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.

Rare earth elements as a fingerprint of soil components solubilization

NASA Astrophysics Data System (ADS)

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

2009-04-01

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

Rare earth 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.

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.

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 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.

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.

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.

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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.

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.

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.

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

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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.

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.

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.

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.

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 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.

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.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Rare earth elements 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.

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.

Fractionation of rare earth elements in the Mississippi River estuary and river sediments

NASA Astrophysics Data System (ADS)

Adebayo, S. B.; Johannesson, K. H.

2017-12-01

This study presents the first set of data on the fractionation of rare earth elements (REE) in the mixing zone between the Mississippi River and the Gulf of Mexico, as well as the fractionation of REE in the operationally defined fractions of Mississippi River sediments. This subject is particularly important because the Mississippi river is one of the world's major rivers, and contributes a substantial amount of water and sediment to the ocean. Hence, it is a major source of trace elements to the oceans. The geochemistry of the REE in natural systems is principally important because of their unique chemical properties, which prompt their application as tracers of mass transportation in modern and paleo-ocean environments. Another important consideration is the growth in the demand and utilization of REE in the green energy and technology industries, which has the potential to bring about a change in the background levels of these trace elements in the environment. The results of this study show a heavy REE enrichment of both the Mississippi River water and the more saline waters of the mixing zone. Our data demonstrate that coagulation and removal of REE in the low salinity region of the estuary is more pronounced among the Light REE ( 35% for Nd) compared to the Heavy REE. Remarkably, our data also indicate that REE removal in the Mississippi River estuary is significantly less than that observed in other estuaries, including the Amazon River system. We propose that the high pH/alkalinity of the Mississippi River is responsible for the greater stability of REE in the Mississippi River estuary. The results of sequential extraction of river sediments reveal different Sm/Nd ratios for the various fractions, which we submit implies different 143Nd/144Nd ratios of the labile fractions of the sediments. The possible impact of such hypothesized different Nd isotope signatures of labile fractions of the river sediments on Gulf of Mexico seawater is under investigation.

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.

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.

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.

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.

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 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.

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

Revisit of rare earth element fractionation during chemical weathering and river sediment transport

NASA Astrophysics Data System (ADS)

Su, Ni; Yang, Shouye; Guo, Yulong; Yue, Wei; Wang, Xiaodan; Yin, Ping; Huang, Xiangtong

2017-03-01

Although rare earth element (REE) has been widely applied for provenance study and paleoenvironmental reconstruction, its mobility and fractionation during earth surface processes from weathering to sediment deposition remain more clarification. We investigated the REE fractionations during chemical weathering and river sediment transport based on the systematic observations from a granodiorite-weathering profile and Mulanxi River sediments in southeast China. Two chemical phases (leachates and residues) were separated by 1 N HCl leaching and the leachates account for 20-70% of the bulk REE concentration. REEs in the weathering profile have been mobilized and fractionated to different extents during chemical weathering and pedogenesis. Remarkable cerium anomalies (Ce/Ce* = 0.1-10.6) occur during weathering as a result of coprecipitation with Mn (hydro)oxides in the profile, while poor or no Ce anomalies in the river sediments were observed. This contrasting feature sheds new light on the indication of Ce anomaly for redox change. The hydraulic sorting-induced mineral redistribution can further homogenize the weathering and pedogenic alterations and thus weaken the REE fractionations in river sediments. The mineral assemblage is the ultimate control on REE composition, and the Mn-Fe (hydro)oxides and secondary phosphate minerals are the main hosts of acid-leachable REEs while the clay minerals could be important reservoirs for residual REEs. We thus suggest that the widely used REE proxies such as (LREE/HREE)UCC ratio in the residues is reliable for the indication of sediment provenance, while the ratio in the leachates can indicate the total weathering process to some extent.

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.

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

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.

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.

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.

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

Geochemical evidence for the provenance of aeolian deposits in the Qaidam Basin, Tibetan Plateau

NASA Astrophysics Data System (ADS)

Du, Shisong; Wu, Yongqiu; Tan, Lihua

2018-06-01

The main purpose of this study is to analyse the material source of different grain-size components of dune sand in the Qaidam Basin. We determined the trace and rare earth element (REE) compositions and Sr-Nd isotopic compositions of the coarse (75-500 μm) and fine (<75 μm) fractions of surface sediment samples. The comparison of the immobile trace element and REE compositions, Sr-Nd isotopic compositions and multidimensional scaling (MDS) results of the dune sands with those of different types of sediments in potential source areas revealed the following information. (1) The fine- and coarse-grained fractions of dune sands in the Qaidam Basin exhibit distinctly different elemental concentrations, elemental patterns and characteristic parameters of REE. Moreover, Sr-Nd isotopic differences also exist between different grain-size fractions of aeolian sand, which means that different grain-size fractions of these dune sands have different source areas. (2) The geochemical characteristics of the coarse particles of dune sand exhibit obvious regional heterogeneity and generally record a local origin derived from local fluvial sediments and alluvial/proluvial sediments. The coarse- and fine-grained dune sand in the southern Qaidam Basin mainly came from Kunlun Mountains, whereas the coarse- and fine-grained dune sand in the northeastern Qaidam Basin mainly came from Qilian Mountains. (3) The fine-grained fractions of sediments throughout the entire Qaidam Basin may have been affected by the input of foreign materials from the Tarim Basin.

