuran Formation of Jara dome, Kachchh basin, India: Implications for provenance and tectonic setting

NASA Astrophysics Data System (ADS)

Periasamy, V.; Venkateshwarlu, M.

2017-06-01

Sandstones of Jhuran Formation from Jara dome, western Kachchh, Gujarat, India were studied for major, trace and rare earth element (REE) geochemistry to deduce their paleo-weathering, tectonic setting, source rock characteristics and provenance. Petrographic analysis shows that sandstones are having quartz grains with minor amount of K-feldspar and lithic fragments in the modal ratio of Q 89:F 7:L 4. On the basis of geochemical results, sandstones are classified into arkose, sub-litharenite, wacke and quartz arenite. The corrected CIA values indicate that the weathering at source region was moderate to intense. The distribution of major and REE elements in the samples normalized to upper continental crust (UCC) and chondrite values indicate similar pattern of UCC. The tectonic discrimination diagram based on the elemental concentrations and elemental ratios of Fe2O3 + MgO vs. TiO2, SiO2 vs. log(K2O/Na2O), Sc/Cr vs. La/Y, Th-Sc-Zr/10, La-Th-Sc plots Jhuran Formation samples in continental rift and collision settings. The plots of Ni against TiO2, La/Sc vs. Th/Co and V-Ni-Th ∗10 reveals that the sediments of Jhuran Formation were derived from felsic rock sources. Additionally, the diagram of (Gd/Yb) N against Eu/Eu ∗ suggest the post-Archean provenance as source possibly Nagar Parkar complex for the studied samples.

Oil-source correlations between the Mississippian Heath Shales and the reservoired oils in the Pennsylvanian Tyler Sands, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, G.A.; Drozd, R.J.; Daniel, J.A.

The Mississippi Heath Formation exposed in Fergus County, central Montana, is comprised predominantly of nearshore, marine, black, calcareous shales and carbonates with minor anhydrite and coal beds. The black shales and limestones have been considered as sources for shale oil via Fischer Assay and pyrolysis analysis. These shales are potential source units for the oils reservoired in the overlying Pennsylvanian Tyler Formation sands located 50 mi (80 km) to the east of the Fergus County Heath sediment studied. Heath Formation rocks from core holes were selectively sampled in 2-ft increments and analyzed for their source rock characteristics. Analyses include percentmore » total organic carbon (%TOC), Rock-Eval pyrolysis, pyrolysis-gas chromatography, and characterization of the total soluble extracts using carbon isotopes and gas chromatography-mass Spectrometry. Results indicated that the Heath was an excellent potential source unit that contained oil-prone, organic-rich (maximum of 17.6% TOC), calcareous, black shale intervals. The Heath and Tyler formations also contained intervals dominated by gas-prone, organic-rich shales of terrestrial origin. Three oils from the Tyler Formation sands in Musselshell and Rosebud counties were characterized by similar methods as the extracts. The oils were normally mature, moderate API gravity, moderate sulfur, low asphaltene crudes. Oil to source correlations between the Heath shale extracts and the oils indicated the Heath was an excellent candidate source rock for the Tyler reservoired oils. Conclusions were based on excellent matches between the carbon isotopes of the oils and the kerogen-kerogen pyrolyzates, and from the biomarkers.« less

A multi-scale micromechanics framework for shale using the nano-tools

NASA Astrophysics Data System (ADS)

Ortega, J.; Ulm, F.; Abousleiman, Y.

2009-12-01

The successful prediction of poroelastic properties of fine-grained rocks such as shale continues to be a formidable challenge for the geophysics community. The highly heterogeneous nature of shale in terms of its compositional and microstructural features translates into a complex anisotropic behavior observed at macroscopic length scales. The recent application of instrumented indentation for the mechanical characterization of shale has revealed the granular response and intrinsic anisotropy of its porous clay phase at nanometer length scales [1-2]. This discovered mechanical behavior at the grain scale has been incorporated into the development of a multi-scale, micromechanics model for shale poroelasticity [3]. The only inputs to the model are two volumetric parameters synthesizing the mineralogy and porosity information of a shale sample. The model is meticulously calibrated and validated, as displayed in Fig. 1, with independent data sets of anisotropic elasticity obtained from nanoindentation experiments and standard laboratory acoustic measurements for shale specimens with and without organic content. The treatment of the elastic anisotropy corresponding to the porous clay fabric, as sensed by nanoindentation, delineates the contribution of the intrinsic anisotropy in shale to its overall anisotropy observed at macroscales. Furthermore, the proposed poroelastic formulation provides access to intrinsic rock parameters such as Biot pore pressure coefficients that are of importance for problems of flow in porous media. In addition, the model becomes a useful tool in geophysics applications for the prediction of shale acoustic properties from material-specific information such as porosity, mineralogy, and density measurements. References: [1] Ulm, F.-J., Abousleiman, Y. (2006) ‘The nanogranular nature of shale.’ Acta Geot. 1(2), 77-88. [2] Bobko, C., Ulm, F.-J. (2008) ‘The nano-mechanical morphology of shale.’ Mech. Mat. 40(4-5), 318-337. [3] Ortega, J. A., Ulm, F.-J., Abousleiman, Y. (2009) ‘The nanogranular acoustic signature of shale.’ Geophysics 74(3), D65-D84. Fig. 1. Comparisons between predicted and experimental elasticity obtained from nanoindentation experiments (left) and acoustic measurements (right) for shale with and without organic content (hollow and solid data points). Nanoindentation elasticity of the porous clay in shale is presented as a function of the clay packing density (one minus the nanoporosity). The x-1, x-3 directions correspond to parallel and normal-to-bedding plane properties, respectively. All nanoindentation data and acoustic measurements for organic-rich shale from [2-3]. Acoustic measurements for organic-free shale were gathered from literature sources compiled in [3].

Multiple Basinal Fluid Events in the Lower Belt Supergroup, Montana: Constraints From CHIME Ages and REE Patterns of Monazites

NASA Astrophysics Data System (ADS)

Gonzalez-Alvarez, I.; Kusiak, M. A.

2004-05-01

Chemical dates (CHIME) on 105 spots and REE patterns of monazites were obtained from coarse sandstones and siltstones in the Mesoproterozoic siliciclastic Appekunny and Grinnell formations, lower Belt Supergroup, Montana, by EMPA. At least three post-depositional events induced by basinal fluids can be recognized: (a) red coloration accompanied by a major K-addition; (b) a green overprint of red siltstones; and (c) dolomitization. Fluid advection in the unmineralized lower Belt is pervasive and may have been alkaline and oxidizing. These three events progressively modified the primary geochemical characteristics of the siliciclastic rocks. Calculated ages show similar ranges in the fine and coarse-grained facies. For siltstones there are two age clusters: (1) at 1,801 ± 21 to 1,968 ± 26 Ma, as well as (2) at 854 ± 7 to 962 ± 13 Ma. Coarse sandstones show similar age clusters (3) at 1,831 ± 14 to 1,982 ± 12 Ma, and (4) at 803 ± 6 to 944 ± 9 Ma. A wide range of dates plots between the clusters for both facies. Clusters (1) and (3) are interpreted as the result of detrital monazites from a source area ~1.8 to 1.9 Ga old. Mineralogical variations and trace element systematic reveal basinal brines, which mobilized MREE and HREE, locally generating secondary monazites, influencing large domains of the lower Belt. The lower Belt Supergroup is estimated to have been deposited between 1.47 Ga and 1.45 Ga; consequently, the second age cluster for sandstones and siltstones is viewed as constraining the timeframe of a major basinal fluid event at ~0.80 to 0.96 Ga. That event is clearly distinct from the hydrothermal system associated with the Sullivan sedex base metal deposit at the base of the Belt. Ages between the clusters are interpreted either as secondary, formed during additional basinal fluid events or as reset of detrital monazites. Accordingly, the Belt basin was intermittently an open system to fluids from ~1.47 to ~0.80 Ga. Chondrite-normalized REE patterns for both facies display three unusual features: (A) on a linear scale for both facies for clusters (1) and (3) monazites reveal a straight line from La to Sm. For clusters (2) and (4) the profiles between La and Sm are concave or convex; concave profiles are produced mainly because of the Ce values. All reset monazites have convex or concave La-Sm profiles; (B) LREE/HREE and La/Y ratios average values for both facies in clusters (1) and (3) exhibit distinctively lower values than in clusters (2) and (4); (C) on log scale, charts show an unusually heterogeneous MREE and HREE profile for all monazites.

Hydrocarbon potential of Upper Devonian black shale, eastern Kentucky

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, I.M.; Frankie, W.T.; Moody, J.R.

The gas-producing Upper Devonian black shales of eastern Kentucky represent cycles of organic units alternating with less-organic units that were dominated by an influx of clastics from a northeastern source. This pattern of sedimentation is typical throughout the southern Appalachian basin in areas basinal to, yet still influenced by, the Catskill delta to the northwest. These black shales, which thin westward onto the Cincinnati arch, dip eastward into the Appalachian basin. To evaluate the future gas potential of Devonian shale, a data base has been compiled, consisting of specific geologic and engineering information from 5920 Devonian shale wells in Letcher,more » Knott, Floyd, Martin, and Pike Counties, Kentucky. The first successful gas completion in eastern Kentucky was drilled in Martin County in 1901. Comparison of initial open-flow potential (IP) and long-term production data for these wells demonstrates that higher IP values generally indicate wells of higher production potential. Areas of higher IP are aligned linearly, and these lineaments are interpreted to be related to fracture systems within the Devonian shale. These fractures may be basement influenced. Temperature log analyses indicate that the greatest number of natural gas shows occur in the lower Huron Member of the Ohio Shale. Using both the temperature log to indicate gas shows and the gamma-ray log to determine the producing unit is a workable method for selecting the interval for treatment.« less

The U.S. Shale Oil and Gas Resource - a Multi-Scale Analysis of Productivity

NASA Astrophysics Data System (ADS)

O'sullivan, F.

2014-12-01

Over the past decade, the large-scale production of natural gas, and more recently oil, from U.S. shale formations has had a transformative impact on the energy industry. The emergence of shale oil and gas as recoverable resources has altered perceptions regarding both the future abundance and cost of hydrocarbons, and has shifted the balance of global energy geopolitics. However, despite the excitement, shale is a resource in its nascency, and many challenges surrounding its exploitation remain. One of the most significant of these is the dramatic variation in resource productivity across multiple length scales, which is a feature of all of today's shale plays. This paper will describe the results of work that has looked to characterize the spatial and temporal variations in the productivity of the contemporary shale resource. Analysis will be presented that shows there is a strong stochastic element to observed shale well productivity in all the major plays. It will be shown that the nature of this stochasticity is consistent regardless of specific play being considered. A characterization of this stochasticity will be proposed. As a parallel to the discussion of productivity, the paper will also address the issue of "learning" in shale development. It will be shown that "creaming" trends are observable and that although "absolute" well productivity levels have increased, "specific" productivity levels (i.e. considering well and stimulation size) have actually falling markedly in many plays. The paper will also show that among individual operators' well ensembles, normalized well-to-well performance distributions are almost identical, and have remained consistent year-to-year. This result suggests little if any systematic learning regarding the effective management of well-to-well performance variability has taken place. The paper will conclude with an articulation of how the productivity characteristics of the shale resource are impacting on the resources' economic profile, and the implications of this in terms of the commercial risks associated with shale production activities.

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults

PubMed Central

Cheng, Yu; Yang, Xue; Na, Li-Xin; Li, Ying; Sun, Chang-Hao

2016-01-01

Basic data on the resting energy expenditure (REE) of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20–79 years old). REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM) ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000) and men (p = 0.000), and we found that men have a higher REE (p = 0.000) and lower REE/FFM (p = 0.021) than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases. PMID:27598192

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults.

PubMed

Cheng, Yu; Yang, Xue; Na, Li-Xin; Li, Ying; Sun, Chang-Hao

2016-09-01

Basic data on the resting energy expenditure (REE) of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20-79 years old). REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM) ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000) and men (p = 0.000), and we found that men have a higher REE (p = 0.000) and lower REE/FFM (p = 0.021) than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases.

Abdominal fat sub-depots and energy expenditure: Magnetic resonance imaging study.

