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.

Origin of heavy rare earth mineralization in South China

PubMed Central

Xu, Cheng; Kynický, Jindřich; Smith, Martin P.; Kopriva, Antonin; Brtnický, Martin; Urubek, Tomas; Yang, Yueheng; Zhao, Zheng; He, Chen; Song, Wenlei

2017-01-01

Heavy rare earth elements (HREE) are dominantly mined from the weathering crusts of granites in South China. Although weathering processes occur globally, no economic HREE resources of this type have yet been found outside China. Here, we report the occurrence of unidentified REE minerals in the granites from South Chinese deposits. They contain high levels of both HREE and light REE, but are strongly depleted in Ce, implying high oxidation state. These REE minerals show higher initial Nd isotope than primary REE-rich minerals (ɛNd(t)=0.9±0.8 versus −11.5±0.5). The mineralized weathering crusts inherited REE signature of the granites, but show more Ce depletion and more overall concentration of the REE. We propose, therefore, that highly oxidized, REE-rich fluids, derived from external, isotopically depleted sources, metasomatized the granites, which resulted in Ce depletion as Ce4+ and enrichment of the remaining REE, especially the HREE, contributing to formation of a globally important REE resource. PMID:28220784

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.

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 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.

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.

Origin of the anomalies in light and middle REE in sediments of an estuary affected by phosphogypsum wastes (south-western Spain).

PubMed

Borrego, J; López-González, N; Carro, B; Lozano-Soria, O

2004-12-01

Sc, Y, Th, Cu and rare earth elements (REE) concentrations have been analyzed in 14 samples of surface sediments and in two gravity cores by means of ICP-MS. Mean concentrations of Sc, Y and Th in surface sediments are 6.23, 4.76 and 16.30 ppm, respectively, lower than those present in the Upper Continental Crust (UCC). Cu concentration in these sediments is very high, 1466 ppm, and is caused by inputs from the Odiel and Tinto rivers, affected by acid mine drainage. SigmaREE mean concentration is 106.8 ppm, lower than that observed in other rivers and estuaries. In the cores, Sc, Y and Th concentrations show a significant increase in the intermediate levels, between 10 and 40 cm depth. The same pattern exists with Cu, where concentrations of 4440 ppm can be reached. Vertical evolution patterns for Sc, Y, Cu and heavy REE (HREE) are similar, and contrary to those shown by Th, light REE (LREE) and middle REE (MREE). Plots of North American Shale Composite (NASC)-normalized REE data of surface sediments show a slight depletion in REE concentrations. Most samples present with middle REE enrichment relative to light REE and heavy REE. Conversely, samples of the intermediate levels of the cores show significant enrichment of REE relative to NASC and high values in the (La/Gd)NASC and (La/Yb)NASC ratios. These anomalies in the fractionation patterns caused by enrichments in LREE and MREE concentrations is related to the presence of high concentrations of Th. They were generated by effluents from fertilizer factories between 1968 and 1998 which used phosphorite as source material.

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.

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.

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.

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.

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.

Rare earth and trace element geochemistry of a fragment of Jurassic seafloor, Point Sal, California

NASA Technical Reports Server (NTRS)

Menzies, M.; Blanchard, D.; Brannon, J.; Korotev, R.

1977-01-01

Rocks from an ophiolite suite once on the seafloor were analyzed for rare earth elements (REE), Sc, Co, Na2O, Cr, Zn and FeO. Strontium isotope exchange noted in some of the lavas is attributed to basalt-seawater interaction; the Ce abundance in smectite- and zeolite-bearing lavas may also be due to prolonged exposure to seawater. The higher grades of metamorphic rock, however, show no variation from the usual flat or slightly light REE depleted profiles. Plutonic igneous rock, all light REE depleted, have total REE abundances varying by a factor of 100 between the dunites and diorites. In order of decreasing REE abundance are hornblende, clinopyroxene, plagioclase, orthopyroxene and olivine. Calculations of REE contents of liquids in equilibrium with early cumulative clinopyroxenes suggest that the parent to the stratiform sequence was more depleted in light REE than the parent to the lava pile.

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).

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.

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.

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.

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.

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.

Rare earth elements in the sedimentary cycle - A pilot study of the first leg

NASA Technical Reports Server (NTRS)

Basu, A.; Blanchard, D. P.; Brannon, J. C.

1982-01-01

The effects of source rock composition and climate on the natural abundances of rare elements (REE) in the first leg of the sedimentary cycle are evaluated using a study with Holocene fluvia sands. The medium grained sand fraction of samples collected from first order streams exclusively draining granitic plutons in Montana (semi-arid), Georgia (humid), and South Carolina (humid) are analyzed. It is found that the REE distribution patterns (but not the total absolute abundances) of the daughter sands are very similar, despite compositional differences between parent plutons. Averages of the three areas are determined to have a La/Lu ratio of about 103, showing a depletion of heavy REE with respect to an average granite (La/Lu = 79) or the composition of North American Shales (La/Lu = 55). However, the Eu/Sm ratio in sands from these areas is about 0.22, which is very close to this ratio in North American Shales (0.21), although the overall REE distribution of these sands is not similar to that of the North American Shales in any way. It is concluded that the major rock type, but neither its minor subdivisions nor the climate, controls the REE distribution patterns in first cycle daughter sands, although the total and the parent rock-normalized abundances of REE in sands from humid areas are much lower than those in sands from arid areas.

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.

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.

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.

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.

Provenance and paleoweathering reconstruction of the Mesoproterozoic Hongshuizhuang Formation (1.4 Ga), northern North China

NASA Astrophysics Data System (ADS)

Luo, Qingyong; Zhong, Ningning; Wang, Yannian; Ma, Ling; Li, Min

2015-10-01

This is the first study presenting major and trace elemental data from the Mesoproterozoic Hongshuizhuang Formation shales in Yanshan basin, North China, in order to reconstruct its provenance and chemical weathering history. The shales are strongly depleted in Na2O and Sr and enriched in Y and transition metal elements relative to upper continental crust. Low Zr concentrations and various discriminant plots (e.g., Th/Sc-Zr/Sc and Al2O3-TiO2-Zr) indicate insignificant mineral sorting or recycling of these shales. The rocks show light rare earth element (REE) enrichment (La/YbCN = 3.99-6.92), flat heavy REE, and significantly negative Eu anomalies (Euan = 0.57-0.68) in chondrite-normalized REE patterns, similar to post-Archean Australian average shales. The fairly uniform REE patterns and trace element ratios indicate that the Hongshuizhuang Formation shales were derived from a felsic source area with granodiorite as the dominant contributor. Mixing calculations suggest a mixture of 30 % granite porphyry, 5 % basalt, and 65 % granodiorite as the possible source of the shales, also supporting that granodiorite was the predominant source. Intense chemical weathering of the source terrain is indicated by high values of the premetasomatized chemical index of alteration, plagioclase index of alteration, Rb/Sr, a strong positive correlation between TiO2 and Al2O3, depletion of CaO, Na2O, and Sr, and mineral compositions. Such strong chemical weathering suggests a warm and wet paleoclimate, perhaps due to high atmospheric CO2 and CH4 concentrations, and a near-equatorial location of the North China Craton in the Columbia supercontinent at 1.4 Ga.

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.

Facile Arsenazo III-Based Assay for Monitoring Rare Earth Element Depletion from Cultivation Media for Methanotrophic and Methylotrophic Bacteria

PubMed Central

Hogendoorn, Carmen; Roszczenko-Jasińska, Paula; Martinez-Gomez, N. Cecilia; de Graaff, Johann; Grassl, Patrick; Pol, Arjan; Op den Camp, Huub J. M.

2018-01-01

ABSTRACT Recently, methanotrophic and methylotrophic bacteria were found to utilize rare earth elements (REEs). To monitor the REE content in culture media of these bacteria, we have developed a rapid screening method using the Arsenazo III (AS III) dye for spectrophotometric REE detection in the low μM (0.1 to 10 μM) range. We designed this assay to follow LaIII and EuIII depletion from the culture medium by the acidophilic verrucomicrobial methanotroph Methylacidiphilum fumariolicum strain SolV. The assay can also be modified to screen the uptake of other REEs, such as PrIII, or to monitor the depletion of LaIII from growth media in neutrophilic methylotrophs such as Methylobacterium extorquens strain AM1. The AS III assay presents a convenient and fast detection method for REE levels in culture media and is a sensitive alternative to inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption spectroscopy (AAS). IMPORTANCE REE-dependent bacterial metabolism is a quickly emerging field, and while the importance of REEs for both methanotrophic and methylotrophic bacteria is now firmly established, many important questions, such as how these insoluble elements are taken up into cells, are still unanswered. Here, an Arsenazo III dye-based assay has been developed for fast, specific, and sensitive determination of REE content in different culture media. This assay presents a useful tool for optimizing cultivation protocols, as well as for routine REE monitoring during bacterial growth without the need for specialized analytical instrumentation. Furthermore, this assay has the potential to promote the discovery of other REE-dependent microorganisms and can help to elucidate the mechanisms for acquisition of REEs by methanotrophic and methylotrophic bacteria. PMID:29453257

Facile Arsenazo III-Based Assay for Monitoring Rare Earth Element Depletion from Cultivation Media for Methanotrophic and Methylotrophic Bacteria.

PubMed

Hogendoorn, Carmen; Roszczenko-Jasińska, Paula; Martinez-Gomez, N Cecilia; de Graaff, Johann; Grassl, Patrick; Pol, Arjan; Op den Camp, Huub J M; Daumann, Lena J

2018-04-15

Recently, methanotrophic and methylotrophic bacteria were found to utilize rare earth elements (REEs). To monitor the REE content in culture media of these bacteria, we have developed a rapid screening method using the Arsenazo III (AS III) dye for spectrophotometric REE detection in the low μM (0.1 to 10 μM) range. We designed this assay to follow La III and Eu III depletion from the culture medium by the acidophilic verrucomicrobial methanotroph Methylacidiphilum fumariolicum strain SolV. The assay can also be modified to screen the uptake of other REEs, such as Pr III , or to monitor the depletion of La III from growth media in neutrophilic methylotrophs such as Methylobacterium extorquens strain AM1. The AS III assay presents a convenient and fast detection method for REE levels in culture media and is a sensitive alternative to inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption spectroscopy (AAS). IMPORTANCE REE-dependent bacterial metabolism is a quickly emerging field, and while the importance of REEs for both methanotrophic and methylotrophic bacteria is now firmly established, many important questions, such as how these insoluble elements are taken up into cells, are still unanswered. Here, an Arsenazo III dye-based assay has been developed for fast, specific, and sensitive determination of REE content in different culture media. This assay presents a useful tool for optimizing cultivation protocols, as well as for routine REE monitoring during bacterial growth without the need for specialized analytical instrumentation. Furthermore, this assay has the potential to promote the discovery of other REE-dependent microorganisms and can help to elucidate the mechanisms for acquisition of REEs by methanotrophic and methylotrophic bacteria. Copyright © 2018 Hogendoorn et al.

200 million years of komatiite evolution in the Barberton Greenstone Belt, South Africa

NASA Astrophysics Data System (ADS)

Christoph, Robin; Arndt, Nick; Byerly, Gary; Puchtel, Igor; Blichert-Toft, Janne; Wilson, Allan

2010-05-01

Komatiites with complex and contrasting chemical compositions erupted throughout the 200 m.y. history of the Barberton greenstone belt in South Africa. The oldest well-preserved examples, from the ca. 3.5 Ga Komati Formation, display a range of volcanic structures, from thin differentiated spinifex-textured flows to much thicker flows or sills composed mainly of massive olivine cumulate. Pyroxene spinifex layers that cap the latter units indicate crystallization from komatiitic basaltic liquids. Although some rare, unusually coarse, vesicular, completely serpentinized units may have contained a small fraction of water, most of the flows are essentially anhydrous. Two geochemical types are present in the Komati Fm; Al-depleted komatiites with moderately enriched LREE and depleted HREE, and Al-undepleted komatiites with near-chondritic REE ratios. Komatiites from the 3.2 Ga Mendon and Weltevreden Fm display two patterns -Al-undepleted with near-chondritic REE ratios and Al-enriched with extremely low REE concentrations and marked depletion of LREE. In many units, both geochemical types are present. The Al- and HREE-depletion of Komati Fm magmas indicates that residual garnet was retained in the mantle source and their high MgO contents require that melting was at great depth. Up to 30% batch melting at 300 km depth is indicated; the high percentage of batch melting is possible because melt is neutrally buoyant at these depths. The Al-undepleted to enrichedmagmas formed by up to 50% cumulative fractional melting that terminated at shallower depth. The. presence of both types inseveral units points to complex dynamics in the mantle plumes that yielded these magmas. Epsilon Nd in all Barbertonkomatiites ranges from 0 to +2; epsilon Hf from +2 to +7; gamma Os from 0 to +3.7. The combination of fractionated REE, positive epsilon Nd and Hf, and near-chondritic Os in certain komatiites is attributed to differentiation of the komatiite sourcevery early in Earth history followed by fractionation during komatiite formation.

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.

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.

Geochemistry of Archean shales from the Pilbara Supergroup, Western Australia

NASA Astrophysics Data System (ADS)

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

1983-07-01

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group ( ca. 3.4 Ae) and shales from the Whim Creek Group ( ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition. Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ( La N/Yb N ≥ 7.5 ) and no or very slight Eu depletion ( Eu/Eu ∗ = 0.82 - 0.99 ). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.

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.

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.

Dating high-grade metamorphism: constraints from zircon and garnet REE compositions

NASA Astrophysics Data System (ADS)

Whitehouse, M. J.; Platt, J. P.

2001-12-01

We present high spatial resolution ion microprobe REE analyses of zircon and garnet from pelitic granulite adjacent to the Ronda peridotite, Betic Cordillera, southern Spain. The zircons exhibit polyphase growth, with thick structureless (in cathodoluminescence) overgrowths over detrital cores. These overgrowths yield a U-Pb age of 21.3 +/- 0.3 Ma [1, unpublished data] which we intepret as dating an episode of zircon growth during the Alpine orogeny. REE analyses of the dated portions of these zircons reveal profound differences between cores and rims. Cores show patterns typical of magmatic zircon (steep upward slopes from La to Lu with marked positive Ce anomaly), while the overgrowths are characterised by flat or even negatively sloping HREE profiles (Gd - Lu). Garnet, which occupies ca. 30 % by volume of the rock, is the most likely phase to host the HREEs in the rock and has been the subject of further ion-microprobe REE, textural and trace element investigations. The garnets are themselves zoned, with dominant central regions that are relatively free of inclusions overgrown by inclusion-rich, more calcic rims. Inclusions of kyanite +rutile in the central regions and sillimanite +ilmenite in the rims suggests that the garnets grew during decompression, and the Ca-enrichment in the rims suggests that their growth coincided with the initiation of partial melting. The presence of rimmed zircons only in the garnet rims and the matrix further suggests that the zircons also grew during this late decompressional history. An REE traverse of the garnet from core to rim reveals marked HREE depletion in the rims relative to the cores which we suggest is consistent with the textural evidence and probably results from early garnet core growth strongly depleting the HREEs available to subsequent growth. This mechanism can also be invoked to explain depletion in the zircon rims and more closely ties their formation to this stage of garnet growth. We therefore interpret the 21.3 +/- 0.3 Ma U-Pb age from the zircon rims as dating a point on the decompressional path rather than peak metamorphic pressure. [1] Platt, J.P. and Whitehouse, M.J. (1999) EPSL 171, 591-605.

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

Multiple melting stages and refertilization as indicators for ridge to subduction formation: The New Caledonia ophiolite

NASA Astrophysics Data System (ADS)

Ulrich, Marc; Picard, Christian; Guillot, Stéphane; Chauvel, Catherine; Cluzel, Dominique; Meffre, Sébastien

2010-03-01

The origin of the New Caledonia ophiolite (South West Pacific), one of the largest in the world, is controversial. This nappe of ultramafic rocks (300 km long, 50 km wide and 2 km thick) is thrust upon a smaller nappe (Poya terrane) composed of basalts from mid-ocean ridges (MORB), back arc basins (BABB) and ocean islands (OIB). This nappe was tectonically accreted from the subducting plate prior and during the obduction of the ultramafic nappe. The bulk of the ophiolite is composed of highly depleted harzburgites (± dunites) with characteristic U-shaped bulk-rock rare-earth element (REE) patterns that are attributed to their formation in a forearc environment. In contrast, the origin of spoon-shaped REE patterns of lherzolites in the northernmost klippes was unclear. Our new major element and REE data on whole rocks, spinel and clinopyroxene establish the abyssal affinity of these lherzolites. Significant LREE enrichment in the lherzolites is best explained by partial melting in a spreading ridge, followed by near in-situ refertilization from deeper mantle melts. Using equilibrium melting equations, we show that melts extracted from these lherzolites are compositionally similar to the MORB of the Poya terrane. This is used to infer that the ultramafic nappe and the mafic Poya terrane represent oceanic lithosphere of a single marginal basin that formed during the late Cretaceous. In contrast, our spinel data highlights the strong forearc affinities of the most depleted harzburgites whose compositions are best modeled by hydrous melting of a source that had previously experienced depletion in a spreading ridge. The New Caledonian boninites probably formed during this second stage of partial melting. The two melting events in the New Caledonia ophiolite record the rapid transition from oceanic accretion to convergence in the South Loyalty Basin during the Late Paleocene, with initiation of a new subduction zone at or near the ridge axis.

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.

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.

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.

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

USGS Publications Warehouse

Calvert, S.E.; Piper, D.Z.; Baedecker, P.A.

1987-01-01

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source. ?? 1987.

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.

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

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.

Mineralogical and geochemical characterization of weathering profiles developed on mylonites in the Fodjomekwet-Fotouni section of the Cameroon Shear Zone (CSZ), West Cameroon

NASA Astrophysics Data System (ADS)

Tematio, P.; Tchaptchet, W. T.; Nguetnkam, J. P.; Mbog, M. B.; Yongue Fouateu, R.

2017-07-01

The mineralogical and geochemical investigation of mylonitic weathering profiles in Fodjomekwet-Fotouni was done to better trace the occurrence of minerals and chemical elements in this area. Four representative soil profiles were identified in two geomorphological units (upland and lowland) differentiating three weathering products (organo-mineral, mineral and weathered materials). Weathering of these mylonites led to some minerals association such as vermiculite, kaolinite, goethite, smectite, halloysite, phlogopite and gibbsite. The minerals in a decreasing order of abundance are: quartz (24.2%-54.8%); kaolinite (8.4%-36.0%); phlogopite (5.5%-21.9%); goethite (7.8%-16.1%); vermiculite (6.7%-15.7%); smectite (10.2%-11.9%); gibbsite (9.0%-11.8%) and halloysite (5.6%-11.5%) respectively. Patterns of chemical elements allow highlighting three behaviors (enriched elements, depleted elements and elements with complex behavior), depending on the landscape position of the profiles. In the upland weathering products, K, Cr and REEs are enriched; Ca, Mg, Na, Mn, Rb, S and Sr are depleted while Si, Al, Fe, Ti, Ba, Co, Cu, Ga, Mo, Nb, Ni, Pb, Sc, V, Y, Zn and Zr portray a complex behavior. Contrarily, the lowland weathering profiles enriched elements are Fe, Ti, Co, Cr, Cu, V, Zr, Pr, Sm, Tb, Dy, Er and Yb; while depleted elements are Ca, Mg, K, Na, Mn, Ba, Ga, S, Sr, Y, Zn, La, Ce and Nd; and Si, Al, Mo, Nb, Ni, Pb, Rb, Sc evidenced complex behaviors. In all the studied weathering products, the REEs fractionation was also noticeable with a landscape-position dependency, showing light REEs (LREEs) enrichment in the upland areas and heavy REEs (HREEs) in lowland areas. SiO2, Al2O3 and Fe2O3 are positively correlated with most of the traces and REEs (Co, Cu, Nb, Ni, Mo, Pb, Sc, V, Zn, Zr, La, Ce, Sm, Tb, Dy, Er, Yb), pointing to the fact that they may be incorporated into newly formed clay minerals and oxides. Ba, Cr, Ga, Rb, S, Sr, Y, Pr and Nd behave like alkalis and alkaline earths, and are thus highly mobile during weathering.

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.

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).

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.

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.

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

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.

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.

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

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.

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.

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.

Average sedimentary rock rare Earth element patterns and crustal evolution: Some observations and implications from the 3800 Ma ISUA supracrustal belt, West Greenland

NASA Technical Reports Server (NTRS)

Dymek, R. F.; Boak, J. L.; Gromet, L. P.

1983-01-01

Rare earth element (REE) data is given on a set of clastic metasediments from the 3800 Ma Isua Supracrustal belt, West Greenland. Each of two units from the same sedimentary sequence has a distinctive REE pattern, but the average of these rocks bears a very strong resemblance to the REE pattern for the North American Shale Composite (NASC), and departs considerably from previous estimates of REE patterns in Archaean sediments. The possibility that the source area for the Isua sediments resembled that of the NASC is regarded as highly unlikely. However, REE patterns like that in the NASC may be produced by sedimentary recycling of material yielding patterns such as are found at Isua. The results lead to the following tentative conclusions: (1) The REE patterns for Isua Seq. B MBG indicate the existence of crustal materials with fractionated REE and negative Eu anomalies at 3800 Ma, (2) The average Seq. B REE pattern resembles that of the North American Shale Composite (NASC), (3) If the Seq. B average is truly representative of its crustal sources, then this early crust could have been extensively differentiated. In this regard, a proper understanding of the NASC pattern, and its relationship to post-Archaean crustal REE reservoirs, is essential, (4) The Isua results may represent a local effect.

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.

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.

Chemical layering in the upper mantle of Mars: Evidence from olivine-hosted melt inclusions in Tissint

NASA Astrophysics Data System (ADS)

Basu Sarbadhikari, A.; Babu, E. V. S. S. K.; Vijaya Kumar, T.

2017-02-01

Melting of Martian mantle, formation, and evolution of primary magma from the depleted mantle were previously modeled from experimental petrology and geochemical studies of Martian meteorites. Based on in situ major and trace element study of a range of olivine-hosted melt inclusions in various stages of crystallization of Tissint, a depleted olivine-phyric shergottite, we further constrain different stages of depletion and enrichment in the depleted mantle source of the shergottite suite. Two types of melt inclusions were petrographically recognized. Type I melt inclusions occur in the megacrystic olivine core (Fo76-70), while type II melt inclusions are hosted by the outer mantle of the olivine (Fo66-55). REE-plot indicates type I melt inclusions, which are unique because they represent the most depleted trace element data from the parent magmas of all the depleted shergottites, are an order of magnitude depleted compared to the type II melt inclusions. The absolute REE content of type II displays parallel trend but somewhat lower value than the Tissint whole-rock. Model calculations indicate two-stage mantle melting events followed by enrichment through mixing with a hypothetical residual melt from solidifying magma ocean. This resulted in 10 times enrichment of incompatible trace elements from parent magma stage to the remaining melt after 45% crystallization, simulating the whole-rock of Tissint. We rule out any assimilation due to crustal recycling into the upper mantle, as proposed by a recent study. Rather, we propose the presence of Al, Ca, Na, P, and REE-rich layer at the shallower upper mantle above the depleted mantle source region during the geologic evolution of Mars.

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.

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.

Chondrule heritage and thermal histories from trace element and oxygen isotope analyses of chondrules and amoeboid olivine aggregates

NASA Astrophysics Data System (ADS)

Jacquet, Emmanuel; Marrocchi, Yves

2017-12-01

We report combined oxygen isotope and mineral-scale trace element analyses of amoeboid olivine aggregates (AOA) and chondrules in ungrouped carbonaceous chondrite, Northwest Africa 5958. The trace element geochemistry of olivine in AOA, for the first time measured by LA-ICP-MS, is consistent with a condensation origin, although the shallow slope of its rare earth element (REE) pattern is yet to be physically explained. Ferromagnesian silicates in type I chondrules resemble those in other carbonaceous chondrites both geochemically and isotopically, and we find a correlation between 16O enrichment and many incompatible elements in olivine. The variation in incompatible element concentrations may relate to varying amounts of olivine crystallization during a subisothermal stage of chondrule-forming events, the duration of which may be anticorrelated with the local solid/gas ratio if this was the determinant of oxygen isotopic ratios as proposed recently. While aqueous alteration has depleted many chondrule mesostases in REE, some chondrules show recognizable subdued group II-like patterns supporting the idea that the immediate precursors of chondrules were nebular condensates.

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.

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.

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.

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

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.

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).

Sphene and zircon in the Highland Range volcanic sequence (Miocene, southern Nevada, USA): Elemental partitioning, phase relations, and influence on evolution of silicic magma

USGS Publications Warehouse

Colombini, L.L.; Miller, C.F.; Gualda, G.A.R.; Wooden, J.L.; Miller, J.S.

2011-01-01

Sphene is prominent in Miocene plutonic rocks ranging from diorite to granite in southern Nevada, USA, but it is restricted to rhyolites in coeval volcanic sequences. In the Highland Range volcanic sequence, sphene appears as a phenocryst only in the most evolved rocks (72-77 mass% SiO2; matrix glass 77-78 mass% SiO2). Zr-in-sphene temperatures of crystallization are mostly restricted to 715 and 755??C, in contrast to zircon (710-920??C, Ti-in-zircon thermometry). Sphene rim/glass Kds for rare earth elements are extremely high (La 120, Sm 1200, Gd 1300, Lu 240). Rare earth elements, especially the middle REE (MREE), decrease from centers to rims of sphene phenocrysts along with Zr, demonstrating the effect of progressive sphene fractionation. Whole rocks and glasses have MREE-depleted, U-shaped REE patterns as a consequence of sphene fractionation. Within the co-genetic, sphene-rich Searchlight pluton, only evolved leucogranites show comparable MREE depletion. These results indicate that sphene saturation in intruded and extruded magmas occurred only in highly evolved melts: abundant sphene in less silicic plutonic rocks represents a late-stage 'bloom' in fractionated interstitial melt. ?? 2011 Springer-Verlag.

Plume magmatism and crustal growth at 2.9 to 3.0 Ga in the Steep Rock and Lumby Lake area, Western Superior Province

NASA Astrophysics Data System (ADS)

Tomlinson, K. Y.; Hughes, D. J.; Thurston, P. C.; Hall, R. P.

1999-01-01

The greenstone belts of the western Superior Province are predominantly 2.78 to 2.69 Ga and provide evidence of oceanic and arc volcanism during the accretionary phase of development of the Superior Province. There is also scattered evidence of Meso-Archean crust (predominantly 2.9 to 3.0 Ga) within the western Superior Province. The Meso-Archean greenstone belts commonly contain platformal sediments and unconformably overlie granitoid basement. The platformal sediments occur associated with komatiitic and tholeiitic volcanic rocks that suggest a history of magmatism associated with rifting during the Meso-Archean. The central Wabigoon Subprovince is a key area of Meso-Archean crust and in its southern portion comprises the Steep Rock, Finlayson and Lumby Lake greenstone belts. The Steep Rock greenstone belt unconformably overlies 3 Ga continental basement and contains platformal sediments succeeded by komatiitic and tholeiitic volcanic rocks. The Lumby Lake greenstone belt contains thick sequences of mafic volcanics, a number of komatiite horizons, and thin platformal sedimentary units. The two belts are joined by the predominantly mafic volcanic Finlayson greenstone belt. The volcanics throughout these three greenstone belts may be correlated to some extent and a range of basaltic and komatiite types is present. Al-undepleted komatiites present in the Lumby Lake greenstone belt have an Al 2O 3/TiO 2 ratio ranging from 14 to 27 and (Gd/Yb) N from 0.7 to 1.3. These are divided into basaltic komatiites with generally unfractionated mantle-normalised multi-element profiles, and spinifex-textured high-Mg basalts with slightly light REE enriched multi-element profiles and small negative Nb and Ta anomalies. The unfractionated basaltic komatiites represent high degree partial melts of the upper mantle whereas the spinifex-textured high-Mg basalts represent evolutionary products of the komatiite liquids following olivine and chromite fractionation and crustal contamination. Al-depleted komatiites are present in both the Lumby Lake and Steep Rock belts and have Al 2O 3/TiO 2 ratio ranges from 2.5 to 5. These display strong enrichment in the light REE and Nb and strong depletion in the heavy REE and Y ((Gd/Yb) N=2-4). They represent a deep mantle plume source generated from a high degree of partial melting in the majorite garnet stability field. The basaltic flows in all three greenstone belts are predominantly slightly light REE depleted and represent a slightly depleted upper mantle source. Basalts spatially associated with the unfractionated basaltic komatiites and the slightly light REE enriched spinifex-textured high-Mg basalts are also slightly enriched in light REE and have negative Nb and Ta anomalies. These basalts represent evolved products of the primitive basaltic komatiites and enriched spinifex-textured high-Mg basalts after further crustal contamination and olivine and clinopyroxene fractionation. The geochemical stratigraphy in the Lumby Lake belt is consistent with an ascending mantle plume model. The light REE depleted basalts were derived from upper mantle melted by an ascending mantle plume. These are overlain by the unfractionated basaltic komatiites and their evolutionary products which represent hotter plume head material derived from a mixture of plume mantle and entrained depleted upper mantle. In turn, these are overlain by strongly light REE and HFSE enriched komatiites that represent a deep plume source that has not been mixed with depleted mantle and are, therefore, likely to have been derived from a plume core or tail. Volcanism was protracted in these three greenstone belts lasting ca. 70 Ma and combined stratigraphic evidence from the Lumby Lake and Steep Rock belts suggests that more than one plume may have ascended and tapped the same mantle sources, over time, within the area. Plume magmatism and rifting of continental platforms thus appears to have been an important feature of crustal development in the Meso-Archean.

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.

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.

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.

Rb-Sr And Sm-Nd Ages, and Petrogenesis of Depleted Shergottite Northwest Africa 5990

NASA Technical Reports Server (NTRS)

Shih, C. Y.; Nyquist, L. E.; Reese, Y.; Irving, A. J.

2011-01-01

Northwest Africa (NWA) 5990 is a very fresh Martian meteorite recently found on Hamada du Draa, Morocco and was classified as an olivine-bearing diabasic igneous rock related to depleted shergottites [1]. The study of [1] also showed that NWA 5990 resembles QUE 94201 in chemical, textural and isotopic aspects, except QUE 94201 contains no olivine. The depleted shergottites are characterized by REE patterns that are highly depleted in LREE, older Sm-Nd ages of 327-575 Ma and highly LREE-depleted sources with Nd= +35+48 [2-7]. Age-dating these samples by Sm-Nd and Rb-Sr methods is very challenging because they have been strongly shocked and contain very low abundances of light rare earth elements (Sm and Nd), Rb and Sr. In addition, terrestrial contaminants which are commonly present in desert meteorites will compromise the equilibrium of isotopic systems. Since NWA 5990 is a very fresh meteorite, it probably has not been subject to significant desert weathering and thus is a good sample for isotopic studies. In this report, we present Rb-Sr and Sm-Nd isotopic results for NWA 5990, discuss the correlation of the determined ages with those of other depleted shergottites, especially QUE 94201, and discuss the petrogenesis of depleted shergottites.

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.

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.

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.

Lateritic, supergene rare earth element (REE) deposits

USGS Publications Warehouse

Cocker, Mark D.

2014-01-01

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

Hydroxylamine hydrochloride-acetic acid-soluble and -insoluble fractions of pelagic sediment: Readsorption revisited

USGS Publications Warehouse

Piper, D.Z.; Wandless, G.A.

1992-01-01

The extraction of the rare earth elements (REE) from deep-ocean pelagic sediment, using hydroxylamine hydrochloride-acetic acid, leads to the separation of approximately 70% of the bulk REE content into the soluble fraction and 30% into the insoluble fraction. The REE pattern of the soluble fraction, i.e., the content of REE normalized to average shale on an element-by-element basis and plotted against atomic number, resembles the pattern for seawater, whereas the pattern, as well as the absolute concentrations, in the insoluble fraction resembles the North American shale composite. These results preclude significant readsorption of the REE by the insoluble phases during the leaching procedure.

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.

Multiple episodes of partial melting, depletion, metasomatism and enrichment processes recorded in the heterogeneous upper mantle sequence of the Neotethyan Eldivan ophiolite, Turkey

NASA Astrophysics Data System (ADS)

Uysal, Ibrahim; Ersoy, E. Yalçın; Dilek, Yildirim; Kapsiotis, Argyrios; Sarıfakıoğlu, Ender

2016-03-01

The Eldivan ophiolite along the Izmir-Ankara-Erzincan suture zone in north-central Anatolia represents a remnant of the Neotethyan oceanic lithosphere. Its upper mantle peridotites include three lithologically and compositionally distinct units: clinopyroxene (cpx)-harzburgite and lherzolite (Group-1), depleted harzburgite (Group-2), and dunite (Group-3). Relics of primary olivine and pyroxene occur in the less refractory harzburgites, and fresh chromian spinel (Cr-spinel) is ubiquitous in all peridotites. The Eldivan peridotites reflect a petrogenetic history evolving from relatively fertile (lherzolite and cpx-harzburgite) toward more depleted (dunite) compositions through time, as indicated by (i) a progressive decrease in the modal cpx distribution, (ii) a progressive increase in the Cr#s [Cr / (Cr + Al)] of Cr-spinel (0.15-0.78), and (iii) an increased depletion in the whole-rock abundances of some magmaphile major oxides (Al2O3, CaO, SiO2 and TiO2) and incompatible trace elements (Zn, Sc, V and Y). The primitive mantle-normalized REE patterns of the Group-1 and some of the Group-2 peridotites display LREE depletions. Higher YbN and lower SmN/YbN ratios of these rocks are compatible with their formation after relatively low degrees (9-25%) of open-system dynamic melting (OSDM) of a Depleted Mid-ocean ridge Mantle (DMM) source, which was then fluxed with small volumes of oceanic mantle-derived melt [fluxing ratio (β): 0.7-1.2%]. Accessory Cr-spinel compositions (Cr# = 015-0.53) of these rocks are consistent with their origin as residual peridotites beneath a mid-ocean ridge axis. Part of the Group-2 harzburgites exhibit lower YbN and higher SmN/YbN ratios, LREE-enriched REE patterns, and higher Cr-spinel Cr#s ranging between 0.54 and 0.61. Trace element compositions of these peridotites can be modeled by approximately 15% OSDM of a previously 17% depleted DMM, which was then fluxed (β: 0.4%) with subduction-influenced melt. The Group-3 dunite samples contain Cr-spinel with elevated Cr#s (0.73-0.78) and low-TiO2 contents (< 0.13 wt.%), implying higher degrees of melting (21-24%) of an already depleted DMM that was triggered by infiltration of low-Ti boninite melt with fluxing rates of 0.4-4.0%. The existence of interstitial, idiomorphic Cr-spinel (high Cr# and low Ti) in the Group-3 dunites is consistent with this interpretation. The occurrence of both MOR- and SSZ-type peridotites in the Eldivan ophiolite suggests that its heterogeneous upper mantle was produced as a result of different partial melting and melt-rock reaction processes in different tectonic settings within the Neotethyan realm.

Mineralogical controls on mobility of rare earth elements in acid mine drainage environments.

PubMed

Soyol-Erdene, T O; Valente, T; Grande, J A; de la Torre, M L

2018-08-01

Rare earth elements (REE) were analyzed in river waters, acid mine waters, and extracts of secondary precipitates collected in the Iberian Pyrite Belt. The obtained concentrations of the REE in river water and mine waters (acid mine drainage - AMD) were in the range of 0.57 μg/L (Lu) and 2579 μg/L (Ce), which is higher than previously reported in surface waters from the Iberian Pyrite Belt, but are comparable with previous findings from AMD worldwide. Total REE concentrations in river waters were ranged between 297 μg/L (Cobica River) and 7032 μg/L (Trimpancho River) with an average of 2468 μg/L. NASC (North American Shale Composite) normalized REE patterns for river and acid mine waters show clear convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE. During the dissolution experiments of AMD-precipitates, heavy-REE and middle-REE generate the most enriched patterns in the solution. A small number of precipitates did not display MREE enrichment (an index Gd n /Lu n  < 1.0) in NASC normalized pattern and produced relatively lower REE concentrations in extracts. Additionally, very few samples, which mainly contained aluminum sulfates, e.g., pickeringite and alunogen, displayed light-REE enrichment relative to heavy-REE (HREE). In general, the highest retention of REE occurs in samples enriched in magnesium (epsomite or hexahydrite) and aluminum sulfates, mainly pickeringite. Copyright © 2018 Elsevier Ltd. All rights reserved.

Petrology and Geochemistry of Serpentinized Peridotites from a Bonin Fore-arc Seamount

NASA Astrophysics Data System (ADS)

Tian, L.; Tuoyu, W.; Dong, Y. H.; Gao, J.; Wu, S.

2016-12-01

Serpentinites, which contain up to 13 wt.% of water, are an important reservoir for chemical recycling in subduction zones. During the last two decades, many observations documented the occurrence of fore-arc mantle serpentinites in different locations. Here, we present petrology and whole rock chemistry for serpentinized peridotites dredged from the Hahajima Seamount, which is located 20-60 km west of the junction of the Bonin Trench and the Mariana Trench. Combined with published geochemical data of serpentinites from the Torishima Seamount, Conical Seamount and South Chamorro Seamount in the Izu-Bonin-Mariana fore-arc region, it will allow us to better understand the average composition of serpentinized fore-arc mantle overlying the subducting slab and the role of serpentinized mantle playing in the subduction zone geochemical cycle. The studied ultramafic rocks from the Hahajima Seamount are extensively serpentinized and hydrated (73 to 83%), with loss of ignition values ranging between 13 and 15 wt.%. Our results show that the serpentinized peridotites have Mg number from 88 to 90, and the average MgO/SiO2 is 0.93. The average Al2O3 (0.48 wt.%) and CaO (0.23 wt.%) contents are very low, consistent with low clinopyroxene abundances, and the overall depleted character of the mantle harzburgite protoliths. The serpentinized peridotites from the Hahajima Seamount exhibit similar "U" shape rare earth element (REE) patterns ([La/Sm]N = 3.1-3.6), at higher overall abundances, to the Conical and South Chamorro Seamount suites. One exceptional sample shows the similar REE pattern as serpentinized peridotites from the Torishima Seamount, with depleted light REE concentration ([La/Sm]N =0.7). All the serpentinized peridotites from these four fore-arc seamounts show strong enrichment in fluid-mobile and lithophile elements (U, Pb, Sr and Li). The geochemical signature of the serpentinized peridotites from the seamounts in the Izu-Bonin-Mariana fore-arc region could be interpreted as the result of the combination of extensive partial melting and subsequent percolation of sediment-derived fluids through the mantle wedge [1]. References: [1] Deschamps et al. (2013), Lithos, 178, 96-127.

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.

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

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.

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.

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.

Grosnaja ABCs: Magnesium isotope compositions

NASA Technical Reports Server (NTRS)

Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

1993-01-01

Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

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.

Evolution of the lithospheric mantle beneath Mt. Baekdu (Changbaishan): Constraints from geochemical and Sr-Nd-Hf isotopic studies on peridotite xenoliths in trachybasalt

NASA Astrophysics Data System (ADS)

Park, Keunsu; Choi, Sung Hi; Cho, Moonsup; Lee, Der-Chuen

2017-08-01

Major and trace element compositions of minerals as well as Sr-Nd-Hf isotopic compositions of clinopyroxenes from spinel peridotite xenoliths entrained in Late Cenozoic trachybasalt from Mt. Baekdu (Changbaishan) were used to elucidate lithospheric mantle formation and evolution in the eastern North China Craton (NCC). The analyzed peridotites were mainly spinel lherzolites with rare harzburgites. They consisted of olivine (Fo89.3-91.0), enstatite (Wo1-2En88-90Fs8-11), diopside (Wo45-50En45-51Fs4-6), and spinel (Cr# = 8.8-54.7). The peridotite residues underwent up to 25% partial melting in fertile mid-ocean-ridge basalt (MORB) mantle. Plots of the Cr# in spinel against the Mg# in coexisting olivine or spinel suggested an affinity with abyssal peridotites. Comparisons of Cr# and TiO2 in spinel were also compatible with an abyssal peridotite-like composition; however, harzburgites were slightly enriched in TiO2 because of the reaction with MORB-like melt. Temperatures estimated using two-pyroxene thermometry ranged from 750 to 1010 °C, reflecting their lithospheric mantle origin. The rare earth element (REE) patterns in clinopyroxenes of the peridotites varied from light REE (LREE) depleted to spoon shaped to LREE enriched, reflecting secondary overprinting effects of metasomatic melts or fluids on the residues from primordial melting. The calculated trace element pattern of metasomatic melt equilibrated with clinopyroxene in Mt. Baekdu peridotite showed strong enrichment in large-ion lithophile elements, Th and U together with slight fractionation in heavy REEs (HREEs) and considerable depletion in Nb and Ti. The Sr-Nd-Hf isotopic compositions of clinopyroxenes separated from the peridotites varied from more depleted than present-day MORB to bulk Earth values. However, some clinopyroxene showed a decoupling between Nd and Sr isotopes, deviating from the mantle array with a high 87Sr/86Sr ratio. This sample also showed a significant Nd-Hf isotope decoupling lying well above the mantle array. The Lu-Hf and Sm-Nd model ages of residual clinopyroxenes yielded Early Proterozoic to Phanerozoic ages. No signature of Archean cratonic mantle was present. Therefore, Mt. Baekdu peridotite is residual lithospheric mantle that has undergone variable degrees of diachronous melt extraction and infiltration metasomatism involving subduction-related, fluid-bearing silicate melts. The predominance of Phanerozoic Hf model ages indicates that the lherzolites represent lithospheric mantle fragments newly accreted underneath the eastern NCC.

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.

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.

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.

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 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 Detailed Geochemical Study of Island Arc Crust: The Talkeetna Arc Section, South-central Alaska

NASA Astrophysics Data System (ADS)

Greene, A. R.; Debari, S. M.; Kelemen, P. B.; Clift, P. D.; Blusztajn, J.

2002-12-01

The Talkeetna arc section in south-central Alaska is recognized as the exposed upper mantle and crust of an accreted, Late Triassic to Middle Jurassic island arc. Detailed geochemical studies of layered gabbronorite from the middle and lower crust of this arc and a diverse suite of volcanic and plutonic rocks from the middle and upper crust provide crucial data for understanding arc magma evolution. We also present new data on parental magma compositions for the arc. The deepest level of the arc section consists of residual mantle and ultramafic cumulates adjacent to garnet gabbro and basal gabbronorite interlayered with pyroxenite. The middle crust is primarily layered gabbronorite, ranging from anorthosite to pyroxenite in composition, and is the most widespread plutonic lithology. The upper mid crust is a heterogenous assemblage of dioritic to tonalitic rocks mixed with gabbro and intruded by abundant mafic dikes and chilled pillows. The upper crust of the arc is comprised of volcanic rocks of the Talkeetna Formation ranging from basalt to rhyolite. Most of these volcanic rocks have evolved compositions (<5% MgO, Mg# <60) and overlap the composition of intermediate to felsic plutonic rocks (<3.5% MgO, Mg# <45). However, several chilled mafic rocks and one basalt have primitive characteristics (>8% MgO, Mg# >60). Ion microprobe analyses of clinopyroxene in mid-crustal layered gabbronorites have parallel REE patterns with positive-sloping LREE segments (La/Sm(N)=0.05-0.17; mean 0.11) and flat HREE segments (5-25xchondrite; mean 10xchondrite). Liquids in REE equilibrium with the clinopyroxene in these gabbronorite cumulates were calculated in order to constrain parental magmas. These calculated liquids(La/Sm(N)=0.77-1.83; mean 1.26) all fall within the range of dike and volcanic rock(La/Sm(N)=0.78-2.12; mean 1.23) compositions. However, three lavas out of the 44 we have analyzed show strong HREE depletion, which is not observed in any of the liquid compositions calculated from clinopyroxene in the gabbronorite samples. Three lavas have Mg# 50-63 (49-57 % SiO2) and two of these are in REE equilibrium with calculated liquids of cumulate gabbronorites. Five chilled samples (three dikes and two mafic inclusions) have Mg# 54-64 (48-52 % SiO2) and lie just below the calculated liquid REE patterns. The most primitive mafic dike (SiO2 =48.1; MgO =8.1 ; Mg# =62.0; Ni =73) represents a well-constrained potential parental magma to the gabbroic cumulates in the mid-crust of the arc, although, like the three primitive basalts, it is not in Fe/Mg equilibrium with the gabbros.The Mg# is too high. Presumably, this parent has lost Ni and MgO to fractionation of ultramafic cumulates at deeper levels of the arc. The average dike REE pattern is nearly identical to the calculated primary magma composition of DeBari and Sleep(1991) for the Talkeetna arc, as are the REE patterns for the chilled pillows. Least-squares mass-balance calculations of mid-crustal gabbronorites indicate pl + cpx + opx + mgt + amph represent the bulk of removed solids. Fractionation of these phases using the most primitive mafic dike described above as the parental composition can produce many of the more evolved volcanic rocks. Fe-Ti oxide accounts for 0.05-12.3 wt% (mean 5.92 wt%) of the sampled cumulates and amphibole represents 0.97-40.1 wt% (mean 16.4 wt%). Fractionation of the observed phases in the cumulate gabbronorite is reflected by TiO2 depletion in the volcanic and intermediate to felsic plutonic rocks of the middle and upper crust.

Geochemical constraints on depth of origin of oceanic carbonatites: The Cape Verde case

NASA Astrophysics Data System (ADS)

Doucelance, Régis; Hammouda, Tahar; Moreira, Manuel; Martins, João C.

2010-12-01

We present new Sr-Nd isotope compositions together with major- and trace element concentrations measured for whole rocks and mineral separate phases (apatite, biotite and calcite) from fifteen Cape Verde oceanic carbonatites (Atlantic Ocean). Trace element patterns of calcio- and magnesio-carbonatites present a strong depletion in K, Hf, Zr and Ti and an overall enrichment in Sr and REE relative to Cape Verde basalts, arguing for distinct source components between carbonatites and basalts. Sr and Nd isotopic ratios show small, but significant variations defining a binary mixing between a depleted end-member with unradiogenic Sr and radiogenic Nd values and a ''enriched'' end-member compatible with old marine carbonates. We interpret the depleted end-member as the Cape Verde oceanic lithosphere by comparison with previous studies on Cape Verde basalts. We thus propose that oceanic carbonatites are resulting from the interaction of a deep rooted mantle plume carrying a lower 4He/ 3He signature from the lower mantle and a carbonated metasomatized lithosphere, which by low degree melting produced carbonatite magmas. Sr-Nd compositions and trace element patterns of carbonatites argue in favor of a metasomatic agent originating from partial melting of recycled, carbonated oceanic crust. We have successfully reproduced the main geochemical features of this model using a Monte-Carlo-type simulation.

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.

Minor and trace element geochemistry of volcanic rocks dredged from the Galapagos spreading center: role of crystal fractionation and mantle heterogeneity.

USGS Publications Warehouse

Clague, D.A.; Frey, F.A.; Thompson, G.; Rindge, S.