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.

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.

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.

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.

Fractionation of rare earth and other trace elements in crabs, Ucides cordatus, from a subtropical mangrove affected by fertilizer industry.

PubMed

Bosco-Santos, Alice; Luiz-Silva, Wanilson; Silva-Filho, Emmanoel Vieira da; Souza, Monique Dias Corrêa de; Dantas, Elton Luiz; Navarro, Margareth Sugano

2017-04-01

Fractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms, and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers (contamination source), which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint. Copyright © 2016. Published by Elsevier B.V.

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

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

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

USGS Publications Warehouse

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

2002-01-01

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

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.

Germanium and rare earth elements in soils under different land use types in the area of Freiberg (Saxony, Germany)

NASA Astrophysics Data System (ADS)

Wiche, Oliver; Moschner, Christin; Székely, Balázs

2017-04-01

A geochemical mapping study was conducted to investigate the spatial distribution and chemical fractionation of germanium (Ge) and selected rare earth elements (REEs) in topsoils and soil-grown plants under different land use types (moist grassland, mesic grassland, arable land) in the area of Freiberg (Saxony, Germany). The area of Freiberg is characterized by the mining of polymetallic sulphide deposits (Pb, As, Zn, Cd) which led to the pollution of top soils with metals and metalloids due to local emissions from metal smelting plants that occur widespread in the area. Since Ge often appears to be associated to sulphide ores like sphalerite, galenite and argyrodite, (post-)mining areas such as the Freiberg region are paradigmatic for phytomining research. The study area covers approximately 1,000 km2 in the south of Central Saxony, and 138 samples from 46 sampling sites were examined. Additionally, at each sampling site plant samples were collected. On arable soils the plant samples represented the cultivated crop species. On sites in mesic and moist grassland, samples from the most dominant plant species were taken and measured with ICP-MS. Ge and REEs in soils were partitioned by a sequential extraction procedure into mobile/exchangeable (Fraction 1), acid soluble (Fraction 2), bound to organic matter (Fraction 3), amorphous Fe/Mn-oxides (Fraction 4), crystalline Fe/Mn-oxides (Fraction 5) and residual fractions (Fraction 6). Total concentrations of Ge and REEs in soil varied considerably ranging from 1.0 µg g-1 to 4.3 µg g-1 for Ge and 97 µg g-1 to 402 µg g-1 for total REE concentrations. Elements in potentially plant available fractions (sums of Fraction 1 - Fraction 4) represented 8% of total Ge and 30% of total REEs, respectively. Soils on moist grasslands contained significantly higher total concentrations of Ge and REEs and higher concentrations of Ge and REEs in potentially plant available soil fractions compared to soils of mesic grasslands and arable land. Highest concentrations of Ge could be measured in plant species growing on moist grassland. The results of this study indicate that moist grasslands may act as sinks for Ge and REEs. In these soils high amounts of soil organic matter may foster the formation of labile element pools, increasing the availability of Ge and REEs. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. BS contributed as an Alexander von Humboldt Research Fellow. The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.

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.

The impact of transport processes on rare earth element patterns in marine authigenic and biogenic phosphates

NASA Astrophysics Data System (ADS)

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

2017-04-01

Rare earth elements (REEs) are commonly used proxies to reconstruct water chemistry and oxygen saturation during the formation of authigenic and biogenic phosphates in marine environments. In the modern ocean REEs exhibit a distinct pattern with enrichment of heavy REEs and strong depletion in cerium (Ce). The wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry has been very different in the Earth's past. However, both early and late diagenesis are known to affect REE signatures in phosphates altering primary marine signals. Herein we present a dataset of REE signatures in 38 grain specific LA-ICP-MS measurements of isolated phosphate and carbonate grains in three discrete rock samples. The phosphates mainly consist of authigenic phosphates and phosphatized microfossils that formed in a microbially mediated micro-milieu. In addition, isolated biogenic and reworked phosphatic grains are also present. The phosphates are emplaced in bioclastic grain- to packstones deposited on a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene Monterey event. The results reveal 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. Grain shape and REE patterns together indicate that authigenic, biogenic and reworked phosphates have distinct REE patterns irrespective of the sample. Our study shows that while REE patterns in phosphates do reflect water chemistry during authigenesis, they are often already heavily altered during reworking, a process, which can occur in geologically negligible timespans. REE patterns are therefore more likely to reflect complex enrichment processes after their formation. Similarities in the REE patterns of reworked and biogenic phosphate further suggest that the frequently observed hat-shaped pattern in biogenic phosphates can result from increased middle REE (Neodymium to Holmium) scavenging during taphonomic processes prior to final deposition. Cluster analysis coupled with sedimentological and previously published geochemical data (bulk carbon isotope and X-ray fluorescence spectrometry) allowed 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.

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.

Size distribution of rare earth elements in coal ash

USGS Publications Warehouse

Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.

2015-01-01

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

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.

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.

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

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.

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.

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.

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.

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.

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

DOE PAGES

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

2017-10-20

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

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

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

Balboni, Enrica; Spano, T; Cook, N

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

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.