PubMed

Serfaty, Dana; Rein, Michal; Schwarzfuchs, Dan; Shelef, Ilan; Gepner, Yftach; Bril, Nitzan; Cohen, Noa; Shemesh, Elad; Sarusi, Benjamin; Kovsan, Julia; Kenigsbuch, Shira; Chassidim, Yoash; Golan, Rachel; Witkow, Shula; Henkin, Yaakov; Stampfer, Meir J; Rudich, Assaf; Shai, Iris

2017-06-01

We aimed to assess the association between the distinct abdominal sub-depots and resting energy expenditure (REE). We performed magnetic resonance imaging (MRI) to quantify abdominal visceral-adipose-tissue (VAT), deep-subcutaneous-adipose-tissue (deep-SAT), and superficial-subcutaneous-adipose-tissue (superficial-SAT). We measured REE by indirect-calorimetry. Non-exercise activity thermogenesis (NEAT) [1-3 metabolic equivalents (METs)] and exercise thermogenesis (activities of 4+MET S ) were estimated based on 6-days of accelerometry to assess total physical activity energy expenditure (PAEE). We studied 282 participants: 249 men [mean age = 47.4 years, body-mass-index (BMI) = 31 kg/m 2 , mean VAT proportion from total abdominal fat = 34.5%, mean superficial-SAT proportion from total abdominal fat = 24.3%] and 33 women (mean age = 51.2 years, BMI = 30.1 kg/m 2 , mean VAT proportion from total abdominal fat = 22.8%, mean superficial-SAT proportion from total abdominal fat = 37.8%). As expected, women had lower REE [by 32.4% (1488 ± 234 kcal/day vs. 1971 ± 257 kcal/day; p < 0.01)] and lower REE/kg [by 8% (19.6 ± 3 kcal/kg vs. 21.2 ± 2 kcal/kg; p < 0.01)] than men. Exercise and total PAEE were positively associated with REE/kg (p < 0.01 for both) and a positive correlation between NEAT and REE/kg was borderline (p = 0.056). Participants, in whom abdominal VAT was the dominant proportional depot, had higher REE (1964 ± 297 kcal/day vs. 1654 ± 352 kcal/day; p < 0.01) and higher REE∖kg (22.2 ± 2.3 kcal/kg/day vs. 19.6 ± 2.5 kcal/kg/day; p < 0.01) than participants in whom superficial-SAT was the largest proportional depot. In multivariate models, adjusted for age, gender and residual BMI, increased VAT proportion was independently associated with higher REE (β = 0.181; p = 0.05). Likewise, increased VAT proportion (β = 0.482; p < 0.01) remained independently associated with higher REE/kg. In this model younger age (β = -0.329; p < 0.01) was associated with higher REE/kg. Abdominal fat distribution patterns are associated with varying levels of resting energy expenditure, potentially reflecting different metabolic rates of adipose sub-depots and providing an anatomic/anthropometric link to physiological obese sub-phenotypes. Copyright © 2016 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

Atmospheric emissions and air quality impacts from natural gas production and use.

PubMed

Allen, David T

2014-01-01

The US Energy Information Administration projects that hydraulic fracturing of shale formations will become a dominant source of domestic natural gas supply over the next several decades, transforming the energy landscape in the United States. However, the environmental impacts associated with fracking for shale gas have made it controversial. This review examines emissions and impacts of air pollutants associated with shale gas production and use. Emissions and impacts of greenhouse gases, photochemically active air pollutants, and toxic air pollutants are described. In addition to the direct atmospheric impacts of expanded natural gas production, indirect effects are also described. Widespread availability of shale gas can drive down natural gas prices, which, in turn, can impact the use patterns for natural gas. Natural gas production and use in electricity generation are used as a case study for examining these indirect consequences of expanded natural gas availability.

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

USGS Publications Warehouse

Emsbo, Poul; McLaughlin, Patrick I.; Breit, George N.; du Bray, Edward A.; Koenig, Alan E.

2015-01-01

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H2SO4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

Health effects and toxicity mechanisms of rare earth elements-Knowledge gaps and research prospects.

PubMed

Pagano, Giovanni; Guida, Marco; Tommasi, Franca; Oral, Rahime

2015-05-01

In the recent decades, rare earth elements (REE) have undergone a steady spread in several industrial and medical applications, and in agriculture. Relatively scarce information has been acquired to date on REE-associated biological effects, from studies of bioaccumulation and of bioassays on animal, plant and models; a few case reports have focused on human health effects following occupational REE exposures, in the present lack of epidemiological studies of occupationally exposed groups. The literature is mostly confined to reports on few REE, namely cerium and lanthanum, whereas substantial information gaps persist on the health effects of other REE. An established action mechanism in REE-associated health effects relates to modulating oxidative stress, analogous to the recognized redox mechanisms observed for other transition elements. Adverse outcomes of REE exposures include a number of endpoints, such as growth inhibition, cytogenetic effects, and organ-specific toxicity. An apparent controversy regarding REE-associated health effects relates to opposed data pointing to either favorable or adverse effects of REE exposures. Several studies have demonstrated that REE, like a number of other xenobiotics, follow hormetic concentration-related trends, implying stimulatory or protective effects at low levels, then adverse effects at higher concentrations. Another major role for REE-associated effects should be focused on pH-dependent REE speciation and hence toxicity. Few reports have demonstrated that environmental acidification enhances REE toxicity; these data may assume particular relevance in REE-polluted acidic soils and in REE mining areas characterized by concomitant REE and acid pollution. The likely environmental threats arising from REE exposures deserve a new line of research efforts. Copyright © 2015 Elsevier Inc. All rights reserved.

Geological and petrological considerations relevant to the disposal of radioactive wastes by hydraulic fracturing: an example at the US Department of Energy's Oak Ridge National Laboratory. [Pumpkin Valley shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haase, C.S.

1982-01-01

At Oak Ridge National Laboratory the Pumpkin Valley Shale is used as a host formation for hydraulic-fracturing waste disposal. Determination of the relationships between the distribution of different lithologies and porosity-permeability trends within this host formation allows these properties, important to hydraulic-fracturing operations, to be related to measurable and mappable geological and petrological parameters. It also permits extrapolation of such patterns to little-studied portions of the Pumpkin Valley Shale. Such knowledge better allows for the satisfactory operation and assessment of the hydraulic fracturing at Oak Ridge National Laboratory.

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

NASA Astrophysics Data System (ADS)

Feng, Mu-hua; Ngwenya, Bryne T.; Wang, Lin; Li, Wenchao; Olive, Valerie; Ellam, Robert M.

2011-10-01

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria ( Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects.

PubMed

Pagano, Giovanni; Guida, Marco; Siciliano, Antonietta; Oral, Rahime; Koçbaş, Fatma; Palumbo, Anna; Castellano, Immacolata; Migliaccio, Oriana; Thomas, Philippe J; Trifuoggi, Marco

2016-05-01

Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. REEs affected P. lividus larvae with concentration-related increase in developmental defects, 10(-6) to 10(-4)M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10(-5) to 10(-4)M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies. Copyright © 2016 Elsevier Inc. All rights reserved.

Hydrothermal transport and deposition of the rare earth elements by fluorine-bearing aqueous liquids

NASA Astrophysics Data System (ADS)

Migdisov, Art A.; Williams-Jones, A. E.

2014-12-01

New technologies, particularly those designed to address environmental concerns, have created a great demand for the rare earth elements (REE), and focused considerable attention on the processes by which they are concentrated to economically exploitable levels in the Earth's crust. There is widespread agreement that hydrothermal fluids played an important role in the formation of the world's largest economic REE deposit, i.e. Bayan Obo, China. Until recently, many researchers have assumed that hydrothermal transport of the REE in fluorine-bearing ore-forming systems occurs mainly due to the formation of REE-fluoride complexes. Consequently, hydrothermal models for REE concentration have commonly involved depositional mechanisms based on saturation of the fluid with REE minerals due to destabilization of REE-fluoride complexes. Here, we demonstrate that these complexes are insignificant in REE transport, and that the above models are therefore flawed. The strong association of H+ and F- as HF° and low solubility of REE-F solids greatly limit transport of the REE as fluoride complexes. However, this limitation does not apply to REE-chloride complexes. Because of this, the high concentration of Cl- in the ore fluids, and the relatively high stability of REE-chloride complexes, the latter can transport appreciable concentrations of REE at low pH. The limitation also does not apply to sulphate complexes and in some fluids, the concentration of sulphate may be sufficient to transport significant concentrations of REE as sulphate complexes, particularly at weakly acidic pH. This article proposes new models for hydrothermal REE deposition based on the transport of the REE as chloride and sulphate complexes.

Chemical systematics of the Shergotty meteorite and the composition of its parent body (Mars)

NASA Technical Reports Server (NTRS)

Laul, J. C.; Smith, M. R.; Waenke, H.; Jagoutz, E.; Dreibus, G.

1986-01-01

Sixty elements in two bulk samples of Shergotty meteorite and 30 elements in various mineral separates of Shergotty were identified, using mainly INAA and RNAA techniques. In addition, elements leached out from powdered samples of Shergotty and EETA 79001 meteorites by 0.1 N HCl, as well as the elements of their residues, were analyzed. The results have indicated that Shergotty meteorite is homogeneous in its major element composition, but heterogeneous with respect to large-ion lithophile elements, such as K, Ba, Sr, Zr, Hf, Ta, Th, and rare-earth elements (REEs). It is even more heterogeneous with respect to volatile elements, such as Cd, Te, Tl, and Bi, and the siderophiles Au and Ag. The REE patterns of the Shergotty and EETA 79001 residues are identical, indicating that the parent magmas of both meteorites are compositionally similar. However, their leachate (phosphate) patterns are different, suggesting two components for the Shergotty, one of which is similar to the EETA 79001 leachate.

The thermal and chemical evolution of hydrothermal vent fluids in shale hosted massive sulphide (SHMS) systems from the MacMillan Pass district (Yukon, Canada)

NASA Astrophysics Data System (ADS)

Magnall, J. M.; Gleeson, S. A.; Blamey, N. J. F.; Paradis, S.; Luo, Y.

2016-11-01

At Macmillan Pass (YT, Canada), the hydrothermal vent complexes beneath two shale-hosted massive sulphide (SHMS) deposits (Tom, Jason) are well preserved within Late Devonian strata. These deposits provide a unique opportunity to constrain key geochemical parameters (temperature, salinity, pH, fO2, ΣS) that are critical for metal transport and deposition in SHMS systems, and to evaluate the interaction between hydrothermal fluids and the mudstone host rock. This has been achieved using a combination of detailed petrography, isotopic techniques (δ34S, δ13C and δ18O values), carbonate rare earth element analysis (LA-ICP-MS), fluid inclusion analysis (microthermometry, gas analysis via incremental crush fast scan mass spectrometry), and thermodynamic modelling. Two main paragenetic stages are preserved in both vent complexes: Stage 1 comprises pervasive ankerite alteration of the organic-rich mudstone host rock and crosscutting stockwork ankerite veining (±pyrobitumen, pyrite and quartz) and; Stage 2 consists of main stage massive sulphide (galena-pyrrhotite-pyrite ± chalcopyrite-sphalerite) and siderite (±quartz and barytocalcite) mineralisation. Co-variation of δ18O and δ13C values in ankerite can be described by temperature dependent fractionation and fluid rock interaction. Together with fluid inclusion microthermometry, this provides evidence of a steep thermal gradient (from 300 to ∼100 °C) over approximately 15 m stratigraphic depth, temporally and spatially constrained within the paragenesis of both vent complexes and developed under shallow lithostatic (<1 km; 250 bars) to hydrostatic (<400 m; 40 bars) conditions. There is evidence of mixing between diagenetic and hydrothermal fluids recorded in chondrite-normalised rare earth element (REE) profiles of ankerite and siderite. Middle REE enrichments and superchondritic Y/Ho ratios (>28), characteristic of diagenetic fluids, are coupled with positive europium anomalies and variable light REE depletion, which are more consistent with chloride complexation in hot (>250 °C) hydrothermal fluids. In this shallow sub-seafloor setting, thermal alteration of organic carbon in the immature, chemically reactive mudstones also had an important role in the evolution of fluid chemistry. Reduced sulphur generation via thermochemical reduction of Late Devonian seawater sulphate produced positive δ34S values in sulphide minerals (+7.5‰ to +19.5‰), coupled with a suite of volatile components (CO2, CH4, C1-C4 hydrocarbons, N2) trapped in Stage 2 quartz. Many of these geochemical features developed during the final stages of fluid ascent, in a system where the fluid cooled close to the site of mineralisation. Using this information, we have modelled the metal transporting capacity of the deep hydrothermal fluid, which even at modest salinities (6 wt.% NaCl) was high (≫100 ppm Pb, Zn), owing to the combined effects of high temperature and low pH (⩽4.5). Therefore in SHMS systems, enhanced geothermal gradients and rapid fluid ascent (with minimal fluid cooling) are considered to be the most important factors for transporting high concentrations of base metals to the site of mineralisation.

Selective Extraction of Rare Earth Elements from Permanent Magnet Scraps with Membrane Solvent Extraction.

PubMed

Kim, Daejin; Powell, Lawrence E; Delmau, Lætitia H; Peterson, Eric S; Herchenroeder, Jim; Bhave, Ramesh R

2015-08-18

The rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acid solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. The resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets.

Source Evolution After Subduction Initiation as Recorded in the Izu-Bonin-Mariana Fore-arc Crust

NASA Astrophysics Data System (ADS)

Shervais, J. W.; Reagan, M. K.; Pearce, J. A.; Shimizu, K.

2015-12-01

Drilling in the Izu-Bonin-Mariana (IBM) fore-arc during IODP Expedition 352 and DSDP Leg 60 recovered consistent stratigraphic sequences of volcanic rocks reminiscent of those found in many ophiolites. The oldest lavas in these sections are "fore-arc basalts" (FAB) with ~51.5 Ma ages. Boninites began eruption approximately 2-3 m.y. later (Ishizuka et al., 2011, EPSL; Reagan et al., 2013, EPSL) and further from the trench. First results from IODP Expedition 352 and preliminary post-cruise data suggest that FAB at Sites U1440 and U1441 were generated by decompression melting during near-trench sea-floor spreading, and that fluids from the subducting slab were not involved in their genesis. Temperatures appear to have been unusually high and pressures of melting appear to have been unusually low compared to mid-ocean ridges. Spreading rates at this time appear to have been robust enough to maintain a stable melt lens. Incompatible trace element abundances are low in FAB compared to even depleted MORB. Nd and Hf Isotopic compositions published before the expedition suggest that FAB were derived from typical MORB source mantle. Thus, their extreme deletion resulted from unusually high degrees of melting immediately after subduction initiation. The oldest boninites from DSDP Site 458 and IODP Sites U1439 and U1442 have relatively high concentrations of fluid-soluble elements, low concentrations of REE, and light depleted REE patterns. Younger boninites, have even lower REE concentrations, but have U-shaped REE patterns. Our first major and trace element compositions for the FAB through boninite sequence suggests that melting pressures and temperatures decreased through time, mantle became more depleted though time, and spreading rates waned during boninite genesis. Subduction zone fluids involved in boninite genesis appear to have been derived from progressively higher temperatures and pressures over time as the subducting slab thermally matured.