1981-01-01

A wide range of rock types (abyssal tholeiite, Fe-Ti-rich basalt, andesite, and rhyodacite) were dredged from near 95oW and 85oW on the Galapagos spreading center. Computer modeling of major element compositions has shown that these rocks could be derived from common parental magmas by successive degrees of fractional crystallization. However, the P2O5/K2O ratio implies distinct mantle source compositions for the two areas. These source regions also have different rare earth element (REE) abundance patterns. The sequence of fractionated lavas differs for the two areas and indicates earlier fractionation of apatite and titanomagnetite in the lavas from 95oW. The mantle source regions for these two areas are interpreted to be depleted in incompatible (and volatile?) elements, although the source region beneath 95oW is less severely depleted in La and K. -Authors

Contrasting thermal and melting histories for segments of mantle lithosphere in the Nahlin ophiolite, British Columbia, Canada

NASA Astrophysics Data System (ADS)

McGoldrick, Siobhan; Canil, Dante; Zagorevski, Alex

2018-03-01

The Permo-Triassic Nahlin ophiolite is the largest and best-preserved ophiolite in the Canadian Cordillera of British Columbia and Yukon, Canada. The ophiolite is well-exposed along its 150 km length with mantle segments divisible into the Hardluck and Menatatuline massifs. Both massifs comprise mostly depleted spinel harzburgite (< 2 wt% Al2O3 and 45 wt% MgO). Chondrite normalized REE abundances in clinopyroxene vary in (Gd/Yb)N from 0.2 to 1.1. Inversion modelling of clinopyroxene REE abundances requires 10-16% and 16-20% partial melting in the Hardluck and Menatatuline massifs, respectively. The two-pyroxene and Fe-Mg exchange temperatures in the mantle of the ophiolite also change systematically along strike with the degree of partial melt depletion. The temperatures recorded by REE and Ca-Mg exchange between coexisting pyroxenes require markedly higher peak temperatures and cooling rates for the Menatatuline massif (1250 °C, 0.1-0.01 °C/year) compared to the Hardluck massif (< 1100 °C, 10- 4 °C/year). The differences between these two contiguous massifs can be reconciled by their evolution as two separate segments along a ridge system having varying melt depletion, with contrasting cooling rates controlled by presence or absence of a crustal section above the mantle lithosphere, or by rapid exhumation along a detachment.

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.

Sedimentary provenance of Maastrichtian oil shales, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

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

2017-04-01

Maastrichtian oil shales are distributed within the Central Eastern Desert in Egypt. In this study elemental geochemical data have been applied to investigate the probable provenance of the sedimentary detrital material of the Maastrichtian oil shale beds within the Duwi and the Dakhla formations. The Maastrichtian oil shales are characterized by the enrichment in Ca, P, Mo, Ni, Zn, U, Cr and Sr versus post-Archean Australian shales (PAAS). The chondrite-normalized patterns of the Maastrichtian oil shale samples are showing LREE enrichment, HREE depletion, slightly negative Eu anomaly, no obvious Ce anomaly and typical shale-like PAAS-normalized patterns. The total REE well correlated with Si, Al, Fe, K and Ti, suggesting that the REE of the Maastrichtian oil shales are derived from terrigenous source. Chemical weathering indices such as Chemical Index of Alteration (CIA), Chemical Proxy of Alteration (CPA) and Plagioclase Index of Alteration (PIA) indicate moderate to strong chemical weathering. We suggest that the Maastrichtian oil shale is mainly derived from first cycle rocks especially intermediate rocks without any significant inputs from recycled or mature sources. The proposed data illustrated the impact of the parent material composition on evolution of oil shale chemistry. Furthermore, the paleo-tectonic setting of the detrital source rocks for the Maastrichtian oil shale is probably related to Proterozoic continental island arcs

Rb-Sr and Sm-Nd Studies of Olivine-Phyric Shergottites RBT 04262 and LAR 06319: Isotopic Evidence for Relationship to Enriched Basaltic Shergottites

NASA Technical Reports Server (NTRS)

Nyquist, L.E.; Shih, C.-Y.; Reese, Y.

2009-01-01

RBT 04262 and LAR 06319 are two Martian meteorites recently discovered in Antarctica. Both contain abundant olivines, and were classified as olivine-phyric shergottites. A detailed petrographic study of RBT 04262 suggested it should be reclassified as a lherzolitic shergottite. However, the moderately LREE-depleted REE distribution pattern indicated that it is closely related to enriched basaltic shergottites like Shergotty, Zagami, Los Angeles, etc. In earlier studies of a similarly olivinephyric shergottite NWA 1068 which contains 21% modal olivine, it was shown that it probably was produced from an enriched basaltic shergottite magma by olivine accumulation . As for LAR 06319, recent petrographic studies suggested that it is different from either lherzolitic shergottites or the highly LREE-depleted olivine-phyric shergottites. We performed Rb-Sr and Sm-Nd isotopic analyses on RBT 04262 and LAR 06319 to determine their crystallization ages and Sr and Nd isotopic signatures, and to better understand the petrogenetic relationships between them and other basaltic, lherzolitic and depleted olivine-phyric shergottites.

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.

Post-Late Glacial calcareous tufas from the Kurai fault zone (Southeastern Gorny Altai, Russia)

NASA Astrophysics Data System (ADS)

Kokh, Svetlana N.; Sokol, Ella V.; Deev, Evgeny V.; Ryapolova, Yuliya M.; Rusanov, Gennady G.; Tomilenko, Anatoliy A.; Bul'bak, Taras A.

2017-06-01

Calcareous tufa deposits have been discovered in the Chibitka River valley near Lake Cheybek-Kohl, at the junction of the Kurai and Teletsk-Kurai large active faults in the southeastern Gorny Altai, Russia, at an altitude of 1800-2000 m. Fossil tufa is composed of calcite and cements Holocene grey colluvium and glacial till deposited by the Late Glacial Chibitka Glacier. Current tufa precipitation has been observed from a low-flow spring with cold (10 °C) HCO3-SO4-Ca-Mg water, pH = 6.86. The stable isotope composition of spring water is - 5.8‰ VPDB δ13C of dissolved inorganic carbon and - 14.5‰ VSMOW δ18O. Modern tufa consists of thin laminated Mg-calcite and Sr-aragonite crusts, with abundant algae and biofilms on their surfaces. Both modern and fossil tufas are depleted in REE (a total of 0.40-16.4 ppm and 0.40-3.80 ppm, respectively) and share similar PAAS-normalised REE + Y spectra with HREE enrichment and slight progressive LREE depletion. The modern tufas show positive δ13C values of 0.1‰ to 0.9‰ VPDB while the fossil ones have an isotopically lighter composition of δ13C = - 4.1‰ to - 1.9‰ VPDB; the δ18O range is very narrow (- 13.0 to - 13.8‰ VPDB). Both stable isotope and trace-element signatures (including REE patterns) of the tufas indicate precipitation from cold groundwaters subjected to prolonged interaction with a carbonate aquifer (the Baratal Group of limestone and dolostone) in a cold continental climate similar to the present conditions. Tufa deposition in the Lake Cheybek-Kohl area began with the onset of post-Late Glacial global warming and permafrost degradation. Unlike the fossil tufa formation, current precipitation of freshwater carbonates has been microbially mediated. The discovered tufa deposits provide new palaeoclimatic and active tectonic proxies in the southeastern Gorny Altai.

Investigating Rare Earth Element Systematics in the Marcellus Shale

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Kim, J. H.; Verba, C.

2014-12-01

The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO3 ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our conclusions on the impact of depositional setting and diagenetic remobilization and authigenic mineral formation on the REE system in the Marcellus Shale.

Provenance and tectonic settings of sands from Puerto Peñasco, Desemboque and Bahia Kino beaches, Gulf of California, Sonora, México

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Tom, Milu; Lee, Yong IL; Balaram, V.; Ramasamy, S.; Carranza-Edwards, A.; Ramachandran, A.

2016-11-01

Textural, heavy minerals and geochemical (major, trace and rare earth elements) studies were undertaken on the sands from Puerto Peñasco, Desemboque and Bahia Kino beaches to determine the provenance and tectonic settings. Puerto Peñasco and Bahia Kino sands are coarse grained to fine grained, while Desemboque sands are fine grained. Geochemically, these sands are classified as arkose. The sands are depleted in most of the trace elements relative to upper continental crust (UCC), except for few trace elements (Sr, Rb and Ba), which are slightly enriched. High ΣREE content are observed in the Desemboque sands (94.43 ± 6.9) than in the Puerto Peñasco and Bahia Kino sands (51.58 ± 17.06; 72.38 ± 9.27; respectively). The chemical index of alteration (CIA) values of Puerto Peñasco, Desemboque and Bahia Kino sands (PP: 42 to 50; DE: 48 to 50; BK: 44 to 50: respectively) indicate the low intensity of chemical weathering in the source rocks. The tectonic discriminant-function-based multidimensional diagram shows arc and rift settings for Puerto Peñasco sands whereas rift setting for both Desemboque and Bahia Kino sands. The heavy mineral assemblage, immobile trace elements, REE patterns, elemental ratios such Eu/Eu*, (La/Lu)cn, La/Sc, Th/Sc, La/Co, Th/Co, and Cr/Th, various bivariate and ternary plots indicate the contribution of sediments from felsic composition. This interpretation is supported by the comparison of REE patterns of the Puerto Peñasco, Desemboque and Bahia Kino sands with the potential source rocks exposed nearby the study areas.

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.

Investigations of the geochemistry of the rare earth elements in the exogenic cycle

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

Olivarez, A.M.

1989-01-01

This study investigates the REE geochemistry of three common sediment types (hydrothermal, eolian, and benthic layers) in order to understand their role in the exogenic cycle. The impact of seafloor hydrothermal activity upon the REE content of seawater was investigated by comparing REE/Fe ratios of hydrothermal sediments with end-member plume values. Hydrothermal activity results in a net depletion in REE's from seawater, primarily due to the large scavenging capacity of iron oxyhydroxides which precipitate from these solutions. The discrepancy between the predicted (positive) versus observed (negative) Eu anomaly of seawater was investigated by calculating REE scavenging indices for DSDP Sitemore » 598 hydrothermal precipitates is proportional to REE concentration in the fluid phase. The REE content of Lake Superior benthic layers are dominated by lithogenous sources, with minor contributions from the water column. The mechanism of REE removal from the water column may involve scavenging by Fe-rich phases. The eolian dust component of Pacific sediments is derived from two sources: the continental crust and oceanic crust, probably ash from circum-Pacific volcanism. The relative amount of the two end-members influences the median grain size. An eolian flux maximum exists between 35{degree}N and 42{degree}N in the northwest Pacific. This region also receives more eolian materials during glacial versus interglacial stages. A comparison of chemically treated versus untreated loess samples suggests that eolian dust is not a significant source of dissolved REE's to the oceans.« less

Nd-Sr isotopic and geochemical systematics in Cambrian boninites and tholeiites from Victoria, Australia

NASA Astrophysics Data System (ADS)

Nelson, D. R.; Crawford, A. J.; McCulloch, M. T.

1984-11-01

Rocks with boninitic affinities have been recognised in a number of “ophiolites”, including the Cambrian Heathcote and Mt Wellington Greenstone Belts of Victoria. Boninites and high-Mg andesites from the Heathcote Greenstone Belt show a restricted range of initial ɛ Nd values of between +3.3 to +5.8. Extremely refractory boninites from the Mt Wellington Greenstone Belt have ɛ Nd ranging from +1.3 to -9. Ti/Zr is positively correlated with Sm/Nd with the Heathcote lavas generally possessing greater depletion of Ti and enrichment of Zr relative to the middle and heavy REE with increasing LREE/HREE. These data are consistent with the generation of boninites by partial melting of refractory peridotite following invasion by LREE- and Zr-enriched, low ɛ Nd fluids. Tholeiites overlying the boninites in both greenstone belts have flat REE patterns and ɛ Nd˜+5, lower than that anticipated for lavas derived from depleted MORB source reservoirs in the Cambrian, suggesting that their source was also contaminated by a LREE-enriched, low ɛ Nd component similar to that involved in the generation of the Howqua boninites. The added components have characteristics compatible with their derivation from subducted altered oceanic crust and/or from wet subducted sediments. The identification of boninites and other low-Ti lavas in the Victorian greenstone belts is strong evidence for island arc development in southeastern Australia during the Lower Cambrian and provides further support for a subduction-related origin for many ophiolites.

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.

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.

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.

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.

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.

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 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.

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.

Granulite fades Nd-isotopic homogenization in the Lewisian complex of northwest Scotland

USGS Publications Warehouse

Whitehouse, M.J.

1988-01-01

A published Sm-Nd whole-rock isochron of 2,920 ?? 50 Myr, obtained from a wide range of lithologies in the Lewisian complex of north-west Scotland, was interpreted1 as the time of protolith formation. This date is ???260 Myr older than estimates for the timing of high-grade metamorphism in the complex at ??? 2,660 Myr2'3, and this period is considered to represent the duration of the Lewisian crustal accretion-differentiation superevent (CADS)4. Here we give new Sm-Nd data, obtained specifically from granulite facies tonalitic gneisses, that yield a date of 2,600 ??155 Myr. Although depleted-mantle model ages (tDM suggest >200 Myr of premetamorphic crustal residence, the regression date and its associated initial Nd-isotopic parameters demonstrate Nd-isotopic homogenization during the high-grade event, as well as the probability of general rare-earth-element (REE) mobility. Models for selective element depletion in the complex have previously assumed REE immobility since 2,920 Myr, but the data presented here suggest that a reappraisal of the depletion mechanism is required. ?? 1988 Nature Publishing Group.

Evaluating crustal contributions to enriched shergottites from the petrology, trace elements, and Rb-Sr and Sm-Nd isotope systematics of Northwest Africa 856

NASA Astrophysics Data System (ADS)

Ferdous, J.; Brandon, A. D.; Peslier, A. H.; Pirotte, Z.

2017-08-01

The origin of the incompatible trace element (ITE) characteristics of enriched shergottites has been critical for examining two contradicting scenarios to explain how these Martian meteorites form. The first scenario is that it reflects ITE enrichment in an early-formed mantle reservoir whereas the second scenario attributes it to assimilation of ancient Martian crust (∼4-4.5 Ga) by ITE-depleted magmas. Strongly differentiated shergottite magmas may yield added constraints for determining which scenario can best explain this signature in enriched shergottites. The meteorite Northwest Africa (NWA) 856 is a basaltic shergottite that, unlike many enriched shergottites, lacks olivine and has undergone extensive differentiation from more primitive parent magma. In similarity to other basaltic shergottites, NWA 856 is comprised primarily of compositionally zoned clinopyroxenes (45% pigeonite and 23% augite), maskelynite (23%) and accessory minerals such as ulvöspinel, merrillite, Cl-apatite, ilmenite, pyrrhotite, baddeleyite and silica polymorph. The CI-chondrite normalized rare earth element (REE) abundance patterns for its maskelynite, phosphates, and its whole rock are flat with corresponding light-REE depletions in clinopyroxenes. The 87Rb-87Sr and 147Sm-143Nd internal isochron ages are 162 ± 14 (all errors are ±2σ) Ma and 162.7 ± 5.5 Ma, respectively, with an initial εNdI = -6.6 ± 0.2. The Rb-Sr isotope systematics are affected by terrestrial alteration resulting in larger scatter and a less precise internal isochron age. The whole rock composition is used in MELTS simulations to model equilibrium and fractional crystallization sequences to compare with the crystallization sequence from textural observations and to the mineral compositions. These models constrain the depth of initial crystallization to a pressure range of 0.4-0.5 GPa (equivalent to 34-42 km) in anhydrous conditions at the Fayalite-Magnetite-Quartz buffer, and consistently reproduce the observed mineralogy throughout the sequence with progressive crystallization. The Ti/Al ratios in the clinopyroxenes are consistent with initial crystallization occurring at these depths followed by polybaric crystallization as the parent magma ascended to the surface. The REE abundances in the clinopyroxenes and maskelynite are consistent with progressive crystallization in a closed system. The new results for NWA 856 are combined with other shergottite data and are compared to mixing and assimilation and fractional crystallization (AFC) models using depleted shergottite magmas and ancient Martian crust as end-members. The models indicate that the range of REE abundances and ratios, when taken in isolation, can be successfully explained for all shergottites by crustal contamination. However, no successful crustal contamination model can explain the restricted εNdI of -6.8 ± 0.2 over the wide range of Mg# (0.65-0.25), and corresponding trace element variations from enriched shergottites to depleted shergottites. The findings indicate that the origin of the long-term ITE-enriched signature in enriched shergottites and the geochemical variability seen in shergottites is not a result of crustal contamination but instead reflects ancient mantle heterogeneity.

Petrology of the Rainy Lake area, Minnesota, USA-implications for petrotectonic setting of the archean southern Wabigoon subprovince of the Canadian Shield

NASA Astrophysics Data System (ADS)

Day, Warren C.

1990-08-01

The Rainy Lake area in northern Minnesota and southwestern, Ontario is a Late Archean (2.7 Ga) granite-greenstone belt within the Wabigoon subprovince of the Canadian Shield. In Minnesota the rocks include mafic and felsic volcanic rocks, volcaniclastic, chemical sedimentary rocks, and graywacke that are intrucded by coeval gabbro, tonalite, and granodiorite. New data presented here focus on the geochemistry and petrology of the Minnesota part of the Rainy Lake area. Igneous rocks in the area are bimodal. The mafic rocks are made up of three distinct suites: (1) low-TiO2 tholeiite and gabbro that have slightly evolved Mg-numbers (63 49) and relatively flat rare-earth element (REE) patterns that range from 20 8 x chondrites (Ce/YbN=0.8 1.5); (2) high-TiO2 tholeiite with evolved Mg-numbers (46 29) and high total REE abundances that range from 70 40 x chondrites (Ce/YbN=1.8 3.3), and (3) calc-alkaline basaltic andesite and geochemically similar monzodiorite and lamprophyre with primitive Mg-numbers (79 63), enriched light rare-earth elements (LREE) and depleted heavy rare-earth elements (HREE). These three suites are not related by partial melting of a similar source or by fractional crystallization of a common parental magma; they resulted from melting of heterogeneous Archean mantle. The felsic rocks are made up of two distinct suites: (1)low-Al2O3 tholeiitic rhyolite, and (2) high-Al2O3 calc-alkaline dacite and rhyolite and consanguineous tonalite. The tholeiitic felsic rocks are high in Y, Zr, Nb, and total REE that are unfractionated and have pronounced negative Eu anomalies. The calcalkaline felsic rocks are depleted in Y, Zr, and Nb, and the REE that are highly fractionated with high LREE and depleted HREE, and display moderate negative Eu anomalies. Both suites of felsic rocks were generated by partial melting of crustal material. The most reasonable modern analog for the paleotectonic setting is an immature island arc. The bimodal volcanic rocks are intercalated with sedimentary rocks and have been intruded by pre- and syntectonic granitoid rocks. However, the geochemistry of the mafic rocks does not correlate fully with that of mafic rocks in modern are evvironments. The low-TiO2 tholeiite is similar to both N-type mid-ocean-ridge basalt (MORB) and low-K tholeiite from immature marginal basins. The calc-alkaline basaltic andesite is like that of low-K calc-alkaline mafic volcanic rocks from oceanic volcanic arcs; however, the high-TiO2 tholeiite is most similar to modern E-type MORB, which occurs in oceanic rifts. The conundrum may be explained by: (1) rifting of a pre-existing immature arc system to produce the bimodal volcanic rocks and high-TiO2 tholeiite; (2) variable enrichment of a previously depleted Archean mantle, to produce both the low- and high-TiO2 tholeiite and the calc-alkaline basaltic andesite, and/or (3) enrichment of the parental rocks of the high-TiO2 tholeiite by crustal contamination.

Petrology of the Rainy Lake area, Minnesota, USA-implications for petrotectonic setting of the archean southern Wabigoon subprovince of the Canadian Shield

USGS Publications Warehouse

Day, W.C.

1990-01-01

The Rainy Lake area in northern Minnesota and southwestern, Ontario is a Late Archean (2.7 Ga) granite-greenstone belt within the Wabigoon subprovince of the Canadian Shield. In Minnesota the rocks include mafic and felsic volcanic rocks, volcaniclastic, chemical sedimentary rocks, and graywacke that are intrucded by coeval gabbro, tonalite, and granodiorite. New data presented here focus on the geochemistry and petrology of the Minnesota part of the Rainy Lake area. Igneous rocks in the area are bimodal. The mafic rocks are made up of three distinct suites: (1) low-TiO2 tholeiite and gabbro that have slightly evolved Mg-numbers (63-49) and relatively flat rare-earth element (REE) patterns that range from 20-8 x chondrites (Ce/YbN=0.8-1.5); (2) high-TiO2 tholeiite with evolved Mg-numbers (46-29) and high total REE abundances that range from 70-40 x chondrites (Ce/YbN=1.8-3.3), and (3) calc-alkaline basaltic andesite and geochemically similar monzodiorite and lamprophyre with primitive Mg-numbers (79-63), enriched light rare-earth elements (LREE) and depleted heavy rare-earth elements (HREE). These three suites are not related by partial melting of a similar source or by fractional crystallization of a common parental magma; they resulted from melting of heterogeneous Archean mantle. The felsic rocks are made up of two distinct suites: (1)low-Al2O3 tholeiitic rhyolite, and (2) high-Al2O3 calc-alkaline dacite and rhyolite and consanguineous tonalite. The tholeiitic felsic rocks are high in Y, Zr, Nb, and total REE that are unfractionated and have pronounced negative Eu anomalies. The calcalkaline felsic rocks are depleted in Y, Zr, and Nb, and the REE that are highly fractionated with high LREE and depleted HREE, and display moderate negative Eu anomalies. Both suites of felsic rocks were generated by partial melting of crustal material. The most reasonable modern analog for the paleotectonic setting is an immature island arc. The bimodal volcanic rocks are intercalated with sedimentary rocks and have been intruded by pre- and syntectonic granitoid rocks. However, the geochemistry of the mafic rocks does not correlate fully with that of mafic rocks in modern are evvironments. The low-TiO2 tholeiite is similar to both N-type mid-ocean-ridge basalt (MORB) and low-K tholeiite from immature marginal basins. The calc-alkaline basaltic andesite is like that of low-K calc-alkaline mafic volcanic rocks from oceanic volcanic arcs; however, the high-TiO2 tholeiite is most similar to modern E-type MORB, which occurs in oceanic rifts. The conundrum may be explained by: (1) rifting of a pre-existing immature arc system to produce the bimodal volcanic rocks and high-TiO2 tholeiite; (2) variable enrichment of a previously depleted Archean mantle, to produce both the low- and high-TiO2 tholeiite and the calc-alkaline basaltic andesite, and/or (3) enrichment of the parental rocks of the high-TiO2 tholeiite by crustal contamination. ?? 1990 Springer-Verlag.

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.

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

N-MORB crust beneath Fuerteventura in the easternmost part of the Canary Islands: evidence from gabbroic xenoliths

NASA Astrophysics Data System (ADS)

Neumann, Else-Ragnhild; Vannucci, Riccardo; Tiepolo, Massimo

2005-09-01

Gabbro xenoliths reported in this paper were collected in northern Fuerteventura, the Canary Island located closest to the coast of Africa. The xenoliths are very fresh and consist of Ti-Al-poor clinopyroxene + plagioclase (An87-67) + olivine (Fo72-86) ± orthopyroxene. Clinopyroxene and orthopyroxene are constantly and markedly depleted in light rare earth elements (LREE) relative to heavy REE (HREE), as expected for cumulus minerals formed from highly refractory N-MORB-type melts. In contrast, whole-rock Primordial Mantle-normalized trace element patterns range from mildly S-shaped (mildly depleted in Pr-Sm relative to both the strongly incompatible elements Rb-La and the HREE) to enriched. Estimates show that the trace element compositions of the rocks and their minerals are compatible with formation as N-MORB gabbro cumulates, which have been infiltrated at various extents (≤1% to >5%) by enriched alkali basaltic melts. The enriched material is mainly concentrated along grain boundaries and cracks through mineral grains, suggesting that the infiltration is relatively recent, and is thus associated with the Canary Islands magmatism. Our data contradict the hypothesis that a mantle plume was present in this area during the opening of the Atlantic Ocean. No evidence of continental material that might reflect attenuated continental crust in the area has been found. Gabbro xenoliths with REE and trace element compositions similar to those exhibited by the Fuerteventura gabbros are also found among gabbro xenoliths from the islands of La Palma (western Canary Islands) and Lanzarote. The compositions of the most depleted samples from these islands are closely similar, implying that there was no significant change in chemistry during the early stages of formation of the Atlantic oceanic crust in this area. Strongly depleted gabbros similar to those collected in Fuerteventura have also been retrieved in the MARK area along the central Mid-Atlantic Ridge. The presence of N-MORB oceanic crust beneath Fuerteventura implies that the continent-ocean transition in the Canary Islands area must be relatively sharp, in contrast to the situation both further north along the coast of Morocco, and along the Iberian peninsula.

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.

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.

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.

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.

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area.

PubMed

Protano, G; Riccobono, F

2002-01-01

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.

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.

Metalliferous sediments from Eolo Seamount (Tyrrhenian Sea): Hydrothermal deposition and re-deposition in a zone of oxygen depletion

USGS Publications Warehouse

Dekov, V.M.; Kamenov, George D.; Savelli, C.; Stummeyer, Jens; Thiry, M.; Shanks, Wayne C.; Willingham, A.L.; Boycheva, T.B.; Rochette, P.; Kuzmann, E.; Fortin, D.; Vertes, A.

2009-01-01

A sediment core taken from the south-east slope of the Eolo Seamount is composed of alternating red-brown and light-brown to bluish-grey layers with signs of re-deposition in the middle-upper section. The red-brown layers are Fe-rich metalliferous sediments formed as a result of low-temperature (??? 77????C) hydrothermal discharge, whereas the bluish-grey layers most probably originated from background sedimentation of Al-rich detrital material. The metalliferous layers are composed mainly of Si-rich goethite containing some Al. Co-precipitation of hydrothermally released SiO44- and Fe2+ as amorphous or poorly crystalline Fe-Si-oxyhydroxides explains the high Si concentration in goethite. The elevated Al content of the goethite is fairly unusual, but reflects the extremely high background Al content of the Tyrrhenian seawater due to the high eolian terrigenous flux from the Sahara desert. The Sr and Nd isotope data suggest that the Eolo metalliferous sediments are the product of a 3-component mixture: hydrothermal fluid, seawater, and detrital material (Saharan dust and Aeolian Arc material). The enrichment in Fe, P, As, Mo, Cd, Be, Sb, W, Y, V, depletion in REE and transition elements (Cu, Co, Ni, Zn) and the REE distribution patterns support the low-temperature hydrothermal deposition of the metalliferous layers. The hydrothermal field is located in a seawater layer of relative O2 depletion, which led to a significant fractionation of the hydrothermally emitted Fe and Mn. Fe-oxyhydroxides precipitated immediately around the vents whereas Mn stayed in solution longer and the Mn-oxides precipitated higher up on the seamount slope in seawater with relatively higher O2 levels. High seismic activity led to sediment re-deposition and slumping of the Mn-rich layers down slope and mixing with the Fe-rich layers. ?? 2009 Elsevier B.V. All rights reserved.

Trace element evidence for a depleted component intrinsic to the Hawaiian plume

NASA Astrophysics Data System (ADS)

DeFelice, C.; Mallick, S.; Saal, A. E.; Huang, S.

2017-12-01

The Hawaii Scientific Drilling Project (HSDP) recovered 3.5 km of Mauna Kea post-shield and shield stage basalts to investigate the geochemical evolution of a Hawaiian shield stage volcano and to constrain the geochemical structure of Hawaiian plume. A group of tholeiitic lavas from 1760-1810 meters below sea level (mbsl) have higher CaO content at given MgO content and are called high-CaO basalts. Isotopes of Pb, Sr, Hf, and Nd of these basalts show they are the most depleted shield basalts ever recovered in Hawaii. Their 206Pb/204Pb-208Pb/204Pb values indicate that they are not related to Pacific MORB. Their Ba/Th values (115-160) are characteristic of Hawaiian plume material and they are isotopically similar to Hawaiian rejuvenated stage lavas. To further investigate this relationship, we compare high-CaO basalts to the Honolulu Volcanics, a set of rejuvenated stage lavas. To determine their possible petrogenetic relation, we calculate their parental melt composition by adding or removing olivine until their geochemical composition is in equilibrium with Fo90. The High-CaO basalt parent magma composition has a much flatter REE pattern and much lower absolute REE contents than that of the Honolulu lavas. Batch melting forward models are calculated to determine potential sources that could contribute to both the Honolulu Volcanics and high-CaO basalts petrogenesis. Both parental magma compositions can be recreated by melting the same rejuvenated-stage source composition to varying degrees. Honolulu Volcanics are the result of a low degree of melting of the rejuvenated source, while higher degrees of melting reproduce the high-CaO basalts. The High-CaO basalts, erupted during shield-stage volcanism, show that the depleted component that rejuvenated stage basalts form from can be sampled during the most voluminous stage of volcanism, and is likely intrinsic to the plume.

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

Proterozoic Eastern Sayan ophiolites (Central Asian Orogenic Belt) record subduction initiation in vicinity of continental block

NASA Astrophysics Data System (ADS)

Belyaev, Vasilii; Gornova, Marina; Medvedev, Alexander; Dril, Sergey; Karimov, Anas

2017-04-01

Geochemical study of cumulate and volcanic rocks from ˜ 1020 Ma Eastern Sayan ophiolites1 (Siberia, Russia) is used to provide a correlation between two ophiolitic belts and link them to subduction initiation setting. Studied areas include Ospin and Ilchir massifs to the East and Dunzhugur to the West of Early Precambrian Gargan block. Ophiolitic cumulates represent peridotite-pyroxenite-gabbro-norite suite with crystallization orders of Cr-Sp - Ol - Cpx - Opx - Plag, and Cr-Sp - Ol - Opx - Amph - (Cpx) - Plag. Clinopyroxene is augite-diopside with Mg# 85-95, low Al2O3 (1-2.5%) and TiO2 (0.05-0.2%). Amph is Mg-hornblende to edenite (Mg# 84-86, 5-8% Al2O3, 0.3-0.6% TiO2). Cr-Sp has Cr# 65-83 and 0.05-0.3% TiO2 in cumulates with high Opx proportion, while in Cpx-dominating pyroxenites chemistry of Cr-Sp is variable (Cr# 40-75, 0.05-0.5% TiO2). Due to alteration, Ol and Opx chemistry is available only for some samples (Ol: Mg# 88, 0.2-0.3% NiO; Opx: Mg# 89, 1.6% Al2O3). Whole-rock MgO ranges 9 to 38%. Amph-free pyroxenites and gabbro-norites show flat to slightly depleted REE pattern with negative HFSE anomalies. Amph-pyroxenites have fractionated trace-element pattern with LREE enrichment, Nb-Ti minima at slightly higher HFSE abundances. In-situ LA-ICP-MS analysis of Cpx in Amph-free pyroxenites and gabbro-norites revealed moderately depleted to flat REE and Nb-Zr-Hf-Ti depletion, with low trace element abundances (La/SmPM = 0.14-0.9, Zr 0.6-2.3, Nd = 0.2-1.1, Yb = 0.2-0.7 ppm). Melts calculated to be in equilibrium with Cpx using distribution coefficients2 are REE-flat to slightly LREE-enriched (La/SmPM = 1-4) at low HREE abundances (0.5-1.5 ppm Yb). Overall, crystallization orders, mineral and whole-rock chemistry suggest origin of ophiolitic cumulates from low-Ca boninites or primitive andesites (higher Opx or Amph proportion) to high-Ca boninites or primitive island arc tholeiites (Cpx-dominating, Amph-free associations with subordinate Opx). Ophiolitic volcanics and dikes are low-Ca and intermediate-Ca boninites, andesite-basalts, andesites, dacites of calc-alkaline (CA) affinity with rare evolved island-arc tholeiitic (IAT) andesite-basalts. They resemble appropriate rocks of intraoceanic island arcs, forearcs, and ophiolites. Boninites and CA-andesites are LREE-enriched (La/SmPM 1.2-3.8) at low HREE (0.5-1.6 ppm Yb) contents while evolved IAT show flat REE (La/SmPM = 1.1) and higher abundances (2.4-2.8 ppm Yb), and both have negative Nb anomalies. Nd-isotopic data expressed as epsilon Nd(1020Ma) values are -2.3 to +4.1 in cumulates, -2.8 to +0.4 in boninites and andesites, and +2.3 to +2.7 in IAT (compared to epsilon Nd(1020Ma) +7.8 in depleted mantle). The ophiolites obducted on the Gargan continental block, which contains Archean gneisses with epsilon Nd(1020) = -20 to -281. Subduction and recycling of sediments derived from these gneisses could explain enriched Nd isotopic characteristics of the studied ophiolitic rocks. The boninite-andesite-IAT association is usually found in subduction initiation settings recorded by modern forearc regions and forearc ophiolites. The difference of the Eastern Sayan ophiolites is their supposed formation close to ancient continental block which supplied recycled material into newly formed subduction zone. 1. Sklyarov et al (2016) Russ Geol Geophys 57, 127-140 2. Sobolev et al (1996) Petrology 3, 326-336.

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.

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.

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.

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.

Timing of pyroxenite formation in supra-subduction Josephine Ophiolite, Oregon.

NASA Astrophysics Data System (ADS)

Hough, T.; Le Roux, V.; Kurz, M. D.

2017-12-01

The Josephine ophiolite is a partly dismembered ophiolite located in southern Oregon and northwestern California (USA). It displays a large ( 640 km2) mantle section that is mostly composed of depleted spinel harzburgite and lherzolite re-equilibrated at temperatures of 900 °C. In addition, the peridotite section of the ophiolite contains minor dunites and pyroxenite veins ranging from orthopyroxenites to clinopyroxenites. Using field, petrological and geochemical data, previous studies have shown that the peridotite experienced 10-20% of hydrous flux melting. In addition, clinopyroxene and orthopyroxene in harzburgites show variable degrees of light rare-earth element (LREE) enrichment, which suggests percolation and re-equilibration with small fractions of boninite melt. Overall, the trace element concentrations of pyroxenes indicate that the harzburgites experienced particularly high degrees of melting in the mantle wedge. We collected a number of orthopyroxenite and clinopyroxenite veins in the mantle section of the Josephine Ophiolite. Here we present the major and rare-earth element (REE) contents of pyroxene in 4 orthopyroxenites and 2 clinopyroxenites and calculate the major element and REE closure temperatures for individual veins. We show that individual pyroxenites record drastic variations in their degree of REE depletion, indicating that multiple generations of melts percolated the peridotite. The pyroxenite veins also record higher REE closure temperatures (>1200 ºC) compared to the surrounding peridotite, potentially indicating rapid cooling after emplacement. REE closure temperatures are also higher than major element closure temperatures. In parallel, we analyzed Sr isotopes by MC-ICPMS in pyroxene separates from 4 veins. Results indicate that the maximum age of emplacement of orthopyroxenite veins corresponds to the age of exhumation. Some clinopyroxenites may have formed during earlier melt percolation events. This study supports the idea that the composition of melts that percolate the mantle wedge can be highly variable and that orthopyroxenites may be the last type of veins to form in those environments.

Quantifying Post-Fire Aeolian Sediment Transport Using Rare Earth Element Tracers.

NASA Astrophysics Data System (ADS)

Dukes, D.; Ravi, S.; Grandstaff, D. E.; Gonzales, H. B.; Li, J. J.; Sankey, J. B.; Wang, G.; Van Pelt, R. S.

2016-12-01

Grasslands and rangelands in arid and semi-arid regions of the world, which provide fundamental ecosystem services, are undergoing rapid increases in fire activity and are highly susceptible to post-fire accelerated soil erosion by wind. A quantitative assessment that integrates fire-wind erosion feedbacks is therefore critically needed in understanding vegetation change, soil biogeochemical cycling, air quality, and landscape evolution. We investigated the applicability of a novel tracer technique - the use of rare earth element (REE) tracers - to quantify soil erosion by wind and to identify sources and sinks of wind-blown sediments in both a burned and unburned shrub-grass transition zone within the Chihuahuan desert (New Mexico, USA). At the beginning of the windy season, March 2016, silt and sand sized particles in shrub, grass, and bare microsites were each tagged with a unique REE oxide, Ho, Eu, and Yb respectively. Samples were then taken directly after application prior to a prescribed fire and again at the end of the windy season in June 2016. All REE tracers showed signs of depletion and mixing, with the depletion in the burned site up to 20% greater than the unburned. REE concentration comparisons between the burned and unburned plots reveal a shift in the source and sink dynamics of sediment post fire. In unburned plots, changes in microsite REE concentrations indicate that sediment moved from the bare to vegetated microsites, whereas the opposite occurred in burned plots. However, burned plot grass microsites acted as a sink for sediment from shrub microsites, whereas unburned plot grass microsites exhibited no enrichment from shrub microsite-sourced sediment. Though fires are known to immediately increase aeolian sediment transport, accompanying changes in the sources and sinks of wind borne sediment may influence biogeochemical cycling and vegetation shifts possibly providing a feedback mechanism for land degradation in dryland ecosystems.

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

The Permian-Triassic granitoids in Bayan Obo, North China Craton: A geochemical and geochronological study

NASA Astrophysics Data System (ADS)

Ling, Ming-Xing; Zhang, Hong; Li, He; Liu, Yu-Long; Liu, Jian; Li, Lin-Qing; Li, Cong-Ying; Yang, Xiao-Yong; Sun, Weidong

2014-03-01

Granitoids near the Bayan Obo giant rare earth element (REE) deposit at the north margin of the North China Craton (NCC), the world's largest light REE (LREE) deposit, have been taken by some authors as the key factors that controlled the mineralization. In contrast, others proposed that the REE deposit has been partially destructed by these granitoids. Here we report systematic studies on geochronology and geochemical characteristics of granitoids of different distances from the orebodies, to investigate the genesis and their relationship to the giant Bayan Obo deposit. Granitoids studied here, including granites and quartz monzonites, are peraluminous with A/CNK = 0.99-1.11, LREE enriched and heavy REE (HREE) depleted, with variable REE concentrations (total REE = 54-330 ppm) and large negative Eu anomaly (δEu = 0.19-0.70). The REE patterns are distinct from those of ore-bearing dolomites. Some samples have slightly higher LREE concentrations, which may have been contaminated by the orebodies during intrusion. Trace elements of the granitoids are characterized by positive Pb anomaly, strong negative Ti anomaly and Nb, Ta and Sr anomalies. The granites exhibit negative Ba anomaly. The granitoids plot within the post-collision granite field in the Pearce diagram, which is consistent with the tectonic regime. The quartz monzonites and one granite have A-type granite characteristics and belong to the A2 subgroup. Zircons in these granitoids have high Th/U values, which are typical for magmatic zircons. High precision U-Pb dating for these zircons by secondary ion mass spectrometry (SIMS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields Permian-Triassic 206Pb/238U ages ranging from 243.2 to 293.8 Ma. The formation of the granitoids is > 55 Ma later than the latest ore forming age. The zircons have low La concentrations (0.02-12 ppm), high (Sm/La)N (0.8-685) and Ce/Ce* (1.4-80). The Ti-in-zircon temperature of the granitoids ranges from 590 to 770 °C. All these evidences suggest that the granitoids have no contribution to the formation of the Bayan Obo deposit. Granitoids that are close to the orebodies had limited interaction with it and gained some LREE-enriched characteristics during magmatisms. Nevertheless, their effects to the orebodies are subtle. All the granitoids formed in a post-collisional tectonic regime at convergent margins, which is consistent with plate subduction during the closure of the Palaeo-Asian Ocean, which started in the Neoproterozoic and lasted until the Carboniferous/Permian.

Trace-Element Evidence for an Aqueous Atmospheric Origin of Desert Varnish: implications for the aqueous atmospheric input flux into the ocean

NASA Astrophysics Data System (ADS)

Thiagarajan, N.; Lee, C.

2003-12-01

Desert varnish is a slow-growing dark patina commonly found on rock surfaces in arid environments. Varnishes consist of about 30% Mn and Fe oxides accompanied by oxides of Si, Al, Mg, K and Ca, which occur primarily in the form of clays. Although it is generally agreed that varnishes have an atmospheric origin, their exact formation mechanism remains highly debated. Two endmember hypotheses are gradual accumulation of wind-blown dust followed by diagenesis, and direct chemical precipitation of dissolved elements from atmospheric aerosols. To rule out one of these hypotheses, we investigated the trace-element systematics of varnishes, in particular, focusing on those elements that have contrasting solubilities in aqueous environments. If our trace element analyses are consistent with the varnishes being derived from dissolved atmospheric constituents then the data can be used to quantify the paleofluxes of the soluble fraction of atmospheric aerosols to various depositional environments. For example, this will have implications for the transport of metals to the ocean that are immediately biologically available. We collected varnishes deposited on smooth basaltic lava flow surfaces in the Cima Volcanic Field (Mojave Desert) and in Death Valley, California. The chosen lava flows retain original flow surface structure and are topographical highs; the effects of erosion are hence minimal. Varnishes were scraped off with a quartz rod to minimize trace element contamination and the trace element compositions were then determined by ICP-MS using an external synthetic standard for calibration. Our analyses show that the rare-earth elements (REEs), Co, Ni, and Pb are enriched 1.5 to 10 times relative to the upper continental crust (UCC) and that Nb, Ti, Ta, Hf, Th, Rb and Cs are depleted to varying degrees relative to UCC and the REEs. These fractionations can be explained by their differing chemical behaviors in aqueous environments. The extreme depletion in Rb and Cs reflect their high solubilities and tendency to be progressively leached out by rain water. Nb, Ti, Ta, Hf and Th are present only in detrital concentrations, reflecting their high insolublities and their probable depletion in the Fe- and Mn-rich components of the varnish. Co, Ni, Pb and Ce are soluble but readily coprecipitate with Mn oxides hence their 10-fold enrichments. Enrichments caused by diagenesis of dust accreted on the varnish substrate cannot achieve the 10-fold enrichments of some elements observed here, indicating that the aqueous component must be derived directly from the atmosphere. Remarkably, we find that ferro-manganese crusts produced by hydrogenous processes in the marine environment have trace-element abundance patterns nearly identical to those of varnishes. Relative to the upper continental crust, they are enriched in REEs, Co, Ni, and Pb, depleted in Nb, Ti, Ta, Hf, Th, Rb and Cs and are anomalously high in Ce. These unexpected similarities provide additional evidence that desert varnishes represent the direct precipitation of aqueous components in the atmosphere. It may be possible to estimate the aqueous atmospheric input of such trace elements as the REEs into the ocean. For example, multiplying the Nd/Fe and Nd/Mn ratios of the varnishes by estimates of modern day Fe and Mn wet deposition inputs to the ocean yields an oceanic input of 4 to 15 x 107 moles of Nd/year. This is slightly larger than the amount of dissolved Nd entering the oceans each year (2.4 x 106 moles/yr) via rivers, hence, there is a significant atmospheric input of REEs into the ocean in aqueous form.

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.

Mobility of rare earth elements, yttrium and scandium from a phosphogypsum stack: Environmental and economic implications.

PubMed

Cánovas, Carlos Ruiz; Macías, Francisco; Pérez López, Rafael; Nieto, José Miguel

2018-03-15

This paper investigates the mobility and fluxes of REE, Y and Sc under weathering conditions from an anomalously metal-rich phosphogypsum stack in SW Spain. The interactions of the phosphogypsum stack with rainfall and organic matter-rich solutions, simulating the weathering processes observed due to its location on salt-marshes, were simulated by leaching tests (e.g. EN 12457-2 and TCLP). Despite the high concentration of REE, Y and Sc contained in the phosphogypsum stack, their mobility during the leaching tests was very low; <0.66% and 1.8% of the total content of these elements were released during both tests. Chemical and mineralogical evidences suggest that phosphate minerals may act as sources of REE and Y in the phosphogypsum stack while fluoride minerals may act as sinks, controlling their mobility. REE fractionation processes were identified in the phosphogypsum stack; a depletion of LREE in the saturated zone was identified due probably to the dissolution of secondary LREE phosphates previously formed during apatite dissolution in the industrial process. Thus, the vadose zone of the stack would preserve the original REE signature of phosphate rocks. On the other hand, an enrichment of MREE in relation to HREE of edge outflows is observed due to the higher influence of estuarine waters on the leaching process of the phosphogypsum stack. Despite the low mobility of REE, Y and Sc in the phosphogypsum, around 104kg/yr of REE and 40kg/yr of Y and Sc are released from the stack to the estuary, which may imply an environmental concern. The information obtained in this study could be used to optimize extraction methods aimed to recover REE, Y and Sc from phosphogypsum, mitigating the pollution to the environment. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluid-induced Crystallization of Majoritic Garnet During Deep Continental Subduction (Western Gneiss Region, Norway)

NASA Astrophysics Data System (ADS)

Scambelluri, M.; Pettke, T.; van Roermund, H. L.

2008-12-01

In ultrahigh pressure (UHP) rocks, garnet containing pyroxene exsolutions derives from breakdown of majorite crystallized at depths > 200 km. Presence of microdiamonds in some of these rocks [1], including those of the Western Gneiss Region (WGR) of Norway [2], may suggest a fluid-bearing environment for the genesis of majorite. The WGR UHP gneisses host garnet peridotite and websterite recording uplift from extraordinary depths prior to uptake in a subducting slab [2]. These ultramafic rocks (islands of Otrøy and Bardane) derive from depleted Archean transition-zone mantle (350 km depth) upwelled and accreted to a cratonic lithosphere (M2 stage). Evidence for this are decimetric garnets (grt) preserved in Otrøy, hosting up to 20 volume% orthopyroxene (opx) and clinopyroxene (cpx) exsolved from precursor majoritic garnet (M1 stage). The pyroxene lamellae (20-30 ¥ìm thick, hundreds of ¥ìm long) [3] were exsolved under high-T, as shown by the garnet/cpx REE distribution [4]. This Archean-mid Proterozoic record is overprinted by the 425- 390 Ma Scandian continental subduction (M3 stage), forming new grt + cpx + opx + phlogopite (phl) + spinel (sp) that contain diamond-bearing micro-inclusions witnessing deep COH subduction fluids [2]. Here we document formation of new majoritic garnet in the M3 assemblage and in veins at Bardane [5]. Textural characteristics, together with the LREE and LILE enrichments of the M3 minerals, indicate that the new majorite is linked to infiltration of subduction fluids during renewed burial towards sub-lithospheric depths. It represents the deepest occurrence of fluid-related microstructures in mantle rocks. The new majoritic garnet crystallized at grain boundaries and in micro-veins at 7 Gpa and 900-1000 °C. It hosts thin pyroxene needles (5 mm thick, 100 mm long) exsolved under comparatively low-T, as indicated by the garnet/cpx REE distribution. The trace element signature of the majorite-bearing subduction assemblage is LREE- (cpx La/Yb = 220) and LILE-enriched (appreciable Li, B, Rb, Ba, Pb, U, Th in cpx and phl), to indicate addition of crustal components. The interstitial and vein M3 majoritic garnet has flat REE patterns (La 1xChondrite; La/Yb= 0.35) and lacks the LREE depletion characteristic of common grt. The px component of majorite thus allows LREE and subordinate LILE storage in this mineral, which becomes a relevant trace element repository in the deep mantle. The REE enriched signature of M3 majorite contrasts the depleted nature of M1 (+ M2) grt: this indicates the presence of two generations of majorite in these rocks and suggests the re-fertilization of initially depleted peridotite by subduction fluid at 200 km depth. Distinct generations of majoritic garnet thus survive in the same terrain, displaying distinct textures, compositions, and exsolution T. The majorite microstructures and compositions enable to discriminate between crystallization environments: hot sub- cratonic lithosphere vs. colder subduction settings. 1 Mposkos ED, Kostopoulos DK, 2001, EPSL 192, 497- 506; 2 Van Roermund HLM. et al., 2002, Geology 30, 959-962; 3 Van Roermund HLM, Drury M., 1998, Terra Nova 10, 295-301; 4 Spengler D. et al., 2006, Nature 440, 913-917; 5 Scambelluri M. et al., 2008, Geology 36, 59-62.