Hydrothermal sediments as a potential record of seawater Nd isotope compositions: The Rainbow vent site (36°14'N, Mid-Atlantic Ridge)

NASA Astrophysics Data System (ADS)

Chavagnac, ValéRie; Palmer, Martin R.; Milton, J. Andrew; Green, Darryl R. H.; German, Christopher R.

2006-09-01

Geochemical compositions and Sr and Nd isotopes were measured in two cores collected ˜2 and 5 km from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge. Overall, the cores record enrichments in Fe and other metals from hydrothermal fallout, but sequential dissolution of the sediments allows discrimination between a leach phase (easily leachable) and a residue phase (refractory). The oxy-anion and transition metal distribution combined with rare earth element (REE) patterns suggest that (1) the leach fraction is a mixture of biogenic carbonate and hydrothermal Fe-Mn oxy-hydroxide with no significant contribution from detrital material and (2) >99.5% of the REE content of the leach fraction is of seawater origin. In addition, the leach fraction has an average 87Sr/86Sr ratio indistinguishable from modern seawater at 0.70916. Although we lack the ɛNd value of present-day deep water at the Rainbow vent site, we believe that the REE budget of the leach fraction is predominantly of seawater origin. We suggest therefore that the leach fraction provides a record of local seawater ɛNd values. Nd isotope data from these cores span the period of 4-14 ka (14C ages) and yield ɛNd values for North East Atlantic Deep Water (NEADW) that are higher (-9.3 to -11.1) than those observed in the nearby Madeira Abyssal Plain from the same depth (-12.4 ± 0.9). This observation suggests that either the Iceland-Scotland Overflow Water (ISOW) and Lower Deep Water contributions to the formation of NEADW are higher along the Mid-Atlantic Ridge than in the surrounding basins or that the relative proportion of ISOW was higher during this period than is observed today. This study indicates that hydrothermal sediments have the potential to provide a higher-resolution record of deep water ɛNd values, and hence deepwater circulation patterns in the oceans, than is possible from other types of sediments.

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.

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

NASA Astrophysics Data System (ADS)

Fan, J.; Kerrich, R.

1997-11-01

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

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

NASA Astrophysics Data System (ADS)

Deutsch, A.

2012-04-01

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

Geochemical 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.

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.

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

NASA Astrophysics Data System (ADS)

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

1994-07-01

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

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling.

PubMed

Ding, ShiMing; Liang, Tao; Zhang, ChaoSheng; Yan, JunCai; Zhang, ZiLi

2006-12-01

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation-proton exchange with HA (i.e., pK(MHA)) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK(MHA) values is more suitable for use in Model V for the simulation of REE complexation with HA.

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone.

PubMed

Dai, Qili; Li, Liwei; Yang, Jiamei; Liu, Baoshuang; Bi, Xiaohui; Wu, Jianhui; Zhang, YuFen; Yao, Lin; Feng, Yinchang

2016-09-01

Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due to the unclear atmospheric signature of these elements and their adverse impact on human health and the environment. In this study, ambient particulate matter of different sizes was collected from one site in an integrated iron and steelmaking industrial zone (HG) and one urban background site with no direct industrial emissions (ZWY) during a 1-year sampling campaign in China. The total concentrations of REEs for TSP, PM10, and PM2.5 were 27.248, 14.989, 3.542 ng/m(3) in HG and 6.326, 5.274, 1.731 ng/m(3), respectively, in ZWY, which revealed the local influence of the steelmaking activities to the air quality. With respect to ZWY, the REEs in HG site are obviously fractionated in the coarser fraction, and LREEs account for more than 80 % of the total REE burden in all of the samples. Additionally, the REEs in HG and ZWY show a homogeneous trend with successively increased LREE/HREE ratios from the coarse particles to the fine particles. In our samples, La, Ce, Nd, and Sm are the most enriched rare earth elements, especially in the HG site. Moreover, ternary diagrams of LaCeSm indicate that the REEs in HG are potentially contributed by steelworks, carrier vehicles, coal combustion, and road dust re-suspension.

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.

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.

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

PubMed

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

2014-07-01

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

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

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

Mattigod, Shas V.

2003-08-01

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

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.

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

NASA Astrophysics Data System (ADS)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

Association of Sub-continental and Asthenosphere related Volcanism in NW Iran,Implication forMantle thermal perturbation induced by slab break off and collision event

NASA Astrophysics Data System (ADS)

Jahangiri, A.