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagano, Giovanni, E-mail: gbpagano@tin.it; Guida, Marco; Siciliano, Antonietta

Background: Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. Methods: Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. Results: REEs affectedmore » P. lividus larvae with concentration-related increase in developmental defects, 10{sup −6} to 10{sup −4} M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10{sup −5} to 10{sup −4} M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. Conclusion: REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies. - Highlights: • Seven rare earth elements exerted different effects on sea urchin early life stages. • Embryo-, spermio- and mitotoxicity, and oxidative/ nitrosative stress were found. • Nominal vs. analytical REE concentrations were checked. • Comparative toxicities were evaluated for the different REE.« less

Rare earth elements in human and animal health: State of art and research priorities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagano, Giovanni, E-mail: gbpagano@tin.it; Aliberti, Francesco; Guida, Marco

Background: A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. Methods: A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. Results: Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures havemore » been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. Conclusion: The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments. - Highlights: • An extensive number of activities have been developed utilizing rare earth elements (REE). • The literature of REE-associated health effects in humans, and on animal studies is reviewed. • The main literature gaps are discussed, in epidemiological and in animal studies. • Prospects studies are suggested, aimed at evaluating long-term effects of REE exposures. • The relevance of REE-related hormesis, speciation and acidic pollution are discussed.« less

Green glass vitrophyre 78526 - An impact of very low-Ti mare basalt composition

NASA Technical Reports Server (NTRS)

Warner, R. D.; Taylor, G. J.; Kiel, K.; Planner, H. H.; Nehru, C. E.; Ma, M.-S.; Schmitt, R. A.

1978-01-01

Rake sample 78526 is an 8.77 g rock consisting primarily of vitrophyric pale green glass with subordinate mineral and lithic relics. Petrographic and compositional evidence leads to the following conclusions: (1) the bulk composition represents that of a mixture formed by impact melting of at least two different textural and compositional varieties of VLT mare basalt that are now present in the rock as lithic relics and a poorly defined low-Ti mare basalt component observed in thin section only in the form of isolated mineral relics; (2) the admixed VLT mare basalts had REE abundances lower than those found in other mare basalts (but probably higher than emerald green glass) and REE patterns showing significant enrichment of the heavy relative to light REE's, suggesting that they were derived by comparatively high degrees of partial melting of a clinopyroxene-rich source region; and (3) the impact melt supercooled to produce the vitrophyre, with rather sharply contrasting textural domains present in the vitrophyre resulting from differences in nucleation kinetics and degrees of supercooling in various portions of the sample.

Shale gas activity and increased rates of sexually transmitted infections in Ohio, 2000–2016

PubMed Central

Humeau, Zoe; Elliott, Elise G.; Warren, Joshua L.; Niccolai, Linda M.

2018-01-01

Background The growing shale gas (“fracking”) industry depends on a mobile workforce, whose influx could have social impacts on host communities. Sexually transmitted infections (STIs) can increase through sexual mixing patterns associated with labor migration. No prior studies have quantified the relationship between shale gas activity and rates of three reportable STIs: chlamydia, gonorrhea, and syphilis. Methods We conducted a longitudinal, ecologic study from 2000–2016 in Ohio, situated in a prolific shale gas region in the United States (US). Data on reported cases of chlamydia, gonorrhea, and syphilis by county and year were obtained from the Ohio Department of Health. All 88 counties were classified as none, low, and high shale gas activity in each year, using data from the Ohio Department of Natural Resources. Annual rate ratios (RR) and 95% confidence intervals (95% CIs) were calculated from mixed-effects Poisson regression models evaluating the relationship between shale gas activity and reported annual STI rates while adjusting for secular trends and potential confounders obtained from the US Census. Results Compared to counties with no shale gas activity, counties with high activity had 21% (RR = 1.21; 95%CI = 1.08–1.36) increased rates of chlamydia and 19% (RR = 1.27; 95%CI 0.98–1.44) increased rates of gonorrhea, respectively. No association was observed for syphilis. Conclusion This first report of a link between shale gas activity and increased rates of both chlamydia and gonorrhea may inform local policies and community health efforts. PMID:29570712

Experimental mineral/liquid partition coefficients of the rare earth elements /REE/, Sc and Sr for perovskite, spinel and melilite

NASA Technical Reports Server (NTRS)

Nagasawa, H.; Schreiber, H. D.; Morris, R. V.

1980-01-01

Experimental determinations of the mineral/liquid partition coefficients of REE (La, Sm, Eu, Gd, Tb, Yb and Lu), Sc and Sr are reported for the minerals perovskite, spinel and melilite in synthetic systems. Perovskite concentrates light REE with respect to the residual liquid but shows no preference for heavy REE. Spinel greatly discriminates against the incorporation of REE, especially light REE, into its crystal structure. The partition of REE into melilite from a silicate liquid is quite dependent upon both the bulk melt and melilite solid-solution (gehlenite and akermanite components) compositions. As such, melilite can be enriched in REE or will reject REE with corresponding strong negative or strong positive Eu anomalies, respectively.

Water sources and disposal related to hydraulic fracturing in the Barnett Shale: a historical perspective

NASA Astrophysics Data System (ADS)

Nicot, J.; Scanlon, B. R.

2013-12-01

During the past few years, hydraulic fracturing (HF) has become a hotly debated topic particularly related to volume of water used and potential for contamination of shallow aquifers. In this communication, we focused on water use in the oldest shale play in the world as an example for an analysis of historical patterns of water use, consumption, and disposal. The Barnett Shale play in Texas provides an ideal case to assess some of the issues related to shale gas production. It was the first shale play to submit to intense slick-water HF (first horizontal wells in 2003, ~15,000 horizontal wells completed to date). An estimated 200, 000 acre-feet (247 million m3) of water has been used so far in the play (included for vertical wells), mostly in the 4-5 counties making up the core area. More than 90% of the water used is consumed and relatively little recycling occurs in the play. Most of the flowback / produced water is disposed of through injection wells. The median Barnett horizontal well produces back ~100% of the amount of water injected for fracturing in the course of the few years following completion, an amount larger than other well-known shale gas plays. The communication will provide detailed material documenting these findings.

Geology and market-dependent significance of rare earth element resources

NASA Astrophysics Data System (ADS)

Simandl, G. J.

2014-12-01

China started to produce rare earth elements (REEs) in the 1980s, and since the mid-1990s, it has become the dominant producer. Rare earth element export quotas first introduced by the Chinese government in the early 2000s were severely reduced in 2010 and 2011. This led to strong government-created disparity between prices within China and the rest of the world. Industrialized countries identified several REEs as strategic metals. Because of rapid price increases of REE outside of China, we have witnessed a world-scale REE exploration rush. The REE resources are concentrated in carbonatite-related deposits, peralkaline igneous rocks, pegmatites, monazite ± apatite veins, ion adsorption clays, placers, and some deep ocean sediments. REE could also be derived as a by-product of phosphate fertilizer production, U processing, mining of Ti-Zr-bearing placers, and exploitation of Olympic Dam subtype iron oxide copper gold (IOCG) deposits. Currently, REEs are produced mostly from carbonatite-related deposits, but ion adsorption clay deposits are an important source of heavy REE (HREE). Small quantities of REE are derived from placer deposits and one peralkaline intrusion-related deposit. The ideal REE development targets would be located in a politically stable jurisdiction with a pro-mining disposition such as Canada and Australia. REE grade, HREE/light REE (LREE) ratio of the mineralization, tonnage, mineralogy, and permissive metallurgy are some of the key technical factors that could be used to screen potential development projects. As REEs are considered strategic metals from economic, national security, and environmental points of view, technical and economic parameters alone are unlikely to be used in REE project development decision-making. Recycling of REE is in its infancy and unless legislated, in the short term, it is not expected to contribute significantly to the supply of REE.

The rare-earth elements: Vital to modern technologies and lifestyles

USGS Publications Warehouse

Van Gosen, Bradley S.; Verplanck, Philip L.; Long, Keith R.; Gambogi, Joseph; Seal, Robert R.

2014-01-01

Until recently, the rare-earth elements (REEs) were familiar to a relatively small number of people, such as chemists, geologists, specialized materials scientists, and engineers. In the 21st century, the REEs have gained visibility through many media outlets because of (1) the public has recognized the critical, specialized properties that REEs contribute to modern technology, as well as (2) China's dominance in production and supply of the REEs and (3) international dependence on China for the majority of the world's REE supply.Since the late 1990s, China has provided 85–95 percent of the world’s REEs. In 2010, China announced their intention to reduce REE exports. During this timeframe, REE use increased substantially. REEs are used as components in high technology devices, including smart phones, digital cameras, computer hard disks, fluorescent and light-emitting-diode (LED) lights, flat screen televisions, computer monitors, and electronic displays. Large quantities of some REEs are used in clean energy and defense technologies. Because of the many important uses of REEs, nations dependent on new technologies, such as Japan, the United States, and members of the European Union, reacted with great concern to China’s intent to reduce its REE exports. Consequently, exploration activities intent on discovering economic deposits of REEs and bringing them into production have increased.

Bacterial Cell Surface Adsorption of Rare Earth Elements

NASA Astrophysics Data System (ADS)

Jiao, Y.; Park, D.; Reed, D.; Fujita, Y.; Yung, M.; Anderko, A.; Eslamimanesh, A.

2015-12-01

Rare earth elements (REE) play a critical role in many emerging clean energy technologies, including high-power magnets, wind turbines, solar panels, hybrid/electric vehicle batteries and lamp phosphors. In order to sustain demand for such technologies given current domestic REE shortages, there is a need to develop new approaches for ore processing/refining and recycling of REE-containing materials. To this end, we have developed a microbially-mediated bioadsorption strategy with application towards enrichment of REE from complex mixtures. Specifically, the bacterium Caulobacter crescentus was genetically engineered to display lanthanide binding tags (LBTs), short peptides that possess high affinity and specificity for rare earth elements, on its cell surface S-layer protein. Under optimal conditions, LBT-displayed cells adsorbed greater than 5-fold more REE than control cells lacking LBTs. Competition binding experiments with a selection of REEs demonstrated that our engineered cells could facilitate separation of light- from heavy- REE. Importantly, binding of REE onto our engineered strains was much more favorable compared to non-REE metals. Finally, REE bound to the cell surface could be stripped off using citrate, providing an effective and non-toxic REE recovery method. Together, this data highlights the potential of our approach for selective REE enrichment from REE containing mixtures.

Fulvic acid like organic compounds control nucleation of marine calcite under suboxic conditions

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; D'Orazio, Valeria; Immenhauser, Adrian; Geipel, Gerhard; Heise, Karl-Heinz; Cocozza, Claudio; Miano, Teodoro M.

2003-08-01

Intracrystalline organic compounds, enclosed within in situ precipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.

Partitioning in REE-saturating minerals - Theory, experiment, and modelling of whitlockite, apatite, and evolution of lunar residual magmas

NASA Technical Reports Server (NTRS)

Jolliff, Bradley L.; Haskin, Larry A.; Colson, Russell O.; Wadhwa, Meenakshi

1993-01-01

Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

Joint Use of the MAB-II and MicroCog for Improvements in the Clinical and Neuropsychological Screening and Aeromedical Waiver Process of Rated USAF Pilots

DTIC Science & Technology

2010-01-01

medical flight screening and the aeromedical waiver process ( Olea & Ree, 1994; Ree & Carretta, 1996; Ree, Carretta, & Teachout, 1995). Currently, the...Student pilots with high scores on ability tests are more likely to complete training ( Olea & Ree, 1994; Ree & Carretta, 1996; Ree, Carretta, & Teachout...Matrix differential calculus with applications in statistics and econometrics. New York, NY: John Wiley. Olea , M., & Ree, M.J. (1994

Origins of mass-dependent and mass-independent Ca isotope variations in meteoritic components and meteorites

NASA Astrophysics Data System (ADS)

Bermingham, K. R.; Gussone, N.; Mezger, K.; Krause, J.

2018-04-01

The Ca isotope composition of meteorites and their components may vary due to mass-dependent and/or -independent isotope effects. In order to evaluate the origin of these effects, five amoeboid olivine aggregates (AOAs), three calcium aluminum inclusions (CAIs), five chondrules (C), a dark inclusion from Allende (CV3), two dark fragments from North West Africa 753 (NWA 753; R3.9), and a whole rock sample of Orgueil (CI1) were analyzed. This is the first coupled mass-dependent and -independent Ca isotope dataset to include AOAs, a dark inclusion, and dark fragments. Where sample masses permit, Ca isotope data are reported with corresponding petrographic analyses and rare earth element (REE) relative abundance patterns. The CAIs and AOAs are enriched in light Ca isotopes (δ44/40Ca -5.32 to +0.72, where δ44/40Ca is reported relative to SRM 915a). Samples CAI 5 and AOA 1 have anomalous Group II REE patterns. These REE and δ44/40Ca data suggest that the CAI 5 and AOA 1 compositions were set via kinetic isotope fractionation during condensation and evaporation. The remaining samples show mass-dependent Ca isotope variations which cluster between δ44/40Ca +0.53 and +1.59, some of which are coupled with unfractionated REE abundance patterns. These meteoritic components likely formed through the coaccretion of the evaporative residue and condensate following Group II CAI formation or their chemical and isotopic signatures were decoupled (e.g., via nebular or parent-body alteration). The whole rock sample of Orgueil has a δ44/40Ca +0.67 ± 0.18 which is in agreement with most published data. Parent-body alteration, terrestrial alteration, and variable sampling of Ca-rich meteoritic components can have an effect on δ44/40Ca compositions in whole rock meteorites. Samples AOA 1, CAI 5, C 2, and C 4 display mass-independent 48/44Ca anomalies (ε48/44Ca +6 to +12) which are resolved from the standard composition. Other samples measured for these effects (AOA 5, CAI 1, CAI 2, C 3, D 1, D 2, D 3) possess the same 48/44Ca isotope composition as the standard within analytical uncertainty. These data indicate a heterogeneous distribution of 48Ca in the early solar nebula during formation of CAIs, AOAs, and chondrules. In a ε48/44Ca vs. δ44/40Ca plot, no strong correlation is evident which suggests that the thermal processing event which caused a heterogeneous distribution of ε48/44Ca in the solar nebula is unlikely to be directly related to the thermal processing event that caused coupled REE and Ca mass-dependent isotopic fractionation in meteoritic components.