[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.

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

Spitz, A.H.; Boynton, W.V.

Six ureilites (ALHA77257, ALHA81101, ALH82130, PCA82506, Kanna, and Novo Urei) were analyzed using neutron activation analysis for Ca, Sc, Cr, Mn, Fe, Co, Ni, Zn, Ga, REE, W, Re, Os, Ir, and Au. The authors examined bulk samples as well as acid-treated samples. In bulk samples the refractory siderophiles' concentrations range from approximately 0.1 to 1.0 times CI chondrites while the volatile siderophiles' concentrations range from approximately 0.1 to 1.0 times CI chondrites while the volatile siderophiles range from about 0.07 to 0.3 times CI chondrites. Rare earth elements (REEs) in ureilites are quite depleted and display light and heavymore » rare earth enrichments. The Antarctic meteorites display either much less pronounced v-shaped patterns or no enrichment in the light rare earths at all. In terms of the new trace-element results, ureilites do not fall into the coherent groups that other workers have defined by chemical or petrographic characteristics. Trace elements do provide additional constraints on the models for the petrogenesis of ureilites. In particular, the siderophile element abundances call for simplified models of chemical processing rather than the complex, multistage processing called for in silicate fractionation models. REE concentrations, on the other hand, imply multistage processing to produce the ureilites. None of the ureilite petrogenesis models extant account for the trace element data. These new data and the considerations of them with respect to the proposed ureilite petrogenesis models indicate that the direction of modeling should be toward contemplation of mixtures and how the components the authors observe in ureilites behave under such conditions.« less

Apatite Mineral Chemistry From IOA Deposits in Northern Chile

NASA Astrophysics Data System (ADS)

Palma, G.; Barra, F.; Reich, M.; Valencia, V.; Simon, A. C.; Vervoort, J. D.

2017-12-01

The Carmen, Fresia and Mariela iron-oxide apatite (IOA) deposits of Cretaceous age, located in the Coastal Cordillera of northern Chile, comprise massive bodies of magnetite with minor apatite and actinolite crystals spatially related to diorite intrusions. In order to provide new insights on the origin of Andean IOA deposits, we provide geochemical data of apatite grains collected from these three deposits. All studied apatite grains are zoned with respect to Cl and F, and show a decoupled behaviour between fluorapatite and chlorapatite. Carmen apatite grains are mostly F-rich, whereas in Mariela apatite grains are Cl-rich. Fresia apatite grains show a variable composition between fluorapatite and chlorapatite. Carmen apatite grains show a high REE content reaching up to 7000 ppm, and both Fresia and Mariela have lower REE content (<1400 ppm). REE patterns for all analyzed apatite grains show the typical LREE enrichment relative to the HREE and pronounced negative Eu anomaly, which indicates crystallization of plagioclase in the source magmas [1]. Chlorapatite zones are characterized by high S, Na, Sr and Fe content relative to fluorapatite zones. Notably S and Na show a coupled behaviour with Cl. Conversely LREE are depleted in chlorapatite zones, which is compatible with metasomatism through dissolution-reprecipitation mechanism and formation of monazite inclusions [2]. These results indicate a magmatic origin for fluorapatite in these Andean IOA deposits followed by variable degrees of hydrothermal overprint which resulted in the formation of Cl-rich apatites.[1] Frietsch & Perdahl (1995) Ore Geology Rev. 9 489-510. [2]Harlov et al. (2005) Contrib Mineral Petrol 150: 268-286

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.

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.

Stratigraphic and geochemical evolution of an oceanic arc upper crustal section: The Jurassic Talkeetna Volcanic Formation, south-central Alaska

USGS Publications Warehouse

Clift, P.D.; Draut, A.E.; Kelemen, P.B.; Blusztajn, J.; Greene, A.

2005-01-01

The Early Jurassic Talkeetna Volcanic Formation forms the upper stratigraphic level of an oceanic volcanic arc complex within the Peninsular Terrane of south-central Alaska. The section comprises a series of lavas, tuffs, and volcaniclastic debris-How and flow turbidite deposits, showing significant lateral facies variability. There is a general trend toward more volcaniclastic sediment at the top of the section and more lavas and tuff breccias toward the base. Evidence for dominant submarine, mostly mid-bathyal or deeper (>500 m) emplacement is seen throughout the section, which totals ???7 km in thickness, similar to modern western Pacific arcs, and far more than any other known exposed section. Subaerial sedimentation was rare but occurred over short intervals in the middle of the section. The Talkeetna Volcanic Formation is dominantly calc-alkatine and shows no clear trend to increasing SiO2 up-section. An oceanic subduction petrogenesis is shown by trace element and Nd isotope data. Rocks at the base of the section show no relative enrichment of light rare earth elements (LREEs) versus heavy rare earth elements (REES) or in melt-incompatible versus compatible high field strength elements (HFSEs). Relative enrichment of LREEs and HFSEs increases slightly up-section. The Talkeetna Volcanic Formation is typically more REE depleted than average continental crust, although small volumes of light REE-enriched and heavy REE-depleted mafic lavas are recognized low in the stratigraphy. The Talkeetna Volcanic Formation was formed in an intraoceanic arc above a north-dipping subduction zone and contains no preserved record of its subsequent collisions with Wrangellia or North America. ?? 2005 Geological Society of America.

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.

Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

2004-01-01

We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.

Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: a new perspective.

PubMed

Delgado, Joaquín; Pérez-López, Rafael; Galván, Laura; Nieto, José Miguel; Boski, Tomasz

2012-09-01

Rare earth elements (REE) were analyzed in surface sediments from the Guadiana Estuary (SW Iberian Pyrite Belt). NASC (North American Shale Composite) normalized REE patterns show clearly convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE, indicating acid-mixing processes between fluvial waters affected by acid mine drainage (AMD) and seawater. However, REE distributions in the mouth (closer to the coastal area) show slightly LREE-enriched and flat patterns, indicating saline-mixing processes typical of the coastal zone. NASC-normalized ratios (La/Gd and La/Yb) do not discriminate between both mixing processes in the estuary. Instead, a new parameter (E(MREE)) has been applied to measure the curvature in the MREE segment. The values of E(MREE)>0 are indicative of acid signatures and their spatial distribution reveal the existence of two decantation zones from flocculation processes related to drought periods and flood events. Studying REE fractionation through the E(MREE) may serve as a good proxy for AMD-pollution in estuarine environments in relation to the traditional methods. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

Geochemical compositions of Neoproterozoic to Lower Palaeozoic (?) shales and siltstones in the Volta Basin (Ghana): Constraints on provenance and tectonic setting

NASA Astrophysics Data System (ADS)

Amedjoe, Chiri G.; Gawu, S. K. Y.; Ali, B.; Aseidu, D. K.; Nude, P. M.

2018-06-01

Many researchers have investigated the provenance and tectonic setting of the Voltaian sediments using the geochemistry of sandstones in the basin. The shales and siltstones in the basin have not been used much in the provenance studies. In this paper, the geochemistry of shales and siltstones in the Kwahu Group and Oti Group of the Voltaian Supergroup from Agogo and environs in the southeastern section of the basin has constrained the provenance and tectonic setting. Trace element ratios La/Sc, Th/Sc and Cr/Th and REEs sensitive to average source compositions revealed sediments in the shales and siltstones may mainly be from felsic rocks, though contributions from old recycled sediments and some andesitic rock sediments were identified. The felsic rocks may be granites and/or granodiorites. Some intermediate rocks of andesitic composition are also identified, while the recycled sediments were probably derived from the basement metasedimentary rocks. The enrichment of light REE (LaN/YbN c. 7.47), negative Eu anomalies (Eu/Eu* c. 0.59), and flat heavy REE chondrite-normalized patterns, denote an upper-continental-crustal granitic source materials for the sediments. Trace-element ternary discriminant diagrams reveal passive margin settings for sediments, though some continental island arc settings sediments were also depicted. Mixing calculations based on REE concentrations and modeled chondrite-normalized REE patterns suggest that the Birimian basement complex may be the source of detritus in the Voltaian Basin. REEs are more associated with shales than siltstones. On this basis chondrite-normalized REE patterns show that shale lithostratigraphic units may be distinguished from siltstone lithostratigraphic units. The significant variability in shales elemental ratios can therefore be used to distinguish between shales of the Oti Group from that of the Kwahu Group.

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.

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.

Determination of rare earth elements concentration at different depth profile of Precambrian pegmatites using instrumental neutron activation analysis.

PubMed

Sadiq Aliyu, Abubakar; Musa, Yahaya; Liman, M S; Abba, Habu T; Chaanda, Mohammed S; Ngene, Nnamani C; Garba, N N

2018-01-01

The Keffi area hosts abundant pegmatite bodies as a result of the surrounding granitic intrusions. Keffi is part of areas that are geologically classified as North Central Basement Complex. Data on the mineralogy and mineralogical zonation of the Keffi pegmatite are scanty. Hence the need to understand the geology and mineralogical zonation of Keffi pegmatites especially at different depth profiles is relevant as a study of the elemental composition of the pegmatite is essential for the estimation of its economic viability. Here, the relative standardization method of instrumental neutron activation analysis (INAA) has been used to investigate the vertical deviations of the elemental concentrations of rare earth elements (REEs) at different depth profile of Keffi pegmatite. This study adopted the following metrics in investigating the vertical variations of REEs concentrations. Namely, the total contents of rare earth elements (∑REE); ratio of light to heavy rare earth elements (LREE/HREE), which defines the enrichment or depletion of REEs; europium anomaly (Eu/Sm); La/Lu ratio relative to chondritic meteorites. The study showed no significant variations in the total content of rare elements between the vertical depth profiles (100-250m). However, higher total concentrations of REEs (~ 92.65ppm) were recorded at the upper depth of the pegmatite and the europium anomaly was consistently negative at all the depth profiles suggesting that the Keffi pegmatite is enriched with light REEs. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

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.

How lithology and climate affect REE mobility and fractionation along a shale weathering transect of the Susquehanna Shale Hills Critical Zone Observatory

NASA Astrophysics Data System (ADS)

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

2012-12-01

Shale weathering is an important process in global elemental cycles. Accompanied by the transformation of bedrock into regolith, many elements including rare earth elements (REE) are mobilized primarily by chemical weathering in the Critical Zone. Then, REE are subsequently transported from the vadose zone to streams, with eventual deposition in the oceans. REE have been identified as crucial and strategic natural resources; and discovery of new REE deposits will be facilitated by understanding global REE cycles. At present, the mechanisms and environmental factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we present a systematic study of soils, stream sediments, stream waters, soil water and bedrock in six small watersheds that are developed on shale bedrock in the eastern USA to constrain the mobility and fractionation of REE during early stages of chemical weathering. The selected watersheds are part of the shale transect established by the Susquehanna Shale Hills Observatory (SSHO) and are well suited to investigate weathering on shales of different compositions or within different climate regimes but on the same shale unit. Our REE study from SSHO, a small gray shale watershed in central Pennsylvania, shows that up to 65% of the REE (relative to parent bedrock) is depleted in the acidic and organic-rich soils due to chemical leaching. Both weathering soil profiles and natural waters show a preferential removal of middle REE (MREE: Sm to Dy) relative to light REE (La to Nd) and heavy REE (Ho to Lu) during shale weathering, due to preferential release of MREE from a phosphate phase (rhabdophane). Strong positive Ce anomalies observed in the regolith and stream sediments point to the fractionation and preferential precipitation of Ce as compared to other REE, in the generally oxidizing conditions of the surface environments. One watershed developed on the Marcellus black shale in Pennsylvania allows comparison of behaviors of REE in the organic-rich vs. organic-poor end members under the same climate conditions. Our study shows that black shale bedrock has much higher REE contents compared to the Rose Hill gray shale. The presence of reactive phases such as organic matter, carbonates and sulfides in black shale and their alteration greatly enhance the release of REE and other metals to surface environments. This observation suggests that weathering of black shale is thus of particular importance in the global REE cycles, in addition to other heavy metals that impact the health of terrestrial and aquatic ecosystems. Finally, our ongoing investigation of four more gray shale watersheds in Virginia, Tennessee, Alabama, and Puerto Rico will allow for a comparison of shale weathering along a climosequence. Such a systematic study will evaluate the control of air temperature and precipitation on REE release from gray shale weathering in eastern USA.

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.

Characterization and evolution of dissolved organic matter in acidic forest soil and its impact on the mobility of major and trace elements (case of the Strengbach watershed)

NASA Astrophysics Data System (ADS)

Gangloff, Sophie; Stille, Peter; Pierret, Marie-Claire; Weber, Tiphaine; Chabaux, François

2014-04-01

Dissolved Organic Carbon (DOC) plays an important role in the behavior of major and trace elements in the soil and influences their transfer from soil to soil solution. The first objective of this study is to characterize different organic functional groups for the Water Extractable Organic Carbon (WEOC) fractions of a forest soil as well as their evolution with depth. The second objective is to clarify the influence of these organic functional groups on the migration of the trace elements in WEOC fractions compared to those in the soil solution obtained by lysimeter plates. All experiments have been performed on an acidic forest soil profile (five depths in the first meter) of the experimental spruce parcel in the Stengbach catchment. The Infra-red spectra of the freeze-dried WEOC fractions show a modification of the molecular structure with depth, i.e. a decrease of the polar compounds such as polysaccharides and an increase of the less polar hydro-carbon functional groups with a maximum value of the aromaticity at 30 cm depth. A Hierarchical Ascending Classification (HAC) of the evolution of Water Extractable Chemical Elements (WECE) with the evolution of the organic functional groups in the organic matter (OM) enriched soil compartments permits recognition of relationships between trace element behavior and the organic functional group variations. More specifically, Pb is preferentially bound to the carboxylic acid function of DOC mainly present in the upper soil compartment and rare earth elements (REE) show similar behavior to Fe, V and Cr with a good affinity to carboxy-phenolic and phenolic groups of DOC. The experimental results show that heavy REE compared to light REE are preferentially bound to the aromatic functional group. This different behavior fractionates the REE pattern of soil solutions at 30 cm depth due to the here observed aromaticity enrichment of DOC. These different affinities for the organic functional groups of the DOC explain some aspects of the behavior of trace elements in soil solutions and in the soil profile but, also the competition between trace elements in complexation with DOC. The results of this study are important for the understanding of the mobility and the migration of pollutants (as heavy metals or radionuclides) as well as nutrients in natural ecosystems. WE PrN/YbN is constant between 3 and 16 cm depth whereas SS PrN/YbN slightly decreases from 0.80 at 5 cm depth to 0.74 at 10 cm depth. This results from Pr (LREE) enrichment in the soil solution of the upper soil compartment caused by vegetation controlled LREE recycling and/or atmospheric depositions (see above). WE PrN/YbN and SS PrN/YbN show similar depth dependent distributions including the enrichment at 30 cm depth. It results from Yb depletion at this depth and enrichment in the deeper soil compartment compared to Pr. Similar to Marsac et al. (2012, 2013) one might suggest that there is competition between Fe3+, Al3+ and REE for the binding with DOC. They have a high affinity with the same organic functional groups which is confirmed by the classification scheme (Fig. 8). The studies of Marsac et al. suggest that at acidic pH and low metal/DOC ratios, Fe3+and Al3+ compete more with HREE than LREE; moreover, at high metal/DOC ratios and acidic pH, Al3+ competes with LREE. The Fig. 13 showing the variations of WECEN for Al and Fe in function of WECEN LREE and HREE confirms Marsac et al.’s observations. The slope of the extrapolation line resulting from WECEN Al and HREE values remains rather unchanged for the OM depleted and enriched soil compartments; thus, the change in the metal/DOC ratio in the soil does not change the extraction behavior of Al and HREE. However, the WECEN Fe strongly increase compared to the corresponding HREE values in the OM enriched compartment pointing to the competition between Fe and HREE. Alternatively, one observes that the WECEN Fe and LREE values in the OM enriched compartment plot on the extrapolation line derived from OM depleted soil samples. Thus, in this case, the change in the metal/DOC ratio does not affect the extraction behavior of Fe and LREE. However, the WECEN values for Al and corresponding LREE of samples from the OM enriched soil compartment plot below the extrapolation line and point to the competition between Al and LREE. These results are also in agreement with the REE distribution pattern of the soil solutions from the same site which are at greater depth LREE depleted (Stille et al., 2009).

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.

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…

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.

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.

Major and trace element chemistry of separated fragments from a hibonite-bearing Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Grossman, L.; Allen, J. M.

1978-01-01

The major and trace elements of separated fragments and a bulk sample from CG-11, a hibonite-bearing inclusion in the Allende meteorite, were analyzed. Major element abundances were used to determine the minerology of separated fragments. The high degree of correlation between Eu/Sm ratios and Lu/Yb ratios for the samples studied indicates that their rare earth element (REE) distributions are governed by two components. One, Lu-, Eu-rich, is probably hibonite; the other, depleted in these elements, seems to be associated with the secondary alteration phases, grossular, nepheline and anorthite. The REE distribution in CG-11 precludes melting events after formation of the secondary alteration phases, but a melting event involving the primary minerals cannot be excluded. The enrichment of Lu with respect to other measured REE in hibonite can be explained by present REE condensation models. Two Hf-bearing components, most likely hibonite and perovskite, are necessary to account for variations in Sc/Hf ratios in the fragments studied. The lithophile volatiles Na, Mn, Fe, Zn, and probably Cr increase in the same order as the amount of secondary alteration minerals; the volatile siderophile elements Co and Au, however, do not.

The role of natural solidification paths on REE partitioning between clinopyroxene and melt

NASA Astrophysics Data System (ADS)

Scarlato, P.; Mollo, S.; Blundy, J. D.; Iezzi, G.; Tiepolo, M.

2014-03-01

We document for the first time the role played by natural solidification paths on the partitioning of rare earth elements (REE) between clinopyroxene and melt. To do this, we investigated the compositional variation of clinopyroxenes formed under increasing cooling rate conditions from core to rim of a dike at Mt. Etna volcano. As the rate of cooling increases, clinopyroxenes are progressively depleted in Si + Ca + Mg counter-balanced by enrichments in Al + Na + Ti. Consequently, the concentration of REE in clinopyroxene increases due to an increased ease of locally balancing the excess charge at the M2 site as the number of surrounding tetrahedral aluminium atoms increases. Since Aliv in clinopyroxene is a charge-balancing cation for REE, the partition coefficients (DREE) measured at the dike chilled margin are distinctly higher than those from the dike interior. We conclude that, in naturally solidifying magmas, kinetically controlled cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations. This finding is corroborated by the near-parabolic dependence of DREE on cation radius due to charge-balance mechanisms described by the lattice strain model.

Trace element determination of zircons from adakites and granitoids: implications for petrogenetic processes

NASA Astrophysics Data System (ADS)

Chen, T. W.; Chu, M. F.; Chung, S. L.; Iizuka, Y.

2017-12-01

Zircon has long been proposed as a time capsule of crustal formation. Concerning of its high capacity of lithophile elements, the dramatic change of crustal chemical composition in late Archean, i.e. from TTG suites to granitoids, may be recorded in zircon remnants. In this study, major- and trace element contents of zircons from adakites, a modern analogue of TTG suites, in southern Tibet were determined by EPMA and LA-ICPMS, respectively, and compared with those in Gangdese granitoids and Sumatra high/low ΣREE granitoids in order to examine the hypothesis. The REE patterns of zircons in this study show little inter-sample discrepancy though there is significant difference in whole-rock HREE contents between adakites and granitoids. Since none of geochemical feature, including REE contents, of zircons correlates with SiO2 content or ASI of corresponding host rocks, fractional crystallization shows insignificant impact on the compositional variation in zircons. In addition to the influence of lattice strain and charge balance requirements, zircons in these rock samples are proposed to crystallize from the magma mush, so they record the composition with least composition difference, not that of the bulk melt. More specifically, the pre-/co-existing mineral phases, e.g. apatite, play a critical role in preferentially taking the LREE and MREE from melt, and eliminating the HREE depletion in residual melt and thus zircons of Gangdese adakites. With the aim of objectively identifying geochemical discriminants of zircons from adakites and granitoids, statistical analysis was used and then 8 parameters were selected, i.e. Ti, V, Yb, Hf, Sc/Yb, U/Yb, Eu/Eu*, ΣHREE. Despite the zircon populations of adakites- and granitoids-origins overlapping in any bivariate plot, the linear combination of discriminants provides a potential way to distinguish zircons from these two groups.

SIMS analyses of minor and trace element distributions in fracture calcite from Yucca Mountain, Nevada, USA

NASA Astrophysics Data System (ADS)

Denniston, Rhawn F.; Shearer, Charles K.; Layne, Graham D.; Vaniman, David T.

1997-05-01

Fracture-lining calcite samples from Yucca Mountain, Nevada, obtained as part of the extensive vertical sampling in studies of this site as a potential high-level waste repository, have been characterized according to microbeam-scale (25-30 μm) trace and minor element chemistry, and cathodoluminescent zonation patterns. As bulk chemical analyses are limited in spatial resolution and are subject to contamination by intergrown phases, a technique for analysis by secondary ion mass spectrometry (SIMS) of minor (Mn, Fe, Sr) and trace (REE) elements in calcite was developed and applied to eighteen calcite samples from four boreholes and one trench. SIMS analyses of REE in calcite and dolomite have been shown to be quantitative to abundances < 1 × chondrite. Although the low secondary ion yields associated with carbonates forced higher counting times than is necessary in most silicates, Mn, Fe, Sr, and REE analyses were obtained with sub-ppm detection limits and 2-15% analytical precision. Bulk chemical signatures noted by Vaniman (1994) allowed correlation of minor and trace element signatures in Yucca Mountain calcite with location of calcite precipitation (saturated vs. unsaturated zone). For example, upper unsaturated zone calcite exhibits pronounced negative Ce and Eu anomalies not observed in calcite collected below in the deep unsaturated zone. These chemical distinctions served as fingerprints which were applied to growth zones in order to examine temporal changes in calcite crystallization histories; analyses of such fine-scale zonal variations are unattainable using bulk analytical techniques. In addition, LREE (particularly Ce) scavenging of calcite-precipitating solutions by manganese oxide phases is discussed as the mechanism for Ce-depletion in unsaturated zone calcite.

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.

The role of garnet in (Y+REE) mobility during fluid-initiated, localized, solid state dehydration of an amphibole-bearing migmatised granitic gneiss to charnockite

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Anczkiewicz, R.; Johansson, L.

2013-12-01

On either side of 1 m wide granitic pegmatoid dyke, Söndrum stone quarry, Halmstad, SW Sweden, extends a 2.5-3 m wide Opx-bearing dehydration zone (DZ) (650-700 °C; 800 MPa; Opx-Cpx-Bt-Amph-Gt-allanite), which overprints the gneissic banding of the surrounding migmatised granitic gneiss (MGG) (Amph-Bt-Gt-allanite) (Harlov et al., 2006, J Petrol 47, 3). Whole-rock chemistry indicates that dehydration of the MGG was predominantly isochemical. Exceptions include (Y+HREE), Ba, Sr, and F, which are markedly depleted throughout the DZ while LREE-bearing allanite remains unaltered. Systematic trends in the Gt, Bt, Amph, and FAp mineral chemistry across the DZ include depletion in Fe, (Y+HREE), Na, K, F, and Cl, and enrichment in Mg, Mn, Ca, and Ti. Fluid inclusion data suggest that the solid state dehydration event was due to advective transport of a CO2-rich fluid with a minor Cl and F component originating from a tectonic fracture represented today by the pegmatoid dyke. LA-ICPMS analysis of (Y+REE) in Gt (NIST 612 Glass standard; for operating conditions cf. Anczkiewicz et al. 2012 Chem Geol 318-319, 16) across the traverse indicates at least two distinct populations of Gt from the DZ variably depleted in (Y+HREE) and LREE (Fig. 1) by an order of magnitude compared to Gt in the MGG (Fig. 2). Depletion most likely is the result of (Y+HREE) and LREE partitioning from the Gt into the dehydrating fluid to complex with F and Cl. Variable depletion suggests preferred inter-granular pathways for fluid flow through the DZ during the dehydration event allowing some Gt grains greater exposure to the fluid than other Gt grains.

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.

Geochemistry of rare earth elements within waste rocks from the Montviel carbonatite deposit, Québec, Canada.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Pelletier, Mia

2018-04-01

Several rare earth element (REE) mine projects around the world are currently at the feasibility stage. Unfortunately, few studies have evaluated the contamination potential of REE and their effects on the environment. In this project, the waste rocks from the carbonatites within the Montviel proterozoic alkaline intrusion (near Lebel-sur-Quévillon, Quebec, Canada) are assessed in this research. The mineralization is mainly constituted by light REE (LREE) fluorocarbonates (qaqarssukite-Ce, kukharenkoite-Ce), LREE carbonates (burbankite, Sr-Ba-Ca-REE, barytocalcite, strontianite, Ba-REE-carbonates), and phosphates (apatite, monazite). The gangue minerals are biotites, chlorite, albite, ankerite, siderite, and calcite. The SEM-EDS analyses show that (i) the majority of REE are associated with the fine fraction (< 106 μm), (ii) REE are mainly associated with carbonates, (iii) all analyzed minerals preferably contain LREE (La, Ce, Pr, Nd, Sm, Eu), (iv) the sum of LREE in each analyzed mineral varies between ~ 3 and 10 wt%, (v) the heavy REE (HREE) identified are Gd and Yb at < 0.4 wt%, and (vi) three groups of carbonate minerals were observed containing variable concentrations of Ca, Na, and F. Furthermore, the mineralogical composition of REE-bearing minerals, REE mobility, and REE speciation was investigated. The leachability and geochemical behavior of these REE-bearing mine wastes were tested using normalized kinetic testing (humidity cells). Leachate results displayed higher LREE concentrations, with decreasing shale-normalized patterns. Thermodynamical equilibrium calculations suggest that the precipitation of secondary REE minerals may control the REE mobility.

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.

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.

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.

Y,REE,Nb,Ta,Ti-oxide (AB 2O 6) minerals from REL-REE euxenite-subtype pegmatites of the Třebíč Pluton, Czech Republic; substitutions and fractionation trends

NASA Astrophysics Data System (ADS)

Škoda, Radek; Novák, Milan

2007-04-01

Aeschynite-group minerals (AGM) and euxenite-group minerals (EGM) occur in REL-REE euxenite-subtype pegmatites from the Třebíč Pluton, Czech Republic. They form strongly metamictized, light brown to black, equigranular to needle-like, subhedral to anhedral grains enclosed in blocky K-feldspar and less commonly in albite, and blocky quartz, and in the graphic unit (quartz and K-feldspar). Both AGM and EGM are homogeneous to slightly heterogeneous in BSE images. They are not commonly associated with the other primary Y,REE,Ti,Nb-bearing minerals, i.e. allanite-(Ce), monazite-(Ce), titanite, and ilmenite, which occur within the same textural-paragenetic unit. Aeschynite-(Y), aeschynite-(Ce), aeschynite-(Nd), nioboaeschynite-(Ce), tantalaeschynite-(Ce), vigezzite and polycrase-(Y) were identified using EMP and canonical discrimination analysis [Ercit, T.S., 2005a. Identification and alteration trends of granitic-pegmatite-hosted (Y,REE,U,Th)-(Nb,Ta,Ti) oxide minerals: a statistical approach. Can. Mineral. 43, 4 1291-1303.]. The exchange vector ACa B(Nb,Ta) A(Y,REE) - 1 BTi - 1 or its combination with the exchange vector ACa 2B(Nb,Ta) 3A(U,Th) - 1 A(Y,REE) - 1 BTi - 3 have been elucidated for the AGM. The exchange vector ACa A(U,Th) A(Y,REE) - 2 is predominant in the EGM. The AGM are enriched in HREE, whereas LREE are concentrated in the EGM. Weak to none-existent geochemical fractionations, as expressed by the U/(U + Th), Y/(Y + REE), Ta/(Ta + Nb) and (Nb + Ta)/(Ti + Nb + Ta) ratios, were noted for single grains from both the AGM and EGM, as well as in grains of polycrase-(Y) from four different textural-paragenetic units located in the Vladislav pegmatite. Simultaneous increase of U/(U + Th) and Y/(Y + REE) in the AGM during fractionation is typical. The Ta/(Ta + Nb) fractionation is usually weak and contradicts the Y/(Y + REE) and U/(U + Th) fractionation trends. This unusual behavior of Nb and Ta may be controlled by associated Ti-rich minerals (titanite, ilmenite, rutile), the composition of parental melt and/or by elevated F activity. The AGM and EGM from pegmatites of the Třebíč Pluton are quite similar in composition to those from REL-REE euxenite-subtype pegmatites in the Trout Creek Pass, Chaffee County, Colorado, USA, which are generally Ca,U,Th-depleted, show lower Ta/(Ta+Nb), and lower variation in HREE/LREE.

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.

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].

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.

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.

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.

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

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

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John

In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In thesemore » samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.« less

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

DOE PAGES

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John; ...

2015-06-26

In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In thesemore » samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.« less

Mantle Water Contents Beneath the Rio Grande Rift (NM, USA): FTIR Analysis of Rio Puerco and Kilbourne Hole Peridotite Xenoliths

NASA Technical Reports Server (NTRS)

Schaffer, L. A.; Peslier, A. H.; Brandon, A.; Selverstone, J.

2015-01-01

Peridotite xenoliths from the Rio Grande Rift (RGR) are being analyzed for H (sub 2) O contents by FTIR (Fourier Transform Infrared) as well as for major and trace element compositions. Nine samples are from the Rio Puerco Volcanic Field (RP) which overlaps the central RGR and southeastern Colorado Plateau; seventeen samples are from Kilbourne Hole (KH) in the southern RGR. Spinel Cr# (Cr/(Cr+Al)) (0.08-0.46) and olivine Mg# (Mg/(Mg plus Fe)) (0.883-0.911) of all RGR samples fall within the olivine-spinel mantle array from [1], an indicator that peridotites are residues of partial melting. Pyroxene H (sub 2) O in KH correlate with bulk rock and pyroxene Al (sub 2) O (sub 3).The KH clinopyroxene rare earth element (REE) variations fit models of 0-13 percent fractional melting of a primitive upper mantle. Most KH peridotites have bulk-rock light REE depleted patterns, but five are enriched in light REEs consistent with metasomatism. Variation in H (sub 2) O content is unrelated to REE enrichment. Metasomatism is seen in RP pyroxenite xenoliths [2] and will be examined in the peridotites studied here. Olivine H (sub 2) O contents are low (less than or equal to 15 parts per million), and decrease from core to rim within grains. This is likely due to H loss during xenolith transport by the host magma [3]. Diffusion models of H suggest that mantle H (sub 2) O contents are still preserved in cores of KH olivine, but not RP olivine. The average H (sub 2) O content of Colorado Plateau clinopyroxene (670 parts per million) [4] is approximately 300 parts per million higher than RGR clinopyroxene (350 parts per million). This upholds the hypothesis that hydration-induced lithospheric melting occurred during flat-slab subduction of the Farallon plate [5]. Numerical models indicate hydration via slab fluids is possible beneath the plateau, approximately 600 kilometers from the paleo-trench, but less likely approximately 850 kilometers away beneath the rift [6].

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.

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.

Fine-Grained Rims in the Allan Hills 81002 and Lewis Cliff 90500 CM2 Meteorites: Their Origin and Modification

NASA Technical Reports Server (NTRS)

Hua, X.; Wang, J.; Buseck, P. R.

2002-01-01

Antarctic CM meteorites Allan Hills (ALH) 8 1002 and Lewis Cliff (LEW) 90500 contain abundant fine-grained rims (FGRs) that surround a variety of coarse-grained objects. FGRs from both meteorites have similar compositions and petrographic features, independent of their enclosed objects. The FGRs are chemically homogeneous at the 10 m scale for major and minor elements and at the 25 m scale for trace elements. They display accretionary features and contain large amounts of volatiles, presumably water. They are depleted in Ca, Mn, and S but enriched in P. All FGRs show a slightly fractionated rare earth element (REE) pattern, with enrichments of Gd and Yb and depletion of Er. Gd is twice as abundant as Er. Our results indicate that those FGRs are not genetically related to their enclosed cores. They were sampled from a reservoir of homogeneously mixed dust, prior to accretion to their parent body. The rim materials subsequently experienced aqueous alteration under identical conditions. Based on their mineral, textural, and especially chemical similarities, we conclude that ALH 8 1002 and LEW 90500 likely have a similar or identical source.

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.

Origin and evolution of the Nakhla meteorite inferred from the Sm-Nd and U-Pb systematics and REE, Ba, Sr, Rb and K abundances

NASA Technical Reports Server (NTRS)

Nakamura, N.; Unruh, D. M.; Tatsumoto, M.; Hutchison, R.

1982-01-01

Analyses of whole rock and mineral separates from the Nakhla meteorite are carried out by means of Sm-Nd and U-Tn-Pb systematics and by determining their REE, Ba, Sr, Rb, and K concentrations. Results show that the Sm-Nd age of the meteorite is 1.26 + or - 0.7 b.y., while the high initial epsilon(Nd) value of +16 suggests that Nakhla was derived from a light REE-depleted, old planetary mantle source. A three-stage Sm-Nd evolution model is developed and used in combination with LIL element data and estimated partition coefficients in order to test partial melting and fractional crystallization models and to estimate LIL abundances in a possible Nakhla source. The calculations indicate that partial melting of the source followed by extensive fractional crystallization of the partial melt could account for the REE abundances in the Nakhla constituent minerals. It is concluded that the significantly younger age of Nakhla than the youngest lunar rock, the young differentiation age inferred from U-Th-Pb data, and the estimated LIL abundances suggest that this meteorite may have been derived from a relatively large, well-differentiated planetary body such as Mars.

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).

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.

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.

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

Heterogeneity of Water Concentrations in the Mantle Lithosphere Beneath Hawaii

NASA Technical Reports Server (NTRS)

Bizimis, M.; Peslier, A. H.; Clague, D.

2017-01-01

The amount and distribution of water in the oceanic mantle lithosphere has implications on its strength and of the role of volatiles during plume/lithosphere interaction. The latter plays a role in the Earth's deep water cycle as water-rich plume lavas could re-enrich an oceanic lithosphere depleted in water at the ridge, and when this heterogeneous lithosphere gets recycled back into the deep mantle. The main host of water in mantle lithologies are nominally anhydrous minerals like olivine, pyroxene and garnet, where hydrogen (H) is incorporated in mineral defects by bonding to structural oxygen. Here, we report water concentrations by Fourier transform infrared spectrometry (FTIR) on olivine, clino- and orthopyroxenes (Cpx & Opx) from spinel peridotites from the Pali vent and garnet pyroxenite xenoliths from Aliamanu vent, both part of the rejuvenated volcanism at Oahu (Hawaii). Pyroxenes from the Aliamanu pyroxenites have high water concentrations, similar to the adjacent Salt Lake Crater (SLC) pyroxenites (Cpx 400-500 ppm H2O, Opx 200 ppm H2O). This confirms that pyroxenite cumulates form water-rich lithologies within the oceanic lithosphere. In contrast, the Pali peridotites have much lower water concentrations than the SLC ones (<25 ppm vs. 50-96 ppm H2O respectively) despite being relatively fertile with >10% modal Cpx and low spinel Cr# (0.09-0.10). The contrast between the two peridotite suites is also evident in their trace elements and radiogenic isotopes. The Pali Cpx are depleted in light REE, consistent with minimal metasomatism. Those of SLC have enriched light REE patterns and Nd and Hf isotopes consistent with metasomatism by alkaline melts. These observations are consistent with heterogeneous water distribution in the oceanic lithosphere that may be related to metasomatism, as well as relatively dry peridotites cross-cut by narrow (?) water-rich melt reaction zones.

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.

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.

Partitioning of Nd, Tb, Lu, and Hf Between Garnet and Ordinary Chondrite Melt at 5 to 9 GPa: Applications to Martian Differentiation

NASA Technical Reports Server (NTRS)

Draper, D. S.; Chabot, N. L.; Xirouchakis, D.; Wasserman, A. A.; Agee, C. B.

2001-01-01

One explanation for Al and REE depletions in SNC meteorites is early majorite fractionation in a deep martian magma ocean. We report initial results from an experimental investigation of partitioning between majoritic garnet and ordinary chondrite liquid. Additional information is contained in the original extended abstract.

Mass changes during hydrothermal alteration/mineralization in the gold-bearing Astaneh granitoid, western Iran

NASA Astrophysics Data System (ADS)

Zahra Afshooni, Seyedeh; Esmaeily, Dariush

2010-05-01

The Astaneh granitoid massif, located in western Iran, is a part of Sanandaj-Sirjan structural Zone. This body, mainly consist of granodioritic rocks, is widely affected under hydrothermal alteration and four alteration zones including phyllic (sericitic), chloritic, propylitic and argillic zones could be identified in this area. Four main mineralization- related alteration episodes have been studied in terms of mass transfer and element mobility during the hydrothermal evolution of Astaneh deposit. In order to illustrate these changes quantitatively, isocon plots have been applied. Isocon plots illustrate that Al, Ti, Ga and Tm was relatively immobile during alteration and that mass were essentially conserved during alteration. Phyllic alteration was accompanied by the depletion of Na and Fe and the enrichment of Si and Cu. The loss of Na and Fe reflects the sericitization of alkali feldspar and the destruction of ferromagnesian minerals. The addition of Si is consistent with widespread silicification wich is a major feature of phyllic alteration. All of the HFSE (except in Y), were enriched but all REEs were depleted in this zone. The overall obtained results show that major oxides such as SiO2, Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, P2O5 and TiO2 and also LOI show dissimilar behaviors in the different zones. All of the LFSE, HFSE and FTSM (except in Cu and Mo) were depleted in argillic alteration but show dissimilar behaviors in the other alteration zones. The results shown strong depletion in REE, in particular LREE, in all of the alteration facies (except in chloritic zone), equivalent fresh rocks. In chloritic zone, compared with HREE, the LREE represent more enrichment.

The deep layers of a Paleozoic arc: geochemistry of the Copley-Balaklala series, northern California

NASA Astrophysics Data System (ADS)

Brouxel, Marc; Lapierre, Henriette; Michard, Annie; Albarède, Francis

1987-10-01

REE, Zr, Nb concentrations and Sr, Nd isotope compositions have been measured in Copley basalts and andesites, Balaklala rhyolites, and Mule Mountain trondhjemites (northern California) which represent the deep layers of a well preserved intra-oceanic island arc of Siluro-Devonian age. 87Sr/ 86Sr is shifted towards high values (up to 0.707) whereas Ce is preferentially removed from rhyolites. A large proportion of the analyzed samples including some acidic rocks shows a pronounced depletion in light REE. The ɛ Nd(T) values of most Copley, Balaklala, and Mule Mountain rocks fall in the range +6 to +8 which suggests that they originated from a normal MORB-type source ( ɛ Nd(T) ≈ +9 ) contaminated with either sediments or an OIB-type component. In modern island arcs, only the shallow levels are accessible: comparison with the Copley-Balaklala-Mule Mountain Series suggests that, at depth, an immature island arc is likely to comprise thick layers of LILE-depleted tholeiites and rhyolites intensely altered by pervasive circulation of seawater. Least-square solutions of trace element models suggest that rhyolites and trondhjemites represent remelting of mafic volcanics from the arc basement rather than residual melts of basalt-andesite differentiation.

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.

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.

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.

Rare earths and other trace elements in Apollo 14 samples.

NASA Technical Reports Server (NTRS)

Helmke, P. A.; Haskin, L. A.; Korotev, R. L.; Ziege, K. E.

1972-01-01

REE and other trace elements have been determined in igneous rocks 14053, 14072, and 14310, in breccias 14063 and 14313, and in fines 14163. All materials analyzed have typical depletions of Eu except for feldspar fragments from the breccias and igneous fragments from 14063. Igneous rocks 14072 and 14053 have REE concentrations very similar to Apollo 12 basalts; 14310 has the highest REE concentrations yet observed for a large fragment of lunar basalt. The effects of crystallization of a basaltic liquid as a closed system on the concentrations of Sm and Eu in feldspar are considered. Small anorthositic fragments may have originated by simple crystallization from very highly differentiated basalt (KREEP) or by closed-system crystallization in a less differentiated starting material. Application of independent models of igneous differentiation to Sm and Eu in massive anorthosite 15415 and to Sm and Eu in lunar basalts suggests a common starting material with a ratio of concentrations of Sm and Eu about the same as that in chondrites and with concentrations of those elements about 15 times enriched over chondrites.

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.

Formation and composition of the moon. [carbonaceous meteorites

NASA Technical Reports Server (NTRS)

Anderson, D. L.

1974-01-01

Many of the properties of the moon are discussed including the enrichment in Ca, Al, Ti, U, Th, Ba, Sr and the REE and the depletion in Fe, Rb, K, Na and other volatiles which could be understood if the moon represents a high temperature condensate from the solar nebula. Thermodynamic calculations show that Ca, Al and Ti rich compounds condense first in a cooling nebula. The initial high temperature mineralogy is gehlenite, spinel, perovskite, Ca-Al-rich pyroxenes and anorthite. Inclusions in Type III carbonaceous chondrites such as the Allende meteorite are composed primarily of these minerals and, in addition, are highly enriched in refractories such as REE relative to carbonaceous chondrites. These inclusions can yield basalt and anorthosite in the proportions required to eliminate the europium anomaly, leaving a residual spinel-melilite interior.

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

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.

Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok

2017-03-01

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data ( 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE2O3, 0-0.8 wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2 - and (VO4)3 - anions, substituting for (PO4)3 -, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO2, 1.5 wt.% SO3 and 660 ppm V). Although (CO3)2 - groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

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.

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru, Kenya, during extreme draught.

PubMed

Jirsa, Franz; Gruber, Martin; Stojanovic, Anja; Omondi, Steve Odour; Mader, Dieter; Körner, Wilfried; Schagerl, Michael

2013-10-01

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO 3  > CO 3  > Cl > F > SO 4 in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33-0.45.

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru, Kenya, during extreme draught

PubMed Central

Jirsa, Franz; Gruber, Martin; Stojanovic, Anja; Omondi, Steve Odour; Mader, Dieter; Körner, Wilfried; Schagerl, Michael

2013-01-01

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO3 > CO3 > Cl > F > SO4 in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33–0.45. PMID:25843965

Compositional variations of ignimbrite magmas in the Central Andes over the past 26 Ma - A multivariate statistical perspective

NASA Astrophysics Data System (ADS)

Brandmeier, M.; Wörner, G.

2016-10-01

Multivariate statistical and geospatial analyses based on a compilation of 890 geochemical and 1200 geochronological data for 194 mapped ignimbrites from the Central Andes document the compositional and temporal patterns of large-volume ignimbrites (so-called "ignimbrite flare-ups") during Neogene times. Rapid advances in computational science during the past decade led to a growing pool of algorithms for multivariate statistics for large datasets with many predictor variables. This study applies cluster analysis (CA) and linear discriminant analysis (LDA) on log-ratio transformed data with the aim of (1) testing a tool for ignimbrite correlation and (2) distinguishing compositional groups that reflect different processes and sources of ignimbrite magmatism during the geodynamic evolution of the Central Andes. CA on major and trace elements allows grouping of ignimbrites according to their geochemical characteristics into rhyolitic and dacitic "end-members" and to differentiate characteristic trace element signatures with respect to Eu anomaly, depletions in middle and heavy rare earth elements (REE) and variable enrichments in light REE. To highlight these distinct compositional signatures, we applied LDA to selected ignimbrites for which comprehensive datasets were available. In comparison to traditional geochemical parameters we found that the advantage of multivariate statistics is their capability of dealing with large datasets and many variables (elements) and to take advantage of this n-dimensional space to detect subtle compositional differences contained in the data. The most important predictors for discriminating ignimbrites are La, Yb, Eu, Al2O3, K2O, P2O5, MgO, FeOt, and TiO2. However, other REE such as Gd, Pr, Tm, Sm, Dy and Er also contribute to the discrimination functions. Significant compositional differences were found between (1) the older (> 13 Ma) large-volume plateau-forming ignimbrites in northernmost Chile and southern Peru and (2) the younger (< 10 Ma) Altiplano-Puna-Volcanic-Complex (APVC) ignimbrites that are of similar volumes. Older ignimbrites are less depleted in HREE and less radiogenic in Sr isotopes, indicating smaller crustal contributions during evolution in a thinner and thermally less evolved crust. These compositional variations indicate a relation to crustal thickening with a "transition" from plagioclase to amphibole and garnet residual mineralogy between 13 and 9 Ma. Compositional and volumetric variations correlate to the N-S passage of the Juan-Fernandéz-Ridge, crustal shortening and thickening, and increased average crustal temperatures during the past 26 Ma. Table DR2 Mapped ignimbrite sheets.

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.

Garnet clinopyroxenite layers from the mantle sequences of the Northern Apennine ophiolites (Italy): Evidence for recycling of crustal material

NASA Astrophysics Data System (ADS)

Montanini, A.; Tribuzio, R.; Thirlwall, M.

2012-10-01

This study aims to define the origin of garnet clinopyroxenite layers from the mantle sequences of the External Ligurian ophiolites. These mantle sequences retain a subcontinental origin and were exposed at a Jurassic ocean-continent transition. The garnet clinopyroxenites are mafic rocks with Mg# values of 66-71. Their chondrite-normalised REE patterns are characterised by severe LREE depletion (CeN/SmN=0.1-0.2) and nearly flat (Type-A pyroxenites) to moderately enriched HREE (Type-B pyroxenites). In addition, Type-A pyroxenites display a small positive Eu anomaly. The whole-rock REE variations are paralleled by the garnet REE compositions. We attribute the major and trace element characteristics of the garnet clinopyroxenites to recycling of gabbroic protoliths that underwent partial melting under eclogite facies conditions. The garnet clinopyroxenites may represent variably evolved garnet+clinopyroxene cumulates formed by eclogite-derived melts. In an alternative hypothesis, Type-A and -B pyroxenites are residual rocks after eclogite melting and cumulates derived from the eclogite melts, respectively. The high pressure fractionation event that gave rise to the garnet clinopyroxenites is considered of Triassic age on the basis of Sm-Nd and Lu-Hf isotope correlations. The Nd-Hf isotopic compositions of the garnet clinopyroxenites in the Triassic (ɛNd=+4.7 to +7.6, ɛHf=+4.4 to +12.8) lie below the mantle array, in agreement with recycled ancient MOR-type material. The oxygen isotopic composition of garnet and clinopyroxene from the garnet clinopyroxenites (δ18O=+4.9‰ to +5.2‰) may be reconciled with subduction-related recycling of the lowermost oceanic crust, or delamination and foundering of underplated gabbros from the continental lithosphere. The potential involvement of the garnet clinopyroxenites in the melting processes that gave rise to the MOR-type oceanic crust in the Jurassic would account for the moderate Nd isotope variability and the garnet geochemical signature of the ophiolitic basalts.