2017-12-01

Cenozoic magmatic rocks occur extensively in the north of the Zagros suture zone and constitute a significant component of the continental crust in this segment of the Alpine-Himalayan orogenic belt. They range in age from Eocene to quaternary. Miocene to Plio-Quaternary volcanism with post-collisional related significant is covered vast areas in NW Iran. These volcanic rocks can be divided into three different sub-groups on the basis of their mineralogy, geochemistry and magma sources including: 1. alkaline leucite-bearing mafic rocks, which are characterized with high ratios of K2O/Na2O, high content LILE and low HFS elements like Ti, Nb and Ta. They are display fractionated REE patterns and based on different discrimination diagrams show similarity with subduction related magmas. 2- Olivine basalt to trachy-basaltic samples which shows similarity to within plate basalts with high content of TiO2, Nb, Ta and fractionated REE pattern. However, compared with a global average of OIB, they are display slightly higher LIL elements and lower HFS elements concentrations, features that resemble to the arc magmas and suggest that the source of the magmas may have been contaminated by slab-derived fluids. These rocks have simple mineralogical composition with plagioclase, clinopyroxene and olivine. 3- Dominant dacitic volcanic rocks with adakitic geochemical characteristics such as highly fractionate REE pattern and high Sr/Y ratio. Generation of adakitic magmas can be related to increased temperatures in the subduction zone due to mantle upwelling and slab tearing. Subsequent asthenospheric upwelling could be caused direct melting of sub-continental mantle to produce the alkaline magmas, with high contents of K2O, MgO and volatile rich phase's potassic magmas that led to crystallization of leucite, phlogopite, apatite and olivine in studied samples. Rupture of the continental lithosphere by strike-slip-related transtensional deformation might have caused decompression partial melting of the asthenospheric mantle and generating alkali basalts. Continental lithosphere rupturing is occurred subsequent to slab breakoff/delamination and sub-continental mantle thermal perturbation processes following closure of Neo-Tethys and collision of Arabian plate with microplate of Iran.

Rare earth element geochemistry of feldspars: examples from Fe-oxide Cu-Au systems in the Olympic Cu-Au Province, South Australia

NASA Astrophysics Data System (ADS)

Kontonikas-Charos, Alkis; Ciobanu, Cristiana L.; Cook, Nigel J.; Ehrig, Kathy; Krneta, Sasha; Kamenetsky, Vadim S.

2018-04-01

Rare earth element (REE) fractionation trends in feldspars are reported from Olympic Dam (including Wirrda Well and Phillip's Ridge) and Cape Donington (Port Lincoln), for comparison with two other igneous-hydrothermal terranes within the eastern Gawler Craton: Moonta-Wallaroo and Hillside. The case studies were selected as they represent 1590 Ma Hiltaba Suite and/or 1845 - 1810 Ma Donington Suite granites, and, aside from Cape Donington, are associated with Mesoproterozoic iron-oxide copper gold (IOCG)-type mineralization. Both plagioclase and alkali feldspar were analyzed within selected samples with the purpose of constraining and linking changes in REE concentrations and fractionation trends in feldspars to local and whole-rock textures and geochemistry. Two unique, reproducible fractionation trends were obtained for igneous plagioclase and alkali feldspars, distinguished from one another by light rare earth element enrichment, Eu-anomalies and degrees of fractionation (e.g. La/Lu slopes). Results for hydrothermal albite and K-feldspar indicate that REE concentrations and fractionation trends are generally inherited from igneous predecessors, however in some instances, significant amounts of REE appear to have been lost to the fluid. These results may have critical implications for the formation of world-class IOCG systems, in which widespread alkali metasomatism plays a key role by altering the physical and chemical properties of the host rocks during early stages of IOCG formation, as well as trapping trace elements (including REE).

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.

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.

Cerium and Neodymium Isotope Fractionation in Geochemical Samples

NASA Astrophysics Data System (ADS)

Ohno, T.; Ishibashi, T.

2014-12-01

The study of naturally occurring isotopic variations of rare earth elements (REE) has a potentially significant influence in geochemical research fields with other traditional studies of REE. One of the key features of REE are their chemical similarities and gradual changes of ionic radius, which may make the isotopic variation of REE a potential tool to understand the mechanisms of isotopic fractionation in nature. Among the REE, geochemical and physicochemical features of Ce could be anomalous, because Ce could be present as the tetravalent (+IV) state as well as the common trivalent (+III) state of other REE. Since the oxidation state of Ce can change by reflecting the redox conditions of the environment, the measured differences in the degree of isotopic fractionation between Ce and other REE can provide unique information about the redox conditions. In this study, we developed a new analytical method to determine the mass-dependent isotopic fractionations of Ce and Nd in geochemical samples. The reproducibility of the isotopic ratio measurements on 142Ce/140Ce, 146Nd/144Nd and 148Nd/144Nd were 0.08‰ (2SD, n=25), 0.06‰ (2SD, n=39) and 0.12‰ (2SD, n=39), respectively. The present technique was applied to determine the variations of the Ce and Nd isotopic ratios for five geochemical reference materials (igneous rocks, JB-1a and JA-2; sedimentary rocks, JMn-1, JCh-1 and JDo-1). The resulting ratios for two igneous rocks (JB-1a and JA-2) and two sedimentary rocks (JMn-1 and JCh-1) did not vary significantly among the samples, whereas the Ce and Nd isotope ratios for the carbonate samples (JDo-1) were significantly higher than those for igneous and sedimentary rock samples. The 1:1 simple correlation between δ142Ce and δ146Nd indicates that there were no significant difference in the degree of isotopic fractionation between the Ce and Nd. This suggests that the isotopic fractionation for Ce found in the JDo-1 could be induced by physicochemical processes without changing the oxidation status of Ce, since the redox-reaction can produce larger isotopic fractionation than the reactions without changing the oxidation state. The variations in the Ce and Nd isotope ratios for geochemical samples could provide new information concerning the physico-chemical processes of the sample formation.

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.

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

USGS Publications Warehouse

Piper, David Z.; Bau, Michael

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

Johannesson, K. H.; Tang, J.