Tectonic context of the penetrative fracture system origin in the Early Paleozoic shale complex (Baltic Basin, Poland/Sweden).

NASA Astrophysics Data System (ADS)

Jarosiński, Marek; Gluszynski, Andrzej; Bobek, Kinga; Dyrka, Ireneusz

2017-04-01

Characterization of natural fracture and fault pattern play significant role for reservoir stimulation design and evaluation of its results. Having structural observations limited to immediate borehole surrounding it is a common need to build up a fracture model of reservoir in a range of stimulation reservoir volume or even beyond. To do this we need both a 3D seismic model and a consistent concept of the regional tectonic evolution. We present the result of integrated tectonic study in several deep boreholes target the Lower Paleozoic shale complex of Baltic Basin (BB), combined with analysis of 3D seismic survey and outcrop screening in Scania (Swedish part of the BB). During deposition of shale complex in the Ordovician and Silurian the research area was located 200-300 km away from the continental margin of Baltica involved in the Caledonian collision with the Eastern Avalonia. This distance allowed the shale complex to avoid significant tectonic deformation. Regional seismic cross section reveals the general pattern of the BB infill characteristic for the foreland basin underwent post-collisional isostatic rebound. Due to stress changes in collisional context the shale complex was cross-cut by steep, mostly inverse faults trending NW-SE and NE-SW. The fault zones oriented NW-SE are associated with an array of en echelon faults characteristic for strike-slip displacement. In our interpretation, these faults of Silurian (Wenlock) age create pattern of the regional pop-up structure, which is simultaneously involved in the plate flexure extension. Seismic attributes (e.g. curvature or ant tracking) highlight lineaments which mostly mimic the faults orientation. However, attributes show also some artefacts that come from regular array of seismic sources and receivers, which mimic the orthogonal joint system. Structural observations on borehole core lead us to conclusion that regular, orthogonal fracture system developed after maximum burial of the complex, triggered by mechanism of natural hydraulic fracturing due to hydrocarbon generation. These fractures create veins filled with calcite that growth was controlled by mechanical layering and the TOC content of the shale complex. The main joint fracture pattern is stable across at least 300 hundred kilometers, from the Polish to Swedish portion of Baltic Basin. Therefore a major tectonic event is expected to govern its origin. The Late Carboniferous thin-skinned compression exerted at the edge of the East European Craton, is preferred tectonic fracture triggering factor. This age of jointing is confirmed by the strike of principal joint set characteristic for Variscan compression. In addition, principal joint system is sensitive (=younger) to a presence of the Caledonian-age faults in Pomerania but insensitive (=older) to the Mesozoic faults in Scania. Above genetic considerations should be taken into account while building the self-consistent discrete fracture network of faults and fractures for the purpose of shale reservoir stimulation.

Not all Rare Earths are the Same to Microbes

NASA Astrophysics Data System (ADS)

Fujita, Y.; Reed, D. W.; St Jeor, J.; Das, G.; Anderko, A.

2017-12-01

Rare earth elements (REE) are important for modern technologies including smart phones and energy efficient lighting, electric and hybrid vehicles, and advanced wind turbines. Greater demand and usage of REE leads to increased potential for ecosystem impacts, as human activities generate higher concentrations of these metals through mining, industrial processing and waste generation than are normally present in natural environments. Biological modules in wastewater treatment plants are among the ecosystems likely to be impacted by higher REE loads because these poorly soluble metals often accumulate in sludges. We have been examining the effects of adding REE to laboratory cultures of Sporacetigenium mesophilum, a fermenting bacterium originally isolated from an anaerobic sludge digester. We observed that the addition of 60 µM ( 9 ppm) europium stimulated growth and hydrogen production by S. mesophilum. The addition of the equivalent amount of samarium, separately, appeared to be even more beneficial to S. mesophilum. However, when we measured soluble metal concentrations in the cultures, we found strikingly different results. After 24 hours, essentially all of the added Eu remained in the aqueous phase, but 60-65% of the added Sm was no longer soluble. To better understand the relationship between the solubility of REE and their impact on microbiological processes, a thermodynamic model was established for Eu and Sm species in simulated aqueous environments. The model was calibrated to reproduce the solubility of both crystalline and amorphous rare earth hydroxides, which control the availability of rare earths in solution. The primary factors influencing solubility are the solution pH, crystallinity of the hydroxide mineral and redox conditions. In the case of Eu, transition between trivalent and divalent cations occurs at moderate potentials and, therefore, it is possible that divalent cations contribute to the solubilization of Eu. In the case of Sm, divalent cations are not likely to occur under typical anaerobic conditions, thus stabilizing the hydroxide of trivalent Sm. The difference in the observed partitioning of Eu and Sm suggests that multiple modes of REE interaction with S. mesophilum may be operative.

Mapping trace element distribution in fossil teeth and bone with LA-ICP-MS

NASA Astrophysics Data System (ADS)

Hinz, E. A.; Kohn, M. J.

2009-12-01

Trace element profiles were measured in fossil bones and teeth from the late Pleistocene (c. 25 ka) Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Laser-ablation ICP-MS can collect element counts along predefined tracks on a sample’s surface using a constant ablation speed allowing for rapid spatial sampling of element distribution. Key elements analyzed included common divalent cations (e.g. Sr, Zn, Ba), a suite of REE (La, Ce, Nd, Sm, Eu, Yb), and U, in addition to Ca for composition normalization and standardization. In teeth, characteristic diffusion penetration distances for all trace elements are at least a factor of 4 greater in traverses parallel to the dentine-enamel interface (parallel to the growth axis of the tooth) than perpendicular to the interface. Multiple parallel traverses in sections parallel and perpendicular to the tooth growth axis were transformed into trace element maps, and illustrate greater uptake of all trace elements along the central axis of dentine compared to areas closer to enamel, or within the enamel itself. Traverses in bone extending from the external surface, through the thickness of cortical bone and several mm into trabecular bone show major differences in trace element uptake compared to teeth: U and Sr are homogeneous, whereas all REE show a kinked profile with high concentrations on outer surfaces that decrease by several orders of magnitude within a few mm inward. The Eu anomaly increases uniformly from the outer edge of bone inward, whereas the Ce anomaly decreases slightly. These observations point to major structural anisotropies in trace element transport and uptake during fossilization, yet transport and uptake of U and REE are not resolvably different. In contrast, transport and uptake of U in bone must proceed orders of magnitude faster than REE as U is homogeneous whereas REE exhibit strong gradients. The kinked REE profiles in bone unequivocally indicate differential transport rates, consistent with a double-medium diffusion model in which microdomains with slow diffusivities are bounded by fast-diffusing pathways.

The Evolution of the Protoplanetary Disk Recorded by Nucleosynthetic Isotope Variations of Variable Stellar Origin in Refractory Inclusions

NASA Astrophysics Data System (ADS)

Schönbächler, M.; Lai, Y.-J.; Henshall, T.; Fehr, M. A.; Cook, D. L.; Bullock, E. S.

2017-07-01

New CAI data confirm the homogeneous distribution of the short-lived p-process isotope 92Nb in the early solar system with the exception of CAIs with group II REE pattern that show increased 92Nb abundances.

Crack classification and evolution in anisotropic shale during cyclic loading tests by acoustic emission

NASA Astrophysics Data System (ADS)

Wang, Miaomiao; Tan, Chengxuan; Meng, Jing; Yang, Baicun; Li, Yuan

2017-08-01

Characterization and evolution of the cracking mode in shale formation is significant, as fracture networks are an important element in shale gas exploitation. In this study we determine the crack modes and evolution in anisotropic shale under cyclic loading using the acoustic emission (AE) parameter-analysis method based on the average frequency and RA (rise-time/amplitude) value. Shale specimens with bedding-plane orientations parallel and perpendicular to the axial loading direction were subjected to loading cycles with increasing peak values until failure occurred. When the loading was parallel to the bedding plane, most of the cracks at failure were shear cracks, while tensile cracks were dominant in the specimens that were loaded normal to the bedding direction. The evolution of the crack mode in the shale specimens observed in the loading-unloading sequence except for the first cycle can be divided into three stages: (I) no or several cracks (AE events) form as a result of the Kaiser effect, (II) tensile and shear cracks increase steadily at nearly equal proportions, (III) tensile cracks and shear cracks increase abruptly, with more cracks forming in one mode than in the other. As the dominant crack motion is influenced by the bedding, the failure mechanism is discussed based on the evolution of the different crack modes. Our conclusions can increase our understanding of the formation mechanism of fracture networks in the field.

Selective Extraction of Rare Earth Elements from Permanent Magnet Scraps with Membrane Solvent Extraction

DOE PAGES

Kim, Daejin; Powell, Lawrence E.; Delmau, Lætitia H.; ...

2015-06-24

In this paper, the rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acidmore » solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. Finally, the resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets.« less

REE in the Great Whale River estuary, northwest Quebec

NASA Technical Reports Server (NTRS)

Goldstein, Steven J.; Jacobsen, Stein B.

1988-01-01

A report on REE concentrations within the estuary of the Great Whale River in northwest Quebec and in Hudson Bay is given, showing concentrations which are less than those predicted by conservative mixing of seawater and river water, indicating removal of REE from solution. REE removal is rapid, occurring primarily at salinities less than 2 percent and ranges from about 70 percent for light REE to no more than 40 percent for heavy REE. At low salinity, Fe removal is essentially complete. The shape of Fe and REE vs. salinity profiles is not consistent with a simple model of destabilization and coagulation of Fe and REE-bearing colloidal material. A linear relationship between the activity of free ion REE(3+) and pH is consistent with a simple ion-exchange model for REE removal. Surface and subsurface samples of Hudson Bay seawater show high REE and La/Yb concentrations relative to average seawater, with the subsurface sample having a Nd concentration of 100 pmol/kg and an epsilon(Nd) of -29.3; characteristics consistent with river inputs of Hudson Bay. This indicates that rivers draining the Canadian Shield are a major source of nonradiogenic Nd and REE to the Atlantic Ocean.

Wastewater management and Marcellus Shale gas development: trends, drivers, and planning implications.

PubMed

Rahm, Brian G; Bates, Josephine T; Bertoia, Lara R; Galford, Amy E; Yoxtheimer, David A; Riha, Susan J

2013-05-15

Extraction of natural gas from tight shale formations has been made possible by recent technological advances, including hydraulic fracturing with horizontal drilling. Global shale gas development is seen as a potential energy and geopolitical "game-changer." However, widespread concern exists with respect to possible environmental consequences of this development, particularly impacts on water resources. In the United States, where the most shale gas extraction has occurred, the Marcellus Shale is now the largest natural gas producing play. To date, over 6,000,000 m(3) of wastewater has been generated in the process of extracting natural gas from this shale in the state of Pennsylvania (PA) alone. Here we examine wastewater management practices and trends for this shale play through analysis of industry-reported, publicly available data collected from the Pennsylvania Department of Environmental Protection Oil and Gas Reporting Website. We also analyze the tracking and transport of shale gas liquid waste streams originating in PA using a combination of web-based and GIS approaches. From 2008 to 2011 wastewater reuse increased, POTW use decreased, and data tracking became more complete, while the average distance traveled by wastewater decreased by over 30%. Likely factors influencing these trends include state regulations and policies, along with low natural gas prices. Regional differences in wastewater management are influenced by industrial treatment capacity, as well as proximity to injection disposal capacity. Using lessons from the Marcellus Shale, we suggest that nations, states, and regulatory agencies facing new unconventional shale development recognize that pace and scale of well drilling leads to commensurate wastewater management challenges. We also suggest they implement wastewater reporting and tracking systems, articulate a policy for adapting management to evolving data and development patterns, assess local and regional wastewater treatment infrastructure in terms of capacity and capability, promote well-regulated on-site treatment technologies, and review and update wastewater management regulations and policies. Copyright © 2013 Elsevier Ltd. All rights reserved.

Are Predictive Equations for Estimating Resting Energy Expenditure Accurate in Asian Indian Male Weightlifters?