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.

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.

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.

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.

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.

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.

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.

Titanite petrochronology in the Fish Canyon Tuff

NASA Astrophysics Data System (ADS)

Schmitz, M. D.; Crowley, J. L.

2014-12-01

The petrologic complexity of the archtypical 'monotonous intermediate' Fish Canyon Tuff (FCT) has been previously established by a variety of mineralogical and geochemical proxies [1-2], and the unusual storage and eruptive dynamics of the FCT have been delineated by several geochronological studies [3-5]. Titanite is an apparent equilibrium phase in the penultimate FCT magma, and can be linked petrographically to hornblende crystals that preserve up-temperature core-to-rim zoning profiles. As a reactive, trace element-rich phase, we hypothesized that titanite may record an intracrystalline record of magma chamber dynamics. Titanite crystals from the same separate analyzed in [4] were oriented and doubly-polished to yield characteristic wedge-shaped cross-sectional wafers approximately 300 µm in thickness. BSE imaging guided LA-ICPMS analyses of a full suite of trace elements using a 25 µm beam diameter and crater depth on multiple locations across both sides of the wafer. Most titanite crystals are characterized by large variations in trace elements, including at least two generations of REE-enriched, actinide-poor, low Sr, large Eu anomaly cores overgrown by REE-depleted, actinide-rich, high Sr domains with small Eu anomalies and distinctive concave-up middle to heavy REE patterns. Trace element contents and patterns correlate strongly with Eu anomaly; intermediate compositions are abundant and spatially correlated to reaction zones between core and rim domains. Within the context of the batholithic rejuvenation model for the FCT magma [1-2], these trace element variations are interpreted to record the partial melting of a differentiated crystalline FCT precursor and its hybridization with a more 'mafic' flux. ID-TIMS dating of end-member titanites confirm older ages (ca 28.4 to 29.0 Ma) for cores and define a younger age for rejuvenation of ca 28.2 Ma, consistent with recent U-Pb zircon and 40Ar/39Ar studies [5-7]. [1] Bachmann & Dungan (2002) Am Mineral 87, 1062-1076. [2] Bachmann et al (2002) J Petrology 43, 1469-1503. [3] Bachmann et al (2007) Chem Geol 236, 134-166. [4] Schmitz & Bowring (2001) GCA 65, 2571-2587. [5] Wotzlaw et al (2013) Geology 41, 867-870. [6] Rivera et al. (2011) EPSL 311, 420-426. [7] Kuiper et al (2008) Science 320, 500-504.

Mantle water contents beneath the Rio Grande Rift (NM, USA): FTIR analysis of Rio Puerco and Kilbourne Hole peridotite xenoliths

NASA Astrophysics Data System (ADS)

Schaffer, L. A.; Peslier, A. H.; Brandon, A. D.; Selverstone, J.

2015-12-01

Peridotite xenoliths from the Rio Grande Rift (RGR) are being analyzed for H2O contents by FTIR as well as for major and trace element compositions. Nine samples are from the Rio Puerco Volcanic Field (RP) which overlaps the central RGR and southeastern Colorado Plateau; seventeen samples are from Kilbourne Hole (KH) in the southern RGR. Spinel Cr# (Cr/(Cr+Al) = 0.08-0.46) and olivine Mg# (Mg/(Mg+Fe) = 0.883-0.911) of samples fall within the olivine-spinel mantle array from [1], an indicator that these are residues of partial melting. Pyroxene H2O contents in KH correlate with bulk rock and pyroxene Al2O3 contents. The KH clinopyroxene rare earth element (REE) variations fit models of 0-13% fractional melting of a primitive upper mantle. Most KH peridotites have bulk-rock light REE depleted patterns, but five are enriched in light REEs consistent with metasomatism. Variation in H2O content seems unrelated to REE enrichment. Metasomatism is seen in RP pyroxenite xenoliths [2] and will be examined in the peridotites studied here. Olivine H2O contents are low (≤20 ppm), and decrease from core to rim within grains. This is likely due to H loss during xenolith transport by the host magma [3]. Diffusion models of H suggest that mantle H2O contents are still preserved in cores of KH olivine, but not those of RP olivine. The average H2O content of Colorado Plateau clinopyroxene (670 ppm) [4] is ~300 ppm higher than RGR clinopyroxene (350 ppm). This upholds the hypothesis that hydration-induced lithospheric melting occurred during flat-slab subduction of the Farallon plate [5]. Numerical models indicate hydration via slab fluids is possible beneath the plateau, ~600 km from the paleo-trench, but less likely ~850 km away beneath the rift [6]. [1]Arai, 1994 CG 113, 191-204.[2]Porreca et al., 2006 Geosp 2, 333-351.[3]Peslier and Luhr, 2006 EPSL 242, 302-319.[4]Li et al., 2008 JGR 113, 1978-2012.[5]Humphreys et al., 2003 Int Geol Rev 45, 575-595.[6]English et al., 2003 EPSL 214, 619-632.

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.

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.

Formation and evolution of a metasomatized lithospheric root at the motionless Antarctic plate: the case of East Island, Crozet Archipelago (Indian Ocean)

NASA Astrophysics Data System (ADS)

Meyzen, Christine; Marzoli, Andrea; Bellieni, Giuliano; Levresse, Gilles

2016-04-01

Sitting atop the nearly stagnant Antarctic plate (ca. 6.46 mm/yr), the Crozet archipelago midway between Madagascar and Antarctica constitutes a region of unusually shallow (1543-1756 m below sea level) and thickened oceanic crust (10-16.5 km), high geoid height, and deep low-velocity zone, which may reflect the surface expression of a mantle plume. Here, we present new major and trace element data for Quaternary sub-aerial alkali basalts from East Island, the easterly and oldest island (ca. 9 Ma) of the Crozet archipelago. Crystallization at uppermost mantle depth and phenocryst accumulation have strongly affected their parental magma compositions. Their trace element patterns show a large negative K anomaly relative to Ta-La, moderate depletions in Rb and Ba with respect to Th-U, and heavy rare earth element (HREE) depletions relative to light REE. These characteristics allow limits to be placed upon the composition and mineralogy of their mantle source. The average trace element spectrum of East Island basalts can be matched by melting of about 2 % of a garnet-phlogopite-bearing peridotite source. The stability field of phlogopite restricts melting depth to lithospheric levels. The modelled source composition requires a multistage evolution, where the mantle has been depleted by melt extraction before having been metasomatized by alkali-rich plume melts. The depleted mantle component may be sourced by residual mantle plume remnants stagnated at the melting locus due to a weak lateral flow velocity inside the melting regime, whose accumulation progressively edifies a depleted lithospheric root above the plume core. Low-degree alkali-rich melts are likely derived from the plume source. Such a mantle source evolution may be general to both terrestrial and extraterrestrial environments where the lateral component velocity of the mantle flow field is extremely slow.

Nd, Sr and Pb isotopic composition of metasomatised xenoliths from the backarc Patagonian Mantle Wedge: Insights into the origin of the uprising melts

NASA Astrophysics Data System (ADS)

Zanetti, Alberto; Mazzucchelli, Maurizio; Hemond, Christope; Cipriani, Anna; Bertotto, Gustavo W.; Cingolani, Carlos; Vannucci, Riccardo

2010-05-01

Information about the geochemical composition of metasomatic melts migrating through the Patagonian mantle wedge is provided by the ultramafic xenoliths occurrence of Tres Lagos (TL; lat. 49.13°S, long. 71.18°W), Argentina. Such a locality is placed at the eastern border of the Meseta de la Muerte backarc basaltic plateau, where a post-plateau volcanic diatreme contains mantle xenoliths in both pyroclastites and lavas. Its latitude corresponds with the Northern limit of the Austral Volcanic Arc (AVZ), which is separated from the Southern Volcanic Zone (SVZ) by a gap in the arc magmatism ranging between 49° and 46°30' latitude S. The analysed xenoliths have been distinguished into two groups (Group 1 & 2). Group 1 consists of lherzolites and harzburgites, whereas Group 2 is formed by harzburgites. The texture of the Group 1 lherzolites varies from protogranular to granoblastic to porphyroblastic, whereas Group 1 harzburgites have always granoblastic texture. Group 2 harzburgites have granular texture, which may change to porphyroblastic owing to the random concentration of large olivine and orthopyroxene crystals. The clinopyroxenes (Cpx) from Group 1 lherzolites have PM-normalised REE patterns ranging from LREE-depleted (LaN/SmN= 0.24-0.37), to LREE-enriched (LaN/YbN up to 4.08) and spoon-shaped: the latter have minimum at Pr and Pr-Yb concentrations similar to those shown by the LREE-depleted Cpx. The Cpx from Group 1 harzburgites have lower REE concentrations with respect to the lherzolite ones and their REE patterns vary from HREE-enriched, steadily fractionated, (LaN/YbN = 0.21-0.35, Ybn ~ 1-2) to spoon-shaped (LaN/SmN = 2.81; SmN/YbN = 0.89; YbN ~ 3. The Cpx from the Group 2 harzburgites have convex-upward (LaN/SmN = 0.31; SmN/YbN = 1.50) to LREE-enriched (LaN/YbN = 2.94) patterns. The Sr, Nd and Pb isotopic compositions of the Group 1 clinopyroxenes form arrays spanning from DM to the field delimited by the TL basaltic lavas, pointing to EMI end-member. Conversely, Group 2 Cpx have much more radiogenic Sr and less radiogenic Nd values, approaching more closely the EMI and EMII end-members: these features are associated to unradiogenic lead isotopic compositions (206Pb/204Pb = 17.4-18.1; 207Pb/204Pb = 15.55-15.60; 208Pb/204Pb = 37.3-38.5). The combination of petrographic, trace element and isotopic features indicate that TL harzburgites are likely residua after melt-assisted partial melting triggered by melt/fluid migration in the hottest, and perhaps deeper, parts of the pristine DM lithosphere. The interpretation of the Pb, Sr and Nd isotope composition of Group 2 Cpx is not trivial. In analogy with the interpretation proposed for SWIR, it could unravel the occurrence of mantle sources which incorporated ancient crust and failed to homogenise with the DM mantle. Alternatively, it could be the evidence for ancient continental crust of the South America plate dragged down into the mantle by slab motion.

High-Ca Boninites From the Modern Tonga Arc

NASA Astrophysics Data System (ADS)

Cooper, L. B.; Plank, T.; Arculus, R. J.; Hauri, E. H.; Worthington, T. J.

2007-12-01

High-Ca boninites are volcanic rocks with unusual compositions (SiO2>53 wt%, Mg#>0.6, CaO/Al2O3>0.75) found in forearcs and trenches, continental cratons, and ophiolites. Generation of high-Ca boninites requires a combination of refractory mantle sources, elevated mantle temperatures and the addition of hydrous fluids. To satisfy these conditions, petrogenetic models invoke unusual tectonic settings such as subduction initiation, ridge subduction, or mantle plume interaction. We have discovered high-Ca boninites from an active arc volcano, Volcano A, a submarine volcano in the Tonga arc dredged during the NoToVE cruise in Nov 2004. Multi-beam sonar images of two pristine volcanic cones and glassy samples lacking Mn coatings suggest that these edifices were formed by modern volcanism. The boninites are represented in both the whole rock and melt inclusion populations of a sample dredged from a ridge on the northern flank of the northern cone. Similarities in the major element compositions of the largely aphyric whole rock and the glassy melt inclusions support both as samples of true boninitic liquids (MgO>9 wt%). These liquids are related by coupled crystal fractionation (from Fo92 to Fo85 in olivine hosts) and degassing (from 4 to 1 wt% H2O in the melt inclusions). Three other dredges from Volc A include whole rocks, glass, and melt inclusions that are related to the boninites by crystal fractionation. Taken together, the samples from Volc A represent a suite of boninites and their differentiates, forming a coherent liquid line of descent with parallel whole rock REE patterns which become more enriched with decreasing Mg#. The REE patterns for Volc A whole rocks are depleted in LREE, however, in contrast to the characteristic U-shaped REE patterns of classic boninites. Volc A is only the second example of boninites being erupted in an active volcanic arc, the first being Bamus volcano in New Britain (Johnson et al., Geol. Rund., 1983). Volc A is not remarkable in its geographical setting, located in the central portion of the Tonga arc, at around 21°S, along-strike with the arc island of Hunga- Ha'apai, and east of the Eastern Lau Spreading Center. Although it contains volcanic rocks with the highest Ba/La (100-130), Si6.00 (56 wt%) and lowest Ti6.00 (0.44 wt%) in the Tonga arc, Volc A forms an end- member within a continuous spectrum of compositions, and much of the Tonga arc appears to have boninite- affinities. Of the three conditions that promote boninite production (mantle depletion, high mantle temperatures, and high mantle water contents), we can exclude mantle temperature as the primary cause of Volc A boninites. Olivine-liquid temperatures are 1348±13°C for Volc A liquids, calculated in equilibrium with Fo92 mantle olivine at 2 GPa (using thermometers in Sisson & Grove, CMP, 1993; Sugawara, JGR, 2000). Such temperatures are very similar to those calculated for Central American arc volcanoes (1315-1320°C; Plank et al., this meeting) where magmas with similar water contents erupt, but boninites do not. Volc A olivine-liquid temperatures also contrast with those recorded in the high-Ca boninites found in the Tonga forearc (~1480°C; Falloon and Danyushevsky, JPet, 2000). Thus, we attribute the presence of boninites in the Tonga arc to the remelting of refractory mantle that melted previously during rapid back-arc spreading in the nearby Lau Basin.

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.

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.

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.

Partial melting of amphibolite to trondhjemite at Nunatak Fiord, St. Elias Mountains, Alaska

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

Barker, F.; McLellan, E.L.; Plafker, G.

1985-01-01

At Nunatak Fiord, 55km NE of Yakutat, Alaska, a uniform layer of Cretaceous basalt ca. 3km thick was metamorphosed ca. 67 million years ago to amphibolite and locally partially melted to pegmatitic trondhjemite. Segregations of plagioclase-quartz+/-biotite rock, leucosomes in amphibolite matrix, range from stringers 5-10mm thick to blunt pods as thick as 6m. They tend to be parallel to foliation of the amphibolite, but crosscutting is common. The assemblage aluminous hornblende-plagioclase-epidote-sphene-quartz gave a hydrous melt that crystallized to plagioclase-quartz+/-biotite pegmatitic trondhjemite. 5-10% of the rock melted. Eu at 2x chondrites is positively anomalous. REE partitioning in melt/residum was controlled largelymore » by hornblende and sphene. Though the mineralogical variability precludes quantitative modeling, partial melting of garnet-free amphibolite to heavy-REE-depleted trondhjemitic melt is a viable process.« less

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Astrophysics Data System (ADS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-09-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-01-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Major and Trace Element Geochemistry and Os Isotopic Compositions of Komatiites From Dundonald Beach, Abitibi Greenstone Belt, Canada

NASA Astrophysics Data System (ADS)

Gangopadhyay, A.; Walker, R. J.; Sproule, R. A.; Lesher, C.

2003-12-01

We have examined the major and trace elements, and Os isotopic compositions of a suite of cumulate and spinifex textured komatiitic rocks from the Dundonald Beach area, part of the ˜2.7 Ga Abitibi greenstone Belt, Ontario, Canada. This suite of rocks forms a series from peridotitic komatiites (MgO ˜ 42 wt.% on a volatile-free basis) to komatiitic basalts (MgO ˜8 wt.%). Based on major element oxide ratios (e.g. Al2O3/TiO2 ˜21-26 and CaO/Al2O3 typically <= 1) and unfractionated HREE characteristics (e.g. (Gd/Yb)N ˜0.9-1.1), these rocks are similar to the spatially associated Al-undepleted komatiites from Alexo and Munro Townships. Also, these rocks are strongly LREE-depleted ((La/Sm)N = 0.41-0.67; (Ce/Yb)N = 0.41-0.70)) and have variable total REE (4-22 ppm). A strong negative correlation between Mg# and total REEs suggests that the REE patterns of these rocks are primary features of their mantle source. The Re-Os isotope results for whole-rock komatiites and chromite separates from a single flow yield a model 3 isochron age of 2606 +/- 55 Ma. This age is slightly younger ( ˜50 Ma) compared to the U-Pb zircon ages of the associated volcanics reported from the presumed extension of the same Kidd-Munro assemblage in Alexo and Munro Townships. The initial 187Os/188Os ratio (0.1090 +/- 0.0019) obtained from the regression is essentially chondritic (γ Os(T) = -0.2 +/- 1.7). The peridotitic komatiites have the highest Os concentrations and low 187Re/188Os ratios (up to ˜4.2 ppb and < 0.5, respectively) among the whole rocks, whereas the komatiitic basalts have relatively low Os concentrations ( ˜0.3 ppb) and high 187Re/188Os ratios ( ˜3.1-11.9). For these komatiites, Os was compatible with the mantle residue (DOsmantle-melt ˜7.6), whereas Re was moderately incompatible (DRe ˜0.6), typical of most komatiitic magmas. The absence of a strong correlation between Os and Ni concentrations in the whole-rocks suggests that the distribution of Os in these rocks is not primarily controlled by fractionation of olivine. The apparent DReol+chmt/liq. ( ˜0.7), on the other hand, suggests that Re was moderately incompatible in olivine and/or chromite during the differentiation of komatiitic magmas. A chondritic initial Os isotopic composition for the mantle source for these komatiites is consistent with that previously reported for the komatiites from Alexo and Munro Townships. Our Os isotopic results for Dundonald komatiites, combined with those reported for Alexo and Pyke Hill komatiites, therefore, suggest that a major portion of the ˜2.7 Ga mantle source for the komatiites in the Abitibi greenstone belt was dominated by Os with chondritic isotopic compositions. Also, the LREE-depleted, yet chondritic Os isotopic composition for the mantle source of these komatiites is indistinguishable from the projected chondritic composition of the contemporaneous depleted convective upper mantle.

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.

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.

The evolution of a calc-alkaline basic to silicic magma system: Geochemical and Rb-Sr, Sm-Nd, and 18O /16O isotopic evidence from the Late Hercynian Atesina-Cima d'Asta volcano-plutonic complex, northern Italy

NASA Astrophysics Data System (ADS)

Barth, Susanne; Oberli, Felix; Meier, Martin; Blattner, Peter; Bargossi, Giuseppe M.; Di Battistini, Gianfranco

1993-09-01

Geochemical and Sr-Nd-O isotopic data presented for basaltic andesitic to rhyolitic and for quartz noritic to monzogranitic rock suites from the Late Hercynian calc-alkaline Atesina volcanic complex (AVC) and the Cima d'Asta pluton (CAP), Southern Alps (northern Italy), provide information on both the primary magmatic processes and the effects of (mainly Triassic) hydrothermal overprint. Fluid infiltration led to mobilization of major and trace elements (K 2O, Na 2O, CaO, Rb, Sr, and Ba), opensystem behavior in total-rock Rb-Sr, and shift in δ18O to elevated values (total rock up to 16.6%. and volcanic matrix up to 17.8%.). Oxygen isotopic disequilibrium between quartz-feldspar pairs suggests water-rock interaction at medium/low temperatures. The δ18O values of quartz, the REE characterized by regular LREE enrichment/HREE depletion, and the Sm-Nd isotopic signatures, however, remained virtually unaffected by secondary processes. The initial ɛNd values (at 270 Ma) of the AVC and CAP magmatites are restricted to overlapping ranges of -3.6 to -6.5 and of -2.7 to -6.5, respectively, indicating significant crustal contribution; these values and associated T DM model ages of 1.1-1.6 Ga agree well with those of typical South Alpine lower crustal magmatites. The AVC and CAP rocks do not follow the "normal" trend of increasingly crustal Nd isotopic signatures with progressive degree of magma evolution expected for a single-stage AFC-type process, but instead display an inversion of this relationship. Geochemical and isotopic constraints favor a model of a large-scale MASH-type melting and mixing zone at or near the base of the continental crust. Distinct elemental enrichment/depletion and REE crossover patterns displayed by high-silica as compared to less silicic AVC rhyolites suggest subsequent magma evolution within a shallow-level compositionally zoned chamber.

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.

Trace-element patterns of fibrous and monocrystalline diamonds: Insights into mantle fluids

NASA Astrophysics Data System (ADS)

Rege, S.; Griffin, W. L.; Pearson, N. J.; Araujo, D.; Zedgenizov, D.; O'Reilly, S. Y.

2010-08-01

During their growth diamonds may trap micron-scale inclusions of the fluids from which they grew, and these "time capsules" provide insights into the metasomatic processes that have modified the subcontinental lithospheric mantle. LAM-ICPMS analysis of trace elements in > 500 fibrous and monocrystalline diamonds worldwide has been used to understand the nature of these fluids. Analyses of fibrous diamonds define two general types of pattern, a "fibrous-high" (FH) one with high contents of LREE, Ba and K, and a "fibrous-low" (FL) pattern characterized by depletion in LREE/MREE, Ba and K, negative anomalies in Sr and Y, and subchondritic Zr/Hf and Nb/Ta. Both types may be found in fibrous diamonds from single deposits, and in three Yakutian pipes some diamonds show abrupt transitions from inclusion-rich cores with FH patterns to clearer rims with FL patterns. Most monocrystalline diamonds show FL-type patterns, but some have patterns that resemble those of FH fibrous diamonds. Peridotitic and eclogitic monocrystalline diamonds may show either patterns with relatively flat REE, or patterns with more strongly depleted LREE. Kimberlites that contain peridotitic diamonds with "high" patterns also contain eclogitic diamonds with "high" patterns. Strong similarities in the patterns of these two groups of diamonds may suggest high fluid/rock ratios. Many diamonds of the "superdeep" paragenesis have trace-element patterns similar to those of other monocrystalline diamonds. This may be evidence that the trace-element compositions of deep-seated fluids are generally similar to those that form diamonds in the subcontinental lithospheric mantle. The element fractionations observed between the FH and FL patterns are consistent with the immiscible separation of a silicic fluid from a carbonatite-silicate fluid, leaving a residual carbonatitic fluid strongly enriched in LREE, Ba and alkalies. This model would suggest that most monocrystalline diamonds crystallized from the more silicic fraction. Comparison with studies of single fluid inclusions in fibrous diamonds suggests that the FH patterns reflect trapped inclusions of high-Mg and low-Mg carbonatitic high-density fluids. In terms of the rock-forming elements, the fluids that precipitated the rims of some fibrous diamonds (FL pattern) and most monocrystalline diamonds are broadly similar to some hydro-silicic high-density fluids found in fibrous diamonds. However, there are still significant differences between the trace-element patterns of most monocrystalline diamonds and known high-density fluids, and further research is required to understand the formation and growth of these diamonds.

REE Mineralization in Kiruna-type Magnetite-Apatite Ore Deposits: Magmatism and Metasomatism

NASA Astrophysics Data System (ADS)

Harlov, D. E.

2015-12-01

Magnetite-apatite ore bodies of the Kiruna type occur worldwide and are generally associated with volcanic rocks or volcanism. They also show strong evidence of extensive metasomatism over a wide P-T range. Notable examples include the Kiirunavaara ore body, northern Sweden (Harlov et al., 2002, Chem. Geol., 191, 47-72); the Grängesberg ore body, central Sweden (Jonsson et al., 2010, NGF abstracts, vol 1, 88-89); the Mineville ore body, Adirondacks, New York, USA (McKeown and Klemc, 1956, U.S. Geol Sur Bull (1956), pp. 9-23); the Pea Ridge ore body, SE Missouri, USA (Kerr, 1998, MS Thesis, Univ. Windsor, Windsor, Ontario, Canada 113 pp); the Jurassic Marcona ore body in south-central Peru (Chen et al., 2010, Econ Geol, 105, 1441-1456); and a collection of ore bodies from the Bafq Region, central Iran (Daliran et al., 2010, Geol. Assoc. Canada, Short Course Notes, v. 20, p.147-159). In these ore bodies, low Th and U monazite, xenotime, allanite, REE carbonates, and/or REE fluorides are commonly associated with the apatite as inclusions, rim grains, or as independent grains in the surrounding mineral matrix. High contrast BSE imaging, coupled with EMPA and LA-ICPMS, indicates that the apatite has experienced fluid-induced alteration in the form of (Y+REE) + Na + Si + Cl depletion implying that it served as the source for the (Y+REE) (e.g. Kiirunavaara, northern Sweden; Harlov et al., 2002). Formation of monazite and xenotime associated with fluorapatite, as inclusions or rim grains, has experimentally been demonstrated to originate from the fluorapatite as the result of fluid-aided, coupled dissolution-reprecipitation processes (Harlov et al., 2005, Contrib. Mineral. Petrol. 150, 268-286). This is explains the low Th and U content of the monazite and xenotime. Fluid sources could range from 700-900 °C, residual, acidic (HCl, H2HSO4) grain boundary fluids, remaining after the last stages of ore body crystallization, to later stage, cooler (< 600 °C) (H2O-CO2-(Na,K)Cl) fluids originating in the surrounding country rock or as fluids associated with metamorphic events such as regional albitization or actinolization. The abundance of (Y+REE)-bearing minerals in these deposits suggests that in addition to being mined for their Fe ore, they could also be economically mined for (Y+REE) as well.

Geochemistry and mineralogy of kimberlites from the Arkhangelsk Region, NW Russia: evidence for transitional kimberlite magma types

NASA Astrophysics Data System (ADS)

Beard, A. D.; Downes, H.; Hegner, E.; Sablukov, S. M.

2000-03-01

The Arkhangelsk kimberlite province (AKP) is situated in the north of the Baltic Shield within the buried southeastern portion of the Kola-Kuloi craton. It forms part of the extensive Devonian magmatic event of the northern Baltic Shield and Kola Peninsula. Two main groups of kimberlites can be distinguished within the province: (1) kimberlites from the diamondiferous Zolotitsa field that have geochemical and isotopic affinities with Group 2 kimberlites and lamproites; (2) diamond-poor Ti-Fe-rich kimberlites from other Arkhangelsk fields that have geochemical and isotopic affinities with Group 1 kimberlites. However, the Zolotitsa and Ti-Fe-rich kimberlites have mineralogical characteristics that are not typical for their respective assigned kimberlite group classifications. Both groups of Arkhangelsk kimberlites are apparently transitional to Group 1 kimberlites, Group 2 kimberlites and lamproites as they are defined elsewhere in the world. An associated kimberlite from the Mela Sill Complex has strong affinities with carbonatites. The low Al 2O 3, high Ni and Cr contents, and high Mg# in both groups of kimberlites indicate strongly depleted lherzolitic-harzburgitic mantle sources. Trace element patterns show a variable enrichment of incompatible elements and strong LREE enrichment. However, kimberlites from the Zolotitsa field have overall lower trace element abundances and less steep REE patterns, suggesting a higher degree of partial melt and/or a less enriched source compared to that of the Ti-Fe-rich kimberlites. A calciocarbonatite of the Mela Sill Complex has trace element and REE patterns typical of other carbonatites closely associated with kimberlites. 87Sr/ 86Sri and 143Nd/ 144Ndi isotope compositions of the Arkhangelsk kimberlites and carbonatite reveal that at least two mantle sources are required to explain the isotopic variation: (1) most of the Zolotitsa and Mela kimberlites and the Mela carbonatite are derived from an ancient enriched lithospheric source (EMI); (2) the Ti-Fe-rich kimberlites are derived from a plume-related asthenospheric mantle source with an isotopic composition close to Bulk Earth. Present-day Pb isotope compositions reveal that the Zolotitsa kimberlites have values close to Group 1 kimberlites. However, the Ti-Fe-rich kimberlites generally have slightly more radiogenic Pb isotope values.

Magnetism of Carbonados

NASA Technical Reports Server (NTRS)

Kletetschka, G.; Taylor, P. T.; Wasilewski, P. J.

1999-01-01

Carbonados are porous polycrystalline (with crystal sizes up to 100 micrometer) diamonds. Carbonado is found only in alluvial deposits in Bahia, Brazil and in the Central African Republic (CAR). Alluvial deposit host is 1.5 Ga while the carbonados are between 2.6 - 3.8 Ga. The process of fusing the carbonado microcrystals together is not fully understood, partly due to fact that the origin of these carbonado, is not known. Several modes of origins are proposed for carbonado. First, a crustal origin. Carbonados have a light carbon and helium isotopic signature. They contain an enrichment of the rare-earth elements (REE). Carbonados have tightly trapped atmospheric noble gases and contain an evidence of high He content despite the carbonado expected depletion of He at mantle temperatures. Carbonados have high porosity incompatible with high pressure mantle conditions. Second, a mantle origin is proposed based on similar REE pattern to kimberlites. The presence of nitrogen platelet (by IR spectra) indicates high temperature origin and syngenetic inclusions of rutile, ilmenite, and magnetite indicates high pressure and high temperature conditions consistent with mantle origin as well. Third, it is proposed that carbonado diamonds are a result of early impacts into crustal rocks. This is indicated by the rare and controversial occurrence of high pressure diamond polymorph, londsdaleite, frequently found in diamonds from meteorite impact sites, and by observation of planar deformation features, possibly indicating shock events. Finally, it is suggested that carbonados have an extraterrestrial origin, as indicated by a long term annealing based on observation of a zero-phonon line, attributed to paired nitrogen atoms in association with a vacancy.

Anthropophile elements in river sediments: Overview from the Seine River, France

NASA Astrophysics Data System (ADS)

Chen, Jiu-Bin; Gaillardet, Jérôme; Bouchez, Julien; Louvat, Pascale; Wang, Yi-Na

2014-11-01

In contrast to larger river systems that drain relatively pristine basins, little is known about the sediment geochemistry of rivers impacted by intense human activities. In this paper, we present a systematic investigation of the anthropogenic overprints on element geochemistry in sediments of the human-impacted Seine River, France. Most elements are fractionated by grain size, as shown by the comparison between suspended particulate matter (SPM) and riverbank deposits (RBD). The RBD are particularly coarse and enriched in carbonates and heavy minerals and thus in elements such as Ba, Ca, Cr, Hf, Mg, Na, REEs, Sr, Ti, Th, and Zr. Although the enrichment/depletion pattern of some elements (e.g., K, REEs, and Zr) can largely be explained by a binary mixture between two sources, other elements such as Ag, Bi, Cr, Cd, Co, Cu, Fe, Mo, Ni, Pb, Sb, Sn, W, and Zn in SPM in Paris show that a third end-member having anthropogenic characteristics is needed to account for their enrichment at low water stage. These "anthropophile" elements, with high enrichment factors (EFs) relative to the upper continental crust (UCC), display a progressive enrichment downstream and different geochemical behaviors with respect to the hydrodynamic conditions (e.g., grain size) compared to elements having mainly a natural origin. Our findings emphasize the need for systematic studies of these anthropophile elements in other human-impacted rivers using geochemical normalization techniques, and stress the importance of studying the chemical variability associated with hydrodynamic conditions when characterizing riverine element geochemistry and assessing their flux to the ocean.

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.

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.

A multi-center, randomized, controlled trial of parenteral nutrition titrated to resting energy expenditure in children undergoing hematopoietic stem cell transplantation (“PNTREE”): Rationale and design

PubMed Central

Bechard, Lori J.; Feldman, Henry A.; Gordon, Catherine; Gura, Kathleen; Sonis, Andrew; Leung, Kathryn; Venick, Robert; Guinan, Eva C.; Duggan, Christopher

2013-01-01

Background Children undergoing hematopoietic stem cell transplantation (HSCT) frequently require prolonged courses of parenteral nutrition (PN) as a consequence of gastrointestinal dysfunction related to preparative chemotherapy and radiation. PN has been associated with shorter engraftment time and decreased mortality during HSCT, however, it is also linked with complications, including infections, liver disease, and metabolic disturbances. Some of these complications may be a result of providing PN in excess of nutrient requirements. We previously described significant reductions in resting energy expenditure (REE), as measured by indirect calorimetry, over the course of HSCT. We also documented a decline in mid-arm muscle area, suggesting depletion of muscle mass, while triceps skinfold, a marker of fat stores, was unchanged. These results suggested the need for further study of energy expenditure, body composition and nutritional intake in this group of high risk patients. Design and hypothesis We hypothesize that changes in body composition affect REE during HSCT, and that standard nutritional support may lead to overfeeding. We are performing a randomized controlled trial of parenteral nutrition among children undergoing allogeneic HSCT. Subjects are randomized to receive PN designed to provide 100% of measured REE, or standard PN, i.e., 140% of estimated energy expenditure. The primary outcome variable is change in percent body fat. Secondary outcomes include glycemic control and frequency of infections, changes in REE and body composition. Conclusion This study will provide unique and comprehensive nutritional data and its results will guide nutritional therapy for children undergoing HSCT and possibly other catabolic patients. PMID:20004739

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.

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

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.

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

Developing biogeochemical tracers of apatite weathering by ectomycorrhizal fungi

NASA Astrophysics Data System (ADS)

Vadeboncoeur, M. A.; Bryce, J. G.; Hobbie, E. A.; Meana-Prado, M. F.; Blichert-Toft, J.

2012-12-01

Chronic acid deposition has depleted calcium (Ca) from many New England forest soils, and intensive harvesting may reduce phosphorus (P) available to future rotations. Thin glacial till soils contain trace amounts of apatite, a primary calcium phosphate mineral, which may be an important long-term source of both P and Ca to ecosystems. The extent to which ECM fungi enhance the weathering rate of primary minerals in soil which contain growth-limiting nutrients remains poorly quantified, in part due to biogeochemical tracers which are subsequently masked by within-plant fractionation. Rare earth elements (REEs) and Pb isotope ratios show some potential for revealing differences in soil apatite weathering rates across forest stands and silvicultural treatments. To test the utility of these tracers, we grew birch seedlings semi-hydroponically under controlled P-limited conditions, supplemented with mesh bags containing granite chips. Our experimental design included nonmycorrhizal (NM) as well as ectomycorrhizal cultures (Cortinarius or Leccinum). Resulting mycorrhizal roots and leachates of granite chips were analyzed for these tracers. REE concentrations in roots were greatly elevated in treatments with granite relative to those without granite, demonstrating uptake of apatite weathering products. Roots with different mycorrhizal fungi accumulated similar concentrations of REEs and were generally elevated compared to the NM cultures. Ammonium chloride leaches of granite chips grown in contact with mycorrhizal hyphae show elevated REE concentrations and significantly radiogenic Pb isotope signatures relative to bulk rock, also supporting enhanced apatite dissolution. Our results in culture are consistent with data from field-collected sporocarps from hardwood stands in the Bartlett Experimental Forest in New Hampshire, in which Cortinarius sporocarp Pb isotope ratios were more radiogenic than those of other ectomycorrhizal sporocarps. Taken together, the experimental and field results imply that the coupled approach of REE and Pb isotopic values afford a means to quantify the degree to which primary mineral weathering inputs are contributing to ecosystem nutrient budgets and potentially the role of different types of ECM fungi in the weathering process.

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.

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.

Accreted fragments of the Late Cretaceous Caribbean Colombian Plateau in Ecuador

NASA Astrophysics Data System (ADS)

Mamberti, Marc; Lapierre, Henriette; Bosch, Delphine; Jaillard, Etienne; Ethien, Raynald; Hernandez, Jean; Polvé, Mireille

2003-02-01

The eastern part of the Western Cordillera of Ecuador includes fragments of an Early Cretaceous (≈123 Ma) oceanic plateau accreted around 85-80 Ma (San Juan-unit). West of this unit and in fault contact with it, another oceanic plateau sequence (Guaranda unit) is marked by the occurrence of picrites, ankaramites, basalts, dolerites and shallow level gabbros. A comparable unit is also exposed in northwestern coastal Ecuador (Pedernales unit). Picrites have LREE-depleted patterns, high ɛNd i and very low Pb isotopic ratios, suggesting that they were derived from an extremely depleted source. In contrast, the ankaramites and Mg-rich basalts are LREE-enriched and have radiogenic Pb isotopic compositions similar to the Galápagos HIMU component; their ɛNd i are slightly lower than those of the picrites. Basalts, dolerites and gabbros differ from the picrites and ankaramites by flat rare earth element (REE) patterns and lower ɛNd; their Pb isotopic compositions are intermediate between those of the picrites and ankaramites. The ankaramites, Mg-rich basalts, and picrites differ from the lavas from the San Juan-Multitud Unit by higher Pb ratios and lower ɛNd i. The Ecuadorian and Gorgona 88-86 Ma picrites are geochemically similar. The Ecuadorian ankaramites and Mg-rich basalts share with the 92-86 Ma Mg-rich basalts of the Caribbean-Colombian Oceanic Plateau (CCOP) similar trace element and Nd and Pb isotopic chemistry. This suggests that the Pedernales and Guaranda units belong to the Late Cretaceous CCOP. The geochemical diversity of the Guaranda and Pedernales rocks illustrates the heterogeneity of the CCOP plume source and suggests a multi-stage model for the emplacement of these rocks. Stratigraphic and geological relations strongly suggest that the Guaranda unit was accreted in the late Maastrichtian (≈68-65 Ma).

Origin of the Permian-Triassic komatiites, northwestern Vietnam

NASA Astrophysics Data System (ADS)

Hanski, Eero; Walker, Richard J.; Huhma, Hannu; Polyakov, Gleb V.; Balykin, Pavel A.; Tran Trong Hoa; Ngo Thi Phuong

Rare examples of Phanerozoic komatiites are found in the Song Da zone, NW Vietnam. These komatiites were erupted through continental crust and may belong to the SE extension of the Permo-Triassic Emeishan volcanic province located in SW China. They provide a good opportunity to study the source characteristics of starting plume magmas in a continental flood basalt province. Erupted on late-Permian carbonate rocks, the komatiitic rocks are interbedded with low-Ti olivine basalts. Basaltic komatiites display pyroxene spinifex textures, while more magnesian rocks (MgO up to 32 wt.%) are porphyritic, containing a single, cognate population of euhedral to elongated olivine phenocrysts with Fo up to 93.0%. This suggests a highly magnesian parental magma with 22-23 wt.% MgO. In terms of major and minor elements, the komatiites are similar to the ca. 89 Ma old Gorgona Island komatiites of Colombia. The Song Da komatiites are also strongly light-rare-earth-element- (LREE) depleted (CeN/YbN 0.30-0.62) and have unfractionated heavy rare earth element (HREE) patterns. The komatiites have high Os concentrations (up to 7.0 ppb), low but variable Re/Os ratios, and define an isochron with an age of 270+/-21 Ma, and an initial 188Os/187Os ratio of 0.12506+/- 0.00041 (γOs=+0.02+/-0.40). The Os isotopic systematics of the komatiites show no effects of crustal contamination. In contrast, their initial ɛNd values range from +3 to +8, reflecting varying but generally small degrees of contamination with Proterozoic sialic basement material. Associated low-Ti basalts have low initial ɛNd values (-0.8 to -7.5), high initial γOs values (>=15), flat or LREE-enriched REE patterns, and Nb-Ta depletion. These characteristics are also attributed to variable extents of crustal contamination.

Rhenium-osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites

NASA Astrophysics Data System (ADS)

Riches, Amy J. V.; Day, James M. D.; Walker, Richard J.; Simonetti, Antonio; Liu, Yang; Neal, Clive R.; Taylor, Lawrence A.

2012-11-01

Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201-0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10-15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056-0.1195), as well as low-Re/Os (0.03-0.13), Pd/Os (0.071-0.946), and relatively low-Pt/Os (0.792-2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage. The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are consistent with protracted post-core formation accretion of materials with chondritic-relative abundances of HSE to the APB, and these accreted materials were rapidly, yet inefficiently, mixed into angrite magma source regions early in Solar System history.

Effect of ultramafic intrusions and associated mineralized rocks on the aqueous geochemistry of the Tangle Lakes Area, Alaska: Chapter C in Studies by the U.S. Geological Survey in Alaska, 2011

USGS Publications Warehouse

Wang, Bronwen; Gough, Larry P.; Wanty, Richard B.; Lee, Gregory K.; Vohden, James; O’Neill, J. Michael; Kerin, L. Jack

2013-01-01

Stream water was collected at 30 sites within the Tangle Lakes area of the Delta mineral belt in Alaska. Sampling focused on streams near the ultramafic rocks of the Fish Lake intrusive complex south of Eureka Creek and the Tangle Complex area east of Fourteen Mile Lake, as well as on those within the deformed metasedimentary, metavolcanic, and intrusive rocks of the Specimen Creek drainage and drainages east of Eureka Glacier. Major, minor, and trace elements were analyzed in aqueous samples for this reconnaissance aqueous geochemistry effort. The lithologic differences within the study area are reflected in the major-ion chemistry of the water. The dominant major cation in streams draining mafic and ultramafic rocks is Mg2+; abundant Mg and low Ca in these streams reflect the abundance of Mg-rich minerals in these intrusions. Nickel and Cu are detected in 84 percent and 87 percent of the filtered samples, respectively. Nickel and Cu concentrations ranged from Ni <0.4 to 10.1 micrograms per liter (mg/L), with a median of 4.2 mg/L, and Cu <0.5 to 27 mg/L, with a median of 1.2 mg/L. Trace-element concentrations in water are generally low relative to U.S. Environmental Protection Agency freshwater aquatic-life criteria; however, Cu concentrations exceed the hardness-based criteria for both chronic and acute exposure at some sites. The entire rare earth element (REE) suite is found in samples from the Specimen Creek sites MH5, MH4, and MH6 and, with the exception of Tb and Tm, at site MH14. These samples were all collected within drainages containing or downstream from Tertiary gabbro, diabase, and metagabbro (Trgb) exposures. Chondrite and source rock fractionation profiles for the aqueous samples were light rare earth element depleted, with negative Ce and Eu anomalies, indicating fractionation of the REE during weathering. Fractionation patterns indicate that the REE are primarily in the dissolved, as opposed to colloidal, phase.

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.

Mantle xenoliths from Central Vietnam: evidence for at least Meso-Proterozoic formation of the lithospheric mantle

NASA Astrophysics Data System (ADS)

Proßegger, Peter; Ntaflos, Theodoros; Ackerman, Lukáš; Hauzenberger, Christoph; Tran, Tuan Anh

2016-04-01

Intraplate Cenozoic basalts that are widely dispersed along the continental margin of East Asia belong to the Western Pacific "diffuse" igneous province. They consist mainly of alkali basalts, basanites,rarely nephelinites, which are mantle xenolith-bearing, potassic rocks and quartz tholeiites. The volcanism in this area has been attributed to the continental extension caused by the collision of India with Asia and by the subduction of the Pacific Ocean below Asia. We studied a suite of 24 mantle xenoliths from La Bang Lake, Dak Doa district and Bien Ho, Pleiku city in the Gia Province, Central Vietnam. They are predominantly spinel lherzolites (19) but spinel harburgites (3) and two garnet pyroxenites are present as well. The sizes of the xenoliths range from 5 to 40 cm in diameter with medium to coarse-grained protogranular textures. Whole rock major and trace element analyses display a wide range of compositions. The MgO concentration varies from 36.0 to 45.8 wt% whereas Al2O3 and CaO range from 0.63 to 4.36 wt% and from 0.52 to 4.21 wt% (with one sample having CaO of 6.63 wt%) respectively. Both CaO and Al2O3 positively correlate with MgO most likely indicating that the sampled rocks were derived from a common mantle source experienced variable degrees of partial melting. Mineral analyses show that the rock forming minerals are chemically homogeneous. The Fo contents of olivine vary between 89.2 and 91.2 and the Mg# of orthopyroxene and clinopyroxene range from 89 to 92 and 89 to 94 respectively. The range of Cr# for spinel is 0.06-0.26. Model calculations in both whole rock and clinopyroxenes show that lithospheric mantle underneath Central Vietnam experienced melt extractions that vary between 2-7, 12-15 and 20-30%. The majority of the primitive mantle-normalized whole rock and clinopyroxene REE patterns are parallel to each other indicating that clinopyroxene is the main repository of the trace elements. Clinopyroxenes are divided into two groups: group A with concave upwards REE and (La/Yb)N < 1 suggesting various degrees of melt extraction and group B with (La/Yb)N ranging between 1 and 10. The group B in a mantle normalized trace element diagram shows negative Pb and Sr anomalies compared to their neighbour elements, which together with the general absence of hydrous phases, suggest variable interaction with percolating silicate melt(s). The primitive-mantle normalized highly siderophile element (HSE) concentration pattern show almost no fractionation among Ir, Ru and Pt with only slight depletion in Os suggesting very limited effect of metasomatism on the HSE contents. On the other hand, most of the samples display clear Re addition from the percolating melts preventing calculation of reliable rhenium depletion ages (TRD). However, one sample with depleted Pd and Re signature yield TRD of 1.0 Ga which can be interpreted as a minimum SCLM stabilization age in this area. Mantle xenoliths from Central Vietnam range from fertile to depleted compositions partly affected by metasomatic silicate melts. Re-Os isotopic composition reveals a Meso-Proterozoic minimum stabilization age of the lithospheric mantle.

Zircon U-Pb chronology, geochemistry and Sr-Nd-Pb isotopic compositions of the Volcanic Rocks in the Elashan area, NW China: petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Zhou, H.; Wei, J.; Shi, W.; Li, P.; Chen, M.; Zhao, X.

2017-12-01

Elashan area is located in the intersection of the East Kunlun Orogenic Belt (EKOB) and the West Qinling Orogenic (WQOB). We present petrology, zircon U-Pb ages, whole-rock geochemistry and Sr-Nd-Pb isotopic compositions from the andesite and felsic volcanic rocks (rhyolite and rhyolitic tuffs) in Elashan group volcanic rock. The LA-ICP-MS zircon U-Pb age data indicate that the volcanic rocks are emplaced at 250 247 Ma. The volcanic rocks have high -K and aluminum - peraluminous characteristics, A/CNK = 1.07 1.82, δ ranges from 1.56 2.95, the main body is calc-alkaline rock. They are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs) and depleted in some high field strength elements (HFSEs, e.g., Nb, Ta, P and Ti), while having a flat heavy REE (HREEs) pattern. The ∑REE values of 178.68 to 298.11 ppm, average 230.50 ppm. The LREE/HREE values of 4.39 to 11.78 ppm, average 6.77 ppm. REE fractionation is obvious, REE distribution curve was right smooth, and have slightly negative Eu anomalies (Eu/Eu*=0.44-0.80, average 0.60), which as similar to the island arc volcanic rocks. The volcanic rocks have initial 87Sr/86Sr ratios of 0.71028-0.71232, ɛNd(t) values of -6.7 to -7.6, with T2DM-Nd ranging from 1561 to 1640 Ma. Pb isotopic composition (206 Pb / 204 Pb)t = 18.055 18.330, (207 Pb / 204 Pb)t = 15.586 15.618, (208 Pb / 204 Pb)t = 37.677 38.332. Geochemical and Sr-Nd-Pb isotopes indicates that Elashan group volcanic magma derived mainly from the lower crust. Elashan group volcanic rocks is the productive East Kunlun block and West Qinling block collision, which makes the thicken crust caused partial melting in the study area. The source rocks is probably from metamorphic sandstone of Bayankala. But with Y-Nb and Rb-(Y+Nb), R1-R2 and Rb/10-Hf-Ta*3 diagrams showing that intermediate-acid rocks mainly formed in volcanic arc-collision environment, probably the collision event is short , therefore rocks retain the original island arc properties. The formation age of intermediate -acidic volcanic rock can represent the time in which the end of transgressive and the beginning of intercontinental evolution in the northeastern Tibetan Plateau.