2003-12-01

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

Rare Earth Elements in Alberta Oil Sand Process Streams

DOE PAGES

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

2017-04-05

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

Rare Earth Elements in Alberta Oil Sand Process Streams

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

Roth, Elliot; Bank, Tracy; Howard, Bret

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

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.

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.

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

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

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

The Northeast Kingdom batholith, Vermont: magmatic evolution and geochemical constraints on the origin of Acadian granitic rocks

USGS Publications Warehouse

Ayuso, R.A.; Arth, Joseph G.

1992-01-01

Five Devonian plutons (West Charleston, Echo Pond, Nulhegan, Derby, and Willoughby) that constitute the Northeast Kingdom batholith in Vermont show wide ranges in elemental abundances and ratios consistent with major crustal contributions during their evolution. The batholith consists of metaluminous quartz gabbro, diorite and quartz monzodiorite, peraluminous granodiorite and granite, and strongly peraluminous leucogranite. Contents of major elements vary systematically with increasingSiO40) and have small negative Eu anomalies. The strongly peraluminous Willoughby leucogranite has unique trace-element abundances and ratios relative to the rest of the batholith, including low contents of Hf, Zr, Sr, and Ba, low values of K/Rb (80-164), Th/Ta (<9), Rb/Cs (7-40), K/Cs (0.1-0.5), Ce/Pb (0.5-4), high values of Rb/Sr (1-18) low to moderate REE contents and light-REE enriched patterns (with small negative Eu anomalies). Flat REE patterns (with large negative Eu anomalies) are found in a small, hydrothermally-altered area characterized by high abundances of Sn (up to 26 ppm), Rb (up to 670 ppm), Li (up to 310 ppm), Ta (up to 13.1 ppm), and U (up to 10 ppm). There is no single mixing trend, fractional crystallization assemblage, or assimilationscheme that accounts for all trace elementvariations from quartz gabbro to granite in the Northeast Kingdom batholith. The plutons originated by mixing mantle-derived components and crustal melts generated at different levels in the heterogeneous lithosphere in a continental collisional environment. Hybrid rocks in the batholith evolved by fractional crystallization and assimilation of country rocks (<50% by mass), and some of the leucogranitic rocks were subsequently disturbed by a mild hydrothermal event that resulted in the deposition of small amounts of sulfide minerals. ?? 1992 Springer-Verlag.

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.

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

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.

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.

Trace-element abundances in several new ureilites

NASA Technical Reports Server (NTRS)

Boynton, William V.; Hill, Dolores H.

1993-01-01

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

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

PubMed

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

2017-11-28

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

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.

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.

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.

REE investigation of the Motru Dyke System components from the Danubian basements (South Carpathians, Romania)

NASA Astrophysics Data System (ADS)

Campeanu, Mara; Balica, Constantin; Balintoni, Ioan; Tănăselia, Claudiu; Cadar, Oana

2017-04-01

Dragsan and Lainici-Paius groups represent the basement components of the Danubian Alpine units (South Carpathians, Romania), which consist of medium-grade metamorphic rocks. A subvolcanic system of dykes (i.e. Motru Dyke System - MDS) crosscut mostly the Lainici Paius basement as an effect of a late-Variscan termo-tectonic event. The geochemical features, frame the MDS components within a wide range of petrotypes (basaltic andesites to rhyolites), and define a wide differentiation series. Classically this subvolcanic system was inferred to be in connection to a unique mantle source [1], however, recent studies [2,3] suggest a mixed mantle-crust source, based on the interpretation of the trace elements in conjunction with Sr and Nd isotope data. Aditionally, the presence of relict zircon grains consolidates this assumption. New REE data collected from eight MDS components, generally confirm the mixed mantle-crust source hypothesis. The distribution patterns reveal two groups of samples. The first group (six samples) is moderately enriched in REE and shows moderately fractionated patterns with (La/Yb)N between 7-21 and low Eu/Eu* (0.81-0.9). The second group, strongly enriched in light REE, have high (La/Yb)N and strong negative Eu anomaly (Eu/Eu* of 0.41 and 0.38 respectively). REE vary between 107-147 ppm for the first group and 612 ppm - 907ppm for the second group. We can assume a stronger fractionation of plagioclase as well as of garnet and amphibole for the second group. With a flatter pattern, for the first group of samples, the fractionation of these minerals appears to be moderate. The emplacement age of MDS has been long disputed, since it was supposed as pre-Silurian for a long time. However, newly zircon U/Pb isotopic dating performed on two collected samples indicate a mean age of 300 My [2,3]. Owing to the croscutting relationships with the post-colisional granitoid plutons emplaced in the Danubian basement during the late Variscan, and based on new geochemical data, we consider that MDS was generated from a mixed mantle and crustal source, and emplaced in a post-collisional tectonic setting during the final stages of the Variscan orogeny. Acknowledgements: study supported by PN-II-ID-PCE-2011-3-0100 Grant, UEFIS-CDI and Core Program - ANCS PN 16.40.02.01. References: [1] Féménias, O., Berza, T., Tatu, M., Diot, H., Demaiffe, D., 2008. Nature and signifiance of a Cambro-Ordovician high-K, calc-alkaline sub-volcanic suite: the late- to post-orogenic Motru Dyke Swarm (Southern Carpathians, Romania), Int. J. Earth Sci. [2] Câmpeanu, M., Balica, C., Balintoni, I.C., 2014. Geochronology and emplacement conditions of Motru Dyke System (South Carpathians, Romania), Bul. Shk. Gjeol.2014- Special Issue, Vol 1/2014, Proceedings of XX CBGA Congress, Tirana, Albania, p.198. [3] Câmpeanu, M., Balica, C., Balintoni, I.C., Tanaselia, C., 2015. Motru Dyke Swarm (South Carpathians, Romania): Emplacement age and geotectonic setting (0) Goldschmidt Abstracts, 2015-459.