PubMed

Joseph, Mini; Gupta, Riddhi Das; Prema, L; Inbakumari, Mercy; Thomas, Nihal

2017-01-01

The accuracy of existing predictive equations to determine the resting energy expenditure (REE) of professional weightlifters remains scarcely studied. Our study aimed at assessing the REE of male Asian Indian weightlifters with indirect calorimetry and to compare the measured REE (mREE) with published equations. A new equation using potential anthropometric variables to predict REE was also evaluated. REE was measured on 30 male professional weightlifters aged between 17 and 28 years using indirect calorimetry and compared with the eight formulas predicted by Harris-Benedicts, Mifflin-St. Jeor, FAO/WHO/UNU, ICMR, Cunninghams, Owen, Katch-McArdle, and Nelson. Pearson correlation coefficient, intraclass correlation coefficient, and multiple linear regression analysis were carried out to study the agreement between the different methods, association with anthropometric variables, and to formulate a new prediction equation for this population. Pearson correlation coefficients between mREE and the anthropometric variables showed positive significance with suprailiac skinfold thickness, lean body mass (LBM), waist circumference, hip circumference, bone mineral mass, and body mass. All eight predictive equations underestimated the REE of the weightlifters when compared with the mREE. The highest mean difference was 636 kcal/day (Owen, 1986) and the lowest difference was 375 kcal/day (Cunninghams, 1980). Multiple linear regression done stepwise showed that LBM was the only significant determinant of REE in this group of sportspersons. A new equation using LBM as the independent variable for calculating REE was computed. REE for weightlifters = -164.065 + 0.039 (LBM) (confidence interval -1122.984, 794.854]. This new equation reduced the mean difference with mREE by 2.36 + 369.15 kcal/day (standard error = 67.40). The significant finding of this study was that all the prediction equations underestimated the REE. The LBM was the sole determinant of REE in this population. In the absence of indirect calorimetry, the REE equation developed by us using LBM is a better predictor for calculating REE of professional male weightlifters of this region.

Uptake of Germanium and Rare Earth Elements (La, Gd, Er, Nd) by white mustard (Brassica alba L.) and common millet (Panicum milliaceum L.) as affected by Phosphorus Nutrition

NASA Astrophysics Data System (ADS)

Zill, Juliane; Wiche, Oliver

2015-04-01

The effect of phosphate nutrition is important due to the future usage of fertilizer treatment in phytomining experiments e.g. in accumulation of the economically important rare earth elements (REE). It is expected that the trivalent charge of REE will result in complexation with phosphate and REEs could be immobilized and not further bioavailable for plants which would cause losses of REE concentration in biomass. To investigate this influence on lanthanum, neodymium, gadolinium and erbium two plant species Brassica alba (white mustard) and Panicum miliaceum (common millet) were cultured in a greenhouse study. The plants were cultivated onto two different substrates and were poured with modified REE and phosphate solutions within an eight-week period. The concentrations of REE in soil, soil solution and plant samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The results show an increase of concentration of REE with increasing levels of element solution applied for both species. REE accumulations are elevated in roots and decrease in the order of roots> leaves> stem> fruit/blossom. Brassica accumulated more REE in root whereas Panicum showed higher REE concentrations in leaves. Exposure to increased phosphate addition did not significantly change the concentrations of REE in both plant species yet the REE concentrations in leaves slightly decreased with increasing phosphate addition. For root and stem no precise trend could be determined. It is most likely that REEs precipitate with phosphate on root surfaces and in the roots. The bioavailability of REE to plants is affected by complexation processes of REEs with phosphate in the rhizosphere. The results indicate that phosphate application plays an important role on REE uptake by roots and accumulation in different parts of a plant and it might have an influence on translocation of REE within the plant.

Melt extraction and mantle source at a Southwest Indian Ridge Dragon Bone amagmatic segment on the Marion Rise

NASA Astrophysics Data System (ADS)

Gao, Changgui; Dick, Henry J. B.; Liu, Yang; Zhou, Huaiyang

2016-03-01

This paper works on the trace and major element compositions of spatially associated basalts and peridotites from the Dragon Bone amagmatic ridge segment at the eastern flank of the Marion Platform on the ultraslow spreading Southwest Indian Ridge. The rare earth element compositions of basalts do not match the pre-alteration Dragon Bone peridotite compositions, but can be modeled by about 5 to 10% non-modal batch equilibrium melting from a DMM source. The Dragon Bone peridotites are clinopyroxene-poor harzburgite with average spinel Cr# 27.7. The spinel Cr# indicates a moderate degree of melting. However, CaO and Al2O3 of the peridotites are lower than other abyssal peridotites at the same Mg# and extent of melting. This requires a pyroxene-poor initial mantle source composition compared to either hypothetical primitive upper mantle or depleted MORB mantle sources. We suggest a hydrous melting of the initial Dragon Bone mantle source, as wet melting depletes pyroxene faster than dry. According to the rare earth element patterns, the Dragon Bone peridotites are divided into two groups. Heavy REE in Group 1 are extremely fractionated from middle REE, which can be modeled by 7% fractional melting in the garnet stability field and another 12.5 to 13.5% in the spinel stability field from depleted and primitive upper mantle sources, respectively. Heavy REE in Group 2 are slightly fractionated from middle REE, which can be modeled by 15 to 20% fractional melting in the spinel stability field from a depleted mantle source. Both groups show similar melting degree to other abyssal peridotites. If all the melt extraction occurred at the middle oceanic ridge where the peridotites were dredged, a normal 6 km thick oceanic crust is expected at the Dragon Bone segment. However, the Dragon Bone peridotites are exposed in an amagmatic ridge segment where only scattered pillow basalts lie on a partially serpentinized mantle pavement. Thus their depletion requires an earlier melting occurred at other place. Considering the hydrous melting of the initial Dragon Bone mantle source, we suggest the earlier melting event occurred in an arc terrain, prior to or during the closure of the Mozambique Ocean in the Neproterozoic, and the subsequent assembly of Gondwana. Then, the Al2O3 depleted and thus buoyant peridotites became the MORB source for Southwest Indian Ridge and formed the Marion Rise during the Gondwana breakup.

Isotope U-Pb age on single zircon and REE distribution in rocks and zircon from paleoproterozoic Kandalaksha-Kolvitsa complex Baltic shield

NASA Astrophysics Data System (ADS)

Steshenko, Ekaterina; Bayanova, Tamara; Drogobuzhskaya, Svetlana; Lyalina, Ludmila; Serov, Pavel; Chashchin, Viktor; Elizarov, Dmitriy

2017-04-01

Kandalaksha-Kolvitsa paleoproterozoic complex located in the N-E part of Baltic shield and consists of three zones. Marginal zone (mesocratic metanorite) lies at the base of the massif. Main zone is composed of leucocratic metagabbro. The upper zone is alteration of mataanorthosite and leucocratic metagabbro. All rocks were subjected to granulate and anorthositic metamorphism. Age of magmatic crystallization of the massif was determined for the first time, using the U-Pb isotope method for single zircon grains. Three fractions of single zircons from anorthosite of the Kandalaksha massif gave precise U-Pb age of 2435.5 ± 4.8 Ma. For the first time REE concentration (WR) was determined using a quadrupole mass spectrometer (Agilent 7500 ce ICP-MS) in the main varieties of rocks of the Kandalaksha-Kolvitsa paleoproterozoic complex. Anorthosite and leucocratic metagabbros (main zone) are characterized by a flat spectrum distribution of HREE, which were normalized by [1]. The REE pattern is characterized by significant positive anomalies of Eu ((Eu / Eu *)n = 3.72-3.91) in anorthosite and leucogabbros and 7.26 - in ortoamfibolitah. General content of individual elements that are common for this type of rocks: Cen = 5.82-8.54, Ybn = 1.54-1.58, which indicates that the process of crystallization of the rock occurred with predominant accumulation of plagioclase. According to geochemical and Nd-Sr isotopic data (ISr=0.702 - 0.706, ɛNd(T) = +1 - (-3)) Kandalaksha Kolvitsa complex, appear to have a general plume source with Paleoproterozoic layered intrusions of the Baltic Shield [2] Distribution of REE (ELAN-9000 ICP-MS) in zircon have a typical magmatic species: a positive Ce, negative Eu anomaly and HREE flat spectrum. Titanium content in zircons were measured for the calculation of their crystallization temperature with 8350C. These data are evidence of magmatic origin of zircon [3]. The scientific researches are supported by RFBR (projects № 15-35-20501, № 16-05-00305, 16-05-00367, 16-05-00427) and theme of state assignment № 0231-2015-0005. References: 1. Boynton W.V. Cosmochemistry of the rare earth elements: meteorite studies // Ed. Henderson P. Rare earth element geochemistry. Amsterdam: Elsevier. 1984. P. 63-114. 2. Watson E. B., Wark D.A., Thomas J.B. Crystallization thermometers for zircon and rutile // Contrib. Miner. Petrol. 2006. V. 151. P. 413-433. 3. Hoskin P.W.O. and Schaltegger U. The Composition of zirconand igneous and metamorphic petrogenesis // Reviews in mineralogy & geochemistry. 2003. V. 53. P. 27-62.

Preferred-rupture propagation to the hangingwall of the shallow part of the out-of-sequence thrust: Ishido Fault in Boso Peninsula, central Japan

NASA Astrophysics Data System (ADS)

Yamamoto, Y.; Fukuyama, M.; Ujiie, K.; Hirose, T.; Hamada, Y.; Kitamura, M.; Kamiya, N.

2016-12-01

Although earthquake ruptures in shallow portion of plate boundary have recently been identified (e.g. Tohoku, Nankai, etc.), their mechanisms why the shallow portion of plate boundary composed mainly of clay minerals can accumulate strain and make seismic slip are under controversial. An ancient out-of-sequence thrust which divided the early and late Miocene accretionary complexes in the Boso Peninsula, central Japan records rupture propagation to the shallow portion of accretionary prism (< 2 km). The fault core is composed of black-colored thin (<1 mm) pseudotachylite and fluidized fault gouge. The former is characterized by homogeneous glassy matrix including fragments of quartz/feldspar, submicron-sized Fe-rich spherules, and vesicles. Based on the mineralogy of the host rock and EDS analyses of matrices, origin of the pseudotachylite was apparently frictional melting of smectite containing Fe. Fe-rich spherules formed by rapid cooling of pseudotachylite. On the other hand, overturned fault-related drag fold developed in the footwall, within about 30 m. Although some Riedel sheared normal faults developed in the overturned footwall, no other brittle deformations were identified. These occurrences imply coexistence of low- and high-speed slips along the same thrust fault. The whole-rock major and trace elemental analyses using XRF and ICP-MS show that mudstone in the hangingwall has similar chemical composition to those of pseudotachylite and fluidized fault gouge with REE enriched patterns, whereas the footwall has different chemical characteristics with relatively flat REE pattern and low LOI. Therefore, the protolith of pseudotachylite and fluidized fault gouge is mudstone in the hangingwall. These data imply that rupture propagation preferably occurred in the hangingwall along the fault zone. The footwall was also deformed apparently during slow-slip deformation leading to formation of the overturn, whereas only the hangingwall, just side of the fault zone, slipped under high-speed shear.

Geochemical, mineralogical and Re-Os isotopic constraints on the origin of Tethyan oceanic mantle and crustal rocks from the Central Pontides, northern Turkey

NASA Astrophysics Data System (ADS)

Çelik, Ömer Faruk; Marzoli, Andrea; Marschik, Robert; Chiaradia, Massimo; Mathur, Ryan

2018-02-01

Chromite, ultramafic and mafic rocks from Eldivan, Yapraklı, Ayli Dağ, Küre, Elekdağ and Kızılırmak in northern Turkey have been studied to determine their mineral and whole-rock geochemical, and Re-Os isotope geochemical characteristics. Most of the studied peridotites display depleted but commonly V-shaped chondrite-normalized rare-earth element (REE) patterns while some peridotites as well as pyroxenites from all areas exhibit light REE depleted patterns. Olivine (forsterite 82 to 92 mol%) and spinel (chromium number 13 to 63) in the studied peridotites exhibit a wide range of compositions. Compositions of spinels suggest that peridotites from Eldivan, Ayli Dağ and Küre experienced relatively large degrees of partial melting ( 15 and 19 wt%), whereas those of the Kızılırmak area most likely reflect lower melting degrees ( 4-6 wt%). Whole-rock and mineral chemical data indicate that the ultramafic rocks are similar to abyssal and supra-subduction zone peridotites. The ultramafic rocks of the investigated areas exhibit a wide range of 187Re/188Os (0.12 to 6.6) and measured 187Os/188Os (0.122-1.14), while the basaltic rocks from Küre, Eldivan and Kızılırmak areas have high 187Re/188Os (128-562) and measured 187Os/188Os (0.724-1.943). On the other hand, chromite from Eldivan, Elekdağ and Kızılırmak show high Os contents (21.81-44.04 ppb) and low 187Re/188Os (0.015-0.818) and 187Os/188Os (0.122-0.133). Re-Os model ages (TChur) for all analyzed samples yielded scattered ages ranging from Jurassic to Proterozoic. Overall, geochemical data are interpreted to reflect different degrees of partial melting, melt - rock interactions and metasomatic effects that produced a heterogeneous mantle in a supra-subduction setting.

Assessing trace element diffusion models in fossil and sub-fossil bone

NASA Astrophysics Data System (ADS)

Suarez, C. A.; Kohn, M. J.