Anomalous abundance and redistribution patterns of rare earth elements in soils of a mining area in Inner Mongolia, China.

PubMed

Wang, Lingqing; Liang, Tao

2016-06-01

The Bayan Obo Mine, the largest rare earth element (REE) deposit ever found in the world, has been mined for nearly 60 years for iron and rare earth elements. To assess the influences of mining activities on geochemical behavior of REEs in soils, 27 surface soil samples and three soil profile samples were collected from different directions in the vicinity of the mine area. The total concentrations of REEs in surface soils varied from 149.75 to 18,891.81 mg kg(-1) with an average value of 1906.12 mg kg(-1), which was apparently higher than the average values in China (181 mg kg(-1)). The order of the average concentrations of individual REEs in surface soils was similar to that in Bayan Obo ores, which confirmed that the concentration and distribution of REEs in the soils was influenced by the mining activities. The concentrations of single REE in the soil profiles showed a similar trend with depth with an increase at 0-25 cm section, then decreased and remained relatively stable in the deep part. The normalized curves inclined to the right side, showing the conspicuous fractionation between the light and heavy REEs, which supported by the North American Shale Composite (NASC) and Post-Archean Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La N /Yb N , La N /Sm N , Gd N /Yb N ). Slight positive Ce anomaly and negative Eu anomaly were also observed.

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.

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

Mineralogy and Chemistry of Continental-like Calc-alkaline Plutons on Adak Island in the Oceanic Aleutian arc: Emplacement and Implications for the Eocene History of the Arc

NASA Astrophysics Data System (ADS)

Kay, S. M.; Citron, G. P.; Kay, R. W.; Jicha, B. R.

2016-12-01

The mineralogy and chemistry of the 15 km wide latest Eocene/Oligocene (34.6-30.9 Ma) Hidden Bay and Miocene (14.2-13.7 Ma) Kagalaska calc-alkaline plutons on Adak and Kagalaska Islands in the central Aleutian arc provide insight into the arc's Tertiary evolution. The plutons intrude the moderately light REE-enriched tholeiitic basaltic to mafic andesites of the Eocene Finger Bay Formation. The Hidden Bay pluton largely consists of mid to high-K amphibole-bearing cumulate diorite (53-55% SiO2) and granodiorite (57-64% & 61-64% SiO2) with lesser amounts of gabbro (50-52%), leucogranodiorite (67-69% SiO2) and aplite (76-77% SiO2). REE patterns indicate important fractionation of amphibole and plagioclase with pyroxene and olivine present in mafic units and orthopyroxene, biotite, quartz and K-feldspar in silicic units. Quartz, K-feldspar and biotite occur in interstices in most units. Plagioclase cores are mostly from AN40-60 with K-feldspar at OR95-OR98. Fractionation of homogeneous gabbros with high-Al basalt compositions (51% SiO2) best explains the chemistry and mineralogy of the Hidden Bay pluton. The presence of pargasitic amphibole in medium to course grained diorite cumulates indicates fractionation at 12-14 km at 950-1000°C with 5.5% H2O and a NNO oxygen fugacity. Two pyroxene, Mg hornblende and Ti-Zr zircon thermometers for granodiorite and late crystallized areas record temperatures of 850-750°C at 3.5- 4.5 % H2O and a NNO+2 oxygen fugacity. The Kagalaska pluton differs in being more calc-alkaline (alkali-rich), more bimodal in being dominated by amphibole-bearing gabbro and granodiorite/ leucogranodiorite (63-68% SiO2) and in requiring more amphibole fractionation. Both plutons have compositions approaching continental crust and characteristics that are similar to plutons intruded into continental crust. Differences with the Finger Bay Volcanic are best explained by thickening of the crust to near modern thicknesses ( 35-38 km) by the time of pluton emplacement. Residual garnet in the source required by REE patterns in some samples as well as depleted isotopic signatures are best explained by oceanic crust removed by forearc subduction erosion entering the mantle wedge as magmatism waned and the arc migrated northward after the emplacement of the plutons.

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

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.

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

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.

Angrites: A Volatile-rich Variety of Asteroidal Basalt (Except for Alkalis and Gallium!)

NASA Astrophysics Data System (ADS)

Warren, P. H.; Kallemeyn, G. W.

1995-09-01

Angrites are commonly viewed as extremely volatile-depleted, and a related notion is that they formed by differentiation of a very CAI-rich material [e.g., 1]. Partial melting experiments reportedly reproduce the bulk compositions (although not fassaite-rich mineralogy) of angrites with Allende as starting material [2], but highly CAI-rich parent materials are difficult to reconcile with isotopic and REE data [3,4]. Mittlefehldt and Lindstrom [5] inferred from the low Na/Al ratios of angrites that outgassing, and thus primordial magmatism, was more intense on their parent body than on the eucrite parent asteroid. Of seven elements that (a) have been adequately determined in angrites, and (b) are far more volatile (solar-nebula 50% condensation T [6] = 690-430 K) than the alkalis (1000-910 K), four are enriched, and none is significantly depleted, in average angrite compared to average eucrite or low-Ti mare basalt (Figure). Gallium, which is of intermediate volatility (830 K), is depleted to roughly the same extent as Na and K. Results for A881371 [3] are incomplete (Zn, 6 micrograms/g, is near INAA detection limit), but even based only on AdoR and the two LEW angrites, this pattern seems firmly established. Apparent gas cavities in A881371 [7] also suggest that volatiles are far from uniformly depleted. The only elements known to be depleted, as volatiles, by clearly significant factors in angrites versus eucrites or lunar basalts, are alkalis plus gallium. Besides being moderately volatile, a noteworthy characteristic shared among Ga and alkalis (and not shared with elements such as Br, Se, and Zn) is that these elements probably tend to partition into crustal feldspar during gross differentiation of small (low-pressure) bodies. If gallium + alkalis were depleted by a single process starting from "normal" chondritic material, that process would seem to require selective exposure of a feldspar-enriched region (i.e., crust) to extremely high temperature. Igneous crystallization of the angrites occurred when the solar system was still extremely young, and apparently <=2 Ma after the volatile-depletion process [4]. The data of [4] eliminate 26Al as a potential heat source for magmatism. The angrite volatile pattern may be the product of heating by an intense, short-lived heat source that melted and partially vaporized the crust of an asteroid(s) (not necessarily the final angrite asteroid), without much affecting the deep interior(s), which later (through mixing and/or magmatism) replenished the angritic materials in most volatiles, but not alkalis and Ga. Exogenic heating, as in the often-conjectured (but hard to test) hypothesis that a major early heat source was enhanced solar luminosity (as in FU-Orionis cycles), would seem to be required. LEW 87051 and A881371 are rich in compositionally diverse olivine xenocrysts, and A881371 contains a possible FeS xenocryst [7]. These, and the angrites' great siderophile diversity [3], tend to suggest that magmatism and intensely disruptive cratering (with mixing of precursor materials) were contemporaneous. This scenario is admittedly speculative, but the volatile-depletion pattern is difficult to rationalize with any other model. References: [1] Prinz M. and Weisberg M. (1995) Antarct. Meteorites, XX, 207-210. [2] Jurewicz A. et al. (1993) GCA, 57, 2123-2139. [3] Warren P. et al. (1995) Antarct. Meteorites, XX, 261-264. [4] Lugmair G. and Galer S. 1992) GCA, 56, 1673-1694. [5] Mittlefehldt D. and Lindstrom M. (1990) GCA, 54, 3209-3218. [6] Wasson J. (1985) Meteorites. [7] Warren P. and Davis A. (1995) Antarct. Meteorites, XX, 257-260.

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.

SHRIMP U–Pb and REE data pertaining to the origins of xenotime in Belt Supergroup rocks: evidence for ages of deposition, hydrothermal alteration, and metamorphism

USGS Publications Warehouse

Aleinikoff, John N.; Lund, Karen; Fanning, C. Mark

2015-01-01

The Belt–Purcell Supergroup, northern Idaho, western Montana, and southern British Columbia, is a thick succession of Mesoproterozoic sedimentary rocks with an age range of about 1470–1400 Ma. Stratigraphic layers within several sedimentary units were sampled to apply the new technique of U–Pb dating of xenotime that sometimes forms as rims on detrital zircon during burial diagenesis; xenotime also can form epitaxial overgrowths on zircon during hydrothermal and metamorphic events. Belt Supergroup units sampled are the Prichard and Revett Formations in the lower Belt, and the McNamara and Garnet Range Formations and Pilcher Quartzite in the upper Belt. Additionally, all samples that yielded xenotime were also processed for detrital zircon to provide maximum age constraints for the time of deposition and information about provenances; the sample of Prichard Formation yielded monazite that was also analyzed. Ten xenotime overgrowths from the Prichard Formation yielded a U–Pb age of 1458 ± 4 Ma. However, because scanning electron microscope – backscattered electrons (SEM–BSE) imagery suggests complications due to possible analysis of multiple age zones, we prefer a slightly older age of 1462 ± 6 Ma derived from the three oldest samples, within error of a previous U–Pb zircon age on the syn-sedimentary Plains sill. We interpret the Prichard xenotime as diagenetic in origin. Monazite from the Prichard Formation, originally thought to be detrital, yielded Cretaceous metamorphic ages. Xenotime from the McNamara and Garnet Range Formations and Pilcher Quartzite formed at about 1160– 1050 Ma, several hundred million years after deposition, and probably also experienced Early Cretaceous growth. These xenotime overgrowths are interpreted as metamorphic–diagenetic in origin (i.e., derived during greenschist facies metamorphism elsewhere in the basin, but deposited in sub-greenschist facies rocks). Several xenotime grains are older detrital grains of igneous derivation. A previous study on the Revett Formation at the Spar Lake Ag–Cu deposit provides data for xenotime overgrowths in several ore zones formed by hydrothermal processes; herein, those results are compared with data from newly analyzed diagenetic, metamorphic, and magmatic xenotime overgrowths. The origin of a xenotime overgrowth is reflected in its rareearth element (REE) pattern. Detrital (i.e., igneous) xenotime has a large negative Eu anomaly and is heavy rare-earth element (HREE)-enriched (similar to REE in igneous zircon). Diagenetic xenotime has a small negative Eu anomaly and flat HREE (Tb to Lu). Hydrothermal xenotime is depleted in light rare-earth element (LREE), has a small negative Eu anomaly, and decreasing HREE. Metamorphic xenotime is very LREE-depleted, has a very small negative Eu anomaly, and is strongly depleted in HREE (from Gd to Lu). Because these characteristics seem to be process related, they may be useful for interpretation of xenotime of unknown origin. The occurrence of 1.16–1.05 Ga metamorphic xenotime, in the apparent absence of pervasive deformation structures, suggests that the heating may be related to poorly understood regional heating due to broad regional underplating of mafic magma. These results may be additional evidence (together with published ages from metamorphic titanite, zircon, monazite, and garnet) for an enigmatic, Grenville-age metamorphic event that is more widely recognized in the southwestern and eastern United States

Petrochemistry and zircon U-Pb geochronology of granitic rocks in the Wang Nam Khiao area, Nakhon Ratchasima, Thailand: Implications for petrogenesis and tectonic setting

NASA Astrophysics Data System (ADS)

Fanka, Alongkot; Tsunogae, Toshiaki; Daorerk, Veerote; Tsutsumi, Yukiyasu; Takamura, Yusuke; Sutthirat, Chakkaphan

2018-05-01

Carboniferous biotite granite, Late Permian hornblende granite, and Triassic biotite-hornblende granite, all of which belong to the Eastern Granite Belt, expose in the Wang Nam Khiao area, Nakhon Ratchasima, northeastern Thailand. The Carboniferous biotite granite is dominated by quartz, K-feldspar, plagioclase, and biotite. The Late Permian hornblende granite contains dominant assemblages of plagioclase, quartz, K-feldspar, hornblende, and minor amount of biotite, while the Triassic biotite-hornblende granite consists of quartz, plagioclase, K-feldspar with small amounts of biotite, and hornblende. The REE patterns with steep decrease from light to heavy REE together with the LILE (e.g. K, Sr) enrichment and depletion of some particular HFSE (e.g. Nb, Ti) indicate low degree of partial melting. Mineral chemistry of biotite and hornblende in the granites reflects crystallization from hydrous calc-alkaline arc-derived magmas possibly formed by subduction. Amphibole-plagioclase thermometry and Al-in-hornblende barometry indicate that the Late Permian hornblende granite and the Triassic biotite-hornblende granite may have equilibrated at 3.0-5.8 kbar/700-820 °C and 2.0-3.2 kbar/600-750 °C, respectively, in the middle-upper crust (about 10-15 km depth). Zircon U-Pb geochronology of the Carboniferous biotite granite, Late Permian hornblende granite and Triassic biotite-hornblende granite yielded intrusion ages of 314.6-284.9 Ma, 253.4 Ma, and 237.8 Ma, respectively, which implies multiple episodes of arc-magmatism formed by Palaeo-Tethys subduction beneath Indochina Terrane during Late Carboniferous/Early Permian, Late Permian and Middle Triassic.

Idetification of the chemical sedimentary protolish of the early Paleoproterozoic banded iron formation from Wuyang area, in the southern margin of the North China Craton

NASA Astrophysics Data System (ADS)

Lan, C.; Zhao, T.

2016-12-01

The Paleoproterozoic banded iron formation (BIF) from Wuyang area in the southern margin of the North China Craton (NCC) were metamorphosed under granulite facies, and are characterized with an assemblage of clinopyroxene, magnetite and orthopyroxene. Two types of iron ores can be identified on the basis of macro- and micro-textures: banded quartz-clinopyroxene (±othopyroxene) -magnetite ores and massive clinopyroxene-magnetite ores. Two-pyroxene geothermometry indicates that the primary counterparts of these ores have undergone metamorphism with a peak temperature of about 762±9°. Both the banded and massive ores have also similarly BIF-like REE+Y features, and thus are proposed to have all formed from chemical sediments. Similarly, clinopyroxenes from both types have BIF-like rare earth element compositions and are rich in Fe (16-23 wt.% FeOtotoal), further suggesting that they are primary Fe-Mg-Ca-rich chemical sediments during metamorphism. Slight enrichments of TiO2, Al2O3, Zr, Hf, Ta and Th of the Wuyang IF suggest relatively low detritus input. The massive ore have magnetite containing V, Cr and Ti much higher than those of the banded ores, suggesting that they may have undergone stronger secondary alteration possibly related to the intrusion of nearby pyroxenite plutons. Different ores have seawater-like REE+Y patterns with LREE depletions and positive anomalies of La, Eu, and Y, showing that granulite facies metamorphism did not essentially modify the primary compositions of the Wuyang IF deposited from paleo-seawater. Our results suggest less than 0.1% contribution from high-temperature hydrothermal fluids.

Geochemical characterization of the largest upland lake of the Brazilian Amazonia: Impact of provenance and processes

NASA Astrophysics Data System (ADS)

Sahoo, Prafulla Kumar; Guimarães, José Tasso Felix; Souza-Filho, Pedro Walfir Martins; da Silva, Marcio Sousa; Nascimento, Wilson, Júnior; Powell, Mike A.; Reis, Luiza Santos; Pessenda, Luiz Carlos Ruiz; Rodrigues, Tarcísio Magevski; da Silva, Delmo Fonseca; Costa, Vladimir Eliodoro

2017-12-01

Lake Três Irmãs (LTI), the largest upland lake in the Brazilian Amazonia, located in Serra dos Carajás, was characterized using multi-elemental and isotope geochemistry (δ13C and δ15N) to understand the significance of organic and inorganic sources, weathering and sedimentary processes on the distribution of elements in lake bottom (surficial) sediments. Carbon and nitrogen isotopes from sedimentary organic matter suggest C3 terrestrial plants (forests > canga vegetation), macrophytes and freshwater DOC as the main sources. Sediments are depleted in most of the major oxides (except Fe2O3 and P2O5) when compared to upper continental crust (UCC) and their spatial distribution is highly influenced by catchment lithology. Principal Component Analysis revealed that most of the trace elements (Ba, Sr, Rb, Sc, Th, U, Zr, Hf, Nb, Y, V, Cr, Ga, Co, Ni) and REEs are closely correlated with Al and Ti (PC1; Group-1), so their redistribution is less influenced by post-depositional process. This is due to their relative immobility and being hosted by Al-bearing minerals during laterization. High Chemical Index of Alteration (CIA), Mafic Index of Alteration (MIA) and Index of Laterization (IOL) values indicate intense chemical weathering at source areas, but the weathering transformation was better quantified by IOL. A-CN-K plot along with elemental ratios (Al/K, Ti/K, Ti/Zr, La/Al, Cr/Th, Co/Th, La/Sm, La/Gd, Zr/Y, and Eu/Eu*) as well as chondrite-normalized REE patterns show that the detritic sediments are mainly sourced from ferruginous laterites and soils in the catchment, which may have characteristics similar to mafic rocks.

Characterization of multiple lithologies within the lunar feldspathic regolith breccia meteorite Northeast Africa 001

NASA Astrophysics Data System (ADS)

Snape, Joshua F.; Joy, Katherine H.; Crawford, Ian A.

2011-09-01

Abstract- Lunar meteorite Northeast Africa (NEA) 001 is a feldspathic regolith breccia. This study presents the results of electron microprobe and LA-ICP-MS analyses of a section of NEA 001. We identify a range of lunar lithologies including feldspathic impact melt, ferroan noritic anorthosite and magnesian feldspathic clasts, and several very-low titanium (VLT) basalt clasts. The largest of these basalt clasts has a rare earth element (REE) pattern with light-REE (LREE) depletion and a positive Euanomaly. This clast also exhibits low incompatible trace element (ITE) concentrations (e.g., <0.1 ppm Th, <0.5 ppm Sm), indicating that it has originated from a parent melt that did not assimilate KREEP material. Positive Eu-anomalies and such low-ITE concentrations are uncharacteristic of most basalts returned by the Apollo and Luna missions, and basaltic lunar meteorite samples. We suggest that these features are consistent with the VLT clasts crystallizing from a parent melt which was derived from early mantle cumulates that formed prior to the separation of plagioclase in the lunar magma ocean, as has previously been proposed for some other lunar VLT basalts. Feldspathic impact melts within the sample are found to be more mafic than estimations for the composition of the upper feldspathic lunar crust, suggesting that they may have melted and incorporated material from the lower lunar crust (possibly in large basin-forming events). The generally feldspathic nature of the impact melt clasts, lack of a KREEP component, and the compositions of the basaltic clasts, leads us to suggest that the meteorite has been sourced from the Outer-Feldspathic Highlands Terrane (FHT-O), probably on the lunar farside and within about 1000 km of sources of both Low-Ti and VLT basalts, the latter possibly existing as cryptomaria deposits.

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.

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.

The Role of Crustal Strength in Controlling Magmatism and Melt Chemistry During Rifting and Breakup

NASA Astrophysics Data System (ADS)

Armitage, John J.; Petersen, Kenni D.; Pérez-Gussinyé, Marta

2018-02-01

The strength of the crust has a strong impact on the evolution of continental extension and breakup. Strong crust may promote focused narrow rifting, while wide rifting might be due to a weaker crustal architecture. The strength of the crust also influences deeper processes within the asthenosphere. To quantitatively test the implications of crustal strength on the evolution of continental rift zones, we developed a 2-D numerical model of lithosphere extension that can predict the rare Earth element (REE) chemistry of erupted lava. We find that a difference in crustal strength leads to a different rate of depletion in light elements relative to heavy elements. By comparing the model predictions to rock samples from the Basin and Range, USA, we can demonstrate that slow extension of a weak continental crust can explain the observed depletion in melt chemistry. The same comparison for the Main Ethiopian Rift suggests that magmatism within this narrow rift zone can be explained by the localization of strain caused by a strong lower crust. We demonstrate that the slow extension of a strong lower crust above a mantle of potential temperature of 1,350 °C can fit the observed REE trends and the upper mantle seismic velocity for the Main Ethiopian Rift. The thermo-mechanical model implies that melt composition could provide quantitative information on the style of breakup and the initial strength of the continental crust.

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.

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.

Evolution of the lithospheric mantle beneath Mt. Baekdu (Changbaishan)

NASA Astrophysics Data System (ADS)

Choi, S. H.; Park, K.; Cho, M.; Lee, D. C.

2017-12-01

Major and trace element compositions of minerals as well as Sr-Nd-Hf isotopic compositions of clinopyroxenes from spinel peridotite xenoliths entrained in Late Cenozoic trachybasalt from Mt. Baekdu (Changbaishan) were used to elucidate lithospheric mantle formation and evolution in the eastern North China Craton (NCC). The analyzed peridotites were mainly spinel lherzolites with rare harzburgites. They consisted of olivine, enstatite, diopside and spinel. Plots of the Cr# in spinel against the Mg# in coexisting olivine or spinel suggested an affinity with abyssal peridotites. Comparisons of Cr# and TiO2 in spinel were also compatible with an abyssal peridotite-like composition; however, harzburgites were slightly enriched in TiO2 because of the reaction with MORB-like melt. Temperatures estimated using two-pyroxene thermometry ranged from 750 to 1,010°C, reflecting their lithospheric mantle origin. The REE patterns in clinopyroxenes of the peridotites varied from LREE-depleted to spoon shaped to LREE-enriched, reflecting secondary overprinting effects of metasomatic melts or fluids on the residues from primordial melting. The calculated trace element pattern of metasomatic melt equilibrated with clinopyroxene in Mt. Baekdu peridotite showed strong enrichment in LILEs, Th and U together with slight fractionation in HREEs and considerable depletion in Nb and Ti. The Sr-Nd-Hf isotopic compositions of clinopyroxenes separated from the peridotites varied from more depleted than present-day MORB to bulk Earth values. However, some clinopyroxene showed a decoupling between Nd and Sr isotopes, deviating from the mantle array with a high 87Sr/86Sr ratio. This sample also showed a significant Nd-Hf isotope decoupling lying well above the mantle array. The Lu-Hf and Sm-Nd model ages of residual clinopyroxenes yielded Early Proterozoic to Phanerozoic ages. No signature of Archean cratonic mantle was present. Therefore, Mt. Baekdu peridotite is residual lithospheric mantle that has undergone variable degrees of diachronous melt extraction and infiltration metasomatism involving subduction-related, fluid-bearing silicate melts. The predominance of Phanerozoic Hf model ages indicates that the lherzolites represent lithospheric mantle fragments newly accreted underneath the eastern NCC.

Occurrence of high-Al N-MORB along the Easternmost Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Meyzen, C. M.; Humler, E.; Ludden, J. N.

2017-12-01

One of the deepest and slowest part of the mid-ocean-ridge system lies within the easternmost part of the Southwest Indian Ridge between 61°E and 69° E. In this region, a distinctive sea-floor terrain characterized by high-relief segments separated by long, deep tectonized sections shows a predominance of tectonic over magmatic extensional processes, suggesting an unstable and weak, but locally focalized magma supply. Other features of this section include the absence of long-lived transforms, thick lithosphere, high upper mantle seismic wave velocities and thin oceanic crust (4-5 km). When compared to other ridge segments, most MORB erupted along this section distinguish themselves by their higher Na2O, Sr and Al2O3 compositions, very low CaO/Al2O3 ratios relative to TiO2 and depleted heavy rare-earth element (REE) distributions. Another peculiar feature is their subparallel LREE enriched patterns. The high-Al-MgO magma type erupted periodically around the ridge system is also found in this region at 61.93°E. These lavas are characterized by high Al2O3 (> 17 wt. %), MgO (> 8.8 wt. %) and FeO contents, low SiO2 (< 49 wt. %) and Na2O and very low TiO2 (< 1 wt. %), and a LREE depleted pattern compared to the main population. At slightly lower MgO, sporadically, two other dredges located at 63.36-63.66°E share some of these distinct compositional characteristics. As a whole, these lavas are the most depleted in highly incompatible elements, but are also characterized by an offset toward lower MREE/HREE ratios relative to the main population. These peculiar basalts are not parental to the more common lower MgO compositions and cannot be related to them by fractional crystallization alone. Instead, their major element features, and the occasional presence of positive Eu and Sr anomalies might indicate assimilation of plagioclase cumulates, while their offset in MREE/HREE might require a multistage melting evolution with an earlier event in the garnet stability field.

Trace element behavior in hydrothermal experiments: Implications for fluid processes at shallow depths in subduction zones

NASA Astrophysics Data System (ADS)

You, C.-F.; Castillo, P. R.; Gieskes, J. M.; Chan, L. H.; Spivack, A. J.

1996-05-01

Chemical evaluation of fluids affected during progressive water-sediment interactions provides critical information regarding the role of slab dehydration and/or crustal recycling in subduction zones. To place some constraints on geochemical processes during sediment subduction, reactions between décollement sediments and synthetic NaCl-CaCl 2 solutions at 25-350°C and 800 bar were monitored in laboratory hydrothermal experiments using an autoclave apparatus. This is the first attempt in a single set of experiments to investigate the relative mobilities of many subduction zone volatiles and trace elements but, because of difficulties in conducting hydrothermal experiments on sediments at high P-T conditions, the experiments could only be designed for a shallow (˜ 10 km) depth. The experimental results demonstrate mobilization of volatiles (B and NH 4) and incompatible elements (As, Be, Cs, Li, Pb, Rb) in hydrothermal fluids at relatively low temperatures (˜ 300°C). In addition, a limited fractionation of light from heavy rare earth elements (REEs) occurs under hydrothermal conditions. On the other hand, the high field strength elements (HFSEs) Cr, Hf, Nb, Ta, Ti, and Zr are not mobile in the reacted fluids. The observed behavior of volatiles and trace elements in hydrothermal fluids is similar to the observed enrichment in As, B, Cs, Li, Pb, Rb, and light REEs and depletion in HFSEs in arc magmas relative to magmas derived directly from the upper mantle. Thus, our work suggests a link between relative mobilities of trace elements in hydrothermal fluids and deep arc magma generation in subduction zones. The experimental results are highly consistent with the proposal that the addition of subduction zone hydrous fluids to the subarc mantle, which has been depleted by previous melting events, can produce the unique characteristics of arc magmas. Moreover, the results suggest that deeply subducted sediments may no longer have the composition necessary to generate the other distinct characteristics, such as the B-δ 11 B and B- 10Be systematics, of arc lavas. Finally, the mobilization of B, Cs, Pb, and light REEs relative to heavy REEs in the hydrothermal fluids fractionate the ratios of B/Be, B/Nb, Cs/Rb, Pb/Ce, La/Ba and LREE/HREE, which behave conservatively during normal magmatic processes. These results demonstrate that the composition of slab-derived fluids has great implications for the recycling of elements; not only in arc magmas but also in mantle plumes.

Rare-earth elements in the Permian Phosphoria Formation: Paleo proxies of ocean geochemistry

USGS Publications Warehouse

Piper, D.Z.; Perkins, R.B.; Rowe, H.D.

2007-01-01

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km2, is ascertained from its rare earth element (REE) composition. Ratios of REE:Al2O3 suggest two sources-seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O2-depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni???Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O2-depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO43-, a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction. ?? 2007 Elsevier Ltd. All rights reserved.

Rare-earth elements in the Permian Phosphoria Formation: Paleo proxies of ocean geochemistry

NASA Astrophysics Data System (ADS)

Piper, D. Z.; Perkins, R. B.; Rowe, H. D.

2007-06-01

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km 2, is ascertained from its rare earth element (REE) composition. Ratios of REE:Al 2O 3 suggest two sources—seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O 2-depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni≫Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O 2-depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO 43-, a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O 2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O 2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction.

[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.

Petrology of peridotite xenoliths from the Miocene alkaline basalt from Baegryeong Island

NASA Astrophysics Data System (ADS)

Park, G. Y.; Kim, E.; Yang, K.

2017-12-01

Peridotite xenoliths occurring in late Miocene intraplate alkaline basalt from Baegryeong Island, west-northern part of the Korean peninsula, are mainly anhydrous spinel lherzolites. Their textures and chemical compositions give a deep insight for upper mantle. This study presents the results of modal, major composition of minerals and trace composition of clinopyroxene. The xenoliths display coarse grained protogranular through inequigranular to cumulate textures, grading into each other. They often show well-developed annealed textures and contain left-over olivine grains within orthopyroxene, suggesting that they went through static(±dynamic) recrystallization. The constituent minerals are compositionally homogeneous and appear to be equilibrated. The xenoliths are characterized by the high Mg#[=100×Mg/(Mg+Fetotal) atomic ratio] of olivine, orthopyroxene and clinopyroxene (89-93) and the Cr#[=100×Cr/(Cr+Al) atomic ratio] of spinel (9-15). The calculated equilibrium temperatures and oxygen fugacities resulted in 920-1070°C and ΔfO2 (QFM) = -1.5 -0.5, respectively. Clinopyroxenes of the xenoliths are mostly enriched in incompatible trace elements, exhibiting three types of REE patterns such as LREE-depleted, LREE-enriched and a enrichment in La over Ce, and depletion in high field strength elements(HFSE; Nb-Ta, Zr-Hf, Ti). From these trace element signatures, we thus propose the Baegryeong peridotite xenoliths represent residues left after early melt extraction, which was subsequently subjected to different degrees of modal/cryptic metasomatism by residual slab-derived, silica- and LREE-enriched fluids (or melts).

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.

The role of trace element partitioning between garnet, zircon and orthopyroxene on the interpretation of zircon U-Pb ages: an example from high-grade basement in Calabria (Southern Italy)

NASA Astrophysics Data System (ADS)

Fornelli, A.; Langone, A.; Micheletti, F.; Pascazio, A.; Piccarreta, G.

2014-03-01

The recognition of the coeval growth of zircon, orthopyroxene and garnet domains formed during the same metamorphic cycle has been attempted with detailed microanalyses coupled with textural analyses. A coronitic garnet-bearing granulite from the lower crust of Calabria has been considered. U-Pb zircon data and zircon, garnet and orthopyroxene chemistries, at different textural sites, on a thin section of the considered granulite have been used to test possible equilibrium and better constrain the geological significance of the U-Pb ages related to zircon separates from other rocks of the same structural level. The garnet is very rich in REE and is characterised by a decrease in HREE from core to outer core and an increase in the margin. Zircons show core-overgrowth structures showing different chemistries, likely reflecting episodic metamorphic new growth. Zircon grains in matrix, corona around garnet and within the inner rim of garnet, are decidedly poorer in HREE up to Ho than garnet interior. Orthopyroxene in matrix and corona is homogeneously poor in REE. Thus, the outer core of garnet and the analysed zircon grains grew or equilibrated in a REE depleted system due to the former growth of garnet core. Zircon ages ranging from 357 to 333 Ma have been determined in the matrix, whereas ages 327-320 Ma and around 300 Ma have been determined, respectively, on cores and overgrowths of zircons from matrix, corona and inner rim of garnet. The calculated DREEzrn/grt and DREEopx/grt are largely different from the equilibrium values of literature due to strong depletion up to Ho in zircon and orthopyroxene with respect to garnet. On the other hand, the literature data show large variability. In the case study, (1) the D zrn/grt values define positive and linear trends from Gd to Lu as many examples from literature do and the values from Er to Lu approach the experimental results at about 900 °C in the combination zircon dated from 339 to 305 Ma with garnet outer core, and (2) D opx/grt values define positive trends reaching values considered as suggestive of equilibrium from Er to Lu only with respect to the outer core of garnet. The presence of a zircon core dated 320 Ma in the inner rim of garnet suggests that it, as well as those dated at 325-320 Ma in the other textural sites and, probably, those dated at 339-336 Ma showing depletion of HREE, grew after the garnet core, which sequestered a lot of HREE and earlier than the HREE rich margin of garnet. The quite uniform REE contents in orthopyroxene from matrix and corona and the low and uniform contents of HREE in the zircon overgrowths dated at about 300 Ma allow to think that homogenisation occurred during or after the corona formation around this age. The domains dated around 325-320 Ma would approximate the stages of decompression, whereas the metamorphic peak probably occurred earlier than 339 Ma.

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.

Sediment Sources, Depositional Environment, and Diagenetic Alteration of the Marcellus Shale, Appalachian Basin, USA: Nd, Sr, Li and U Isotopic Constraints

NASA Astrophysics Data System (ADS)

Phan, T. T.; Capo, R. C.; Gardiner, J. B.; Stewart, B. W.

2017-12-01

The organic-rich Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, is a major target of natural gas exploration. Constraints on local and regional sediment sources, depositional environments, and post-depositional processes are essential for understanding the evolution of the basin. In this study, multiple proxies, including trace metals, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U and Li isotopes were applied to bulk rocks and authigenic fractions of the Marcellus Shale and adjacent limestone/sandstone units from two locations separated by 400 km. The range of ɛNd values (-7.8 to -6.4 at 390 Ma) is consistent with a clastic sedimentary component derived from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt. The Sm-Nd isotope system and bulk REE distributions appear to have been minimally affected by post-depositional processes, while the Rb-Sr isotope system shows evidence of limited post-depositional redistribution. While REE are primarily associated with silicate minerals (80-95%), REE patterns of sequentially extracted fractions reflect post-depositional alteration at the intergranular scale. Although the chemical index of alteration (CIA = 54 to 60) suggests the sediment source was not heavily weathered, Li isotope data are consistent with progressively increasing weathering of the source region during Marcellus Shale deposition. δ238U values in bulk shale and reduced phases (oxidizable fraction) are higher than those of modern seawater and upper crust. The isotopically heavy U accumulated in these authigenic phases can be explained by the precipitation of insoluble U in anoxic/euxinic bottom water. Unlike carbonate cement within the shale, the similarity between δ238U values and REE patterns of the limestone units and those of modern seawater indicates that the limestone formed under open ocean (oxic) conditions.

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

Hf and Nd Isotopic and REE Investigations of Magnetite in a Proterozoic IOCG system: Fingerprinting Sources and Timing of Mineralisation

NASA Astrophysics Data System (ADS)

Schaefer, B. F.

2016-12-01

The Stuart Shelf on the margin of the Gawler Craton, South Australia, contains numerous economic and sub-econmic IOCG mineralised systems, including the giant Olympic Dam Cu-Au-U deposit. Hematite and magnetite have played a critical in the genesis of all of these deposits, and increasingly it appears that magnetite has been in equilibrium with either the final mineralised assemblage or was critical in transporting metals during the ore forming event. 14 magnetites and one hematite from three separate styles of iron oxide mineralisation associated with the Prominent Hill Cu-Au deposit were selected for detailed analysis. The REE and isotopic separations were all conducted by low blank wet chemistry and isotopes determined by TIMS (Nd) and MC-ICPMS (Hf). Magnetites associated with skarn style mineralsiation proximal to the ore body are unformly depleted in REE, whereas hematite within the ore and magmatic magmatites and whole rock gabbros from the nearby 1590Ma White Hill Gabbro intrusion are all relatively LREE enriched and display a comparable range in REE. Significantly however, magnetite separates almost invariably display more evolved Hf isotopic signatures than the host lithologies adjacent the economic mineralisation (dacites and metasediments at Prominent Hill mine) implying that the magnetites were sourcing their REE inventory dominantly from the local crust rather than a mantle derived source. In contrast, the magmatic magnetites from the White Hill Complex display Nd and Hf isotopes which are slightly more primitive, recording a greater relative mantle component, however still requiring a significant crustal input. Significantly, the hematite which contains the Au mineralisation preserves ɛNd (1590) = -4.04 and ɛHf (1590) = -6.05 essentially identical to the magmatic magnetites and their host gabbros in the White Hill complex and the basalts and dacites of the host Gawler Range Volcanics (ɛNd (1590) = -7.10 - -3.72 and ɛHf (1590) = -7.69 - -1.89). Therefore it would appear that the mineralising event was driven by the intrusion of the White Hills Complex and proximal Gawler Range Volcanics.

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.

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.

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.

The geology and geochemistry of Isla Floreana, Galápagos: A different type of late-stage ocean island volcanism: Chapter 6 in The Galápagos: A natural laboratory for the earth sciences

USGS Publications Warehouse

Harpp, Karen S.; Geist, Dennis J.; Koleszar, Alison M.; Christensen, Branden; Lyons, John; Sabga, Melissa; Rollins, Nathan; Harpp, Karen S.; Mittelstaedt, Eric; d'Ozouville, Noémi; Graham, David W

2014-01-01

Isla Floreana, the southernmost volcano in the Galápagos Archipelago, has erupted a diverse suite of alkaline basalts continually since 1.5 Ma. Because these basalts have different compositions than xenoliths and older lavas from the deep submarine sector of the volcano, Floreana is interpreted as being in a rejuvenescent or late-stage phase of volcanism. Most lavas contain xenoliths, or their disaggregated remains. The xenolithic debris and large ranges in composition, including during single eruptions, indicate that the magmas do not reside in crustal magma chambers, unlike magmas in the western Galápagos. Floreana lavas have distinctive trace element compositions that are rich in fluid-immobile elements (e.g., Ta, Nb, Th, Zr) and even richer in fluid-mobile elements (e.g., Ba, Sr, Pb). Rare earth element (REE) patterns are light REE-enriched and distinctively concave-up. Neodymium isotopic ratios are comparable to those from Fernandina, at the core of the Galápagos plume, but Floreana has the most radiogenic Sr and Pb isotopic ratios in the archipelago. These trace element patterns and isotopic ratios are attributed to a mixed source originating within the Galápagos plume, which includes depleted upper mantle, plume material rich in TITAN elements (Ti, Ta, Nb), and recycled oceanic crust that has undergone partial dehydration in an ancient subduction zone. Because Floreana lies at the periphery of the Galápagos plume, melting occurs mostly in the spinel zone, and enriched components dominate; the Floreana recycled mantle component influence is detectable in volcanoes along the entire southern periphery of the archipelago as well. Floreana is the only Galápagos volcano known to have undergone late-stage volcanism. Here, however, the secondary stage activity is more compositionally enriched than the shield-building phase, in contrast to what is observed in Hawai‘i, suggesting that the mechanism driving late-stage volcanism may vary among ocean island provinces.

"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.

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.

Mo-mineralized porphyries are relatively hydrous and differentiated: insights from the Permian-Triassic granitic complex in the Baituyingzi Mo-Cu district, eastern Inner Mongolia, NE China

NASA Astrophysics Data System (ADS)

Sun, Yan; Liu, Jianming; Zeng, Qingdong; Wang, Jingbin; Wang, Yuwang; Hu, Ruizhong; Zhou, Lingli; Wu, Guanbin

2017-08-01

Mo-Cu mineralization in the Baituyingzi district of eastern Inner Mongolia occurs within a granitic complex. This paper presents and discusses zircon U-Pb ages and whole-rock geochemical and Sr-Nd-Pb isotopic data from the granitic complex as potential indicators for porphyry Mo fertility. The U-Pb ages indicate that five units of the granitic complex were emplaced between 265.2 ± 0.7 and 246.5 ± 1.0 Ma. Constrained by crosscutting dikes, Mo-Cu mineralization was probably related to the Baituyingzi monzogranite porphyry dated at 248.2 ± 0.64 Ma. The intrusions belong to high-K calc-alkaline to shoshonitic series that are characterized by highly fractionated rare earth element (REE) patterns and strong enrichments of large ion lithophile elements, relative to high-field strength elements. Apart from the ˜246-Ma dike that shows negative ɛNd ( t) values (-14.9 to -13.1), the intrusions have ɛNd( t) values ranging from -3.9 to 1.0, relatively young depleted mantle model ages (811 to 1183 Ma), 206Pb/204Pb of 18.137-18.335, and 207Pb/204Pb of 15.591-15.625, which are consistent with a juvenile lower crustal origin. Among the intrusions, the ˜248-Ma porphyry and the ˜246-Ma dike show adakite-like characteristics (e.g., Sr/Y = 44.9-185) and listric-shaped REE patterns that indicate amphibole fractionation and a hydrous magma source. However, the porphyry exhibits a higher differentiation index (81.4-91.5) and a steeper REE profile (e.g., LaN/YbN = 25.6-87.0) than those of the ˜246-Ma dike, which suggests that it is highly differentiated. We propose that the complex was generated by the partial melting of juvenile mafic lower crust (containing minor old crustal relicts) that was triggered by collision between the North China Craton and Siberian Craton. As indicated by the Th/Nb, Th/Yb, Ba/Th, and Ba/La ratios of the intrusions, the crust may have been derived from the melting of the fertile mantle wedge that was metasomatized by various amounts of slab-derived fluids or melts due to earlier subduction and was heterogeneous in terms of water, Cu, Mo, and S contents and possible oxidation state. The fertility of the porphyry was likely associated with the addition of earlier subduction-related slab melts to the magma source (leading to a hydrous and possible high oxidation state) and the long-time (˜20 Ma) collision tectonic setting in which it formed (resulting in a highly differentiated state).

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.

Tertiary or Mesozoic komatiites from Gorgona Island, Colombia: Field relations and geochemistry

NASA Astrophysics Data System (ADS)

Echeverría, Lina M.

1980-08-01

An exceptional occurrence of ultramafic lavas within the volcanic member of the Mesozoic (or younger) Gorgona Igneous Complex represents the first known komatiites of post-Precambrian age. Gorgona komatiites are virtually unaltered and display typical spinifex textures, with 7 10 cm long plates of olivine (Fo 88 to 91) surrounded by acicular aluminous augite, subordinate plagioclase (An 56 to 78), basaltic glass, and two spinel phases. The MgO contents of the komatiites range from 15 to 22 wt.%. Sr and Nd isotopic compositions are indicative of depletion of incompatible elements in the mantle source region, as is the case for “normal” mid-ocean ridge basalts. The komatiites are low in total REE abundances and extremely depleted in LREE. They represent primary melts generated by high degree of partial melting of the mantle. Eruption temperatures are estimated at 1,450° to 1,500° C.

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.

Origin of unusual HREE-Mo-rich carbonatites in the Qinling orogen, China

NASA Astrophysics Data System (ADS)

Song, Wenlei; Xu, Cheng; Smith, Martin P.; Kynicky, Jindrich; Huang, Kangjun; Wei, Chunwan; Zhou, Li; Shu, Qihai

2016-11-01

Carbonatites, usually occurring within intra-continental rift-related settings, have strong light rare earth element (LREE) enrichment; they rarely contain economic heavy REE (HREE). Here, we report the identification of Late Triassic HREE-Mo-rich carbonatites in the northernmost Qinling orogen. The rocks contain abundant primary HREE minerals and molybdenite. Calcite-hosted fluid inclusions, inferred to represent a magmatic-derived aqueous fluid phase, contain significant concentrations of Mo (~17 ppm), reinforcing the inference that these carbonatitic magmas had high Mo concentrations. By contrast, Late Triassic carbonatites in southernmost Qinling have economic LREE concentrations, but are depleted in HREE and Mo. Both of these carbonatite types have low δ26Mg values (-1.89 to -1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution for REE enrichment in their mantle sources. We propose that the carbonatites in the Qinling orogen were formed, at least in part, by the melting of a subducted carbonate-bearing slab, and that 10 Ma younger carbonatite magmas in the northernmost Qinling metasomatized the thickened eclogitic lower crust to produce high levels of HREE and Mo.

Origin of unusual HREE-Mo-rich carbonatites in the Qinling orogen, China.

PubMed

Song, Wenlei; Xu, Cheng; Smith, Martin P; Kynicky, Jindrich; Huang, Kangjun; Wei, Chunwan; Zhou, Li; Shu, Qihai

2016-11-18

Carbonatites, usually occurring within intra-continental rift-related settings, have strong light rare earth element (LREE) enrichment; they rarely contain economic heavy REE (HREE). Here, we report the identification of Late Triassic HREE-Mo-rich carbonatites in the northernmost Qinling orogen. The rocks contain abundant primary HREE minerals and molybdenite. Calcite-hosted fluid inclusions, inferred to represent a magmatic-derived aqueous fluid phase, contain significant concentrations of Mo (~17 ppm), reinforcing the inference that these carbonatitic magmas had high Mo concentrations. By contrast, Late Triassic carbonatites in southernmost Qinling have economic LREE concentrations, but are depleted in HREE and Mo. Both of these carbonatite types have low δ 26 Mg values (-1.89 to -1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution for REE enrichment in their mantle sources. We propose that the carbonatites in the Qinling orogen were formed, at least in part, by the melting of a subducted carbonate-bearing slab, and that 10 Ma younger carbonatite magmas in the northernmost Qinling metasomatized the thickened eclogitic lower crust to produce high levels of HREE and Mo.

Mantle melting and melt refertilization beneath the Southwest Indian Ridge: Mineral composition of abyssal peridotites

NASA Astrophysics Data System (ADS)

Chen, Ling; Zhu, Jihao; Chu, Fengyou; Dong, Yan-hui; Liu, Jiqiang; Li, Zhenggang; Zhu, Zhimin; Tang, Limei

2017-04-01

As one of the slowest spreading ridges of the global ocean ridge system, the Southwest Indian Ridge (SWIR) is characterized by discontinued magmatism. The 53°E segment between the Gallieni fracture zone (FZ) (52°20'E) and the Gazelle FZ (53°30'E) is a typical amagmatic segment (crustal thickness <2km) (Zhou and Dick, 2013) that opens a window to the mantle thus provides a chance to detect the mantle composition directly. We examine the mineral compositions of 17 peridotite samples from the 53°E amagmatic segment. The results show that the peridotites can be divided into two groups. The Group 1 peridotites are characterized by clinopyroxenes having LREE depleted patterns that is typical for the abyssal peridotite, thus are thought to be the residue of the mantle melting. The Group 2 peridotites show the lowest HREE content within the SWIR peridotites but are anomaly enriched in LREE, with flat or U-type REE patterns, thus cannot be the pure residue of mantle melting. Mineral compositions of the Group 2 peridotites are more depleted than that of peridotites sampled near the Bouvet hot spot (Johnson et al., 1990), implying that the depleted mantle beneath the 53°E segment may be the residue of ancient melting event. This hypothesis is supported by the the low Ol/Opx ratios, coarse grain sizes (>1cm) Opx, and Mg-rich mineral compositions akin to harzburgite xenoliths that sample old continental lithospheric mantle (Kelemen et al., 1998). Melt refertilization model shows that Group 2 peridotites were affected by an enriched low-degree partial melt from the garnet stability field. These results indicate that depleted mantle which experiences ancient melting event are more sensitive to melt refertilization, thus may reduce the melt flux, leading to extremely thin crust at 53°E segment. This research was granted by the National Basic Research Programme of China (973 programme) (grant No. 2013CB429705) and the Fundamental Research Funds of Second Institute of Oceanography, State Oceanic Administration (JG1603, SZ1507). References: Johnson K T M, Dick H J B, Shimizu N. Melting in the oceanic upper mantle: An ion microprobe study of diopsides in abyssal peridotites[J]. Journal of Geophysical Research, 1990, 95(B3):2661-2678. Kelemen P B, Hart S R, Bernstein S. Silica enrichment in the continental upper mantle via melt/rock reaction[J]. Earth & Planetary Science Letters, 1998, 164(1-2):387-406. Zhou H, Dick H J. Thin crust as evidence for depleted mantle supporting the Marion Rise.[J]. Nature, 2013, 494(7436):195-200.