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.

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.

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.

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.

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.

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.

REE Sorption Study of Seived -50 +100 Mesh Fraction of Media #1 in Brine #1 at Different Concentrations of REE at 70C

DOE Data Explorer

Gary Garland

2015-06-29

This dataset shows the sorption capacities of smaller grain size (-50 +100 mesh) of media #1 in brine #1 at different starting concentrations of REE's at elevated temperature of 70C. The experimental conditions are 2g of -50 +100 mesh media #1 to 150mL of REE solution at concentartions of .2ppm each, 2ppm each, and 20ppm each. The pH of the solution is 5.5, and the temperature was at 70C.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

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

The chemistry of rare earth elements in the solar nebula

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Rare earth elements in sinters from the geothermal waters (hot springs) on the Tibetan Plateau, China

NASA Astrophysics Data System (ADS)

Feng, Jin-Liang; Zhao, Zhen-Hong; Chen, Feng; Hu, Hai-Ping

2014-10-01

The mineralogical and geochemical composition of sinters from the geothermal areas on the Tibetan Plateau was determined. They occur as siliceous, salty and calcareous sinters but biogenic siliceous sinters were also found. The analyses indicate that there are no distinct inter -element relationships between individual rare earth elements (REEs) and other elements. Formed from the same geothermal water, the mineralogical and chemical composition of the sinters is influenced by their genesis and formation conditions. The REE distributions depend on the origin of the sinters. Fe-Mn phases in sinters tend to scavenge more REEs from geothermal water. Neither the REE fractionation nor the Ce anomaly seems to be associated with Fe-Mn phases in the sinters. The fourth tetrads of some sinters display weak W-type (concave) effects. In contrast, the third tetrads present large effects in some sinters due to positive Gd anomalies. The origin of the positive Eu anomalies in some sinters seems to be caused by preferential dissolution of feldspars during water-rock interaction. The complexing ligands in geothermal water may contribute significantly to the fractionation of REEs in sinters. The dominant CO32- and HCO3- complexing in geothermal water favors enrichment of heavy REEs in calcareous sinters.

Rare earth elements in German soils - A review.

PubMed

Mihajlovic, Julia; Rinklebe, Jörg

2018-08-01

Rare earth elements (REEs) are increasingly used in high-tech industry, agriculture, and healthcare technologies what leads to their release into soils and waters, and to the transfer into plants what may have negative impacts on human health and the environment. The toxicity and potential mobilization of REEs in soils can be assessed by their content and geochemical behavior along with soil properties. However, those interactions are so far not reviewed in German soils although such a review is important for a better understanding and prediction of the potential mobilization and toxicity. Therefore, this review summarizes the recent knowledge about REE contents and potential mobilization in different soil profiles in Germany. We found that the REE content tends to decrease in dependence on the parent material in the following order: Carbonatite > basalt > orthogneiss > clay slate > loess > sandstone > Pleistocene and Holocene sediments > organic material. Also, we used data of earlier studies, summarized and newly evaluated those data aiming to quantify the factors influencing the total REE content in German soil profiles. The contents of REEs in soil profiles of different parent material showed significant relations with content of clay, carbonate, organic matter, aluminium, iron, and manganese. Geochemical fractionation results suggest that the bioavailability of REEs is relatively low while the residual fraction is relatively high in German soils. In soils, where water fluctuations are important, the redox potential is a key factor controlling the mobilization of REEs also via related changes of pH. Copyright © 2018 Elsevier Ltd. All rights reserved.

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 river waters

NASA Technical Reports Server (NTRS)

Goldstein, Steven J.; Jacobsen, Stein B.

1988-01-01

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

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

PubMed

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

2017-10-18

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

Anomalous REE patterns in unequilibrated enstatite chondrites: Evidence and implications

NASA Technical Reports Server (NTRS)

Crozaz, Ghislaine; Hsu, Weibiao

1993-01-01

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

Rare earths in the Leadville Limestone and its marble derivates

USGS Publications Warehouse

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

1975-01-01

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

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau, East Sea

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Jeong, Kap-Sik; Cho, Jin Hyung; Lee, Jun Ho; Jang, Seok; Kim, Seong Ryul

2014-03-01

We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.

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.