2012-12-01

Three different diffusion models have been proposed to explain trace element uptake during fossilization of bone: diffusion-adsorption (DA), diffusion-recrystallization (DR), and double-medium diffusion (DMD). Theoretically, differences in trace element profiles, particularly the rare earth elements (REE) and U, can discriminate among these possibilities. In this study, we tested which model best explains natural samples by analyzing trace element profiles in natural bone using laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS). Fossil bones ranging in age from a few ka to over 100 Ma were analyzed along traverses from the outer cortical edge to the inner marrow cavity margin. Forty major, minor and trace elements were analyzed, notably Ca, P, transition metals, Sr, Ba, REE, U, Th and Pb. Spatial and analytical resolutions were ~10 μm and ~100 ppb respectively. Many specimens show commonly observed exponential decreases in REE from the outer edge and marrow cavity, with relatively homogeneous U distributions. Yet, most significantly, specimens from American Falls (last interglacial) and Duck Point (last glacial maximum) show distinctive U plateaus adjacent to the outer and inner cortical bone margins. Whereas exponential profiles can be produced by different uptake processes, such plateaus are diagnostic of a DR mechanism. Our work is consistent with recent investigation of trace element diffusivities in modern fresh and deproteinated bone. These studies show similar diffusion rates for REE and U, so the profound disparity in U vs. REE profiles in most fossils cannot result solely from differences in volume diffusion within the context of DA and DMD. Rather, as a recrystallization front propagates into bone, the bone appears to encode changing soil water compositions with earlier vs. later compositions reflected in the bone margin vs. interior. Soil water U concentrations apparently remain nearly fixed during fossilization, whereas REE are rapidly stripped from the surrounding matrix, leading to nearly homogeneous U vs. steep REE profiles. However in our Pleistocene bones (American Falls and Duck Point), changes to U concentrations on the bone margin reveal more complex changes to boundary compositions, and eliminate both DA and DMD (alone) as the dominant mechanisms of trace element uptake. Our work reconciles disparate zoning patterns observed in fossil bone, and simplifies interpretations of soil or sediment water chemistry, but complicates U-series dating of fossils.

Rare earth elements in human and animal health: State of art and research priorities.

PubMed

Pagano, Giovanni; Aliberti, Francesco; Guida, Marco; Oral, Rahime; Siciliano, Antonietta; Trifuoggi, Marco; Tommasi, Franca

2015-10-01

A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures have been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments. Copyright © 2015 Elsevier Inc. All rights reserved.

Tectonic Setting and Bimodal Magmatic Evolution of Eocene Volcanic Rocks of the Bijgerd-Kuh-e Kharchin area, Uromieh-Dokhtar Zone, Iran

NASA Astrophysics Data System (ADS)

Davarpanah, A.; Khalatbari-Jafari, M.; Babaie, H. A.; Krogstad, E. J.; Mobasher, K.; La Tour, T. E.; Deocampo, D. M.

2008-12-01

Geochemical composition and texture of the Middle and Late Eocene volcanic, volcaniclastic, and volcanic- sedimentary rocks in the Bijgerd-Kuh-e Kharchin area, northwest of Saveh, provide significant geochemical and geological clues for the tectonic and magmatic evolution of the Uromieh-Dokhtar volcanic-plutonic zone of Iran. The Middle Eocene volcanic rocks have an intermediate composition and include green tuff and tuffaceous sandstone with intercalated sandstone, sandy tuff, and shale. The shale has lenses of nummulite- bearing limestone with a Middle Eocene detrital age. The time between the Middle and Late Eocene volcanic activities in this area is marked by the presence of andesite and rhyolitic tuff. The Late Eocene succession is distinguished by the presence of four alternating levels (horizons) of intermediate lava and ignimbrite which we designate as Eig. The ignimbrites of the Eig sequence have a rhyolitic composition and include ignimbrite- breccia, ignimbrite-tuff, and ignimbrite-lava pairs. The volume of the felsic volcanic rocks in this sequence far exceeds that of the intermediate rocks, which makes it unlikely that they evolved through the magmatic differentiation of a basaltic magma. The presence of the nummulite-bearing limestone lenses, and sandstone and conglomerate interbeds between the ignimbrites, suggests a shallow marine environment for the pyroclastic deposition and probably the eruptions. The tuff and siltstone of the Est unit that sits above the first ignimbrite may represent deep water, Late Eocene deposit. Oligo-Miocene limestone of the Qom Formation unconformably overlies the uppermost Late Eocene ignimbrite. Washings from red marls give microfossils with Late Eocene age for the Eig sequence, which is synchronous with other paleontological evidence that puts the peak volcanic activity as Late Eocene in the Bijgerd-Kuh-e Kharchin area. Field and petrographic evidence for magma mixing/mingling is given by the presence of mafic- intermediate enclaves in the ignimbrite, hybrid breccias with felsic and mafic clasts, felsic pseudo-flames filled with intermediate lava, heterogeneity in the ignimbrite texture, and sieve texture and oscillatory zoning of plagioclase and opacitization of olivine in the intermediate lava. Geochemical analyses of the major and trace elements (including the REE) and rock texture and assemblages indicate the bimodal magmatic characteristics of the mafic-intermediate lavas and ignimbrites. The tuff and the breccia show a hybrid elemental distribution between those of rhyolite and basalt. The ignimbrites show more enriched compositions than those of the mafic and intermediate rocks on the chondrite-normalized trace element distribution diagram. The higher enrichment of the LREE in the ignimbrites may be due to a crustal contribution. The primitive mantle-normalized elemental distributions show a distinct depletion of Nb and Ti, which suggests a subduction-related volcanism during Eocene.

Rare earth element selenochemistry of immiscible liquids and zircon at Apollo 14 - An ion probe study of evolved rocks on the moon

NASA Technical Reports Server (NTRS)

Snyder, Gregory A.; Taylor, Lawrence A.; Crozaz, Ghislaine

1993-01-01

Results are presented of trace-element analyses of three lunar zircons. The major-element and REE compositions were determined using electron microprobes, and a correction was made for zircon for Zr-Si-O molecular interferences in the La to Pr mass region. The three zircons were found to exhibit similar REE abundances and patterns. Results of the analyses confirm earlier studies (Hess et al., 1975; Watson, 1976; Neal and Taylor, 1989) on the partitioning behavior of trace elements in immiscible liquid-liquid pairs. The results also support the postulated importance of silicate liquid immiscibility in the differentiation of the upper mantle and crust of the moon.

Changes in Lava Compositions and With Time From the Eocene Through the Miocene for the Mariana Forearc

NASA Astrophysics Data System (ADS)

Reagan, M. K.; Mohler, D.; Brian, H.; Hickey-Vargas, R.; Hanan, B.

2003-12-01

We are investigating the evolution of volcanism in the Mariana arc from the initiation of subduction of the Pacific plate beneath the Philippine plate in the Eocene through the Miocene. The oldest lavas in the Mariana fore-arc region are a ca 49 Ma tholeiite to boninite sequence from DSDP sites 458 and 459. These tholeiites have NMORB-like REE, HFSE, and Th concentrations, but are enriched in LIL elements, Pb, and U. The capping boninite-series glasses have similar slab-derived trace element abundance patterns, but lower and flatter REE contents (1-2 x PUM). 40Ar/39Ar ages obtained on boninite series lavas from Guam stretch back to 44Ma. These lavas have U-shaped REE patterns and HREE concentrations about 3-8 x PUM. La/Nb decrease and Hf/Sm increase with increasing Ba/La for both the DSDP and Guam lavas. Pb isotope values plot within fields defined by Pacific plate lavas and volcanogenic sediments (Meijer, 1976, GSA Bull., v. 87; Pearce et al., 1999, J. Petrol., v. 40). Hf and Pb isotopic compositions change consistently with Hf/Sm and Ba/La ratios for lavas from the DSDP sites, but not for those from Guam. The data suggest either that little of the Pb in these lavas was derived from subducting sediments, or that the contrast in Pb isotopes between lavas from Guam and slab fluids was inconsequential. The source of the DSDP site lavas was similar to a Pacific or transitional Pacific-Indian Ocean MORB-source. Fluxed melting at high-P generated the tholeiites. Boninites were generated at low-P by continued fluxed melting. The mantle source for the boninite-series lavas from Guam was less depleted. Progressive fluxed melting here apparently occurred with less mantle upwelling. In both locations, the variations in La/Nb and perhaps the Hf/Sm ratios appear to be related to changes in the residual mantle source mineralogy with progressive melting. Rhyolites erupted on Saipan at 45- 46 Ma are unusually high in silica for an oceanic island arc setting. These lavas are enigmatic in that they have trace element and isotopic compositions similar to those of Oligocene (36-32 Ma) mature arc andesites and dacites from forearc sites. Pb isotope values for all of these lavas plot along a trend that stretches from the NHRL toward Pacific siliceous sediments, with the rhyolites plotting at the least radiogenic end of the array. Basalt dikes with ages of ca. 41 Ma cut the boninite series lavas in Guam. These basalts have trace element patterns of typical arc tholeiites, and mark the first appearance of relatively normal mafic arc lavas in this system. Pb isotope compositions for these samples indicate that siliceous sediment also makes its first appearance at this time. A second stage of normal arc volcanism began on Guam and Saipan at about 14 Ma, after spreading in the Parece Vela Basin ceased. These lavas have incompatible trace element and isotopic ratios that are remarkably similar to those of the modern Mariana arc. In conclusion: lavas from DSDP sites 458 and 459 were apparently generated from upwelling mantle that rushed in behind the newly subducting Pacific lithosphere (see Stern and Bloomer, 1992, GSA Bull. v. 104; Hall et al., 2003, EPSL, v. 212). The transition from an upwelling mantle wedge to relatively normal mantle counterflow and P-T distributions in the mantle wedge apparently required several million years of subduction and cooling of the corner of the mantle wedge. The compositions of the mantle (Pacific to Indian) and the subducted components (basaltic to silicic sediment) both changed with the mantle convection regime.

Predictive Validity of the Air Force Officer Qualifying Test for USAF Air Battle Manager Training Performance

DTIC Science & Technology

2008-09-01

performance criteria including passing/failing training, training grades, class rank (Carretta & Ree, 2003; Olea & Ree, 1994), and several non...are consistent with prior validations of the AFOQT versus academic performance criteria in pilot (Carretta & Ree, 1995; Olea & Ree, 1994; Ree...Carretta, & Teachout, 1995)) and navigator ( Olea & Ree, 1994) training. Subsequent analyses took three different approaches to examine the

Rare earth elements in human hair from a mining area of China.

PubMed

Wei, Binggan; Li, Yonghua; Li, Hairong; Yu, Jiangping; Ye, Bixiong; Liang, Tao

2013-10-01

Rare earth minerals have been mined for more than 50 years in Inner Mongolia of China. In the mining area rare earth elements (REE) may be significantly accumulated in humans. Therefore, the aim of this paper is to characterize the REE concentrations in hair of local residents. REE concentrations in hair of 118 subjects were determined. The results showed that the mean concentrations of the determined REE in the hair of both females and males were usually higher from mining area than from control area. The mean concentrations of all the fifteen REE were much higher in hair of males than in hair of females from mining area. This suggested that males might be more sensitive to REE than females. In addition, the mean contents of the REE in hair of miners, particularly light REE (La, Ce, Pr and Nd), were usually much higher than the values in hair of non-miners from both mining area and control area, indicating that the miners were exposed to higher concentrations of REE in occupational environment. Among age groups, the relationships between REE concentrations and age groups showed that more and more concentrations of light REE accumulated in body of both females and males with age until 60 years, while heavy REE concentrations decreased with age in males who were exposed to low concentrations of heavy REE. Copyright © 2013 Elsevier Inc. All rights reserved.

Fracture patterns and their origin in the upper Devonian Antrim Shale gas reservoir of the Michigan basin; a review

USGS Publications Warehouse

Ryder, Robert T.

1996-01-01

INTRODUCTION: Black shale members of the Upper Devonian Antrim Shale are both the source and reservoir for a regional gas accumulation that presently extends across parts of six counties in the northern part of the Michigan basin (fig. 1). Natural fractures are considered by most petroleum geologists and oil and gas operators who work the Michigan basin to be a necessary condition for commercial gas production in the Antrim Shale. Fractures provide the conduits for free gas and associated water to flow to the borehole through the black shale which, otherwise, has a low matrix permeability. Moreover, the fractures assist in the release of gas adsorbed on mineral and(or) organic matter in the shale (Curtis, 1992). Depths to the gas-producing intervals (Norwood and Lachine Members) generally range from 1,200 to 1,800 ft (Oil and Gas Journal, 1994). Locally, wells that produce gas from the accumulation are as deep as 2,200 (Oil and Gas Journal, 1994). Even though natural fractures are an important control on Antrim Shale gas production, most wells require stimulation by hydraulic fracturing to attain commercial production rates (Kelly, 1992). In the U.S. Geological Survey's National Assessment of United States oil and gas, Dolton (1995) estimates that, at a mean value, 4.45 trillion cubic feet (TCF) of gas are recoverable as additions to already discovered quantities from the Antrim Shale in the productive area of the northern Michigan trend. Dolton (1995) also suggests that undiscovered Antrim Shale gas accumulations exist in other parts of the Michigan basin. The character, distribution, and origin of natural fractures in the Antrim Shale gas accumulation have been studied recently by academia and industry. The intent of these investigations is to: 1) predict 'sweet spots', prior to drilling, in the existing gas-producing trend, 2) improve production practices in the existing trend, 3) predict analogous fracture-controlled gas accumulations in other parts of the Michigan basin, and 4) improve estimates of the recoverable gas in the Antrim Shale gas plays (Dolton, 1995). This review of published literature on the characteristics of Antrim Shale fractures, their origin, and their controls on gas production will help to define objectives and goals in future U.S. Geological Survey studies of Antrim Shale gas resources.