A three-dimensional model for lubricant depletion under sliding condition on bit patterned media of hard disk drives

NASA Astrophysics Data System (ADS)

Wu, Lin

2018-05-01

In this paper, we model the depletion dynamics of the molecularly thin layer of lubricants on a bit patterned media disk of hard disk drives under a sliding air bearing head. The dominant physics and consequently, the lubricant depletion dynamics on a patterned disk are shown to be significantly different from the well-studied cases of a smooth disk. Our results indicate that the surface tension effect, which is negligible on a flat disk, apparently suppresses depletion by enforcing a bottleneck effect around the disk pattern peak regions to thwart the migration of lubricants. When the disjoining pressure is relatively small, it assists the depletion. But, when the disjoining pressure becomes dominant, the disjoining pressure resists depletion. Disk pattern orientation plays a critical role in the depletion process. The effect of disk pattern orientation on depletion originates from its complex interaction with other intermingled factors of external air shearing stress distribution and lubricant particle trajectory. Patterning a disk surface with nanostructures of high density, large height/pitch ratio, and particular orientation is demonstrated to be one efficient way to alleviate the formation of lubricant depletion tracks.

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.

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.

Geochemistry of the Bonin Fore-arc Volcanic Sequence: Results from IODP Expedition 352

NASA Astrophysics Data System (ADS)

Godard, M.; Ryan, J. G.; Shervais, J. W.; Whattam, S. A.; Sakuyama, T.; Kirchenbaur, M.; Li, H.; Nelson, W. R.; Prytulak, J.; Pearce, J. A.; Reagan, M. K.

2015-12-01

The Izu-Bonin-Mariana intraoceanic arc system, in the western Pacific, results from ~52 My of subduction of the Pacific plate beneath the eastern margin of the Philippine Sea plate. Four sites were drilled south of the Bonin Islands during IODP Expedition 352 and 1.22 km of igneous basement was cored upslope to the west of the trough. These stratigraphically controlled igneous suites allow study of the earliest stages of arc development from seafloor spreading to convergence. We present the preliminary results of a detailed major and trace element (ICPMS) study on 128 igneous rocks drilled during Expedition 352. Mainly basalts and basaltic andesites were recovered at the two deeper water sites (U1440 and U1441) and boninites at the two westernmost sites (U1439 and U1442). Sites U1440 and U1441 basaltic suites are trace element depleted (e.g. Yb 4-6 x PM); they have fractionated REE patterns (LREE/HREE = 0.2-0.4 x C1-chondrites) compared to mid-ocean ridge basalts. They have compositions overlapping that of previously sampled Fore-Arc Basalts (FAB) series. They are characterized also by an increase in LILE contents relative to neighboring elements up-section (e.g. Rb/La ranging from <1 to 3-7 x PM at Site U1440) suggesting a progressive contamination of their source by fluids. This process in turn may have favored melting and efficient melt extraction from the source and thus its extreme depletion. Boninites are depleted in moderately incompatible elements with a decrease in their contents up-section (e.g. Yb = ~6.2 to 2.8 x C1-chondrite at Site U1439). These changes in trace element contents are associated with the development of a positive Zr-Hf anomaly relative to neighboring elements and a strong increase in LILE (e.g., Zr/Sm=~1 to 2.6 x PM and Rb/La=1-2 to 10-18). The progressive upward depletion of boninitic lavas could reveal the incorporation of harzburgitic residues from FAB generation into their mantle source.

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.

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

USGS Publications Warehouse

Wang, Jingyuan; Tatsumoto, M.; Li, X.; Premo, W.R.; Chao, E.C.T.

1994-01-01

We have obtained precise Th-Pb internal isochron ages on monazite and bastnaesite for the world's largest known rare earth elements (REE)-Fe-Nb ore deposit, the Bayan Obo of Inner Mongolia, China. The monazite samples, collected from the carbonate-hosted ore zone, contain extremely small amounts of uranium (less than 10 ppm) but up to 0.7% ThO2. Previous estimates of the age of mineralization ranged from 1.8 to 0.255 Ga. Magnetic fractions of monazite and bastnaesite samples (<60-??m size) showed large ranges in 232Th 204Pb values (900-400,000) and provided precise Th-Pb internal isochron ages for paragenetic monazite mineralization ranging from 555 to 398 Ma within a few percent error (0.8% for two samples). These results are the first indication that REE mineralization within the giant Bayan Obo ore deposit occurred over a long period of time. The initial lead isotopic compositions (low 206Pb 204Pb and high 208Pb 204Pb) and large negative ??{lunate}Nd values for Bayan Obo ore minerals indicate that the main source(s) for the ores was the lower crust which was depleted in uranium, but enriched in thorium and light rare earth elements for a long period of time. Zircon from a quartz monzonite, located 50 km south of the ore complex and thought to be related to Caledonian subduction, gave an age of 451 Ma, within the range of monazite ages. Textural relations together with the mineral ages favor an epigenetic rather than a syngenetic origin for the orebodies. REE mineralization started around 555 Ma (disseminated monazite in the West, the Main, and south of the East Orebody), but the main mineralization (banded ores) was related to the Caledonian subduction event ca. 474-400 Ma. ?? 1994.

Major and trace element investigation of the Pine Mountain massif--The southernmost exposure of Grenville age crust in North America

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

Salpas, P.A.; Daniell, N.

1992-01-01

The Pine Mountain massif is a 1.1 Ga basement massif exposed in Alabama and Georgia. The Whatley Mill Gneiss (WMG) constitutes a major exposure of rock in the Pine Mountain massif of eastern Alabama. Based on appearance in outcrop, the WMG can be divided into three distinct lithologies. The first is a massive augen gneiss (AG) consisting of K-spar augen in a finer grained matrix of biotite, K-spar, plagioclase, and quartz. The second lithology is a fine-grained gneiss (FG) composed predominantly of quartz with minor muscovite. The FG occurs sporadically as band of mylonite within the AG. The third lithologymore » is generally accepted to be the protolith of the AG. It is a relatively unfoliated and undeformed rock (UN) of sparse occurrence whose mineralogy is similar to that of the AG but also contains hornblende and rounded mafic inclusions of biotite gneiss. AG and FG samples were collected along a traverse through over 220 meters of stratigraphic thickness of the WMG and were analyzed for major element compositions by XRF and for trace element compositions by INAA. Relative to the AG samples, the FG samples are enriched in SiO[sub 2] and depleted in FeO and ferromagnesian trace elements such as Sc. REE concentrations are generally higher in the AG than in the FG but the sizes of the ranges in concentrations among both groups of rocks are similar. REE systematics indicate that the silica-rich fluid introduced into the AG during shearing appears to have made negligible contributions to the absolute and relative whole-rock REE concentrations but, instead, simply diluted the REE in the parent AG. Based upon the limited sampling of UN so far, deformation to produce the foliated AG, including augen formation, appears to have occurred isochemically.« less

The Sanfengshan copper deposit and early Carboniferous volcanogenic massive sulfide mineralization in the Beishan orogenic belt, Northwestern China

NASA Astrophysics Data System (ADS)

Wang, Jialin; Gu, Xuexiang; Zhang, Yongmei; Zhou, Chao; He, Ge; Liu, Ruiping

2018-03-01

The Sanfengshan copper deposit, located in the Beishan orogenic belt, Northwestern China, is hosted in the lower member of the Hongliuyuan Formation, an early Carboniferous metavolcanic-sedimentary sequence. Mineralization occurs as stratiform, stratiform-like and lenticular orebodies, and comprises of laminated, brecciated, banded, massive, and disseminated ores. The mineralogy is dominated by pyrite, chalcopyrite and sphalerite. Fe-Mn chert is widely distributed and generally occurs as massive, laminated, bands or lenses, which are consistent with the orebody. Alteration at Sanfengshan displays a clear concentric zoning pattern and the footwall alteration is more intense and somewhat thicker than the hanging-wall alteration. Systematic geochemical investigation on the volcanic rocks in this area shows that the basalts of the Hongliuyuan Formation (HLY) are predominantly tholeiites with nearly flat rare earth element (REE) pattern, insignificant negative anomalies of high field strength elements (HFSEs), and low Ti/V and Th/Nb ratios. They were most likely derived from partial melting of depleted asthenospheric mantle and formed in a fore-arc setting during initiation of the southward subduction of the Paleo-Asian Ocean. The basalts of the Maotoushan Formation (MTS) display a calc-alkaline nature and are enriched in large ion lithophile elements (LILEs) and depleted in HFSEs, suggesting an active continental margin setting. Sulfur isotope (δ34S) values of the sulfide and sulfate minerals vary between 0‰ and 5.4‰, which are consistent with sulfur derivation from leaching of the host volcanic rocks, although a direct magmatic contribution cannot be ruled out. The Re-Os isotope data of pyrite yield an isochron age of 353 ± 35 Ma, consistent with the age of the host HLY basalts. Thus, a syngenetic (volcanogenic massive sulfide) model is proposed and it is concluded that the Sanfengshan copper deposit is a typical Cyprus-type VMS deposit that formed in an early Carboniferous fore-arc setting in the Beishan orogenic belt.

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.

Origin of cratonic lithospheric mantle roots: A geochemical study of peridotites from the North Atlantic Craton, West Greenland

NASA Astrophysics Data System (ADS)

Wittig, N.; Pearson, D. G.; Webb, M.; Ottley, C. J.; Irvine, G. J.; Kopylova, M.; Jensen, S. M.; Nowell, G. M.

2008-09-01

A critical examination of the extent to which geodynamic information on the initial mantle depletion and accretion event(s) is preserved in kimberlite-borne cratonic SCLM peridotite xenoliths is attempted by using new major and trace element data of whole-rock peridotites ( n = 55) sampled across the North Atlantic Craton (NAC; West Greenland). We also present additional whole-rock trace element data of mantle xenoliths from Somerset Island, the Slave and Kaapvaal cratons for comparison. Peridotites comprising the West Greenland SCLM are distinctly more olivine-rich and orthopyroxene-poor than most other cratonic peridotites, in particular those from the Kaapvaal craton. The West Greenland peridotites have higher Mg/Si but lower Al/Si, Al 2O 3 and CaO than cratonic mantle from the Kaapvaal Craton. We suggest that the more orthopyroxene depleted, harzburgite to dunite character of the NAC peridotites reflects more of the original melting history than peridotites from other cratons and in that sense may be more typical of cratonic lithosphere compositions prior to extensive modification. Despite this, some modal and cryptic metasomatism has clearly taken place in the West Greenland lithosphere. The insensitivity of major elements to pressure of melting at high degrees of melt extraction combined with the ease with which these elements may be changed by modal metasomatism mean that we cannot confidently constrain the depth of melting of peridotites using this approach. Mildly incompatible trace elements offer much more promise in terms of providing geodynamic information about the original Archean melting regime. The very low, systematically varying heavy REE abundances in NAC whole-rock peridotites and in peridotites from all other cratons where high-quality data are available provide ubiquitous evidence for a shallow melting regime in the absence of, or to the exhaustion of garnet. This finding explicitly excludes large extents of deep (iso- and polybaric) melting, which results in high initial garnet abundances and increasing heavy REE abundances. This evidence renders models that invoke large plume-like melting environments redundant in explaining SCLM formation and suggests broadly modern plate tectonic environments are responsible for the depletion of cratonic SCLM. A combination of the shallow melting environment and uniformly high levels of depletion indicate that melting to form the NAC lithosphere and that of other cratons probably took place in a subduction-zone environment.

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.

On the nature and origin of garnet in highly-refractory Archean lithosphere: implications for continent stabilisation

NASA Astrophysics Data System (ADS)

Gibson, Sally

2014-05-01

The nature and timescales of garnet formation in the Earth's subcontinental lithospheric mantle (SCLM) are important to our understanding of how this rigid outer shell has evolved and stabilised since the Archean. Nevertheless, the widespread occurrence of pyrope garnet in the sub-cratonic mantle remains one of the 'holy grails' of mantle petrology. The paradox is that garnet often occurs in mantle lithologies (dunites and harzburgites) which represent residues of major melting events (up to 40 %) whereas experimental studies on fertile peridotite suggest this phase should be exhausted by <20 % melting. Furthermore, garnets commonly found in mantle peridotite suites have diverse compositions that are typically in equilibrium with high-pressure, small-fraction, mantle melts suggesting they formed as a result of enrichment of the lithospheric mantle following cratonisation. This refertilisation -- which typically involves addition of Fe, incompatible trace elements and volatiles -- affects the lower 30 km of the lithosphere and potentially leads to negative buoyancy and destabilisation. Pyrope garnets found in mantle xenoliths from the eastern margin of the Tanzanian Craton (Lashaine) have diverse compositions and provide major constraints on how the underlying deep (120 to 160 km) mantle stabilised and evolved during the last 3 billion years. The garnets display systematic trends from ultra-depleted to enriched compositions that have not been recognised in peridotite suites from elsewhere (Gibson et al., 2013). Certain harzburgite members of the xenolith suite contain the first reported occurrence of pyrope garnets with rare-earth element (REE) patterns similar to hypothetical garnets proposed by Stachel et al. (2004) to have formed in the Earth's SCLM during the Archean, prior to metasomatism. These rare ultra-depleted low-Cr garnets occur in low temperature (~1050 oC) xenoliths derived from depths of ~120 km and coexist in chemical and textural equilibrium with highly-refractory olivine (Fo95.4) and orthopyroxene (Mg#=96.4). These phases are all more magnesian than generally encountered in global samples of depleted mantle, i.e. harzburgites and diamond inclusion suites. The Tanzanian ultra-depleted garnets form interconnecting networks ('necklaces') around grains of orthopyroxene, which is of key importance to their origin. This close spatial relationship of garnet and orthopyroxene together with the major, trace and REE contents of the ultra-depleted garnets, are consistent with an origin by isochemical exsolution. The significance of ultra-depleted low-Cr garnets has not previously been recognised in global suites of mantle xenoliths or diamond inclusions: they appear to have been overlooked, primarily because of their unusual pre-metasomatic compositions. We believe they are rare because the low concentrations of trace elements make them readily susceptible to geochemical overprinting. This highly-refractory low-density peridotite may be common in the 'shallow' SCLM but is not normally brought to the surface by ascending melts, which tend to metasomatise and preferentially sample their source regions. The modal abundance of garnet formed by isochemical exsolution from orthopyroxene in sub-cratonic mantle is unclear but may prove to be an important consideration in isopycnic models related to the long-term stability of the Earth's continental lithosphere, e.g. Lee et al. (2011). Gibson, S. A., McMahon, S. C., Day, J. A. & Dawson, J. B. (2013). Highly Refractory Lithospheric Mantle beneath the Tanzanian Craton: Evidence from Lashaine Pre-metasomatic Garnet-bearing Peridotites. J. Petrol. doi:10.1093/petrology/egt020 Stachel, T., Aulbach, A., Brey, G.P., Harris, J.W., Leost, I., Tappert, R. & Viljoen, K.S. (2004). The trace element composition of silicate inclusions in diamonds: a review. Lithos 77, 1-19 Lee, C.-T., Luffi, P. & Chin, E. J. (2011). Building and Destroying Continental Mantle. Annu. Rev. Earth Planet. Sci. 39, 59-90

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.

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.

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.

Use of arsenic and REE in black shales as potential environmental tracers in hydraulic fracturing operations

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Haley, B. A.; McKay, J. L.; Algeo, T. J.; Hakala, A.; Joseph, C.; Edenborn, H. M.

2013-12-01

Black shales commonly targeted for shale gas development were deposited under low oxygen concentrations, and typically contain high As levels. The depositional environment governs its solid-phase association in the sediment, which in turn will influence degree of remobilization during hydraulic fracturing. Organic carbon (OC), trace element (TE) and REE distributions have been used as tracers for assessing deep water redox conditions at the time of deposition in the Midcontinent Sea of North America (Algeo and Heckel, 2008), during large-scale oceanic anoxic events (e.g., Bunte, 2009) and in modern OC-rich sediments underlying coastal upwelling areas (e.g., Brumsack, 2006). We will present REE and As data from a collection of six different locations in the continental US (Kansas, Iowa, Oklahoma, Kentucky, North Dakota and Pennsylvania), ranging in age from Devonian to Upper Pennsylvanian, and from a Cretaceous black shale drilled on the Demerara Rise during ODP Leg 207. We interpret our data in light of the depositional framework previously developed for these locations based on OC and TE patterns, to document the mechanisms leading to REE and As accumulation, and explore their potential use as environmental proxies and their diagenetic remobilization during burial, as part of our future goal to develop a predictive evaluation of arsenic release from shales and transport with flowback waters. Total REE abundance (ΣREE) ranged from 35 to 420 ppm in an organic rich sample from Stark shale, KS. PAAS-normalized REE concentrations ranged from 0.5 to 7, with the highest enrichments observed in the MREE (Sm to Ho). Neither the ΣREE nor the MREE enrichments correlated with OC concentrations or postulated depositional redox conditions, suggesting a principal association with aluminosilicates and selective REE fractionation during diagenesis. In the anoxic reducing environments in which black shales were deposited, sulfide minerals such as FeS2 trap aqueous arsenic in the crystal lattice, but As is also known to bind to the charged surfaces of clay minerals. Our arsenic concentration data show that the highest abundances (up to 70 ppm) are found in sediments with the highest total sulfur concentration (to 2.6 ppm), but there was no clear correlation with organic carbon or aluminosilicate content. We compare our results with preliminary data from a series of flowback waters sampled from ten producing wells in Pennsylvania and from high-pressure high-temperature experimental leaching of Marcellus shale samples.

Petrogenesis of metaultramafic rocks from the Quadrilátero Ferrífero and adjacent terrains, Minas Gerais, Brazil: Two events of ultramafic magmatism?

NASA Astrophysics Data System (ADS)

da Fonseca, Gabriela Magalhães; Jordt-Evangelista, Hanna; Queiroga, Gláucia Nascimento

2018-03-01

In the worldwide known Quadrilátero Ferrífero and the adjacent terrains, southeastern Brazil, many serpentinite and soapstone quarries, and some rare bodies of metaultramafic rocks that partially preserve minerals or textures from the original igneous protolith can be found. It is not known if the protoliths and the ages of the metaultramafic rocks found in the Quadrilátero Ferrífero (and its oriental basement) and Mineiro Belt regions are the same or if they represent distinct magmatic episodes. The petrogenetic investigation, specially concerning the REE contents, aimed to gather informations about the type of magmatism and the mantle source in order to compare the metaultramafic rocks of both regions. The interpretation of the data concerning petrography, mineral chemistry and geochemistry shows that the metaultramafic rocks are similar to komatiitic peridotites, with MgO contents > 22 wt % and TiO2 < 0.9 wt %. The plot of the REE for the lithotypes found in the Quadrilátero Ferrífero shows decrease in LREE possibly reflecting the depletion of the mantle source. On the other hand the samples from the Mineiro Belt are enriched in LREE suggesting a mantle source enriched in these elements. This enrichment may have been caused by mantle metassomatism that occurred during accretion of the Paleoproterozoic magmatic arc that generated the Mineiro belt. In this paper, we therefore suggest two periods of ultramafic magmatism. The first one found in the Archean basement of the Quadrilátero Ferrífero, with a depleted mantle source. The second occurred in the Paleoproterozoic basement of the Mineiro belt, having a metassomatized mantle as source.

Carbon-oxygen isotopes and rare earth elements as an exploration vector for Carlin-type gold deposits: A case study of the Shuiyindong gold deposit, Guizhou Province, SW China

NASA Astrophysics Data System (ADS)

Tan, Qin-Ping; Xia, Yong; Wang, Xueqiu; Xie, Zhuo-Jun; Wei, Dong-Tian

2017-10-01

The Shuiyindong gold deposit is a deeply concealed strata-bound Carlin-type deposit in southwestern Guizhou Province, China. The deposit lies on the eastern limb of the Huijiabao anticline with ores mainly along the anticline axis and hosted in bioclastic limestone, containing calcite veins, of the Permian Longtan Formation units. In this study, we measured carbon and oxygen isotopic ratios and rare earth element (REE) concentrations of the host rocks and calcite veins along a profile across the Shuiyindong deposit. Orebodies in the upper unit of the Longtan Formation have higher δ18O values (20.6-22.4‰) and lower δ13C values (-3.7 to -0.5‰) than the country rocks (δ18O: 18.8-21.4‰; δ13C: -0.7 to 0.8‰). However, there are no obvious trends of δ18O and δ13C values from the country rocks to the orebodies in the middle unit of the Longtan Formation. The spatial distribution of the calcite veins displays distinct halos of δ13C and δ18O values and REE concentrations. Calcite veins along the anticlinal axis and major reverse fault are enriched in Middle REE (Sm, Eu, Gd, and Tb) and 18O and depleted in 13C. Surficial veining calcite-filled fractures/faults that connect to deep concealed strata-bound gold mineralization systems can be vectors toward deep ores in southwestern Guizhou Province, China.

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).

Genesis of the central zone of the Nolans Bore rare earth element deposit, Northern Territory, Australia

NASA Astrophysics Data System (ADS)

Schoneveld, Louise; Spandler, Carl; Hussey, Kelvin

2015-08-01

The Nolans Bore rare earth element (REE) deposit consists of a network of fluorapatite-bearing veins and breccias hosted within Proterozoic granulites of the Reynolds Range, Central Australia. Mineralisation is divided into three zones (north, central, and south-east), with the north and south-east zones consisting of massive REE-bearing fluorapatite veins, with minor brecciation and carbonate infill. The central zone is distinctively different in mineralogy and structure; it features extensive brecciation, a high allanite content, and a large, epidote-rich enveloping alteration zone. The central zone is a reworking of the original solid apatite veins that formed during the Chewings Orogeny at ca. 1525 Ma. These original apatite veins are thought to derive from phosphate-rich magmatic-hydrothermal fluid exsolved from as-yet unrecognised alkaline magmatic bodies at depth. We define four ore breccia types (BX1-4) in the central zone on the basis of detailed petrological and geochemical analysis of drillcore and thin sections. BX1 ore comprises fluorapatite with minor crackle brecciation with carbonate infill and resembles ore of the north and south-east zones. Breccia types BX2, BX3, and BX4 represent progressive stages of ore brecciation and development of calc-silicate mineral (amphibole, epidote, allanite, calcite) infill. Comparison of bulk ore sample geochemistry between breccia types indicates that REEs were not mobilised more than a few centimetres during hydrothermal alteration and brecciation. Instead, most of the REEs were partitioned from the original REE fluorapatite into newly formed allanite, REE-poor fluorapatite and minor REE carbonate in the breccias. Negative europium (Eu) anomalies in the breccia minerals are accounted for by a large positive Eu anomaly in epidote from the alteration zones surrounding the ore breccias. This observation provides a direct link between ore recrystallisation and brecciation, and the formation of the alteration halo in the surrounding host rocks. Where allanite and fluorapatite are texturally related, the fluorapatite is relatively depleted in the light rare earth elements (LREEs), whereas allanite is relatively LREE enriched, suggesting co-crystallisation. We tentatively date the BX1 ore stage to 1440 ± 80 Ma based on U-Pb dating of thorianite. Sm-Nd isotope isochrons derived from in situ isotope analysis of cognate apatite and allanite date the BX2 and BX3 events to ca. 400 Ma, while U-Pb dating of late-stage monazite from the BX4 ore stage returned an age of ca. 350 Ma. Therefore, formation of the central zone at Nolans Bore involved multiple alteration/brecciation events that collectively span over 1 billion years in duration. We suggest that the BX1-type veins and breccias were formed from REE-rich, saline (F- and Cl-bearing) fluids that infiltrated the granulite-grade host rocks in association with either shear activation events of the Redbank Shear Zone (1500-1400 Ma) or intrusion of late-stage pegmatites of the Mt Boothby area. BX2, BX3, and BX4 events record deformation and hydrothermal alteration associated with the Alice Springs Orogeny (400-350 Ma). These hydrothermal events occurred at temperatures of 450 to ~600 °C, due to inflow of highly acidic hydrous fluids derived from a magmatic source, or from mixing of meteoric and metamorphic fluids. Our data testify to the long and complex geological history of not only the Nolans Bore REE deposit, but also of the rocks of the eastern Reynolds Range, and demonstrate the great utility of using hydrothermally derived REE minerals to trace the timing of crustal deformation events and source of associated hydrothermal fluids.

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.

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.

Petrography and geochemistry of the primary ore zone of the Kenticha rare metal granite-pegmatite field, Adola Belt, Southern Ethiopia: Implications for ore genesis and tectonic setting

NASA Astrophysics Data System (ADS)

Mohammedyasin, Mohammed Seid; Desta, Zerihun; Getaneh, Worash

2017-10-01

The aim of this work is to evaluate the genesis and tectonic setting of the Kenticha rare metal granite-pegmatite deposit using petrography and whole-rock geochemical analysis. The samples were analysed for major elements, and trace and rare earth elements by ICP-AES and ICP-MS, respectively. The Kenticha rare metal granite-pegmatite deposit is controlled by the N-S deep-seated normal fault that allow the emplacement of the granite-pegmatite in the study area. Six main mineral assemblages have been identified: (a) alaskitic granite (quartz + microcline + albite with subordinate muscovite), (b) aplitic layer (quartz + albite), (c) muscovite-quartz-microcline-albite pegmatite, (d) spodumene-microcline-albite pegmatite, partly albitized or greisenized, (e) microcline-albite-green and pink spodumene pegmatite with quartz-microcline block, which is partly albitized and greisenized, and (f) quartz core. This mineralogical zonation is also accompanied by variation in Ta ore concentration and trace and rare earth elements content. The Kenticha granite-pegmatite is strongly differentiated with high SiO2 (72-84 wt %) and enriched with Rb (∼689 ppm), Be (∼196 ppm), Nb (∼129 ppm), Ta (∼92 ppm) and Cs (∼150 ppm) and depleted in Ba and Sr. The rare earth element (REE) patterns of the primary ore zone (below 60 m depth) shows moderate enrichment in light REE ((La/Yb)N = ∼8, and LREE/HREE = ∼9.96) and negative Eu-anomaly (Eu/Eu* = ∼0.4). The whole-rock geochemical data display the Within Plate Granite (WPG) and syn-Collisional Granite (syn-COLG) suites and interpret as its formation is crustal related melting. The mineralogical assemblage, tectonic setting and geochemical signatures implies that the Kenticha rare metal bearing granite pegmatite is formed by partial melting of metasedimentary rocks during post-Gondwana assembly and further tantalite enrichment through later hydrothermal-metasomatic processes.

Trondhjemitic leucosomes in paragneisses from NE Sardinia: Geochemistry and P-T conditions of melting and crystallization

NASA Astrophysics Data System (ADS)

Fancello, D.; Cruciani, G.; Franceschelli, M.; Massonne, H.-J.

2018-04-01

The sedimentary-derived migmatites from Porto Ottiolu consist of mesosomes and tonalitic to trondhjemitic leucosomes. These rocks contain quartz + plagioclase + muscovite + biotite in different proportions and locally fibrolite, K-feldspar and kyanite relicts. The contact between leucosomes and mesosomes is commonly marked by mm- to cm-thick melanosomes mainly formed by oriented biotite and fibrolite, muscovite, and variable amounts of quartz and plagioclase. Pressure-temperature (P-T) modeling using pseudosections and their contouring by isopleths for modal abundances of minerals and melt and Si/Al and Na/K ratios of the melt suggests that anatexis occurred at 700 °C and 1.1 GPa with the contribution of 2 wt% of free water. The complete crystallization of the leucosome melt was finalized at P-T conditions of 640-690 °C and 0.40-0.55 GPa. The leucosomes are folded or parallel to the S2 schistosity indicating their pre to syn-D2 formation. The leucosomes are enriched in SiO2, CaO, Na2O, Sr and depleted in Fe2O3, MgO, TiO2, K2O, Rb, Ba, Cr, V, Zr, Nb, and REE, except Eu, compared to the surrounding mesosomes. The high CaO contents up to 3.3 wt%, the low K2O contents (mean 0.57 wt%) and Rb/Sr ratios (<0.15), and the moderately fractionated REE pattern with positive Eu anomalies support the formation of water-fluxed melts from a sedimentary source. Mica segregation during crystallization of the melt and/or disequilibrium melting contributed to the geochemical signature of these leucosomes. Especially the former process is responsible for the very low K content in the leucosomes and the mismatch between measured and predicted Si/Al and Na/K ratios in the leucosomes without mica segregation.

Geochemistry and Temperatures Recorded by Zircon During the Final Stages of the Youngest Toba Tuff Magma Chamber, Sumatra, Indonesia

NASA Astrophysics Data System (ADS)

Gaither, T.; Reid, M. R.; Vazquez, J. A.

2009-12-01

The ~74 ka eruption of the Youngest Toba Tuff (YTT) in Sumatra, Indonesia, was one of the largest single volcanic eruptions in geologic history, on par with other voluminous silicic eruptions such as the Huckleberry Ridge Tuff of Yellowstone and the Bishop Tuff of Long Valley, California. We are exploring how zircon and other accessory mineral phases record compositional and thermal changes that occurred in the YTT magma, and the important clues these crystal scale records hold for magma chamber dynamics and processes that lead up to supervolcano eruptions. In this study, we report trace element (REE, U, Th, Ti, and Hf) characteristics, Ti-in-zircon crystallization temperatures, and apparent REE partition coefficients obtained for YTT zircon rims. Twenty-nine zircons from pumices with a compositional range of 70-76 wt% SiO2 were analyzed on the UCLA Cameca ims 1270 ion microprobe. The grains were mounted so that only the outermost ~1.5 microns of the crystals were analyzed. Median Zr/Hf ratios of 34 to 38 characterize zircons from the pumices; the high silica rhyolite grains have lower Zr/Hf. Chondrite-normalized REE patterns are strongly LREE-depleted. Positive Ce anomalies are large (Ce/Ce* ranges up to 88) and Eu/Eu* varies by a factor of four (0.05 to 0.21). Eu/Eu*, Nd/Yb, and Th/U decrease with decreasing Zr/Hf, showing that the variation in zircon rim compositions may be related by co-precipitation of feldspar and allanite along with zircon. Titanium contents also decrease with decreasing Zr/Hf, suggesting that the chemical differences could be related to temperature changes. REE partition coefficients calculated from zircon rim compositions and pumice glass compositions give a good fit to a lattice strain model. They are also quite similar to the partition coefficients of Sano et al. (2002) which have been shown to be successful at reproducing melt compositions in other settings. Temperatures of crystallization calculated using the Ti-in-zircon geothermometer (Watson et al., 1996), assuming a melt aTiO2 of 0.5, yield very low median values (even without a possible pressure correction of -40 to -80°C), ranging from 640-667°C. Virtually all of the zircon rims record temperatures lower than eruption temperatures of 700-780°C estimated for the YTT by Chesner (1998) using FeTi oxide equilibria. It is possible that the low zircon temperatures reflect uncertainties in the Ti-in-zircon geothermometer but they are nonetheless permissive of re-entrainment of zircon from a near-solidus mush close to the time of eruption. The analytically significant chemical variations within the individual zircon populations, especially those of Zr/Hf, Eu/Eu*, and Nd/Yb, suggest that crystals from distinct compositional domains were brought together during a final merging/coalescence of magma that catalyzed the eruption.

A middle Permian ophiolite fragment in Late Triassic greenschist- to blueschist-facies rocks in NW Turkey: An earlier pulse of suprasubduction-zone ophiolite formation in the Tethyan belt

NASA Astrophysics Data System (ADS)

Topuz, Gültekin; Okay, Aral I.; Schwarz, Winfried H.; Sunal, Gürsel; Altherr, Rainer; Kylander-Clark, Andrew R. C.

2018-02-01

The Eastern Mediterranean region within the Tethyan belt is characterised by two main pulses of suprasubduction-zone ophiolite formation during the Early-Middle Jurassic and Late Cretaceous. Despite vast exposures of the Permo-Triassic accretionary complexes, related suprasubduction-zone ophiolites and the timing of subduction initiation leading to the formation of Permo-Triassic accretionary complexes are unknown so far. Here we report on a 40 km long and 0.3 to 1.8 km wide metaophiolite fragment within transitional greenschist- to blueschist-facies oceanic rocks from NW Turkey. The metaophiolite fragment is made up mainly of serpentinite and minor dykes or stocks of strongly sheared metagabbro with mineral assemblages involving actinolite/winchite, chlorite, epidote, albite, titanite and phengite. The metagabbro displays (i) variable CaO and MgO contents, (ii) anomalously high Mg# (= 100 ∗ molar MgO/(MgO + FeOtot)) of 75-88, and (iii) positive Eu anomalies, together with low contents of incompatible elements such as Ti, P and Zr, suggesting derivation from former plagioclase cumulates. The serpentinites comprise serpentine, ± chlorite, ± talc, ± calcite and relict Cr-Al spinel surrounded by ferrichromite to magnetite. Relict Cr-Al spinels are characterised by (i) Cr/(Cr + Al) ratios of 0.45-0.56 and Mg/(Mg + Fe2 +) ratio of 0.76-0.22, (ii) variable contents of ZnO and MnO, and (iii) extremely low TiO2 contents. Zn and Mn contents are probably introduced into Cr-Al spinels during greenschist- to blueschist metamorphism. Compositional features of the serpentinite such as (i) Ca- and Al-depleted bulk compositions, (ii) concave U-shaped, chondrite-normalised rare earth element patterns (REE) with enrichment of light and heavy REEs, imply that serpentinites were probably derived from depleted peridotites which were refertilised by light rare earth element enriched melts in a suprasubduction-zone mantle wedge. U-Pb dating on igneous zircons from three metagabbro samples indicates igneous crystallisation at 262 Ma (middle Permian). Timing of the metamorphism is constrained by incremental 40Ar/39Ar dating on phengitic white mica at 201 Ma (latest Triassic). We conclude that the metaophiolite represents a fragment of middle Permian suprasubduction-zone oceanic lithosphere, involved in a latest Triassic subduction zone. These data, together with several reports in literature, indicate that the middle Permian was a time of suprasubduction-zone ophiolite formation in the Tethyan belt.

Pliocene to late Pleistocene magmatism in the Aurora Volcanic Field, Nevada and California, USA

NASA Astrophysics Data System (ADS)

Kingdon, S.; Cousens, B.; John, D. A.; du Bray, E. A.

2013-12-01

The 3.9- 0.1 Ma Aurora Volcanic Field (AVF) covers 325 km2 east and southeast of the Bodie Hills, north of Mono Lake, California, USA. The AVF is located immediately northwest of the Long Valley magmatic system and adjacent and overlapping the Miocene Bodie Hills Volcanic Field (BHVF). Rock types range from trachybasalt to trachydacite, and high-silica rhyolite. The trachybasalts to trachydacites are weakly to moderately porphyritic (1-30%) with variable phenocryst assemblages that are some combination of plagioclase, hornblende, clinopyroxene, and lesser orthopyroxene, olivine, and/or biotite. Microphenocrysts are dominated by plagioclase, and include opaque oxides, clinopyroxene, and apatite. These rocks are weakly to strongly devitrified. The high-silica rhyolites are sparsely porphyritic with trace to 10% phenocrysts of quartz, sanidine, plagioclase, biotite, (+/- hornblende), accessory opaque oxide minerals, titanite, allanite, (+/-apatite, zircon), and have glassy groundmasses. Rocks in the AVF are less strongly porphyritic than those of BHVF. Plagioclase phenocrysts are often oscillatory zoned and many have sieve texture. Amphiboles have distinct black opaque rims. Xenocrystic quartz and plagioclase are rare. AVF lavas have bimodal SiO2 compositions, ranging from 49 to 78 wt%, with a gap between 65 and 75 wt%. They are high-K calc-alkaline to shoshonitic in composition, and are metaluminous to weakly peraluminous. They are enriched in rare earth elements (REE), especially light REEs, compared to the Miocene BHVF rocks. Primordial mantle-normalized incompatible element patterns show arc- or subduction-related signatures, with enrichment in Ba and Pb, and depletion in Nb and Ta. Enrichment in K and Sr and depletion in Ti are less pronounced than in the BHVF rocks. There is no correlation between lead isotope ratios and silica (initial 206Pb/204Pb ratios range from 18.974 to 19.151). Neodymium isotope ratios show a moderate negative correlation with silica within the range of 50 to 75 wt% SiO2 (initial 143Nd/144Nd ratios range from 0.51238 to 0.51258, and ɛNdt ranges from -1.09 to -4.01). Strontium ratios show a strong positive correlation with silica for SiO2 above 50 wt% (initial 87Sr/86Sr ratios range from 0.70513 to 0.70691). Pb, Nd, and Sr isotope compositions do not systematically change with time. The Aurora volcanic rocks are interpreted to be postsubduction erupted from an extensional tectonic setting. Compared with the BHVF rocks, the AVF rocks are more radiogenic and crustal assimilation is a more influential process.

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.

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

Origin of unusual HREE-Mo-rich carbonatites in the Qinling orogen, China

PubMed Central

Song, Wenlei; Xu, Cheng; Smith, Martin P.; Kynicky, Jindrich; Huang, Kangjun; Wei, Chunwan; Zhou, Li; Shu, Qihai

2016-01-01

Carbonatites, usually occurring within intra-continental rift-related settings, have strong light rare earth element (LREE) enrichment; they rarely contain economic heavy REE (HREE). Here, we report the identification of Late Triassic HREE-Mo-rich carbonatites in the northernmost Qinling orogen. The rocks contain abundant primary HREE minerals and molybdenite. Calcite-hosted fluid inclusions, inferred to represent a magmatic-derived aqueous fluid phase, contain significant concentrations of Mo (~17 ppm), reinforcing the inference that these carbonatitic magmas had high Mo concentrations. By contrast, Late Triassic carbonatites in southernmost Qinling have economic LREE concentrations, but are depleted in HREE and Mo. Both of these carbonatite types have low δ26Mg values (−1.89 to −1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution for REE enrichment in their mantle sources. We propose that the carbonatites in the Qinling orogen were formed, at least in part, by the melting of a subducted carbonate-bearing slab, and that 10 Ma younger carbonatite magmas in the northernmost Qinling metasomatized the thickened eclogitic lower crust to produce high levels of HREE and Mo. PMID:27857170

Light rare earth element depletion during Deepwater Horizon blowout methanotrophy.

PubMed

Shiller, A M; Chan, E W; Joung, D J; Redmond, M C; Kessler, J D

2017-09-04

Rare earth elements have generally not been thought to have a biological role. However, recent work has demonstrated that the light REEs (LREEs: La, Ce, Pr, and Nd) are essential for at least some methanotrophs, being co-factors in the XoxF type of methanol dehydrogenase (MDH). We show here that dissolved LREEs were significantly removed in a submerged plume of methane-rich water during the Deepwater Horizon (DWH) well blowout. Furthermore, incubation experiments conducted with naturally methane-enriched waters from hydrocarbon seeps in the vicinity of the DWH wellhead also showed LREE removal concurrent with methane consumption. Metagenomic sequencing of incubation samples revealed that LREE-containing MDHs were present. Our field and laboratory observations provide further insight into the biochemical pathways of methanotrophy during the DWH blowout. Additionally, our results are the first observations of direct biological alteration of REE distributions in oceanic systems. In view of the ubiquity of LREE-containing MDHs in oceanic systems, our results suggest that biological uptake of LREEs is an overlooked aspect of the oceanic geochemistry of this group of elements previously thought to be biologically inactive and an unresolved factor in the flux of methane, a potent greenhouse gas, from the ocean.

Rb-Sr and Sm-Nd Isotopic Studies of Martian Depleted Shergottes SaU 094/005

NASA Technical Reports Server (NTRS)

Shih, C.-Y.; Nyquist, L. E.; Reese, Y.

2007-01-01

Sayh al Uhaymir (SaU) 094 and SaU 005 are olivine-phyric shergottites from the Oman desert and are considered as pairs. [e.g., 1]. They are very similar to the Libyan desert shergottite Dar al Gani (DaG) 476 in petrology, chemistry and ejection age [2-6]. This group of shergottites, also recognized as depleted shergottites [e.g. 7] has been strongly shocked and contains very low abundances of light rare earth elements (REE). In addition, terrestrial contaminants are commonly present in meteorites found in desert environments. Age-dating these samples is very challenging, but lower calcite contents in the SaU meteorites suggest that they have been subjected to less severe desert weathering than their DaG counterparts [3-4]. In this report, we present Rb-Sr and Sm-Nd isotopic results for SaU 094 and SaU 005, discuss the correlation of their ages with those of other similar shergottites, and discuss their petrogenesis.

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.

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.

Petrogenesis of meta-volcanic rocks from the Maimón Formation (Dominican Republic): Geochemical record of the nascent Greater Antilles paleo-arc

NASA Astrophysics Data System (ADS)

Torró, Lisard; Proenza, Joaquín A.; Marchesi, Claudio; Garcia-Casco, Antonio; Lewis, John F.

2017-05-01

Metamorphosed basalts, basaltic andesites, andesites and plagiorhyolites of the Early Cretaceous, probably pre-Albian, Maimón Formation, located in the Cordillera Central of the Dominican Republic, are some of the earliest products of the Greater Antilles arc magmatism. In this article, new whole-rock element and Nd-Pb radiogenic isotope data are used to give new insights into the petrogenesis of the Maimón meta-volcanic rocks and constrain the early evolution of the Greater Antilles paleo-arc system. Three different groups of mafic volcanic rocks are recognized on the basis of their immobile element contents. Group 1 comprises basalts with compositions similar to low-Ti island arc tholeiites (IAT), which are depleted in light rare earth elements (LREE) and resemble the forearc basalts (FAB) and transitional FAB-boninitic basalts of the Izu-Bonin-Mariana forearc. Group 2 rocks have boninite-like compositions relatively rich in Cr and poor in TiO2. Group 3 comprises low-Ti island arc tholeiitic basalts with near-flat chondrite-normalized REE patterns. Plagiorhyolites and rare andesites present near-flat to subtly LREE-depleted chondrite normalized patterns typical of tholeiitic affinity. Nd and Pb isotopic ratios of plagiorhyolites, which are similar to those of Groups 1 and 3 basalts, support that these felsic lavas formed by anatexis of the arc lower crust. Geochemical modelling points that the parental basic magmas of the Maimón meta-volcanic rocks formed by hydrous melting of a heterogeneous spinel-facies mantle source, similar to depleted MORB mantle (DMM) or depleted DMM (D-DMM), fluxed by fluids from subducted oceanic crust and Atlantic Cretaceous pelagic sediments. Variations of subduction-sensitive element concentrations and ratios from Group 1 to the younger rocks of Groups 2 and 3 generally match the geochemical progression from FAB-like to boninite and IAT lavas described in subduction-initiation ophiolites. Group 1 basalts likely formed at magmatic stages transitional between FAB and first-island arc magmatism, whereas Group 2 boninitic lavas resulted from focused flux melting and higher degrees of melt extraction in a more mature stage of subduction. Group 3 basalts probably represent magmatism taking place immediately before the establishment of a steady-state subduction regime. The relatively high extents of flux melting and slab input recorded in the Maimón lavas support a scenario of hot subduction beneath the nascent Greater Antilles paleo-arc. Paleotectonic reconstructions and the markedly depleted, though heterogeneous character of the mantle source, indicate the rise of shallow asthenosphere which had sourced mid-ocean ridge basalts (MORB) and/or back-arc basin basalts (BABB) in the proto-Caribbean domain prior to the inception of SW-dipping subduction. Relative to the neighbouring Aptian-Albian Los Ranchos Formation, we suggest that Maimón volcanic rocks extruded more proximal to the vertical projection of the subducting proto-Caribbean spreading ridge.

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.

The southwestern extension of the Jiao-Liao-Ji belt in the North China Craton: Geochronological and geochemical evidence from the Wuhe Group in the Bengbu area

NASA Astrophysics Data System (ADS)

Liu, Chaohui; Zhao, Guochun; Liu, Fulai; Cai, Jia

2018-04-01

The Wuhe complex is located at the southeastern margin of the North China Craton. The complex consists of metamorphosed Paleoproterozoic potassic granitoids and supracrustal rocks, of which the latter include the Fengyang and Wuhe groups. Meta-mafic rocks from the lower Wuhe Group have igneous zircon U-Pb ages of 2126 ± 37 Ma with εHf(t) values of -6.22 to +8.38, and xenocrystic zircons of 2.39-2.36 Ga, 2.55-2.54 Ga and 2.77-2.69 Ga. Geochemically, the meta-mafic rocks can be classified into two groups. Group 1 island arc tholeiites display flat to slightly right declined REE patterns and moderately negative Nb, Ta, Zr, and Ti anomalies. Group 2 mature arc calcalkaline basalts display strongly fractionated chondrite-normalized REE patterns and evidently negative Nb, Ta and Ti anomalies. These meta-mafic rocks formed by partial melting of sub-arc depleted mantle wedge which had been modified by slab-derived melts at an active continental margin. Depositional age of the group can be constrained in the period of 2.16-2.10 Ga based on ages of the youngest detrital zircons and latter intrusions. U-Pb ages of detrital zircons yield major age peaks of 2.69 Ga and 2.52 Ga, with minor peaks at 2.88 Ga, 2.78 Ga, 2.35 Ga and 2.17 Ga, most of which are derived from the late Mesoarchean to early Paleoproterozoic granitoids in the Wuhe complex and the Jiaodong Terrane. Metamorphic zircons in the marbles coexisting with garnet amphibolites or granulites occur as either single grains or overgrowth (or recrystallization) rims surrounding magmatic zircon cores and yield ages of 1882 ± 19 Ma to 1844 ± 15 Ma. The comparable ca. 2.1 Ga potassic granites with A-type granite affinity, the ca. 2.1 Ga meta-mafic rocks with arc-like geochemical features, the 2.1-1.9 Ga meta-sedimentary units and the 1.9-1.8 Ga subduction- and collision-related granulite-facies metamorphism suggest that the Wuhe complex and the Jiao-Liao-Ji Belt share the same late Paleoproterozoic tectonic evolution process and the former is the southwestern extension of the latter.

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.

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.

Geochemical fingerprinting of ∼2.5 Ga forearc-arc-backarc related magmatic suites in the Bastar Craton, central India

NASA Astrophysics Data System (ADS)

Asthana, Deepanker; Kumar, Sirish; Vind, Aditya Kumar; Zehra, Fatima; Kumar, Harshavardhan; Pophare, Anil M.

2018-05-01

The Pitepani volcanic suite of the Dongargarh Supergroup, central India comprises of a calc-alkaline suite and a tholeiitic suite, respectively. The rare earth element (REE) patterns, mantle normalized plots and relict clinopyroxene chemistry of the Pitepani calc-alkaline suite are akin to high-Mg andesites (HMA) and reveal remarkable similarity to the Cenozoic Setouchi HMA from Japan. The Pitepani HMAs are geochemically correlated with similar rocks in the Kotri-Dongargarh mobile belt (KDMB) and in the mafic dykes of the Bastar Craton. The rationale behind lithogeochemical correlations are that sanukitic HMAs represent fore-arc volcanism over a very limited period of time, under abnormally high temperature conditions and are excellent regional and tectonic time markers. Furthermore, the tholeiitic suites that are temporally and spatially associated with the HMAs in the KDMB and in the mafic dykes of the Bastar Craton are classified into: (a) a continental back-arc suite that are depleted in incompatible elements, and (b) a continental arc suite that are more depleted in incompatible elements, respectively. The HMA suite, the continental back-arc and continental arc suites are lithogeochemically correlated in the KDMB and in the mafic dykes of the Bastar Craton. The three geochemically distinct Neoarchaean magmatic suites are temporally and spatially related to each other and to an active continental margin. The identification of three active continental margin magmatic suites for the first time, provides a robust conceptual framework to unravel the Neoarchaean geodynamic evolution of the Bastar Craton. We propose an active continental margin along the Neoarchaen KDMB with eastward subduction coupled with slab roll back or preferably, ridge-subduction along the Central Indian Tectonic Zone (CITZ) to account for the three distinct magmatic suites and the Neoarchean geodynamic evolution of the Bastar Craton.