Trace elements in Gem-Quality Diamonds - Origin and evolution of diamond-forming fluid inclusions

NASA Astrophysics Data System (ADS)

Pearson, Graham; Krebs, Mandy; Stachel, Thomas; Woodland, Sarah; Chinn, Ingrid; Kong, Julie

2017-04-01

In the same way that melt inclusions in phenocrysts have expanded our idea of melt formation and evolution in basalts, studying fluids trapped in diamonds is providing important new constraints on the nature of diamond-forming fluids. Fibrous and cloudy diamonds trap a high but variable density of fluid inclusions and so have been extensively studied using major and trace element compositions. In contrast, constraining the nature of the diamond-forming fluid for high purity gem-quality diamonds has been restricted by the rarity of available high quality trace element data. This is due to the extremely low concentrations of impurities that gem diamonds contain - often in the ppt range. The recent discovery of fluids in gem diamonds showing similar major element chemistry to fluid-rich diamonds suggest that many diamonds may share a common spectrum of parental fluids. Here we test this idea further. Recent advances in analytical techniques, in particular the development of the "off-line" laser ablation pre-concentration approach, have allowed fully quantitative trace element data to be recovered from "fluid-poor", high quality gem diamonds. We present trace element data for gem diamonds from a variety of locations from Canada, S. Africa and Russia, containing either silicate or sulphide inclusions to examine possible paragenetic or genetic differences between fluids. REE abundance in the "gem" diamonds vary from 0.1 to 0.0001 x chondrite. To a first order, we observe the same spectrum of trace element compositions in the gem diamonds as that seen in fluid-rich "fibrous" diamonds, supporting a common origin for the fluids. REE patterns range from extremely flat (Ce/Yb)n 2.5 to 5 (commonly in sulphide-bearing diamonds) to >70, the latter having significantly greater inter-element HFSE/LILE fractionation. In general, the fluids from the sulphide-bearing diamonds are less REE-enriched than the silicate-bearing diamonds, but the ranges overlap significantly. The very large range in REE fractionation mimics very closely that produced in high pressure (5-6 GPa) experimental melts of CO2-H2O fluxed peridotite. Hence, the elemental characteristics of the fluids could be reconciled by the diamonds growing from such melts over a range of T and hence F, with the sulphide-bearing diamonds generally being produced by larger fraction (higher T) melts that have reacted less with their wall rocks. It is also possible that the less REE enriched fluids are consistent with derivation from more reduced CH4-bearing fluids that have lower solute capacity than oxidised fluids. This option is being evaluated.

Annual budget of Gd and related Rare Earth Elements in a river basin heavily disturbed by anthropogenic activities.

NASA Astrophysics Data System (ADS)

Hissler, Christophe; Stille, Peter; Guignard, Cédric; François Iffly, Jean; Pfister, Laurent

2014-05-01

The real environmental impact of micropollutants in river systems can be difficult to assess, essentially due to uncertainties in the estimation of the relative significance of both anthropogenic and natural sources. The natural geochemical background is characterized by important variations at global, regional or local scales. Moreover, elements currently considered to be undisturbed by human activities and used as tracers of continental crust derived material have become more and more involved in industrial or agricultural processes. The global production of lanthanides (REE), used in industry, medicine and agriculture, for instance, has increased exponentially from a few tons in 1950 to projected 185 kt in 2015. Consequently, these new anthropogenic contributions impact the natural cycle of the REE. Gd and related REE are now worldwide recognized as emergent micropollutants in river systems. Nevertheless, there is still a gap concerning their temporal dynamics in rivers and especially the quantification of both the anthropogenic and natural contributions in surface water. The acquisition of such quantitative information is of primordial interest because elements from both origins may present different bioavailability and toxicity levels. Working at the river basin scale allows for quantifying micropollutant fluxes. For this reason, we monitored water quality and discharge of the Alzette River (Luxembourg, Europe) over two complete hydrological cycles (2010-2013). The substantial contamination, is principally due to the steel industry in the basin, which has been active from 1875 until now, and to the related increase of urban areas. The particulate and dissolved fractions of river water were monitored using a multitracer approach (standard parameters for water quality including REE concentrations, Pb, Sr, Nd radiogenic isotopes) with two sampling setups (bi-weekly and flood event based sampling). This extensive sampling design allowed quantifying the annual budget of the REE in the particulate and dissolved fractions of the river water and the waste water treatment plant effluents. Enrichments in Gd have been observed for the dissolved fraction of the water during low water levels. This enrichment has not been detected in the surrounding soils of the basin and can be related to the effluents of the waste water treatment plants, which control the REE chemistry of the dissolved fraction during the low water period. When flood events occur, the Gd anomaly progressively disappears and gives way to the chemical signature of the basin soils. The REE and intense hydrological monitoring we performed at the same time allowed for the annual quantification of the anthropogenic vs. natural REE fluxes in the river water of this heavily polluted basin.

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.

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.

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

Record of Fluctuating Magmatic Environments, Melt Fractionation, and Mixing of Crystals: Elemental Compositions of Zircon Zones, Spirit Mountain Batholith, Nevada

NASA Astrophysics Data System (ADS)

Miller, C. F.; Claiborne, L. L.; Wooden, J. L.; Mazdab, F. K.; Walker, B. A.