Geophysical evaluation of sandstone aquifers in the Reconcavo-Tucano Basin, Bahia -- Brazil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lima, O.A.L. de

1993-11-01

The upper clastic sediments in the Reconcavo-Tucano basin comprise a multilayer aquifer system of Jurassic age. Its groundwater is normally fresh down to depths of more than 1,000 m. Locally, however, there are zones producing high salinity or sulfur geothermal water. Analysis of electrical logs of more than 150 wells enabled the identification of the most typical sedimentary structures and the gross geometries for the sandstone units in selected areas of the basin. Based on this information, the thick sands are interpreted as coalescent point bars and the shales as flood plain deposits of a large fluvial environment. The resistivitymore » logs and core laboratory data are combined to develop empirical equations relating aquifer porosity and permeability to log-derived parameters such as formation factor and cementation exponent. Temperature logs of 15 wells were useful to quantify the water leakage through semiconfining shales. The groundwater quality was inferred from spontaneous potential (SP) log deflections under control of chemical analysis of water samples. An empirical chart is developed that relates the SP-derived water resistivity to the true water resistivity within the formations. The patterns of salinity variation with depth inferred from SP logs were helpful in identifying subsurface flows along major fault zones, where extensive mixing of water is taking place. A total of 49 vertical Schlumberger resistivity soundings aid in defining aquifer structures and in extrapolating the log derived results. Transition zones between fresh and saline waters have also been detected based on a combination of logging and surface sounding data. Ionic filtering by water leakage across regional shales, local convection and mixing along major faults and hydrodynamic dispersion away from lateral permeability contrasts are the main mechanisms controlling the observed distributions of salinity and temperature within the basin.« less

Effects of rare earth elements and REE-binding proteins on physiological responses in plants.

PubMed

Liu, Dongwu; Wang, Xue; Chen, Zhiwei

2012-02-01

Rare earth elements (REEs), which include 17 elements in the periodic table, share chemical properties related to a similar external electronic configuration. REEs enriched fertilizers have been used in China since the 1980s. REEs could enter the cell and cell organelles, influence plant growth, and mainly be bound with the biological macromolecules. REE-binding proteins have been found in some plants. In addition, the chlorophyll activities and photosynthetic rate can be regulated by REEs. REEs could promote the protective function of cell membrane and enhance the plant resistance capability to stress produced by environmental factors, and affect the plant physiological mechanism by regulating the Ca²⁺ level in the plant cells. The focus of present review is to describe how REEs and REE-binding proteins participate in the physiological responses in plants.

Steric hindrance and the enhanced stability of light rare-earth elements in hydrothermal fluids

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2009-01-01

A series of X-ray absorption spectroscopy (XAS) experiments were made to determine the structure and stability of aqueous REE (La, Nd, Gd, and Yb) chloride complexes to 500 ??C and 520 MPa. The REE3+ ions exhibit inner-sphere chloroaqua complexation with a steady increase of chloride coordination with increasing temperature in the 150 to 500 ??C range. Furthermore, the degree of chloride coordination of REE3+ inner-sphere chloroaqua complexes decreases significantly from light to heavy REE. These results indicate that steric hindrance drives the reduction of chloride coordination of REE3+ inner-sphere chloroaqua complexes from light to heavy REE. This results in greater stability and preferential transport of light REE3+ over heavy REE3+ ions in saline hydrothermal fluids. Accordingly, the preferential mobility of light REE directly influences the relative abundance of REE in rocks and minerals and thus needs to be considered in geochemical modeling of petrogenetic and ore-forming processes affected by chloride-bearing hydrothermal fluids.

Landscape consequences of natural gas extraction in Lackawanna and Wayne Counties, Pennsylvania, 2004-2010

USGS Publications Warehouse

Milheim, L.E.; Slonecker, E.T.; Roig-Silva, C.M.; Malizia, A.R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells, which sometimes use the same technique, are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Lackawanna County and Wayne County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Greene and Tioga Counties, Pennsylvania, 2004-2010

USGS Publications Warehouse

Slonecker, E.T.; Milheim, L.E.; Roig-Silva, C.M.; Fisher, G.B.

2012-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in the area of Pennsylvania. Coalbed methane, which is sometimes extracted using the same technique, is commonly located in the same general area as the Marcellus Shale and is frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Greene County and Tioga County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics are also used to quantify these changes and are included in this publication.

Landscape consequences of natural gas extraction in Bradford and Washington Counties, Pennsylvania, 2004-2010

USGS Publications Warehouse

Slonecker, E.T.; Milheim, L.E.; Roig-Silva, C.M.; Malizia, A.R.; Marr, D.A.; Fisher, G.B.

2012-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in the area of Pennsylvania. Coalbed methane, which is sometimes extracted using the same technique, is often located in the same general area as the Marcellus Shale and is frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Bradford County and Washington County, Pennsylvania, between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is used to quantify these changes and are included in this publication.

Landscape consequences of natural gas extraction in Armstrong and Indiana Counties, Pennsylvania, 2004–2010

USGS Publications Warehouse

Slonecker, Terry E.; Milheim, Lesley E.; Roig-Silva, Coral M.; Malizia, Alexander R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Armstrong County and Indiana County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Somerset and Westmoreland Counties, Pennsylvania,2004--2010

USGS Publications Warehouse

Milheim, L.E.; Slonecker, E.T.; Roig-Silva, C.M.; Malizia, A.R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells, which sometimes use the same technique, are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Somerset County and Westmoreland County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Allegheny and Susquehanna Counties, Pennsylvania, 2004--2010

USGS Publications Warehouse

Slonecker, E.T.; Milheim, L.E.; Roig-Silva, C.M.; Malizia, A.R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Coalbed methane, which is sometimes extracted using the same technique, is commonly located in the same general area as the Marcellus Shale and is frequently developed in clusters of wells across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Allegheny County and Susquehanna County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Sullivan and Wyoming Counties, Pennsylvania, 2004–2010

USGS Publications Warehouse

Slonecker, Terry E.; Milheim, Lesley E.; Roig-Silva, Coral M.; Malizia, Alexander R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells, which sometimes use the same technique, are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Sullivan County and Wyoming County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Fayette and Lycoming Counties, Pennsylvania, 2004–2010

USGS Publications Warehouse

Slonecker, E.T.; Milheim, L.E.; Roig-Silva, C.M.; Malizia, A.R.; Gillenwater, B.H.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells, which sometimes use the same technique, are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Fayette County and Lycoming County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

Landscape consequences of natural gas extraction in Beaver and Butler Counties, Pennsylvania, 2004-2010

USGS Publications Warehouse

Roig-Silva, Coral M.; Slonecker, E. Terry; Milheim, Lesley E.; Malizia, Alexander R.

2013-01-01

Increased demands for cleaner burning energy, coupled with the relatively recent technological advances in accessing unconventional hydrocarbon-rich geologic formations, have led to an intense effort to find and extract natural gas from various underground sources around the country. One of these sources, the Marcellus Shale, located in the Allegheny Plateau, is currently undergoing extensive drilling and production. The technology used to extract gas in the Marcellus Shale is known as hydraulic fracturing and has garnered much attention because of its use of large amounts of fresh water, its use of proprietary fluids for the hydraulic-fracturing process, its potential to release contaminants into the environment, and its potential effect on water resources. Nonetheless, development of natural gas extraction wells in the Marcellus Shale is only part of the overall natural gas story in this area of Pennsylvania. Conventional natural gas wells, which sometimes use the same technique, are commonly located in the same general area as the Marcellus Shale and are frequently developed in clusters across the landscape. The combined effects of these two natural gas extraction methods create potentially serious patterns of disturbance on the landscape. This document quantifies the landscape changes and consequences of natural gas extraction for Beaver County and Butler County in Pennsylvania between 2004 and 2010. Patterns of landscape disturbance related to natural gas extraction activities were collected and digitized using National Agriculture Imagery Program (NAIP) imagery for 2004, 2005/2006, 2008, and 2010. The disturbance patterns were then used to measure changes in land cover and land use using the National Land Cover Database (NLCD) of 2001. A series of landscape metrics is also used to quantify these changes and is included in this publication.

U.S. shale gas trends - economic and global implications

NASA Astrophysics Data System (ADS)

Murphy, T.

2016-09-01

Natural gas from shale has moved the U.S., and North America more broadly, to become one of the largest producers of the commodity worldwide. Large technological gains have allowed reservoirs of unconventional hydrocarbons to become commercially viable to extract and market. The addition of this growing supply into the global marketplace, has upended longstanding trading patterns, and created new economic outcomes worth noting. This paper will discuss the recent trends of shale energy development in the U.S., the impact it is having on domestic and international markets, and the implications as the world shifts to a new low carbon energy paradigm. It will cover changes in workforce, midstream build out, power generation trends, petrochemicals, and emerging LNG export capacities.

Characterization and growth mechanism of a peculiar nodular structure in shale: Comprehensive study over the Sitakund anticline, Bengal basin.

NASA Astrophysics Data System (ADS)

Gazi, M. Y.; Kabir, S. M. M.; Imam, M. B.

2017-12-01

Nodular shales commonly occur in comparatively older and silty shales near the axial (proximity to core) region of Sitakund Anticline (Study area), Sitapahar Anticline, Patharia Structure, Sylhet Anticline and Mirinja Anticline as observed. Stratigraphically, they are pronounced in the Surma group of Neogene succession. They are less abundant in limb portion. In many outcrop, they are found in the incompetent bed with the obliterated bedding bounded by well bedded competent beds. Their occurrence are sporadic rather than continuous along and across the strike of the bed. At some places huge number cluster of small and big nodular shales occur while in the other places, they occur as isolated mass in the highly disturbed or obliterated beds. The Surma group is the prime startigraphic unit in Bangladesh with major economic and academic importance. Yet there is a lack of comprehensive characterization of mudrocks of Surma group. This has prompted the present research to be undertaken. An initial field based study has been followed by detail textural, mineralogical, petrological and geochemical by using upscale laboratory techniques that include Thin Section Microscopy, Laser Particle Size Analyses, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and X-ray Florescence (XRF). From laser diffraction analysis, it is evident that nodular shales are silty in nature containing approximately 60% silt (Mainly quartz). XRD pattern shows that Nodular shale contains clay minerals, predominantly illite, Kaolinite, Chlorite and expandable mixed layer clay mineral. Detail geochemical analysis of some nodular shale samples shows that there are no significant variation from other samples in major and trace element concentration. Microcrack's within the quartz grains were observed in nodular shale. Projection of 15 nodular shale long axes in outcrop shows their orientation in NNW-SSE that is parallel to the fold axis. The study suggests a new name of conventionally called nodular shales. The proposed name is "Clay Cabbage". A new model naming as "Tectono-Diagenetic (TD) Model" is proposed in this study concerning the origin of nodular shale.

Rare-earth elements

USGS Publications Warehouse

Van Gosen, Bradley S.; Verplanck, Philip L.; Seal, Robert R.; Long, Keith R.; Gambogi, Joseph; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

The rare-earth elements (REEs) are 15 elements that range in atomic number from 57 (lanthanum) to 71 (lutetium); they are commonly referred to as the “lanthanides.” Yttrium (atomic number 39) is also commonly regarded as an REE because it shares chemical and physical similarities and has affinities with the lanthanides. Although REEs are not rare in terms of average crustal abundance, the concentrated deposits of REEs are limited in number.Because of their unusual physical and chemical properties, the REEs have diverse defense, energy, industrial, and military technology applications. The glass industry is the leading consumer of REE raw materials, which are used for glass polishing and as additives that provide color and special optical properties to the glass. Lanthanum-based catalysts are used in petroleum refining, and cerium-based catalysts are used in automotive catalytic converters. The use of REEs in magnets is a rapidly increasing application. Neodymium-iron-boron magnets, which are the strongest known type of magnets, are used when space and weight are restrictions. Nickel-metal hydride batteries use anodes made of a lanthanum-based alloys.China, which has led the world production of REEs for decades, accounted for more than 90 percent of global production and supply, on average, during the past decade. Citing a need to retain its limited REE resources to meet domestic requirements as well as concerns about the environmental effects of mining, China began placing restrictions on the supply of REEs in 2010 through the imposition of quotas, licenses, and taxes. As a result, the global rare-earth industry has increased its stockpiling of REEs; explored for deposits outside of China; and promoted new efforts to conserve, recycle, and substitute for REEs. New mine production began at Mount Weld in Western Australia, and numerous other exploration and development projects noted in this chapter are ongoing throughout the world.The REE-bearing minerals are diverse and often complex in composition. At least 245 individual REE-bearing minerals are recognized; they are mainly carbonates, fluorocarbonates, and hydroxylcarbonates (n = 42); oxides (n = 59); silicates (n = 85); and phosphates (n = 26).Many of the world’s significant REE deposits occur in carbonatites, which are carbonate igneous rocks. The REEs also have a strong genetic association with alkaline magmatism. The systematic geologic and chemical processes that explain these observations are not well understood. Economic or potentially economic REE deposits have been found in (a) carbonatites, (b) peralkaline igneous systems, (c) magmatic magnetite-hematite bodies, (d) iron oxide-copper-gold (IOCG) deposits, (e) xenotime-monazite accumulations in mafic gneiss, (f) ion-absorption clay deposits, and (g) monazite-xenotime-bearing placer deposits. Carbonatites have been the world’s main source for the light REEs since the 1960s. Ion-adsorption clay deposits in southern China are the world’s primary source of the heavy REEs. Monazite-bearing placer deposits were important sources of REEs before the mid-1960s and may be again in the future. In recent years, REEs have been produced from large carbonatite bodies mined at the Mountain Pass deposit in California and, in China, at the Bayan Obo deposit in Nei Mongol Autonomous Region, the Maoniuping deposit in Sichuan Province, the Daluxiang deposit in Sichuan Province, and the Weishan deposit in Anhui Province. Alkaline igneous complexes have recently been targeted for exploration because of their enrichments in the heavy REEs.Information relevant to the environmental aspects of REE mining is limited. Little is known about the aquatic toxicity of REEs. The United States lacks drinking water standards for REEs. The concentrations of REEs in environmental media are influenced by their low abundances in crustal rocks and their limited solubility in most groundwaters and surface waters. The scarcity of sulfide minerals, including pyrite, minimizes or eliminates concerns about acid-mine drainage for carbonatite-hosted deposits and alkaline-intrusion-related REE deposits. For now, insights into environmental responses of REE mine wastes must rely on predictive models.