Hydrothermal alteration in oceanic ridge volcanics: A detailed study at the Galapagos Fossil Hydrothermal Field

USGS Publications Warehouse

Ridley, W.I.; Perfit, M.R.; Josnasson, I.R.; Smith, M.F.

1994-01-01

The Galapagos Fossil Hydrothermal Field is composed of altered oceanic crust and extinct hydrothermal vents within the eastern Galapagos Rift between 85??49???W and 85??55???W. The discharge zone of the hydrothermal system is revealed along scarps, thus providing an opportunity to examine the uppermost mineralized, and highly altered interior parts of the crust. Altered rocks collected in situ by the submersible ALVIN show complex concentric alteration zones. Microsamples of individual zones have been analysed for major/minor, trace elements, and strontium isotopes in order to describe the complex compositional details of the hydrothermal alteration. Interlayered chlorite-smectite and chlorite with disequilibrium compositions dominate the secondary mineralogy as replacement phases of primary glass and acicular pyroxene. Phenocrysts and matrix grains of plagioclase are unaffected during alteration. Using a modification of the Gresens' equation we demonstrate that the trivalent rare earth elements (REEs) are relatively immobile, and calculate degrees of enrichment and depletion in other elements. Strontium isotopic ratios increase as Sr concentrations decrease from least-altered cores to most-altered rims and cross-cutting veins in individual samples, and can be modeled by open system behaviour under low fluid-rock ratio (< 10) conditions following a period of lower-temperature weathering of volcanics within the rift zone. The complex patterns of element enrichment and depletion and strontium isotope variations indicate mixing between pristine seawater and ascending hot fluids to produce a compositional spectrum of fluids. The precipitation of base-metal sulfides beneath the seafloor is probably a result of fluid mixing and cooling. If, as suggested here, the discharge zone alteration occurred under relatively low fluid-rock ratios, then this shallow region must play an important role in determining the exit composition of vent fluids in marine hydrothermal systems. ?? 1994.

Chemical evidence for differentiation, evaporation and recondensation from silicate clasts in Gujba

NASA Astrophysics Data System (ADS)

Oulton, Jonathan; Humayun, Munir; Fedkin, Alexei; Grossman, Lawrence

2016-03-01

The silicate and metal clasts in CB chondrites have been inferred to form as condensates from an impact-generated vapor plume between a metal-rich body and a silicate body. A detailed study of the condensation of impact-generated vapor plumes showed that the range of CB silicate clast compositions could not be successfully explained without invoking a chemically differentiated target. Here, we report the most comprehensive elemental study yet performed on CB silicates with 32 silicate clasts from nine slices of Gujba analyzed by laser ablation inductively coupled plasma mass spectrometry for 53 elements. Like in other studies of CBs, the silicate clasts are either barred olivine (BO) or cryptocrystalline (CC) in texture. In major elements, the Gujba silicate clasts ranged from chondritic to refractory enriched. Refractory element abundances ranged from 2 to 10 × CI, with notable anomalies in Ba, Ce, Eu, and U abundances. The two most refractory-enriched BO clasts exhibited negative Ce anomalies and were depleted in U relative to Th, characteristic of volatilization residues, while other BO clasts and the CC clasts exhibited positive Ce anomalies with excess U (1-3 × CI), and Ba (1-6 × CI) anomalies indicating re-condensation of ultra-refractory element depleted vapor. The Rare Earth Elements (REE) also exhibit light REE (LREE) enrichment or depletion in several clasts with a range of (La/Sm)CI of 0.9-1.8. This variation in the LREE is essentially impossible to accomplish by processes involving vapor-liquid or vapor-solid exchange of REE, and appears to have been inherited from a differentiated target. The most distinctive evidence for inherited chemical differentiation is observed in highly refractory element (Sc, Zr, Nb, Hf, Ta, Th) systematics. The Gujba clasts exhibit fractionations in Nb/Ta that correlate positively with Zr/Hf and span the range known from lunar and Martian basalts, and exceed the range in Zr/Hf variation known from eucrites. Variations of highly incompatible refractory elements (e.g., Th) against less incompatible elements (e.g., Zr, Sr, Sc) are not chondritic, but exhibit distinctly higher Th abundances requiring a differentiated crust to be admixed with depleted mantle in ratios that are biased to higher crust/mantle ratios than in a chondritic body. The possibility that these variations are due to admixture of refractory inclusion-debris into normal chondritic matter is raised but cannot be definitively tested because existing ;bulk; analyses of CAIs carry artifacts of unrepresentative sampling. The inferences drawn from the compositions of Gujba silicate clasts, here, complement what has been inferred from the compositions of metallic clasts, but provide surprisingly detailed insight into the structure of the target. Evidence that metal and silicate in CB chondrites both formed from impact-generated vapor plumes, taken together with recent work on metallic nodules in E chondrites, and on ordinary chondrites, indicates that chondrule formation occurs by this mechanism quite widely. However, the nature of the impact on the CB body is quite different than the popular conceptions of impact of partially or wholly molten chondritic bodies and the younger (5 Ma) age of CB chondrules is consistent with origin in a disk with more evolved targets and impactors gravitationally perturbed by nascent planets.

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.

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.

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.

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.

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.

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.

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.

Volume gain during shearing of the Whatley Mill Gneiss, Pine Mountain Basement massif, eastern Alabama--A trace element approach

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

Salpas, P.A.; Daniell, N.

1993-03-01

The Whatley Mill Gneiss is the most voluminous exposure of the Pine Mountain Basement massif in eastern Alabama. Its type lithology is a proto-mylonitic gneiss composed of K-spar augen, up to 5 cm in diameter, in a finer matrix of biotite, microcline, and quartz. Granulite-facies mineral assemblages in the Whatley Mill Gneiss have been completely retrograded to amphibolite- and greenschist-facies assemblages in response to deformation that produced shear zones paralleling the foliation of the gneiss. The augen gneiss and its associated mylonites are well-exposed in a creek bed in Chewacla State Park. At this location the mineralogy of the mylonitesmore » is dominated by quartz indicating that shearing was associated with influx of a silica-rich fluid. A detailed geochemical study of these rocks shows that the augen gneiss displays relatively little variation in its major and trace element compositions while the quartz-rich mylonites display wider ranges, are enriched in SiO[sub 2] and depleted in the REE and other incompatible trace elements relative to the augen gneiss. When standard composition/volume calculations are applied to the mylonites the results show (1) the bulk of all of the elements, including the REE, were immobile during shearing with the exceptions of Si and Al which were added; and, (2) volume changes calculated using the REE as immobile elements range from +70% to +350%. Though these volume changes seem excessive, they apply to meter-thick shear zones which may actually represent only a small fraction of the total volume of the augen gneiss. Consistent with previous interpretations of these shear zones, the calculated volume gains imply shearing during extension.« less

Geochemistry, geochronology, and tectonic setting of Early Cretaceous volcanic rocks in the northern segment of the Tan-Lu Fault region, northeast China

NASA Astrophysics Data System (ADS)

Ling, Yi-Yun; Zhang, Jin-Jiang; Liu, Kai; Ge, Mao-Hui; Wang, Meng; Wang, Jia-Min

2017-08-01

We present new geochemical and geochronological data for volcanic and related rocks in the regions of the Jia-Yi and Dun-Mi faults, in order to constrain the late Mesozoic tectonic evolution of the northern segment of the Tan-Lu Fault. Zircon U-Pb dating shows that rhyolite and intermediate-mafic rocks along the southern part of the Jia-Yi Fault formed at 124 and 113 Ma, respectively, whereas the volcanic rocks along the northern parts of the Jia-Yi and Dun-Mi faults formed at 100 Ma. The rhyolite has an A-type granitoid affinity, with high alkalis, low MgO, Ti, and P contents, high rare earth element (REE) contents and Ga/Al ratios, enrichments in large-ion lithophile (LILEs; e.g., Rb, Th, and U) and high-field-strength element (HFSEs; e.g., Nb, Ta, Zr, and Y), and marked negative Eu anomalies. These features indicate that the rhyolites were derived from partial melting of crustal material in an extensional environment. The basaltic rocks are enriched in light REEs and LILEs (e.g., Rb, K, Th, and U), and depleted in heavy REEs, HFSEs (e.g., Nb, Ta, Ti, and P), and Sr. These geochemical characteristics indicate that these rocks are calc-alkaline basalts that formed in an intraplate extensional tectonic setting. The dacite is a medium- to high-K, calc-alkaline, I-type granite that was derived from a mixed source involving both crustal and mantle components in a magmatic arc. Therefore, the volcanic rocks along the Jia-Yi and Dun-Mi faults were formed in an extensional regime at 124-100 Ma (Early Cretaceous), and these faults were extensional strike-slip faults at this time.

Comparison of Estimated Energy Requirements in Severely Burned Patients With Measurements by Using Indirect Calorimetry

PubMed Central

Tancheva, D.; Arabadziev, J.; Gergov, G.; Lachev, N.; Todorova, S.; Hristova, A.

2005-01-01

Summary Severe burn injuries give rise to an extreme state of physiological stress. No other trauma results in such an accelerated rate of tissue catabolism, loss of lean body mass, and depletion of energy and protein reserves. A heightened attention to energy needs is essential, and the significance of adequate nutritional support in the complex management of patients with major burns is very important. The purpose of this study is to compare the results obtained by three of the most popular methods of estimating energy requirements in severely burned adult patients with the measurements of resting energy (REE) expenditure by indirect calorimetry (IC). A prospective study was carried out of 20 patients (male/female ratio, 17/3; mean age, 37.83 ± 10.86 yr), without accompanying morbidities, with burn injuries covering a mean body surface area of 34.27 ± 11.55% and a mean abbreviated burn severity index of 7.44 ± 1.58. During the first 30 days after trauma, the energy requirements were estimated using the Curreri, Long, and Toronto formulas. Twice weekly measurements of REE by IC were obtained. It was found that the Curreri and Long formulas overestimated the energy requirements in severely burned patients, as found by other investigators. However, no significant difference was found between the daily energy requirements calculated by the Toronto formula and the measured REE values by IC. It is concluded that the Toronto formula can be used as an alternative method for estimating the energy requirements of patients with major burns in cases where IC is not available or not applicable. PMID:21990973

Geochemical (LA-ICP-MS) investigations of baddeleyite from the Palaeoproterozoic mafic and Palaeozoic alkaline intrusions in the Arctic part of the Baltic shield

NASA Astrophysics Data System (ADS)

Drogobuzhskaya, Svetlana; Bayanova, Tamara; Novikov, Andrey

2017-04-01

Baddeleyite is a zirconium dioxide mineral, which is very important, but less common as zircon. While the zircon microelementary composition study is widely applicable, the baddeleyite geochemical features are poorly known. The first data on REE concentrations and distribution in baddeleyite were published in the past century. Baddeleyite is used as a geochronometer for dating mafic and alkaline rocks. It may be noted that the data on its geochemical composition are quite contradictory with a strongly varying Ce anomaly value and absent Eu anomaly in some samples. The new data on the elementary composition of baddeleyite (REE, Hf, U, Th, Y, and Ti) from the Monchegorsk pluton mafic rocks (2.5 Ga) and Kovdor and Vuoriyarvi deposits (380 Ma) was obtained. The sample morphology was studied using an electronic spectroscopy method (Hitachi S-430), and the position of local analysis on baddeleyite crystals was chosen based on analyzed optic images of minerals. The content of REE and other elements was measured using LA-ICP-MS technique on quadrupole mass-spectrometer ELAN 9000 DRC-e (Perkin Elmer) with laser evaporator UP-266 MACRO (New Wave Research) with a wave length of 266 nm for sampling. The laser ablation was made in argon atmosphere in a 35 and 70 μm diameter spot or when scanning to a line with a pulse repetition rate of 10 Hz and pulse energy of 14-15 J/cm2. The device was calibrated using the NIST SRM 612 standard with a REE, U, and Th concentration of about 40 ppm. The baddeleyite from reference rocks of mafic intrusions are characterized by medium concentrations of Hf (0.69-1.9 %), Th (7.6-21.1), REE (50.3-162), U (164-357), Y (5.0-149) ppm for the sample M-2 from Monchegorsk. Another rocks of alkaline intrusions are depleted in Th (0.25-5.9), REE (9.2-103), U (1.8-48.1), Y(2.9-65.9) ppm and Hf (0.20-1.9%) for the sample Bd-400 from Vuoriyarvi and Hf (0.18-1.3 %), Th (0.4-5.2), REE (2.1-17.7), U (4.2-32.6), Y(2.2-68.4) ppm for the samples Bd-300 and Bd-300 prism. from Kovdor. The titanium content in the samples widely varies being 10-37 ppm for sample Bd-300 and 28-72 ppm for Bd-300 prism., 47-150 ppm for sample Bd-400 and 0.31-0.79% for older baddeleyite M-2. The average baddeleyite crystallization and U-Pb system closure temperature calculated using a zircon-applied method is 804-888°C (Kovdor) and 984°C (Vuoriyarvi). The baddeleyite from the Monchegorsk pluton has shown high crystallization temperatures of about 1,000 degrees centigrade. The research is supported by RFBR Grant No. 16-05-00305 and dedicated to the blessed memory of mentors: academicians of the RAS V.T. Kalinnikov and F.P. Mitrofanov.

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.

Slab and Sediment Melting during Subduction Initiation: Mantle Plagiogranites from the Oman Ophiolite

NASA Astrophysics Data System (ADS)

Rollinson, H. R.

2014-12-01

Granitoid dykes up to several hundred metres wide and 2 km long are found in depleted harzburgites in the mantle section of the Oman ophiolite. They vary in composition from tonalite to potassic granite and are generally more potassic than the crustal plagiogranites found within the sheeted dyke complex higher up within the ophiolite stratigraphy. Some granites are strongly peraluminous and contain garnet and andalusite. They are geochemically variable, some with REE that are relatively unfractionated ((La/Yb)n= 3.5-6.0, flat middle to heavy REE, steep light REE) to those which are highly fractionated ((La/Yb)n= 28-220). On primitive-mantle normalised plots some have very high concentrations of fluid-mobile elements - Cs, Rb, Th, U and Pb. Few have significant Ta-Nb anomalies. On the Ca-Fe-Mg-Ti discrimination diagram of Patino Douce (J. Petrol., 1999) whole-rock compositions define a spectrum between felsic-pelite derived melts and amphibolite-derived melts. There is a chemical similarity between the least REE fractionated plagiogranites (generally tonalites and granodiorites) and melts of an amphibolitic parent. This is supported by the occurrence of mafic xenoliths in some dykes, the presence of hornblende and highly calcic cores (up to An85) in some plagioclase grains. Trace element modelling using Oman Geotimes lavas as the starting composition indicates that melting took place in the garnet stability field, although enrichment in the melt in Cs, Rb, Ba and Pb suggests that there was another component present in addition to the mafic parent. Other plagiogranites (trondhjemites and granites) have a strongly peraluminous chemistry and mineralogy and geochemical similarities with the Himalayan leucogranites implying that they were derived from a sedimentary protolith. These mantle plagiogranites are more prevalent in the northern outcrops of the ophiolite. The volume of granitoid melt and the depth of melting preclude their derivation from the sole of the ophiolite, rather they were derived during subduction by the partial melting of the slab and associated sediment and emplaced into the overlying mantle wedge. Current subduction-initiation models for supra-subduction ophiolites should integrate this process into their thinking.

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.

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.

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.

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.

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.

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.

Geochemistry and geochronology of the Mesozoic Lanong ophiolitic mélange, northern Tibet: Implications for petrogenesis and tectonic evolution

NASA Astrophysics Data System (ADS)

Zhong, Yun; Liu, Wei-Liang; Xia, Bin; Liu, Jing-Nan; Guan, Yao; Yin, Zhen-Xing; Huang, Qiang-Tai

2017-11-01

The Lanong ophiolitic mélange is a typical ophiolitic mélange in the middle section of the Bangong-Nujiang suture zone in northern Tibet. It mainly consists of ultramafic and mafic rocks, and its tectonic setting and formation age remain poorly constrained. In this paper, new geochemical and LA-ICP-MS (laser ablation-inductively coupled plasma mass spectrometer) zircon U-Pb age data obtained from gabbro, gabbro-dolerite, dolerite and basalt of the Lanong ophiolitic mélange are provided. The pillow basalts exhibit N-MORB (normal mid-ocean ridge basalt)-like geochemical features with a zircon U-Pb age of 147.6 ± 2.3 Ma. They were generated by 20-30% partial melting of a depleted mantle source composed of spinel lherzolite. The gabbro, massive basalt and gabbro-dolerite samples are characterised by more depleted and "V"-shaped REE (rare earth element) patterns, and they exhibit variable degrees of boninite-like geochemical characteristics, with a zircon U-Pb age of 149.1 ± 1.2 Ma (gabbro-dolerite). They were derived from the remelting of a significantly refractory mantle source following one or more episodes of previous basaltic melt extraction. Geochemical data of these mafic rocks indicate that they were developed in a continental fore-arc setting, and magmas were derived from depleted mantle sources modified by subducted slab-derived fluids and melts with minor crustal contamination. On the other hand, the dolerites show distinct OIB (oceanic island basalt)-like geochemical features, with a zircon U-Pb age of 244.1 ± 3.0 Ma. They were formed in a rift setting on a continental shelf-slope and originated from a low degree of partial melting of a depleted asthenospheric magma source mixed with some ancient sub-continental lithospheric mantle materials. The signatures presented here, combined with the results of previous studies, suggest that the Lanong ophiolitic mélange probably developed in a convergent plate margin under the southward subduction of the Bangong-Nujiang Tethys Ocean beneath the Lhasa terrane during the Middle Triassic-Early Cretaceous. Namely, the OIB-like dolerites likely reflect an extensional rift setting featuring thin continental crust in the Middle Triassic, and the gabbros, gabbro-dolerites and basalts represent a later stage of a fore-arc basin during the Late Jurassic-Early Cretaceous.

Petrology, geochemistry and Resbnd Os isotopes of peridotite xenoliths from Maguan, Yunnan Province: Implications for the Cenozoic mantle replacement in southwestern China

NASA Astrophysics Data System (ADS)

Liu, Chuan-Zhou; Wu, Fu-Yuan; Sun, Jing; Chu, Zhu-Yin; Yu, Xue-Hui

2013-05-01

Petrology, geochemistry and Resbnd Os isotopes of peridotite xenoliths from Maguan (Yunnan Province) are reported in this paper with the aims of constraining the age and evolution of the lithospheric mantle beneath the western margin of the Cathyasia block. The Maguan mantle xenoliths contain predominantly fertile lherzolites with whole-rock Al2O3 contents of 2.42-4.99 wt.%, and subordinate clinopyroxene-poor lherzolites with Al2O3 contents of 1.19-1.98 wt.%. Their whole-rock CaO, Al2O3 and Na2O decrease along with the increase of MgO, following melt depletion trends. This suggests that the Maguan lherzolites represent mantle residues after variable degrees of partial melting. Clinopyroxenes in the fertile lherzolites display flat to depleted REE patterns, whereas those in the clinopyroxene-poor lherzolites are variably enriched in LREE. Modeling results of Y and Yb contents in clinopyroxenes suggest that the fertile lherzolites have experienced ~ 1-5% degrees of partial melting, in contrast with ~ 10-15% for the clinopyroxene-poor lherzolites. Both fertile and clinopyroxene-poor lherzolites have similarly high equilibrium temperatures, i.e., 911-1120 °C versus 919-941 °C, respectively. The whole-rock 187Os/188Os ratios of clinopyroxene-poor lherzolites vary from 0.11764 to 0.12506, which are slightly lower than most fertile lherzolites (0.12272-0.12854). Their 187Os/188Os ratios show no correlation with 187Re/188Os ratios or bulk-rock Al2O3 contents. The rhenium depletion ages (TRD) of the lherzolites range from 0.15 to 1.08 Ga, whereas the clinopyroxene-poor lherzolites have TRD ages of 0.64-1.67 Ga. This suggests the co-existence of Phanerozoic and Proterozoic mantle beneath the western Cathyasia block. Alternatively, the whole lithospheric mantle beneath Maguan was likely formed during the Phanerozoic, given the resemblance of their Os isotopic ratios with those of abyssal peridotites. The latter explanation is consistent with the fact that all the studied samples plot along the oceanic trend in a plot of olivine modes versus Fo contents. We suggest that the enriched mantle that was existed beneath the western Cathyasia block during the Late Cretaceous or Eocene-Oligocene has been replaced by juvenile and depleted mantle, which probably occurred during the Cenozoic.

Thorium partitioning in Greek industrial bauxite investigated by synchrotron radiation and laser-ablation techniques

NASA Astrophysics Data System (ADS)

Gamaletsos, P.; Godelitsas, A.; Mertzimekis, T. J.; Göttlicher, J.; Steininger, R.; Xanthos, S.; Berndt, J.; Klemme, S.; Kuzmin, A.; Bárdossy, G.

2011-12-01

Typical red-brown (Fe-rich) and high-quality white-grey (Fe-depleted) bauxite samples from active mines of the Parnassos-Ghiona area, central Greece, were investigated. According to XRF and ICP-MS analyses their actinide content, and particularly of Th, is relatively increased. Fe-depleted samples contain up to 62.75 ppm Th corresponding to 220 Bq/kg due to 228Ac ( 232Th-series), whereas Fe-rich samples are less Th-radioactive (up to 58.25 ppm Th, 180 Bq/kg due to 228Ac). Powder-XRD patterns showed that Th-enriched (Fe-depleted) bauxite consists mostly of diaspore (AlOOH polymorph), anatase and rutile (TiO 2 polymorphs). SEM-EDS indicated the presence of Ti-Fe-containing phases (e.g. ilmenite, FeTiO 3), chromite (Cr-spinel) and besides LREE-minerals (mostly bastnäsite/parisite-group) and zircon (ZrSiO 4) hosting a part of the bulk Th. The presence of Th in diaspore and in Ti-containing phases (not detected by SEM-EDS as in the case of REE-minerals and zircon) was investigated, into distinct pisoliths of Fe-depleted bauxite, using μ-XRF and μ-XAFS in the SUL-X beamline of the ANKA Synchrotron facility (KIT, Germany). XAFS spectra of Th salts and Th-containing reference materials were obtained as well. Accordingly it was revealed, for the first time in the literature, that Ti-phases, and particularly anatase, host significant amounts of Th. This novel conclusion was complementary supported by LA-ICP-MS analyses indicated an average of 73 ppm Th in anatase grains together with abundant Nb (3356 ppm), Ta (247 ppm) and U (33 ppm). The Th LIII-edge XAFS spectra as compared to reference materials, give also evidence that Th 4+ may not replace Ti 4+ in distorted [TiO 6] fundamental octahedral units of anatase and ilmenite lattice (CN = 6). The occupation of either extraframework sites of higher coordination (CN = 6.9 or even CN = 7.4), according to EXAFS signals evaluation, or of defected/vacant (**) sites is more probable. This is likely explained by the difficulty of Th 4+ to replace directly Ti 4+ in [6]-coordinated (octahedral) sites due to the large difference in the relevant ionic radii (0.940 and 0.605 Å respectively).

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.

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

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.

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.

Applying a new understanding of supergene REE deposit formation to global exploration initiatives for environmentally sustainable resources

NASA Astrophysics Data System (ADS)

Hardy, Liam; Smith, Martin; Hood, Leo; Heller, Shaun; Faltyn, Rowan; Blum, Astrid; Bamberger, Axel

2017-04-01

Two new models have recently been proposed for the formation of REE ion-adsorption deposits and it is likely that they are both active in their related study profiles described in the Ambohimirahavavy Complex in Madagascar (Marquis et al, 2016) and the Serra de Monchique (SDM) complex in Portugal (Hardy et al, 2016). These are two separate environments presenting two different soil systems in terms of flora, protolith and structure. In the latosol profiles of SDM the natural sweating cycle of eucalyptus trees is proposed as the main geochemical cycling control for some 40% of Fe and 30% of Y, which have been observed migrating up and down profile seasonally between upper horizons and the rooting depths of these intensively farmed trees. If, through their natural cycle, eucalyptus trees in SDM are capable of concentrating depleted protolithic Y contents of 4-10ppm to some 140-160ppm in their enriched 150-200cm deep E horizons in only the 40 years since they were introduced to the region (Jenkins, 1979), then what potential deposits and concentrations may lay underneath older plantations across Brazil, Chile, China and most importantly, Australia, where these trees naturally cover some 16% of the entire continent. Eucalyptus is mostly farmed as pulp for paper mills and has lost its market value with the demand for paper decreasing, as the demand for REEs increases, ironically driven by the demand for the accessible technology to replace paper (EPA, 2012). Not only might there be great resources below these forests, but the removal of the aggressive intrusive species would be welcomed across Southern Europe and South America where they have limited market value and have destroyed local ecosystems and water supplies (Brito, 1999), where local people are actively seeking an alternative use of their lands. References: Brito, J. G. (1999). Management strategies for conservation of the lizard Lacerta schreiberi in Portugal. Biological conservation, 311-319. EPA. (2012). Rare earth elements: A review of production, processing, recycling and associated environmental issues; EPA600/R-12/572. United States Environmental Protection Agency. Hardy, L. (2016). A novel mechanism for the formation of REE ion-adsorption deposits. Presented to: MDSG Winter Meeting, Bristol University, 20/12/16. Jenkins, R. (1979). The Road to Alto: An account of peasants, capitalists and their soil in the mountains of Southern Portugal. London: Pluto, ISBN: 0861040767. Marquis, E. (2016). Ion Adsorption-Type REE Deposit associated with the Ambohimirahavavy Alkaline Complex: Potential Controls on Mineralisation. Presented to: MDSG Winter Meeting, Bristol University, 20/12/16.

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.

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.

Space-time patterns in ignimbrite compositions revealed by GIS and R based statistical analysis

NASA Astrophysics Data System (ADS)

Brandmeier, Melanie; Wörner, Gerhard

2017-04-01

GIS-based multivariate statistical and geospatial analysis of a compilation of 890 geochemical and ca. 1,200 geochronological data for 194 mapped ignimbrites from Central Andes documents the compositional and temporal pattern of large volume ignimbrites (so-called "ignimbrite flare-ups") during Neogene times. Rapid advances in computational sciences during the past decade lead to a growing pool of algorithms for multivariate statistics on big datasets with many predictor variables. This study uses the potential of R and ArcGIS and applies cluster (CA) and linear discriminant analysis (LDA) on log-ratio transformed spatial data. CA on major and trace element data allows to group ignimbrites according to their geochemical characteristics into rhyolitic and a dacitic "end-members" and differentiates characteristic trace element signatures with respect to Eu anomaly, depletion of MREEs and variable enrichment in LREE. To highlight these distinct compositional signatures, we applied LDA to selected ignimbrites for which comprehensive data sets were available. The most important predictors for discriminating ignimbrites are La (LREE), Yb (HREE), Eu, Al2O3, K2O, P2O5, MgO, FeOt and TiO2. However, other REEs such as Gd, Pr, Tm, Sm and Er also contribute to the discrimination functions. Significant compositional differences were found between the older (>14 Ma) large-volume plateau-forming ignimbrites in northernmost Chile and southern Peru and the younger (< 10 Ma) Altiplano-Puna-Volcanic-Complex ignimbrites that are of similar volumes. Older ignimbrites are less depleted in HREEs and less radiogenic in Sr isotopes, indicating smaller crustal contributions during evolution in thinner and thermally less evolved crust. These compositional variations indicate a relation to crustal thickening with a "transition" from plagioclase to amphibole and garnet residual mineralogy between 13 to 9 Ma. We correlate compositional and volumetric variations to the N-S passage of the Juan-Fernandéz ridge and crustal shortening and thickening during the past 26 Ma. The value of GIS and multivariate statistics in comparison to traditional geochemical parameters are highlighted working with large datasets with many predictors in a spatial and temporal context. Algorithms implemented in R allow taking advantage of an n-dimensional space and, thus, of subtle compositional differences contained in the data, while space-time patterns can be analyzed easily in GIS.

Trace-element record in zircons during exhumation from UHP conditions, North-East Greenland Caledonides

USGS Publications Warehouse

McClelland, W.C.; Gilotti, J.A.; Mazdab, F.K.; Wooden, J.L.

2009-01-01

Coesite-bearing zircon formed at ultrahigh-pressure (UHP) conditions share general characteristics of eclogite-facies zircon with trace-element signatures characterized by depleted heavy rare earth elements (HREE), lack of an Eu anomaly, and low Th/ U ratios. Trace-element signatures of zircons from the Caledonian UHP terrane in North-East Greenland were used to examine the possible changes in signature with age during exhumation. Collection and interpretation of age and trace-element analyses of zircon from three samples of quartzofeldspathic gneiss and two leucocratic intrusions were guided by core vs. rim zoning patterns as imaged by cathodoluminesence. Change from igneous to eclogite-facies metamorphic trace-element signature in protolith zircon is characterized by gradual depletion of HREE, whereas newly formed metamorphic rims have flat HREE patterns and REE concentrations that are distinct from the recrystallized inherited cores. The signature associated with eclogite-facies metamorphic zircon is observed in coesite-bearing zircon formed at 358 ?? 4 Ma, metamorphic rims formed at 348 ?? 5 Ma during the initial stages of exhumation, and metamorphic rims formed at 337 ?? 5 Ma. Zircons from a garnet-bearing granite emplaced in the neck of an eclogite boudin and a leucocratic dike that cross-cuts amphibolite-facies structural fabrics have steeply sloping HREE patterns, variably developed negative Eu anomalies, and low Th/U ratios. The granite records initial decompression melting and exhumation at 347 ?? 2 Ma and later zircon rim growth at 329 ?? 5. The leucocratic dike was likely emplaced at amphibolite-facies conditions at 330 ?? 2 Ma, but records additional growth of compositionally similar zircon at 321 ??2 Ma. The difference between the trace-element signature of metamorphic zircon in the gneisses and in part coeval leucocratic intrusions indicates that the zircon signature varies as a function of lithology and context, thus enhancing its ability to aid in the interpretation of U-Pb data and track the exhumation history of UHP terranes. The differences may reflect variation in elemental availability through breakdown reactions in quartzofeldpathic gneiss vs. availability during melt production and/or crystallization. UHP rocks in North-East Greenland began exhumation by 347 ?? 2 Ma, were still at HP eclogite-facies conditions at 337 ?? 5 Ma and were at amphibolite-facies conditions by 330 ?? 2 Ma. ?? 2009 E. Schweizerbart'sche Verlagsbuchhandlung.

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.

Two major Cenozoic episodes of phosphogenesis recorded in equatorial Pacific seamount deposits

USGS Publications Warehouse

Hein, J.R.; Hsueh-Wen, Yeh; Gunn, S.H.; Sliter, W.V.; Benninger, L.M.; Chung-Ho, Wang

1993-01-01

The phosphorites occur in a wide variety of forms, but most commonly carbonate fluorapatite (CFA) replaced middle Eocene and older carbonate sediment in a deep water environment (>1000 m). Element ratios distinguish seamount phosphorites from continental margin, plateau, and insular phosphorites. Uranium and thorium contents are low and total rare earch element (REE) contents are generally high. The paleoceanographic conditions initiated and sustained development of phosphorite by accumulation of dissolved phosphorus in the deep sea during relatively stable climatic conditions when oceanic circulation was sluggish. Fluctuations in climate, sealevel, and upwelling that accompanied the climate transitions may have driven cycles of enrichment and depletion of the deep-sea phosphorus reservoir. -from Authors

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.

REE mobility during the alteration of Carbonatite and their economic potential.

NASA Astrophysics Data System (ADS)

Marien, Christian; Dijkstra, Arjan; Wilkins, Colin

2016-04-01

The supply risk of Rare Earth Elements is an unpredictable economic factor for the future application and development of modern technology for the EU. Therefore a better understanding of REE mobilisation during hydrothermal alteration of Carbonatites is essential for a safer supply of REE in general. The hydrothermal alteration of Carbonatite within the Fen Complex (Norway) forms a fine grained red hematized rock type, called Rødbergite, which is partially enriched in REE. The variation of REE within the Rødbergite is poorly understood and problematic for any future REE exploitation from Rødbergite. A genetic model of the formation of Rødbergite will provide more information about the economic potential of Rødbergite. The gradual transformation of carbonatite to Rødbergite is not easily observable due to sparse outcrop in the Fen Complex. A fresh road cut near the Bjørndallen farm (Fen Complex) provides a unique insight to the progressive hydrothermal alteration from carbonatite to Rødbergite and is therefore crucial for a genetic model of the formation of Rødbergite. 14 Samples were taken along the profile. The mineralogical, geochemical and textural characterization of the samples using the SEM as well as major-, trace- and isotopic elemental data revealed the breakdown of the primary minerals due to the infiltration of an oxidizing fluid along grain boundaries. The primary REE-minerals in unaltered Carbonatite are REE fluorocarbonates. With the increasing alteration to Rødbergite REE fluorocarbonates are progressively replaced by hematite. In contrast, monazite - a REE-phosphate - is the dominant REE mineral species in the Rødbergite. A transitional Rødbergite sample shows apatite aggregates with a strong preferential concentration of monazite along the rim of the apatite aggregates. This observation provides strong evidence for the solution of REE in the primary rock (carbonatite) by fluids and later precipitation of REE along phosphate bearing minerals (e.g. apatite) in order to form monazite. The latest results of the mineralogical investigation on the structural control of the REE mineralization, different generations of REE minerals and the potential concentration of REE in distinct zones in the profile, will also be presented. Future work will contribute to a better understanding of the REE mineralization process and therefore help to identify economically promising areas for a potential REE exploitation within the Fen Complex.

Energy Expenditure in Critically Ill Elderly Patients: Indirect Calorimetry vs Predictive Equations.

PubMed

Segadilha, Nara L A L; Rocha, Eduardo E M; Tanaka, Lilian M S; Gomes, Karla L P; Espinoza, Rodolfo E A; Peres, Wilza A F

2017-07-01

Predictive equations (PEs) are used for estimating resting energy expenditure (REE) when the measurements obtained from indirect calorimetry (IC) are not available. This study evaluated the degree of agreement and the accuracy between the REE measured by IC (REE-IC) and REE estimated by PE (REE-PE) in mechanically ventilated elderly patients admitted to the intensive care unit (ICU). REE-IC of 97 critically ill elderly patients was compared with REE-PE by 6 PEs: Harris and Benedict (HB) multiplied by the correction factor of 1.2; European Society for Clinical Nutrition and Metabolism (ESPEN) using the minimum (ESPENmi), average (ESPENme), and maximum (ESPENma) values; Mifflin-St Jeor; Ireton-Jones (IJ); Fredrix; and Lührmann. Degree of agreement between REE-PE and REE-IC was analyzed by the interclass correlation coefficient and the Bland-Altman test. The accuracy was calculated by the percentage of male and/or female patients whose REE-PE values differ by up to ±10% in relation to REE-IC. For both sexes, there was no difference for average REE-IC in kcal/kg when the values obtained with REE-PE by corrected HB and ESPENme were compared. A high level of agreement was demonstrated by corrected HB for both sexes, with greater accuracy for women. The best accuracy in the male group was obtained with the IJ equation but with a low level of agreement. The effectiveness of PEs is limited for estimating REE of critically ill elderly patients. Nonetheless, HB multiplied by a correction factor of 1.2 can be used until a specific PE for this group of patients is developed.

Towards the challenging REE exploration in Indonesia

NASA Astrophysics Data System (ADS)

Setiawan, Iwan

2018-02-01

Rare earth elements (REE) are the seventeen elements, including fifteen from 57La to 71Lu, in addition to 21Sc and 39Y. In rock-forming minerals, rare earth elements typically occur in compounds as trivalent cations in carbonates, oxides, phosphates, and silicates. The REE occur in a wide range of rock types: igneous, sedimentary and metamorphic rocks. REE are one of the critical metals in the world. Their occurrences are important to supply the world needs on high technology materials. Indonesia has a lot of potential sources of REE that are mainly from residual tin mining processes in Bangka islands, which are associated with radioactive minerals e.g. monazite and xenotime. However, the REE from monazite and xenotime are difficult to extract and contain high radioactivity. Granitoids are widely distributed in Sumatra, Sulawesi, Kalimantan and Papua. They also have a very thick weathering crusts. Important REE-bearing minerals are allanite and titanite. Their low susceptibilities during weathering result an economically potential REE concentration. I-/A- type granitoids and their weathered crusts are important REE sources in Indonesia. Unfortunately, their distribution and genesis have not been deeply studied. Future REE explorations challenge are mainly of the granitoids their weathered crusts. Geochemical and mineralogical characterization of type of granitoids and their weathered crusts, the hydrothermally altered rocks, and clear REE regulation will help discover REE deposits in Indonesia.

Magmatic and hydrothermal R.E.E. fractionation in the Xihuashan granites (SE China)

NASA Astrophysics Data System (ADS)

Maruéjol, Patricia; Cuney, Michel; Turpin, Laurent

1990-11-01

The Xihuashan stock (South Jiangxi, China) is composed of cogenetic granitic units (granites Xe, γa, γc, γd and γb) and emplaced during the Yanshanian orogeny (153±0.2 Ma). They are two feldspars, Fe-rich biotite±garnet and slightly peraluminous granites. Primary accessory minerals are apatite 1, monazite, zircon, uranothorite±xenotime in granites Xe and γa, zircon, uranothorite, uraninite, betafite, xenotime 1; hydrothermal minerals are monazite altered into parisite and apatite 2, Y-rich parisite, yttroparisite, Y-rich fluorite and xenotime 2 in granites γc and γb. Petrographic observations, major element, REE, Y and Rb-Sr isotropic data point to a magmatic suite (granites Xe and γa → granites γc and γd → granite γb) distinct from hydrothermal Na-or K-alteration of γb. From granite Xe to granite γb, LREE, Eu, Th and Zr content are strongly depleted, while HREE, Y and U content increase. During K-alteration of γb, these variations are of minor importance. Major and accessory mineral evidences, geochemical and fluid inclusion results indicate two successive alteration fluids interacting with γb, (1) a late-magmatic F- and CO2-rich fluid and (2) a post-magmatic, aqueous and slightly saline fluid. The depletion of LREE and Th content and the increase in HREE, Y and U content correspond, in the magmatic suite to the early fractionation of monazite in the granites where there is no hydrothermal alteration (granites Xe and γe) and to the hydrothermal alteration of monazite into parisite and secondary apatite, intense new formation of yttroparisite, Y enrichment and U loss in the uranothorite and late crystallization of uraninite in the granites γc and γb. Moreover, simulated crystallization of monazite and temperature of monazite saturation show early fractionation of monazite from the magma in the less evolved granites (Xe and γe) and prevailing hydrothermal leaching of monazite in the most evolved granites (γc-γd and γb) related to a late-magmetic event. The slight variations of REE, Y, Th and U content in the K-altered granites compared to granite γb emphazes the distinct chemical nature of the successive hydrothermal fluids. Rb-Sr and Sm-Nd isotopic results point to a 30 Ma period of time between the late-magmatic and the post-magmatic fluid circulation.

Mineralogy and geochemistry of the Mahi River sediments in tectonically active western India: Implications for Deccan large igneous province source, weathering and mobility of elements in a semi-arid climate

NASA Astrophysics Data System (ADS)

Sharma, Anupam; Sensarma, Sarajit; Kumar, Kamlesh; Khanna, P. P.; Saini, N. K.

2013-03-01

Large igneous provinces (LIPs) hosting mafic rocks over million km2 are likely to influence global sediment production and distribution and help in resolving discrepancies in upper continental crust (UCC) compositions. This work focuses on the texture, mineralogy, and compositions including REE of fine sand/silt deposited by a small to medium-sized river, the Mahi River (about 600 km) in a tectonically active, semi-arid region draining the Deccan Traps in western India, one of the largest LIPs in the world. The results are also applied to a sedimentary rock of fluvial origin (Siwalik mudstone/siltstone) to ascertain the source characteristics of this alluvium and evaluate comparative element (K, Ba, Sr, Na, Ca and Mg) mobility. The Mahi sediments are lithiarenite, mostly composed of quartz and basalt fragments with lesser pyroxene, biotite, feldspar, calcite and clay minerals (smectite ± illite). The Mahi sediments have higher FeOt (⩽10.9 wt.%), TiO2 (⩽2.41 wt.%), Al2O3 (⩽15.2 wt.%), Cr (⩽737 ppm), Co (⩽36 ppm), Cu (⩽107 ppm) than the UCC and PAAS; Ni (⩽54 ppm) higher than the UCC (33.5 ppm), but similar to PAAS (60 ppm). The low CIA (37-59) values and presence of basalt fragments and smectite in the samples suggest incipient weathering in the semi-arid Mahi catchment. In agreement with the mineralogy, the UCC-normalized LREE depleted patterns (LREE/HREE < 1) in the Mahi sediments confirm Deccan basalt contributions from the provenance with about 70-75% basalts and 25-30% Archean biotite-rich granitoids. The mafic contribution, in addition to the UCC, is important for the Siwalik rocks too. Similarly limited depletion of Ba, K and Ca (Ba ⩾ K > Ca) in weathering-limited Mahi (aver CIA 47.5) and transport-limited Siwalik (aver CIA 69) systems indicate their climate insensitivity. At the same time, more Ba depletion than Ca is new for the Deccan Traps River. Decoupling of Ca and Sr, however, could be mineralogy controlled.

Lu-Hf and Sm-Nd evolution in lunar mare basalts

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

Unruh, D.M.; Stille, P.; Patchett, P.J.

1984-02-15

Lu-Hf and Sm-Nd data for mare basalts combined with Rb-Sr and total REE data taken from the literature suggest that the mare basalts were derived by small (< or =10%) degrees of partial melting of cumulate sources, but that the magma ocean from which these sources formed was light REE and Hf-enriched. Calculated source compositions range fromm lherzolite to olivine websterite. Nonmodal melting of small amounts of ilmenite (< or =3%) in the sources seems to be required by the Lu/Hf data. A comparison of the Hf and Nd isotopic characteristics between the mare basalts and terrestrial oceanic basalts revealsmore » that the epsilonHf/epsilonNd ratios of low-Ti mare basalts are much higher than in terrestrial oceanic basalts. The results are qualitatively consistent with the hypothesis that terrestrial basalt sources are partial melt residues whereas mare basalt sources are cumulates. Alternatively, the results may imply that the terrestrial mantle has evolved in two (or more) stages of evolution, and that the net effect was depletion of the mantle during the first approx.1-3 b.y. followed by enrichment during the last 1-2 b.y.; or simply that there is a difference in Lu-Hf crystal-liquid partitioning (relative to Sm-Nd) between the lunar and terrestrial mantles.« less

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 metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

USGS Publications Warehouse

Piper, D.Z.

1988-01-01

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151??W, 9?? 15???N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 ?? 10-2. The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have ??-MnO2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the ??-MnO2 nodules. ?? 1988.

High REE and Y concentrations in Co-Cu-Au ores of the Blackbird district, Idaho

USGS Publications Warehouse

Slack, J.F.

2006-01-01

Analysis of 11 samples of strata-bound Co-Cu-Au ore from the Blackbird district in Idaho shows previously unknown high concentrations of rare earth elements (REE) and Y, averaging 0.53 wt percent ???REE + Y oxides. Scanning electron microscopy indicates REE and Y residence in monazite, xenotime, and allanite that form complex intergrowths with cobaltite, suggesting coeval Co and REE + Y mineralization during the Mesoproterozoic. Occurrence of high REE and Y concentrations in the Blackbird ores, together with previously documented saline-rich fluid inclusions and Cl-rich biotite, suggest that these are not volcanogenic massive sulfide or sedimentary exhalative deposits but instead are iron oxide-copper-gold (IOCG) deposits. Other strata-bound Co deposits of Proterozoic age in the North American Cordillera and elsewhere in the world may have potential for REE and Y resources. IOCG deposits with abundant light REE should also be evaluated for possible unrecognized heavy REE and Y mineralization. ?? 2006 by Economic Geology.

Petrology, geochemistry and isotopic ages of eclogites from the Dulan UHPM Terrane, the North Qaidam, NW China

NASA Astrophysics Data System (ADS)

Song, Shuguang; Yang, Jingsui; Liou, J. G.; Wu, Cailai; Shi, Rendeng; Xu, Zhiqin

2003-10-01

The Dulan eclogite-gneiss region is located in the eastern part of the North Qaidam eclogite belt, NW China. Widespread evidence demonstrates that this region is a typical ultrahigh-pressure (UHP) metamorphic terrane. Eclogites occur as lenses or layers in both granitic and pelitic gneisses. Two distinguished sub-belts can be recognized and differ in mineralogy, petrology and geochemistry. The North Dulan Belt (NDB) has tholeiitic protoliths with high TiO 2 and lower Al 2O 3 and MgO contents. REE patterns and trace element contents resemble those of N-type and E-type MORB. In contrast, eclogites in the South Dulan Belt (SDB) are of island arc protoliths with low TiO 2, high Al 2O 3 and show LREE-enriched and HFSE-depleted patterns. Sm-Nd isotope analyses give isochron ages of 458-497 Ma for eclogite-facies metamorphism for the two sub-belts. The ages are similar to those of Yuka and Altun eclogites in the western extension of the North Qaidam-Altun eclogite belt. The Dulan UHP metamorphic terrane, together with several other recently recognized eclogite-bearing terrenes within the North Qaidam-Altun HP-UHP belt, constitute the key to the understanding of the tectonic evolution of the northern Tibetan Plateau. The entire UHP belt extends for more than 1000 km from the Dulan UHP terrane in the southeast to the Altun eclogite-gneiss terrane in the west. This super-belt marks an early Paleozoic continental collision zone between the Qaidam Massif and the Qilian Massif.

Using Rare Earth Elements (REE) to determine wind-driven soil dispersal from a point source

USDA-ARS?s Scientific Manuscript database

Although erosion of soil by water is a predictably directional process, the erosion of soil by wind is determined by wind direction on an event-wise basis. The wind-driven dispersal patterns of chemical constituents including natural soil components and anthropogenic contaminants are not well under...

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

Petrography and the REE-composition of apatite in the Paleoproterozoic Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia

NASA Astrophysics Data System (ADS)

Joosu, Lauri; Lepland, Aivo; Kreitsmann, Timmu; Üpraus, Kärt; Roberts, Nick M. W.; Paiste, Päärn; Martin, Adam P.; Kirsimäe, Kalle

2016-08-01

The first globally significant phosphorous-rich deposits appear in the Paleoproterozoic at around 2 Ga, however, the specific triggers leading to apatite precipitation are debated. We examine phosphorous-rich rocks (up to 8 wt% P2O5) in 1.98-1.92 Ga old Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia. Phosphates in these rocks occur as locally derived and resedimented sand-to-gravel/pebble sized grains consisting of apatite-cemented muddy sediments. Phosphatic grains can be subdivided into four petrographic types (A-D), each has a distinct REE signature reflecting different early-to-late diagenetic conditions and/or metamorphic overprint. Pyrite containing petrographic type D, which typically has a flat REE pattern, negative Ce anomaly and positive Eu anomaly, is the best preserved of the four types and best records conditions present during apatite precipitation. Type D phosphatic grains precipitated under (sub)oxic basinal conditions with a significant hydrothermal influence. These characteristics are similar to Zaonega Formation phosphates of NW Russia's Onega Basin, and consistent with phosphogenesis triggered by the development of anoxic(sulfidic)-(sub)oxic redoxclines at shallow sediment depth during the Paleoproterozoic.

Scarcity of rare earth elements.

PubMed

de Boer, M A; Lammertsma, K

2013-11-01

Rare earth elements (REEs) are important for green and a large variety of high-tech technologies and are, therefore, in high demand. As a result, supply with REEs is likely to be disrupted (the degree of depends on the REE) in the near future. The 17 REEs are divided into heavy and light REEs. Other critical elements besides REEs, identified by the European Commission, are also becoming less easily available. Although there is no deficiency in the earth's crust of rare earth oxides, the economic accessibility is limited. The increased demand for REEs, the decreasing export from China, and geopolitical concerns on availability contributed to the (re)opening of mines in Australia and the USA and other mines are slow to follow. As a result, short supply of particularly terbium, dysprosium, praseodymium, and neodymium is expected to be problematic for at least the short term, also because they cannot be substituted. Recycling REEs from electronic waste would be a solution, but so far there are hardly any established REE recycling methods. Decreasing the dependency on REEs, for example, by identifying possible replacements or increasing their efficient use, represents another possibility. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The behavior of rare earth elements in naturally and anthropogenically acidified waters

USGS Publications Warehouse

Wood, Scott A.; Gammons, Christopher H.; Parker, Stephen R.

2006-01-01

In this paper, the behavior of rare earth elements (REE) in a watershed impacted by acid-mine drainage (Fisher Creek, Montana) is compared to that in a volcanically acidified watershed (Rio Agrio and Lake Caviahue, Argentina). The REE behave conservatively in acidic waters with pH values less than approximately 5.5. However, above pH 5.5, REE concentrations are controlled by adsorption onto or co-precipitation with a variety of Fe or Al oxyhydroxides. The heavy REE partition to a greater extent into the solid phase than the light REE as pH rises above 6. Concentrations of REE exhibit diel (24-h) cycling in waters that were initially acidic, but have become neutralized downstream. In Fisher Creek, at the most downstream sampling station investigated (pH 6.8), concentrations of dissolved REE were 190–840% higher in the early morning versus the late afternoon. This cycling can be related to temperature-dependent, cyclic adsorption–desorption of REE onto hydrous ferric or aluminum oxide or both. Similar but gentler diel cycling of the REE was found at Rio Agrio. The existence of such cycling has important ramifications for the study of REE in natural waters.

Characteristics and genesis of Rare Earth Element (REE) in western Indonesia

NASA Astrophysics Data System (ADS)

Handoko, A. D.; Sanjaya, E.

2018-02-01

Rare Earth Element (REE) has unique properties that have been used in many hightech applications. The demand of REE increased recently in the world due to its special properties. Although REE concentration in the crust is higher than gold, economically viable deposits are still rare. Reduction of REE exports by China cause increased prices of REE. Due to this condition, exploration of potential REE mines emerged. Indonesia also participates in this phenomenon, and explore the possibility of REE mines in its area. This review will discuss the characteristics and genesis of REE and its occurrence in western Indonesia; focused in Sumatera, Tin Island, and Kalimantan. The review is done based on literature research from several resources about characteristics of rare earth element in general and in the given area. The research shows that the potential REE mines can be found in several different locations in Indonesia, such as Tin Island, Sumatera, and Kalimantan. Most of them are composed of monazite, zircon, and xenotime as rare earth minerals. Monazite iss known for its elevated number of radioactive elements, so study about radioactive content and more environment friendly ore processing becomes compulsory.

Do Melt Inclusions Answer Big Questions?

NASA Astrophysics Data System (ADS)

Hofmann, A. W.; Sobolev, A. V.

2009-12-01

In a pioneering paper, Sobolev and Shimizu (1993) demonstrated the existence of ultra-depleted melt inclusions in olivine phenocrysts in MORB. They interpreted these as evidence for the preservation of parental melts formed by progressive near-fractional melting. Subsequently many cases have been described where melt inclusions from single basalt samples display enormous chemical and isotopic heterogeneity. The interpretation of these observations hinges critically on whether such melt inclusions can faithfully preserve primary or parental melt composition. If they do, melt inclusion data can truly answer big questions from small-scale observations. If they do not, they answer rather small questions. Favoring the second possibility, Danyushevsky et al. (2004) have suggested that much of the observed variability of highly incompatible trace elements in melt inclusions “may not represent geologically significant melts, but instead reflect localized, grain-scale reaction processes within the magmatic plumbing system.” We disagree and show that this mechanism cannot, for example, explain isotopic heterogeneity measured in several suites of melt inclusions, nor does it not account for the presence of ultra-depleted melts and "ghost" plagioclase signatures in other inclusions. More recently, Spandler et al. (2007) have suggested on the basis of experimental evidence that diffusion rates for REE in olivine are so rapid that parental melt compositions in melt inclusions are rapidly falsified by diffusional exchange with (evolved) host lava. We show that the very fact that extreme chemical and isotopic heterogeneities are routinely preserved in melt inclusions demonstrates that this conclusion is unwarranted, either because residence times of the olivine phenocrysts are much shorter than assumed by Spandler et al. or because the high experimental diffusion rates are caused by an unknown experimental artifact. Although there is no obvious flaw in design and execution of their experiments, geologically relevant diffusion rates are notoriously difficult to determine and may depend on factors not incorporated in the laboratory experiments. More recent diffusion experiments by Remmert et al. (2008) and by Cherniak (2009) have yielded diffusion coefficients three order of magnitude lower than those measured by Spandler. The heavy REE represent a possible exception to the above conclusions. We present data from olivine melt inclusions from Iceland basalts, which show unusual HREE patterns possibly caused by diffusional exchange with the host lava. Sobolev, A.V. & Shimizu, N. (1993) Nature 363, 151-154. Danyushevskii, L.V. et al. (2004) J. Petrol. 45, 2531-2553. Spandler, G., O’Neill, H.St.C., Kamenetsky, V.S. (2007) Nature, 447, 303-306. Remmert, P. Dohmen, R., Chakraborty, S. (2008) EOS Trans. AGU abs. MR331-1844. Cherniak, D.J. (2009) Am. Mineral. Ms. subm.

Paleoproterozoic mafic dike swarms of the Dunhuang Block: record of initial breakup of the Columbia suppercontinent?

NASA Astrophysics Data System (ADS)

Ye, X. T.; Zhang, C. L.

2017-12-01

Mafic dike swarms have been described as igneous record related to the breakup and dispersal of continental masses. Studying their origin and distribution are thus important for the understanding of the regional magmatic-tectonic evolution during the late Paleoproterozoic and possible relationship between the Dunhuang Block and the Columbia supercontinent. Here detail petrolography, zircon U-Pb age, and geochemistry are presented of the mafic dikes in the Dunhuang Block. The mafic dikes are tabular, E-W trending, mainly consist of the diabase and diabasic gabbro. Fine-grained gabbroic rocks are seen in the center of some of the thick dikes. These rocks are massive, showing ophitic texture with tholeiitic affinity and dominated by basaltic compositions. Zircon SHRIMP U-Pb dating of these dykes yields emplacement age of 1867 ± 8 Ma. According to their geochemical features, the mafic dikes are subdivided into three groups (G1, G2, and G3). G1 dikes have low SiO2 (47.80-48.82%), high MgO (6.00-8.44%), Cr (92-170 ppm), and Ni (46-106 ppm), indicating that they were not significantly affected by fractional crystallization or crustal assimilations. This result is consistent with their insignificant Nb-Ta troughs on the incompatible elements spider diagrams. Compared to G1 dikes, G2 dikes show higher SiO2 (49.18-49.76%), lower MgO (4.92-5.23%), Cr (35-44 ppm), and Ni (72-82 ppm). They show moderate Nb-Ta depletion on the primitive mantle normalized spider diagrams. Compared with G1 and G2 dikes, G3 dikes exhibit lowest SiO2 (46.05-49.76%) and MgO (4.07-4.37%) and highest TiO2 (3.38-3.50%), P2O5 (1.81-1.94%), and total alkalis (5.04-5.73%). In addition, G3 dikes have higher total REE abundances and extremely depleted in Nb-Ta with Nb/La ratios from 0.25 to 0.27. Although these mafic dikes show different REE and trace element patterns, the element signatures (Nb/La, Th/La, Ce/Nb, Th/Nb, and (Zr/Nb)N ratios) are similar to those of the intraplate basalts, while different from the volcanic arc basalts or mid-ocean ridge basalts. This may suggest that the primitive magmas of G1, G2, and G3 were derived from an OIB-like mantle source, which may be related to the plume magmatism or to an intracontinental extension setting, associated with the initial breakup of the Columbia suppercontinent.

Resting Energy Expenditure in Adults with Becker’s Muscular Dystrophy

PubMed Central

Jacques, Matthew F.; Orme, Paul; Smith, Jonathon; Morse, Christopher I.

2017-01-01

Purpose The purpose of this study was: 1) To compare Resting energy expenditure (REE) in adult males with Becker’s Muscular Dystrophy (BeMD, n = 21, 39 ±12 years) and healthy controls (CTRL, n = 12, 37 ±12 years) 2) Determine whether other physiological parameters correlate with REE in BeMD, and 3) Compare current prediction methods of REE with measured REE. Methods REE was calculated via indirect calorimetry using continuous, expired gas analysis following an overnight fast. Fat free mass (FFM) and fat mass were measured by bioelectrical impedance. B-mode ultrasound measured Tibialis Anterior (TA) and Gastrocnemius Medialis (GM) anatomical cross sectional area (ACSA). The Bone Specific Physical Activity Questionnaire measured physical activity. Results No difference in REE was found between CTRL and BeMD groups (1913 ±203 & 1786 ±324 Kcal respectively). Other physiological comparisons showed increased fat mass (+54%), decreased TA ACSA (-42%), increased GM ACSA (+25%) as well as reduced respiratory function (FVC -28%; FEV1−27%) in BeMD adults compared to controls. REE estimated from prediction equations (Schofield’s) in Muscular Dystrophy were different from measured REE (P<0.05, bias = -728kcal), while the Mifflin equation was no different from measured REE (r2 = 0.58, Bias = -8kcal). Within the present BeMD, REE predicted from FFM (REE = FFM x 34.57–270; r2 = 0.85) and body mass (REE = BM x 15.65 + 421.5; r2 = 0.66), were not different from measured REE (bias equals 0 and 0.2kcals, respectively) Conclusions Despite no differences in REE between CTRL and BeMD adults, increased fat masses highlights the requirement for explicit nutritional guidelines, as well as maintenance of physical activity levels, where possible. Prediction equations are frequently used in clinical settings, however these have been shown to be less accurate in BeMD; therefore, the equations proposed here should be used where possible. PMID:28060911

Sources, behaviour, and environmental and human health risks of high-technology rare earth elements as emerging contaminants.

PubMed

Gwenzi, Willis; Mangori, Lynda; Danha, Concilia; Chaukura, Nhamo; Dunjana, Nothando; Sanganyado, Edmond

2018-04-26

Recent studies show that high-technology rare earth elements (REEs) of anthropogenic origin occur in the environment including in aquatic systems, suggesting REEs are contaminants of emerging concern. However, compared to organic contaminants, there is a lack of comprehensive reviews on the anthropogenic sources, environmental behaviour, and public and ecological health risks of REEs. The current review aims to: (1) identify anthropogenic sources, transfer mechanisms, and environmental behaviour of REEs; (2) highlight the human and ecological health risks of REEs and propose mitigation measures; and (3) identify knowledge gaps and future research directions. Out of the 17 REEs, La, Gd, Ce and Eu are the most studied. The main sources of anthropogenic REE include; medical facilities, petroleum refining, mining and technology industries, fertilizers, livestock feeds, and electronic wastes and recycling plants. REEs are mobilized and transported in the environment by hydrological and wind-driven processes. Ecotoxicological effects include reduced plant growth, function and nutritional quality, genotoxicity and neurotoxicity in animals, trophic bioaccumulation, chronic and acute toxicities in soil organisms. Human exposure to REEs occurs via ingestion of contaminated water and food, inhalation, and direct intake during medical administration. REEs have been detected in human hair, nails, and biofluids. In humans, REEs cause nephrogenic systemic fibrosis and severe damage to nephrological systems associated with Gd-based contrast agents, dysfunctional neurological disorder, fibrotic tissue injury, oxidative stress, pneumoconiosis, cytotoxicity, anti-testicular effects, and male sterility. Barring REEs in medical devices, epidemiological evidence directly linking REEs in the environment to human health conditions remains weak. To minimize health risks, a conceptual framework and possible mitigation measures are highlighted. Future research is needed to better understand sources, environmental behaviour, ecotoxicology, and human epidemiology. Moreover, research on REEs in developing regions, including Africa, is needed given prevailing conditions predisposing humans to health risks (e.g., untreated drinking water). Copyright © 2018 Elsevier B.V. All rights reserved.

Validity of Predictive Equations for Resting Energy Expenditure Developed for Obese Patients: Impact of Body Composition Method

PubMed Central

Achamrah, Najate; Jésus, Pierre; Grigioni, Sébastien; Rimbert, Agnès; Petit, André; Déchelotte, Pierre; Folope, Vanessa; Coëffier, Moïse

2018-01-01

Predictive equations have been specifically developed for obese patients to estimate resting energy expenditure (REE). Body composition (BC) assessment is needed for some of these equations. We assessed the impact of BC methods on the accuracy of specific predictive equations developed in obese patients. REE was measured (mREE) by indirect calorimetry and BC assessed by bioelectrical impedance analysis (BIA) and dual-energy X-ray absorptiometry (DXA). mREE, percentages of prediction accuracy (±10% of mREE) were compared. Predictive equations were studied in 2588 obese patients. Mean mREE was 1788 ± 6.3 kcal/24 h. Only the Müller (BIA) and Harris & Benedict (HB) equations provided REE with no difference from mREE. The Huang, Müller, Horie-Waitzberg, and HB formulas provided a higher accurate prediction (>60% of cases). The use of BIA provided better predictions of REE than DXA for the Huang and Müller equations. Inversely, the Horie-Waitzberg and Lazzer formulas provided a higher accuracy using DXA. Accuracy decreased when applied to patients with BMI ≥ 40, except for the Horie-Waitzberg and Lazzer (DXA) formulas. Müller equations based on BIA provided a marked improvement of REE prediction accuracy than equations not based on BC. The interest of BC to improve REE predictive equations accuracy in obese patients should be confirmed. PMID:29320432

Submarine groundwater discharge is an important source of REEs to the coastal ocean

NASA Astrophysics Data System (ADS)

Johannesson, K. H.; Chevis, D. A.; Palmore, C. D.; Telfeyan, K.; Burdige, D.; Cable, J. E.; Hemming, S. R.; Rasbury, T.; Moran, S. B.; Prouty, N.; Swarzenski, P. W.

2014-12-01

Rare earth element (REE) concentrations of submarine groundwater discharge (SGD) were measured in three subterranean estuaries (i.e., Indian River Lagoon, Florida; Pettaquamscutt estuary, Rhode Island; Kona Coast, Hawaii). Using site-specific SGD estimates previously obtained by a variety of techniques (e.g., seepage meters, Ra, and Rn), we estimated SGD-derived fluxes of REEs to the coastal ocean using simple, one-dimensional modeling techniques. Our results indicate that the SGD fluxes of REEs are either of the same magnitude as riverine REE fluxes (Indian River Lagoon; Pettaquamscutt estuary), or far exceed surface runoff sources of REEs to the coastal ocean (Kona Coast). At each site important biogeochemical reactions occurring in the subterranean estuary, such as redox reactions, sediment bioirrigation, mineral dissolution and re-precipitation, and salt-induced mobilization from "nano-colloids", appear to facilitate release of REEs into solution, which are then advected to the coastal ocean via SGD. Neodymium isotope analysis of SGD and aquifer sediment are consistent with sediment diagenesis and redox transformations of Fe(III) oxides/oxyhydroxides, as well as preferential weathering of REE-bearing minerals like apatite, as being important sources of REEs to coastal seawater. Our investigations demonstrate that geochemical reactions occurring in the studied subterranean estuaries represent a net source of light and middle REEs to coastal seawater, whereas the heavy REEs appear to be sequestered in the subterranean estuary sediment.

Fractionations of rare earth elements in plants and their conceptive model.

PubMed

Ding, ShiMing; Liang, Tao; Yan, JunCai; Zhang, ZiLi; Huang, ZeChun; Xie, YaNing

2007-02-01

Fractionations of rare earth elements (REEs) and their mechanisms in soybean were studied through application of exogenous mixed REEs under hydroponic conditions. Significant enrichment of middle REEs (MREEs) and heavy REEs (HREEs) was observed in plant roots and leaves respectively, with slight fractionation between light REEs (LREEs) and HREEs in stems. Moreover, the tetrad effect was observed in these organs. Investigations into REE speciation in roots and in the xylem sap using X-ray absorption spectroscopy (XAS) and nanometer-sized TiO2 adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations should be dominated by fixation mechanism in roots caused by cell wall absorption and phosphate precipitation, and by the combined effects of fixation mechanism and transport mechanism in aboveground parts caused by solution complexation by intrinsic organic ligands. A conceptive model was established for REE fractionations in plants based on the above studies.

Rapid and highly reproducible analysis of rare earth elements by multiple collector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Baker, Joel; Waight, Tod; Ulfbeck, David

2002-10-01

A method has been developed for the rapid chemical separation and highly reproducible analysis of the rare earth elements (REE) by isotope dilution analysis by means of a multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS). This technique is superior in terms of the analytical reproducibility or rapidity of analysis compared with quadrupole ICP-MS or with thermal ionization mass spectrometric isotope dilution techniques. Samples are digested by standard hydrofluoric-nitric acid-based techniques and spiked with two mixed spikes. The bulk REE are separated from the sample on a cation exchange column, collecting the middle-heavy and light REE as two groups, which provides a middle-heavy REE cut with sufficient separation of the light from the heavier REE to render oxide interferences trivial, and a Ba-free light REE cut. The heavy (Er-Lu), middle (Eu-Gd), and light REE (La-Eu) concentrations are determined by three short (1 to 2 min) analyses with a CETAC Aridus desolvating nebulizer introduction system. Replicate digestions of international rock standards demonstrate that concentrations can be reproduced to <1%, which reflects weighing errors during digestion and aliquotting as inter-REE ratios reproduce to ≤0.2% (2 SD). Eu and Ce anomalies reproduce to <0.15%. In addition to determining the concentrations of polyisotopic REE by isotope dilution analysis, the concentration of monoisotopic Pr can be measured during the light REE isotope dilution run, by reference to Pr/Ce and Pr/Nd ratios measured in a REE standard solution. Pr concentrations determined in this way reproduce to <1%, and Pr/REE ratios reproduce to <0.4%. Ce anomalies calculated with La and Pr also reproduce to <0.15% (2 SD). The precise Ce (and Eu) anomaly measurements should allow greater use of these features in studying the recycling of materials with these anomalies into the mantle, or redox-induced effects on the REE during recycling and dehydration of oceanic lithosphere, partial melting, metamorphism, alteration, or sedimentation processes. Moreover, this technique consumes very small amounts (subnanograms) of the REE and will allow precise REE determinations to be made on much smaller samples than hitherto possible.

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

USGS Publications Warehouse

Chen, J.R.; Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Rivers, M.L.; Sutton, S.R.; Cygan, G.L.; Grossman, J.N.; Reed, M.J.

1993-01-01

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

A RELICT Spinel Grain in an Allende Ferromagnesian Chondrule

NASA Astrophysics Data System (ADS)

Misawa, K.; Fujita, T.; Kitamura, M.; Nakamura, N.; Yurimoto, H.

1993-07-01

It is suggested that one of the refractory lithophile precursors in CV-CO chondrules was a hightemperature condensate from the nebular gas and was related to Ca,Al-rich inclusions (CAIs) [1-3]. However, little is known about refractory siderophile precursors in chondrules [4]. Allende barred olivine chondrule R-11 consists mainly of olivine (Fa(sub)7- 18), pyroxene (En(sub)93Fs(sub)1Wo(sub)6, En(sub)66Fs(sub)1Wo(sub)33), plagioclase (An(sub)80), Fe-poor spinel, and alkali-rich glass. The CI- chondrite normalized REE pattern of the chondrule, excluding a spinel grain, are fractionated, HREEdepleted (4.6-7.8 x CI) with a large positive Yb anomaly. The REE abundances are hump-shaped functions of elemental volatility, moderately refractory REE-enriched, suggesting that the refractory lithophile precursor component of R-11 could be a condensate from the nebular gas and related to Group 11 CAIs [1,2]. An interior portion of spinel is almost Fe-free, but in an outer zone (2040 micrometers in width) FeO contents increase rapidly. TiO(sub)2, Cr(sub)2O(sub)3, and V(sub)2O(sub)3 contents in core spinel are less than 0.5%, which is different from the V-rich nature of spinel in fluffy Type A CAIs [5]. The Fe-Mg zoning of spinel may have been generated by diffusional emplacement of Mg and Fe during chondrule-forming events. The spinel contains silicate inclusions and tiny metallic grains. The largest silicate inclusion is composed of Al,Ti-rich pyroxene and Ak 40 melilite. One of the submicrometersized grains was analyzed by SEM-EDS and found to be composed of refractory Pt-group metals with minor amounts of Fe and Ni. This is the first occurrence of refractory Pt-group metal nuggets in a ferromagnesian chondrule from the Allende meteorite. Tungsten, Os, Ir, Mo, and Ru are enriched 2-6 x 10^5 relative to CIs, and abundances of Pt and Rh decrease 2-10 x 10^4 with increasing volatility. In addition, abundances of Fe and Ni in the nugget are equal to or less than that CI chondrites. A depletion of Mo relative to other refractory metals may have resulted from high- temperature oxidation [6]. Chondrule R-11 exhibits both similarities (spinel and plagioclase chemistry; Group II REE pattern) and differences (fassaite chemistry; existence of refractory Pt-group metal nuggets and melilite) with respect to POIs [3] carrying isotopically fractionated Mg. Refractory Pt-group metal nuggets in CAIs are considered to have been produced during high-temperature events (at least 1300 degrees C) before total condensation of Fe in the early solar nebula [8-10]. In analogy with the formation history with CAIs, we suggest that one of the refractory siderophile precursor components of Allende chondrules is a high-temperature condensate from the nebular gas and is associated with refractory oxide and silicates. References: [1] Misawa K. and Nakamura N. (1988) GCA, 52, 1669. [2] Misawa K. and Nakamura N. (1988) Nature, 334, 47. [3] Sheng Y. J. et al. (1991) GCA, 55, 581. [4] Grossman J. N. et al. (1988) In Meteorites and the Early Solar System (J. F. Kerridge and M. S. Matthews, eds.), 619, Univ. of Arizona. [5] MacPherson G. J. and Grossman L. (1984) GCA, 48, 29. [6] Fegley B. Jr. and Palme H. (1985) EPSL, 72, 311. [7] Wark D. A. and Lovering J. F. (1976) LS VII, 912. [8] Palme H. and Wlotzka F. (1976) EPSL, 33, 45. [9] El Goresy A. et al. (1978) Proc. LPSC 9th, 1279. [10] Blander M. and Fuchs L. H. (1980) Proc. LPSC 11th, 929.

Bioadsorption of Rare Earth Elements through Cell Surface Display of Lanthanide Binding Tags.

PubMed

Park, Dan M; Reed, David W; Yung, Mimi C; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Fujita, Yoshiko; Riman, Richard E; Navrotsky, Alexandra; Jiao, Yongqin

2016-03-01

With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

Bioadsorption of rare earth elements through cell surface display of lanthanide binding tags

DOE PAGES

Park, Dan M.; Reed, David W.; Yung, Mimi C.; ...

2016-02-02

In this study, with the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb 3+ could be effectively recovered usingmore » citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb 3+ by citrate. No reduction in Tb 3+ adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.« less

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.

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.

Direct dating and characterization of the Pope's Hill REE Deposit, Labrador

NASA Astrophysics Data System (ADS)

Chafe, A. N.; Hanchar, J. M.; Fisher, C.; Piccoli, P. M.; Crowley, J. L.; Dimmell, P. M.

2012-12-01

The Pope's Hill rare earth element (REE) trend (PHT) is located approximately 100 km southwest of Happy Valley-Goose Bay, along the Trans Labrador Highway, in central Labrador. Whole-rock geochemical analyses of the main REE-bearing unit indicate total rare earth element contents ranging from 1 to 22 weight percent (wt%) REE3+. The REE-enriched unit is hosted within a hydrothermally altered syenite, trending northeast and traceable for approximately 2.8km. Samples of ore, host rock, and country rock, were collected from throughout the trend in order to: 1) quantify which phases concentrate the REE and their abundances and distribution in the ore; and 2) use in situ LA-ICPMS and ID-TIMS U-Pb geochronology and in situ Sm-Nd isotopes using LA-MC-ICPMS in monazite from the ore and host rock to constrain the timing of mineralization and determine the source of the REE. These data will help develop predictive models for this type of mineral deposit elsewhere. The PHT is defined as the host syenite and REE-enriched segregations; two contrasting lithologies. The rare earth element minerals (REE) occur in millimeter- to centimeter-scale pods that are locally discontinuous. The REE are hosted in a variety of silicate, phosphate, carbonate, and niobate phases; with a majority hosted in allanite(-Ce), titanite(-Ce), monazite(-Ce), britholite(-Ce); and a minor percentage in REE-carbonates and fergusonite(-Nd). Both apatite and titanite occur in two different compositional forms that range in chemistry from end-member stoichiometric apatite and titanite to highly REE-enriched - apatite-britholite and titanite(-Ce), where chemical substitutions, such as Si4+ + REE3+ substitute for Ca2+ + P5+ in apatite and REE3+ + Fe3+ substitute for Ca2+ + Ti4+ in titanite in order to incorporate up to ~40 wt% REE2O3 in both minerals. The U-Pb geochronology indicate that allanite, titanite(-Ce), monazite and fergusonite crystallized from ~1060 to ~940 Ma, a period spanning ~120 Ma. Sm-Nd tracer isotope data from the same minerals indicate that the syenite and ore have initial Nd within a single ɛNd unit. This combined with their field relationship to the foliation and the microtextures observed in thin section suggests that the REE minerals experienced syndeformational growth from a hydrothermal fluid, acting on both host and ore, where REEs in aqueous hard ligand complexes became saturated in silicate, phosphate, carbonate, and niobate minerals through the changing T, P and chemical conditions brought on by deformation.

Rare earth element deposits in China

USGS Publications Warehouse

Xie, Yu-Ling; Hou, Zeng-qian; Goldfarb, Richard J.; Guo, Xiang; Wang, Lei

2016-01-01

China is the world’s leading rare earth element (REE) producer and hosts a variety of deposit types. Carbonatite- related REE deposits, the most significant deposit type, include two giant deposits presently being mined in China, Bayan Obo and Maoniuping, the first and third largest deposits of this type in the world, respectively. The carbonatite-related deposits host the majority of China’s REE resource and are the primary supplier of the world’s light REE. The REE-bearing clay deposits, or ion adsorption-type deposits, are second in importance and are the main source in China for heavy REE resources. Other REE resources include those within monazite or xenotime placers, beach placers, alkaline granites, pegmatites, and hydrothermal veins, as well as some additional deposit types in which REE are recovered as by-products. Carbonatite-related REE deposits in China occur along craton margins, both in rifts (e.g., Bayan Obo) and in reactivated transpressional margins (e.g., Maoniuping). They comprise those along the northern, eastern, and southern margins of the North China block, and along the western margin of the Yangtze block. Major structural features along the craton margins provide first-order controls for REE-related Proterozoic to Cenozoic carbonatite alkaline complexes; these are emplaced in continental margin rifts or strike-slip faults. The ion adsorption-type REE deposits, mainly situated in the South China block, are genetically linked to the weathering of granite and, less commonly, volcanic rocks and lamprophyres. Indosinian (early Mesozoic) and Yanshanian (late Mesozoic) granites are the most important parent rocks for these REE deposits, although Caledonian (early Paleozoic) granites are also of local importance. The primary REE enrichment is hosted in various mineral phases in the igneous rocks and, during the weathering process, the REE are released and adsorbed by clay minerals in the weathering profile. Currently, these REE-rich clays are primarily mined from open-pit operations in southern China. The complex geologic evolution of China’s Precambrian blocks, particularly the long-term subduction of ocean crust below the North and South China blocks, enabled recycling of REE-rich pelagic sediments into mantle lithosphere. This resulted in the REE-enriched nature of the mantle below the Precambrian cratons, which were reactivated and thus essentially decratonized during various tectonic episodes throughout the Proterozoic and Phanerozoic. Deep fault zones within and along the edges of the blocks, including continental rifts and strike-slip faults, provided pathways for upwelling of mantle material.

Palaeoproterozoic tectonic evolution of the Alto Tererê Group, southernmost Amazonian Craton, based on field mapping, zircon dating and rock geochemistry

NASA Astrophysics Data System (ADS)

Lacerda Filho, J. V.; Fuck, R. A.; Ruiz, A. S.; Dantas, E. L.; Scandolara, J. E.; Rodrigues, J. B.; Nascimento, N. D. C.

2016-01-01

New geochemical and geochronological U-Pb and Sm-Nd data from amphibolites of the Alto Tererê Group, which are of Palaeoproterozoic age, are presented. The amphibolites are exposed in the central-eastern portion of the Rio Apa Block, southern Amazonian Craton, Mato Grosso do Sul, Brazil, and are composed of hornblende, plagioclase, quartz, biotite, cummingtonite and epidote. The amphibolites are subdivided into three lithofacies: (i) thinly banded amphibolites (metabasalts), (ii) coarse- and medium-grained amphibolites with relic subophitic texture (metagabbros), and (iii) amphibolites with relic cumulate texture (metapyroxenites). Chemical data also suggest the subdivision of the amphibolites into three different types. These rocks yield a U-Pb zircon age of 1768 ± 6 Ma and are therefore older than rocks of part of the Rio Apa Complex. Their Sm-Nd model ages range between 2.89 and 1.88 Ga, and their εNd (T) values range between -3.40 and + 3.74. Chemical analyses of these rocks indicate SiO2 concentrations between 45.23 and 50.65 wt.%, MgO concentrations between 4.34 and 8.01 wt.%, TiO2 concentrations between 0.91 and 1.74 wt.%, weakly fractionated rare-earth element (REE) patterns with mild depletion in heavy REEs, enrichment in large-ion lithophile elements (LILEs) and high-field-strength element (HFSEs), negative Nb, Ta and Co anomalies, positive Ba and Pb anomalies, low Ce concentrations, high Rb/Y ratios and low Th/La and Hf/Sm ratios. These features reflect metasomatism of the mantle wedge produced by sediments from the subducted plate. Various degrees of melting mark the evolution of the parent basic magmas, although subordinate crustal contamination may also have occurred. The geochemical signature of the amphibolites corresponds to that of tholeiitic basalts generated in an extensional back-arc-basin environment. The deposition in the basin apparently ceased during the first episode of compression and deformation at approximately 1.68 Ga, and the main deformation was most likely related to the San Ignácio Orogeny, which dates to approximately 1.3 Ga.

Correlation of nasopharyngeal carcinoma with rare earth elements and the Epstein-Barr virus.

PubMed

Zhang, Xiangmin; Zeng, Xiangfu; Liu, Lianbin; Lan, Xiaolin; Huang, Jing; Zeng, Hongxue; Li, Rong; Luo, Keqing; Wu, Wei; Zhou, Maohua; Li, Shaojin

2018-04-01

The concentration and distribution of rare earth elements (REE) in nasopharyngeal carcinoma (NPC) were measured to investigate connections with tumor size, lymph node metastasis, clinical stages, and Epstein-Barr virus (EBV) infection. There were 30 patients with NPC who met the criteria for inclusion in the present study. The EBV copy number, as well as the concentration and distribution of REE, was analyzed. EBV was detected using reverse transcription-polymerase chain reaction, with the concentrations of REE in NPC tissues measured using inductively coupled plasma-tandem mass spectrometry. The mean values were used when comparing concentrations of REE in NPC tissues as the standard deviation of this parameter was the lowest. Light REE had the highest concentrations, followed by medium, and then heavy REE. The concentrations of REE decreased with increasing tumor size and with the presence of lymph node metastasis. The concentrations of REE gradually increased between stage II and IVa, but markedly decreased thereafter. The elements that exhibited the greatest decreases were terbium, holmium and ytterbium. Furthermore, the concentrations of REE in NPC were not associated with sex (r=0.301, P=0.106) or age (r=-0.011, P=0.955), and were negatively associated with EBV (r=-0.744, P<0.001). By contrast, the EBV copy number increased alongside advancements in clinical stage. Changes in the concentrations of REE in NPC were more prominent for medium and heavy elements. Additionally, alterations in the concentrations of heavy REE may affect the occurrence and development of NPC.

Geochemical zoning and early differentiation in the moon

NASA Technical Reports Server (NTRS)

Taylor, S. R.; Jakes, P.

1977-01-01

The volatile elements (e.g., Rb, Pb, Tl, Bi, Cs) seem to have been depleted at the time of lunar accretion. Accordingly, it may be assumed that the moon initially accreted from refractory material. The good correlation between volatile/involatile element ratios (e.g., Cs/U, K/La, K/Zr) in both highland and maria samples means that element distribution in lunar crustal rocks is not governed by volatility differences. This and other evidence encourages the view that the moon was accreted homogeneously. A consequence of homogeneous accretion theories is that very efficient large-scale element fractionation is required to account both for the high near-surface concentrations of refractory elements (e.g., Th, U, REE, Zr, Ba, etc.) and for the Ca-Al-rich crust.

Evidence for a Light-Rare-Earth-Element-Depleted Source for Some Ferroan Anorthosites

NASA Astrophysics Data System (ADS)

Borg, L. E.; Norman, M.; Nyquist, L. E.; Bogard, D.; Snyder, G.; Taylor, L.

1998-01-01

In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial EpsilonNd(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.

Evidence for a Light-Rare-Earth-Element-Depleted Source for Some Ferroan Anorthosites

NASA Technical Reports Server (NTRS)

Borg, L. E.; Norman, M.; Nyquist, L. E.; Bogard, D.; Snyder, G.; Taylor, L.

1998-01-01

In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial Epsilon(sub Nd)(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.

Ocean plateau-seamount origin of basaltic rocks, Angayucham terrane, central Alaska

USGS Publications Warehouse

Barker, F.; Jones, D.L.; Budahn, J.R.; Coney, P.J.

1988-01-01

The Angayucham terrane of north-central Alaska (immediately S of the Brooks Range) is a large (ca. 500 km E-W), allochthonous complex of Devonian to Lower Jurassic pillow basalt, diabase sills, gabbro plutons, and chert. The mafic rocks are transitional normal-to-enriched, mid-ocean-ridge (MORB) type tholeiites (TiO2 1.2-3.4%, Nb 7-23 ppm, Ta 0.24-1.08 ppm, Zr 69-214 ppm, and light REE's slightly depleted to moderately enriched). Geologic and geochemical constraints indicate that Angayucham terrane is the upper "skin' (ca. 3-4 km thick) of a long-lived (ca. 170-200 ma) oceanic plateau whose basaltic-gabbroic rocks are like those of seamounts of the East Pacific Rise. -Authors

Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition

NASA Astrophysics Data System (ADS)

Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty

2004-07-01

Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are derived from leaching of dust particles entrained in rain or fog droplets either in the atmosphere or during wet atmospheric deposition. The high trace metal enrichment factors require that most of the dust was physically removed before or during varnish formation. The remaining aqueous counterpart would be depleted in HFSEs and Th relative to the REEs, Co, Ni and Pb because the former are more insoluble and hence largely retained in the removed dust fraction. The high Ce/La ratios suggest that precipitation of trace metals may have been governed by equilibrium partitioning in an excess of wet atmospheric deposition. If varnishes are indeed derived from wet atmospheric deposition, they may provide a record of the aqueous component of atmospheric dust inputs to various environments.

Trends in the Rare Earth Element Content of U.S.-Based Coal Combustion Fly Ashes.

PubMed

Taggart, Ross K; Hower, James C; Dwyer, Gary S; Hsu-Kim, Heileen

2016-06-07

Rare earth elements (REEs) are critical and strategic materials in the defense, energy, electronics, and automotive industries. The reclamation of REEs from coal combustion fly ash has been proposed as a way to supplement REE mining. However, the typical REE contents in coal fly ash, particularly in the United States, have not been comprehensively documented or compared among the major types of coal feedstocks that determine fly ash composition. The objective of this study was to characterize a broad selection of U.S. fly ashes of varied geological origin in order to rank their potential for REE recovery. The total and nitric acid-extractable REE content for more than 100 ash samples were correlated with characteristics such as the major element content and coal basin to elucidate trends in REE enrichment. Average total REE content (defined as the sum of the lanthanides, yttrium, and scandium) for ashes derived from Appalachian sources was 591 mg kg(-1) and significantly greater than in ashes from Illinois and Powder River basin coals (403 and 337 mg kg(-1), respectively). The fraction of critical REEs (Nd, Eu, Tb, Dy, Y, and Er) in the fly ashes was 34-38% of the total and considerably higher than in conventional ores (typically less than 15%). Powder River Basin ashes had the highest extractable REE content, with 70% of the total REE recovered by heated nitric acid digestion. This is likely due to the higher calcium content of Powder River Basin ashes, which enhances their solubility in nitric acid. Sc, Nd, and Dy were the major contributors to the total REE value in fly ash, based on their contents and recent market prices. Overall, this study shows that coal fly ash production could provide a substantial domestic supply of REEs, but the feasibility of recovery depends on the development of extraction technologies that could be tailored to the major mineral content and origins of the feed coal for the ash.

Effect of low doses of dietary rare earth elements on growth performance of broilers.

PubMed

He, M L; Wehr, U; Rambeck, W A

2010-02-01

The present study was designed to investigate effect of dietary rare earth elements (REE), including both organic and inorganic compounds, on growth performance of broilers. In experiment 1, a total of 180 male Ross broiler chicks were allocated to 72 pens with different assignment: four chicks per pen or individually. The following three treatment diets were applied: control, REE-chlorides at a dose of 40 mg/kg and REE-citrate at a dose of 70 mg/kg. Each treatment group had 24 pens containing both assignments (12 pens each). In experiment 2, a total of 72 male 3-day-old Ross broiler chicks were separated to four groups: control, REE-chlorides at a dose of 70 mg/kg and REE-citrate at doses of 70 mg/kg and 100 mg/kg. In experiment 1, dietary REE-citrate improved body weight gain during the overall period by 5.0% (p < 0.05) while the increase with REE-chloride was not significant. In experiment 2, growth effects (p < 0.05) were only found in the period from day 21 to slaughter with all REE forms, and feed conversion ratio was improved by 3.4% (p < 0.05) with REE-citrate. No significant effects of REE were found on chill weight, percentages of breast meat, thigh weight, drumstick weight and wing weight. Concentrations of La and Ce in the liver and muscles were very low, accounting for 0.11-0.76 and 0.02-0.30 mg/kg respectively. There was weak tendency for a dose-response relationship especially in the groups supplemented with REE-chlorides. The main blood serum biochemical parameters were not significantly affected by REE in the diets. The results suggest that dietary supplementation of low doses of REE-citrates might improve growth performance of broilers without affecting carcass composition and health of the broilers.

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

DOE PAGES

Migdisov, Artaches; Williams-Jones, A. E.; Brugger, J.; ...

2016-06-11

For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C. Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamicmore » properties of even the most common REE minerals. The discrepancies between the predictions and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Here, our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.« less

Sr-Nd-Hf isotopes of the intrusive rocks in the Cretaceous Xigaze ophiolite, southern Tibet: Constraints on its formation setting

NASA Astrophysics Data System (ADS)

Zhang, Liang-Liang; Liu, Chuan-Zhou; Wu, Fu-Yuan; Zhang, Chang; Ji, Wei-Qiang; Wang, Jian-Gang

2016-08-01

The Cretaceous Xigaze ophiolite is best exposed at the central part of the Yarlung-Zangbo Suture Zone, Tibet Plateau. It consists of a thick section of mantle peridotites, but a relatively thin mafic sequence. This study presents geochronological and geochemical data for intrusive dykes (both mafic and felsic) and basalts to revisit the formation setting of the Xigaze ophiolite. The rodingites are characterized by high CaO and low Na2O contents relative to mafic dykes and show big variations in trace element compositions. Both gabbros and diabases have similar geochemical compositions, with MgO contents of 6.42-11.48 wt% and Mg# of 0.56-0.71. They display REE patterns similar to N-MORB and are variably enriched in large ion lithophile elements. Basalts have fractionated compositions and display LREE-depleted patterns very similar to N-MORB. They do not show obvious enrichment in LILE and depletion in high-field-strength elements, but a negative Nb anomaly is present. The studied plagiogranites have compositions of trondhjemite to tonalite, with high Na2O and low K2O contents. They have low TiO2 contents less than 1 wt%, consistent with melts formed by anatexis of gabbros rather than by differentiation of basalts. Zircons from seven samples, including three rodingites, three plagiogranites, and one gabbro, have been dated and yielded U-Pb ages of 124.6 130.5 Ma, indicating the Xigaze ophiolite was formed during the Early Cretaceous. They have mantle-like δ18O values of + 4.92 + 5.26‰ and very positive εHf(t) values of + 16 + 13.3. Ages of the rodingites and less altered gabbros indicate that serpentinization was occurred at 125 Ma. Occurrence of both gabbroic and diabase dykes within the serpentinites suggests that the mantle lithosphere of the Xigaze ophiolite was rapidly exhumed. Both mafic and felsic dykes have slightly more radiogenic 87Sr/86Sr ratios relative to MORB, but depleted Hf-Nd isotpe compositions. They have a limited range of εNd(t) values of + 7.9 + 8.9 but variable εHf(t) values ranging from + 9.9 to + 16.7, which are similar to the global MORB. This indicates that the intrusive dykes within the Xigaze ophiolite were derived from a depleted mantle source, which has not been obviously affected by recycling of subducted materials. The MOR-type basalts in this study, combined with the basalts with SSZ signatures previous reported in the literature indicate the diversity of basalts in the Xigaze ophiolite. We apply the forearc hyperextension model to reconcile the occurrence of both MOR- and SSZ-type basalts in the Xigaze ophiolite. In this model, the SSZ-type basalts were produced by melting of the metasomatized mantle wedge during exhumation, whereas the MOR-type basalts were derived from the upwelling asthenosphere triggered by forearc hyperextension.

Economic assessment for recycling critical metals from hard disk drives using a comprehensive recovery process

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

Nguyen, Ruby Thuy; Diaz, Luis A.; Imholte, D. Devin

Since the 2011 price spike of rare earth elements (REEs), research on permanent magnet recycling has blossomed globally to reduce future REE criticality. Hard disk drives (HDDs) have emerged as one feasible feedstock for recovering valuable REEs such as praseodymium, neodymium, and dysprosium. However, current processes for recycling e-waste only focus on certain metals due to feedstock and metal price uncertainties. In addition, some believe that recycling REEs is unprofitable. To shed some light on the economic viability of REE recycling from HDDs, this paper combines techno-economic information of a hydrometallurgical process with end-of-life HDD availability in a simulation model.more » Results showed that adding REEs to HDD recycling was profitable given current prices. As a result, recovered REEs could meet up to 5.1% rest of world (excluding China) magnet demand. Aluminum, gold, copper scrap and REEs were the primary main revenue streams from HDD recycling.« less

Economic assessment for recycling critical metals from hard disk drives using a comprehensive recovery process

DOE PAGES

Nguyen, Ruby Thuy; Diaz, Luis A.; Imholte, D. Devin; ...

2017-06-05

Since the 2011 price spike of rare earth elements (REEs), research on permanent magnet recycling has blossomed globally to reduce future REE criticality. Hard disk drives (HDDs) have emerged as one feasible feedstock for recovering valuable REEs such as praseodymium, neodymium, and dysprosium. However, current processes for recycling e-waste only focus on certain metals due to feedstock and metal price uncertainties. In addition, some believe that recycling REEs is unprofitable. To shed some light on the economic viability of REE recycling from HDDs, this paper combines techno-economic information of a hydrometallurgical process with end-of-life HDD availability in a simulation model.more » Results showed that adding REEs to HDD recycling was profitable given current prices. As a result, recovered REEs could meet up to 5.1% rest of world (excluding China) magnet demand. Aluminum, gold, copper scrap and REEs were the primary main revenue streams from HDD recycling.« less

Zircon/fluid trace element partition coefficients measured by recrystallization of Mud Tank zircon at 1.5 GPa and 800-1000 °C

NASA Astrophysics Data System (ADS)

Ayers, John C.; Peters, Timothy J.

2018-02-01

Hydrothermal zircon grains have trace element characteristics such as low Th/U, high U, and high rare earth element (REE) concentrations that distinguish them from magmatic, metamorphic, and altered zircon grains, but it is unclear whether these characteristics result from distinctive fluid compositions or zircon/fluid fractionation effects. New experiments aimed at measuring zircon/fluid trace element partition coefficients Dz/f involved recrystallizing natural Mud Tank zircon with low trace element concentrations in the presence of H2O, 1 m NaOH, or 1 m HCl doped with ∼1000 ppm of rare earth elements (REE), Y, U and Th and ∼500 ppm of Li, B, P, Nb, Ba, Hf, and Ta. Experiments were run for 168 h at 1.5 GPa, 800-1000 °C, and fO2 = NNO in a piston cylinder apparatus using the double capsule method. LA-ICP-MS analysis shows that run product zircon crystals have much higher trace element concentrations than in Mud Tank zircon starting material. Dz/f values were estimated from run product zircon analyses and bulk composition using mass balance. Most elements behave incompatibly, with median Dz/f being highest for Hf = 8 and lowest for B = 0.02. Addition of NaOH or HCl had little influence on Dz/f values. Dz/f for LREE are anomalously high, likely due to contamination of run product zircon with quenched solutes enriched in incompatible elements, so DLREE were estimated using lattice strain theory. Brice curves for +3 ions yield zircon/fluid DLu/DLa of ∼800-5000. A Brice curve fit to +4 ions yielded DCe4+ values. Estimated concentrations of Ce3+ and Ce4+ show that the average Ce4+/Ce3+ in zircon of 27 is much higher than in fluid of 0.02. Th and U show little fractionation, with median DTh/DU = 0.7, indicating that the low Th/U in natural hydrothermal zircon is inherited from the fluid. Natural fluid compositions estimated from measured Dz/f and published compositions of hydrothermal zircon grains from aplite and eclogite reflect the mineralogy of the host rock, e.g., fluid in equilibrium with eclogite garnet is depleted in heavy REE relative to middle REE, and has low Th/U.