Major to ultra trace elements in rainfall collected in suburban Tokyo

NASA Astrophysics Data System (ADS)

Shimamura, Tadashi; Iwashita, Masato; Iijima, Satoe; Shintani, Megumi; Takaku, Yuichi

Major to ultra trace elements such as rare earth elements (REEs), platinum group elements (PGEs) in 20 rainfall events from suburban Tokyo were determined by inductively coupled plasma mass spectrometry (ICP-MS). Anion species were also determined by an ion chromatography (IC). The concentrations of PGEs were so low that only Pt was detected in some rainfall events. Enrichment factors (EFs), refer to soil and sea salt components, were calculated for the measured elements (with Al and Na as references). Be, (Na), Mg, (Al), Si, Cl, K, Fe, Rb, Sr, REEs (except La, Gd), Ta, and U were mostly originated from natural materials (soil and sea salt). For Li, B, Ca, Mn, Sr, Ba, and Cs, the contribution of natural materials was significant. EFs for Cu, Zn, As, Se, Sb, Cd, Pb, Bi, Ag, Te, Au, Pt, SO 4-S and NO 3-N exceeded 100 indicating non-crustal, non-sea salt origin, presumably anthropogenic; however, contribution of volcanic gases could not be excluded for As, Se, Te and Bi. Pt seemed to be uniformly distributed worldwide and a catalyst for automobile emission control may be the main source. Au also showed uniform distribution. On the other hand, EFs for Zr, Nb, Hf and Th were less than unity. Probably these elements resided in acid resistant refractory fine minerals that did not decompose with acid treatment, and did not evaporate and ionize in the ICP. An alternative explanation is that the concentration of these elements was lower in the soil of the sampling area than the average crust. In the crust normalized REE pattern plot, La, Eu and Gd showed clear positive anomalies. La and Gd could have anthropogenic components. A possible source of La and Gd is cracking catalyst for petrol refining, but this source does not fully explain the anomaly. The source of Gd may also be Gd-DTPA (Gadolinium (III) diethyltriaminepentaacetic acid) used for Magnetic Resonance Imaging (MRI) contrast agents. The Eu origin may be soil with higher concentration than the crust average.

Exploring Cumulates in Small, Shallow Parts of a Large Mafic Magma System to Provide Baseline Models for Crystallization in Larger Intrusions

NASA Astrophysics Data System (ADS)

Srogi, L.; Willis, K. V.; Lutz, T. M.; Plank, T. A.; Pollock, M.; Connolly, B.; Wood, A. M.

2016-12-01

Small, shallow portions of large magmatic systems cool more rapidly and potentially have less subsolidus overprinting than large mafic intrusions, but it is unclear whether they are small-scale analogs for the same crystallization processes. The Morgantown-Jacksonwald magmatic system (MJS), western Newark Basin, Pennsylvania, is part of the 201-Ma Central Atlantic Magmatic Province (CAMP) formed during Pangean rifting. The MJS consists of several interconnected intrusions exposed in cross-section from the Jacksonwald basalt at the paleosurface to 6 km depth (<0.2 GPa). Mg-rich orthopyroxene (opx) phenocrysts form crystal accumulations in some dikes and in basal and roof zones of sills in the MJS, in many CAMP intrusions, and in younger Ferrar dolerites, Antarctica. Some samples with opx phenocrysts have dm-scale modal layering. Despite ubiquitous occurrence, the opx is little-studied and our work tests most previous authors' assumption that opx was brought in from deeper intrusions. Opx cores with Mg/(Mg+Fe) of 80-77% yield mid-crustal pressures of 0.4-0.6 GPa (using method of Putirka, 2008). LA-ICPMS was used to obtain trace element concentrations in mm-size phenocrysts in a chill margin within 0.5m of the basal contact and cm-size phenocrysts from cumulate about 10m above. REE concentrations are similar in both samples: LREE-depleted cores (normalized La/Sm = 0.05-0.1); variably LREE-enriched rims; some negative Eu anomalies. REE patterns calculated for liquids in equilibrium with opx using published Kd values are roughly parallel to but significantly higher than REE in host chill margin diabase. CSDs of opx and matrix plagioclase from several samples within 10m of the basal contact will be used to evaluate models of crystal growth vs. mechanical sorting. Modes and mineral compositions are not consistent with MELTS fractionation models: opx crystallizes in place of pigeonite; pyroxenes are zoned in Ca not Fe-Mg; late-crystallizing quartz and K-feldspar are lacking. These features suggest crystallization buffered by earlier phases in the crystal mush with some melt migration, similar to processes that produce more extreme layering in large mafic intrusions.

Tracking the source of the enriched martian meteorites in olivine-hosted melt inclusions of two depleted shergottites, Yamato 980459 and Tissint

NASA Astrophysics Data System (ADS)

Peters, T. J.; Simon, J. I.; Jones, J. H.; Usui, T.; Moriwaki, R.; Economos, R. C.; Schmitt, A. K.; McKeegan, K. D.

2015-05-01

The apparent lack of plate tectonics on all terrestrial planets other than Earth has been used to support the notion that for most planets, once a primitive crust forms, the crust and mantle evolve geochemically-independent through time. This view has had a particularly large impact on models for the evolution of Mars and its silicate interior. Recent data indicating a greater potential that there may have been exchange between the martian crust and mantle has led to a search for additional geochemical evidence to support the alternative hypothesis, that some mechanism of crustal recycling may have operated early in the history of Mars. In order to study the most juvenile melts available to investigate martian mantle source(s) and melting processes, the trace element compositions of olivine-hosted melt inclusions for two incompatible-element-depleted olivine-phyric shergottites, Yamato 980459 (Y98) and Tissint, and the interstitial glass of Y98, have been measured by Secondary Ionization Mass Spectrometry (SIMS). Chondrite-normalized Rare Earth Element (REE) patterns for both Y98 and Tissint melt inclusions, and the Y98 interstitial glass, are characteristically light-REE depleted and parallel those of their host rock. For Y98, a clear flattening and upward inflection of La and Ce, relative to predictions based on middle and heavier REE, provides evidence for involvement of an enriched component early in their magmatic history; either inherited from a metasomatized mantle or crustal source, early on and prior to extensive host crystallization. Comparing these melt inclusion and interstitial glass analyses to existing melt inclusion and whole-rock data sets for the shergottite meteorite suite, defines mixing relationships between depleted and enriched end members, analogous to mixing relationships between whole rock Sr and Nd isotopic measurements. When considered in light of their petrologic context, the origin of these trace element enriched and isotopically evolved signatures represents either (1) crustal assimilation during the final few km of melt ascent towards the martian surface, or (2) assimilation soon after melt segregation, through melt-rock interaction with a portion of the martian crust recycled back into the mantle.

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE PAGES

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

2017-10-26

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

A supported liquid membrane system for the selective recovery of rare earth elements from neodymium-based permanent magnets

DOE PAGES

Kim, Daejin; Powell, Lawrence; Delmau, Lætitia H.; ...

2016-04-04

We present that the rare earth elements (REEs) play a vital role in the development of green energy and high-tech industries. In order to meet the fast-growing demand and to ensure sufficient supply of the REEs, it is essential to develop an efficient REE recovery process from post-consumer REE-containing products. In this research effort, we have developed a supported liquid membrane system utilizing polymeric hollow fiber modules to extract REEs from neodymium-based magnets with neutral extractants such as tetraoctyl digylcol amide (TODGA). The effect of process variables such as REE concentration, molar concentration of acid, and membrane area on REEmore » recovery was investigated. We have demonstrated the selective extraction and recovery of REEs such as Nd, Pr, and Dy without co-extraction of non-REEs from permanent NdFeB magnets through the supported liquid membrane system. The extracted REEs were then recovered by precipitation followed by the annealing step to obtain crystalline REE powders in nearly pure form. Finally, the recovered REE oxides were characterized by X-ray diffraction, scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, and inductively coupled plasma–optical emission spectroscopy.« less

Comparison of respiratory quotient and resting energy expenditure in two regimens of enteral feeding – continuous vs. intermittent in head-injured critically ill patients

PubMed Central

Maurya, Indubala; Pawar, Mridula; Garg, Rakesh; Kaur, Mohandeep; Sood, Rajesh

2011-01-01

Introduction: Measurement of respiratory quotient (RQ) and resting energy expenditure (REE) has been shown to be helpful in designing nutritional regimens. There is a paucity of the literature describing the impact of a feeding regimen on the energy expenditure patterns. Therefore, we studied the effect of continuous vs. intermittent feeding regimen in head-injured patients on mechanical ventilation on RQ and REE. Methods: After institutional ethical approval, this randomized study was conducted in 40 adult male patients with head injury requiring controlled mode of ventilation. Patients were randomly allocated into two groups. Group C: Feeds (30 kcal/kg/day) were given for 18 h/day, with night rest for 6 h. Group I: Six bolus feeds (30 kcal/kg/day) were given three hourly for 18 h with night rest for 6 h. RQ and REE were recorded every 30 min for 24 h. Blood sugar was measured 4 hourly. Other adverse effects such as feed intolerance, aspiration were noted. Results: Demographic profile and SOFA score were comparable in the two groups. Base line RQ (0.8 vs. 0.86) and REE (1527 vs. 1599 kcal/day) were comparable in both the groups (P>0.05). RQ was comparable in both groups during the study period at any time of the day (P>0.05). Base line RQ was compared with all other RQ values measured every half hour and fluctuation from the base line value was insignificant in both groups (P>0.05). REE was comparable in both the groups throughout the study period (P>0.5). Adequacy of feeding as assessed by EI/MREE was 105.7% and 105.3% in group C and group I, respectively. There was no significant difference in the blood sugar levels between the two groups (P>0.05). Conclusion: We found from our study that RQ, REE, and blood sugar remain comparable with two regimens of enteral feeding – continuous vs. intermittent in neurosurgical patients on ventilator support in a ICU setup. PMID:21804803

Comparison of respiratory quotient and resting energy expenditure in two regimens of enteral feeding - continuous vs. intermittent in head-injured critically ill patients.

PubMed

Maurya, Indubala; Pawar, Mridula; Garg, Rakesh; Kaur, Mohandeep; Sood, Rajesh

2011-04-01

Measurement of respiratory quotient (RQ) and resting energy expenditure (REE) has been shown to be helpful in designing nutritional regimens. There is a paucity of the literature describing the impact of a feeding regimen on the energy expenditure patterns. Therefore, we studied the effect of continuous vs. intermittent feeding regimen in head-injured patients on mechanical ventilation on RQ and REE. After institutional ethical approval, this randomized study was conducted in 40 adult male patients with head injury requiring controlled mode of ventilation. Patients were randomly allocated into two groups. Group C: Feeds (30 kcal/kg/day) were given for 18 h/day, with night rest for 6 h. Group I: Six bolus feeds (30 kcal/kg/day) were given three hourly for 18 h with night rest for 6 h. RQ and REE were recorded every 30 min for 24 h. Blood sugar was measured 4 hourly. Other adverse effects such as feed intolerance, aspiration were noted. Demographic profile and SOFA score were comparable in the two groups. Base line RQ (0.8 vs. 0.86) and REE (1527 vs. 1599 kcal/day) were comparable in both the groups (P>0.05). RQ was comparable in both groups during the study period at any time of the day (P>0.05). Base line RQ was compared with all other RQ values measured every half hour and fluctuation from the base line value was insignificant in both groups (P>0.05). REE was comparable in both the groups throughout the study period (P>0.5). Adequacy of feeding as assessed by EI/MREE was 105.7% and 105.3% in group C and group I, respectively. There was no significant difference in the blood sugar levels between the two groups (P>0.05). We found from our study that RQ, REE, and blood sugar remain comparable with two regimens of enteral feeding - continuous vs. intermittent in neurosurgical patients on ventilator support in a ICU setup.

POLICY ANALYSIS OF PRODUCED WATER ISSUES ASSOCIATED WITH IN-SITU THERMAL TECHNOLOGIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robert Keiter; John Ruple; Heather Tanana

2011-02-01

Commercial scale oil shale and oil sands development will require water, the amount of which will depend on the technologies adopted and the scale of development that occurs. Water in oil shale and oil sands country is already in scarce supply, and because of the arid nature of the region and limitations on water consumption imposed by interstate compacts and the Endangered Species Act, the State of Utah normally does not issue new water rights in oil shale or oil sands rich areas. Prospective oil shale and oil sands developers that do not already hold adequate water rights can acquiremore » water rights from willing sellers, but large and secure water supplies may be difficult and expensive to acquire, driving oil shale and oil sands developers to seek alternative sources of supply. Produced water is one such potential source of supply. When oil and gas are developed, operators often encounter ground water that must be removed and disposed of to facilitate hydrocarbon extraction. Water produced through mineral extraction was traditionally poor in quality and treated as a waste product rather than a valuable resource. However, the increase in produced water volume and the often-higher quality water associated with coalbed methane development have drawn attention to potential uses of produced water and its treatment under appropriations law. This growing interest in produced water has led to litigation and statutory changes that must be understood and evaluated if produced water is to be harnessed in the oil shale and oil sands development process. Conversely, if water is generated as a byproduct of oil shale and oil sands production, consideration must be given to how this water will be disposed of or utilized in the shale oil production process. This report explores the role produced water could play in commercial oil shale and oil sands production, explaining the evolving regulatory framework associated with produced water, Utah water law and produced water regulation, and the obstacles that must be overcome in order for produced water to support the nascent oil shale and oil sands industries.« less