2006-12-01

Spirit Mountain batholith is a large, tilted, subvolcanic intrusion in southernmost Nevada (Walker et al., in press; Lowery Claiborne et al., in press). Field relations and elemental chemistry of rocks ranging from felsic cumulates to leucogranites demonstrate both fractionation and frequent recharging. SHRIMP U-Pb analysis of zircon reveals a 2 m.y. history (17.4-15.3 Ma) for the batholith; almost all of the samples record multiple age populations. Elemental concentrations and zoning patterns document the utility of zircon in tracking magmatic environments and crystal transfer processes and provide important insights into the complex and protracted history of the batholith. The data lend strong support to the Watson et al. (2006) Ti-in-zircon thermometer. At reasonable a(TiO2) between 0.5 and 0.9, all calculated T's are consistent with petrological constraints and granite phase equilibria; using a(TiO2) = 0.7, T ranges from 675-900 C. Over this apparent T interval, which reflects a range in Ti from 3.2-34 ppm, concentrations of Hf (6000-18000 ppm), U (20-5000 ppm), and Th (50-13,000 ppm), and REE patterns all vary dramatically and systematically. Hf, U, Th, and Ce/Ce* are negatively correlated with T; LREE/MREE, MREE/HREE, and Eu/Eu* are positively correlated with T. These variations indicate that zircon preferentially incorporated Zr over Hf (hence falling Zr/Hf); U and Th behaved as strongly incompatible elements in the crystallizing assemblage as a whole; compatibility of REE increased with decreasing atomic number (effect of LREE accessories?); Eu+2 was more compatible (feldspars) and Ce+4 less compatible than equivalent +3 REE. All of these trends are consistent with the observed crystallizing assemblage and with general trends in whole rocks. More striking, however, is intrasample and intragrain variability. Although leucogranite samples have a larger proportion of zircon with compositions indicating low T and growth from fractionated melt, all samples have a very wide, and overlapping, range of zircon compositions. Many grains are very strongly zoned, and some individual grains show almost the full range of calculated T and elemental composition. Rims of zircons from the leucogranites are typically "cold" and evolved, but many have high-T interiors that contrast with host rock. Core-to-rim zoning is commonly not monotonic but rather strongly fluctuating, indicating that during growth zircon experienced episodes of increased T and immersion in less evolved melts. These patterns of compositional variability reveal that zircons survived heating events; were entrained in ascending fractionated melt; and were exchanged among contrasting magma batches. Such a history is consistent with protracted residence in a large, multiply replenished and rejuvenated mushy magma system in which melt fraction fluctuated in space and time.

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.

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.

Titanium isotopes and rare earth patterns in CAIs: Evidence for thermal processing and gas-dust decoupling in the protoplanetary disk

NASA Astrophysics Data System (ADS)

Davis, Andrew M.; Zhang, Junjun; Greber, Nicolas D.; Hu, Jingya; Tissot, François L. H.; Dauphas, Nicolas

2018-01-01

Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to 49Ti/47Ti, we found that ε50Ti values are somewhat variable among CAIs, and that ε46Ti is highly correlated with ε50Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between ε46Ti and ε50Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ‧49Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ‧49Ti is from ∼-4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

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.

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.

Physico-chemical characterisation of material fractions in residual and source-segregated household waste in Denmark.

PubMed

Götze, R; Pivnenko, K; Boldrin, A; Scheutz, C; Astrup, T Fruergaard

2016-08-01

Physico-chemical waste composition data are paramount for the assessment and planning of waste management systems. However, the applicability of data is limited by the regional, temporal and technical scope of waste characterisation studies. As Danish and European legislation aims for higher recycling rates evaluation of source-segregation and recycling chains gain importance. This paper provides a consistent up-to-date dataset for 74 physico-chemical parameters in 49 material fractions from residual and 24 material fractions from source-segregated Danish household waste. Significant differences in the physico-chemical properties of residual and source-segregated waste fractions were found for many parameters related to organic matter, but also for elements of environmental concern. Considerable differences in potentially toxic metal concentrations between the individual recyclable fractions within one material type were observed. This indicates that careful planning and performance evaluation of recycling schemes are important to ensure a high quality of collected recyclables. Rare earth elements (REE) were quantified in all waste fractions analysed, with the highest concentrations of REE found in fractions with high content of mineral raw materials, soil materials and dust. The observed REE concentrations represent the background concentration level in non-hazardous waste materials that may serve as a reference point for future investigations related to hazardous waste management. The detailed dataset provided here can be used for assessments of waste management solutions in Denmark and for the evaluation of the quality of recyclable materials in waste. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

Late Cenzoic rhyolites from the Kern Plateau, southern Sierra Nevada, California.

USGS Publications Warehouse

Bacon, C.R.; Duffield, W.A.

1981-01-01

Four late Cenozoic rhyolite domes lie atop the Kern Plateau, 30 to 40km S-SE of Mount Whitney. K-Ar and 40Ar/39Ar dating shows that Monache, Templeton, and Little Templeton Mountains are all about 2.4Ma old; a small dome nearby is approx 0.2Ma old. The three older rhyolites have SiO2 = 73-74% and have steep, fractionated rare earth element (REE) patterns; the youngest has SiO2 = 76% and a concave-upward REE pattern with a large negative Eu anomaly, Monache rhyolite contains the unusual phenocryst assemblage almandine + fayalite + biotite + oligoclase. The 2.4Ma old rocks may be nearly unmodified partial melts of crustal sources, whereas the 0.2Ma old rhyolite may be a product of relatively shallow differentiation. The rhyolites and nearby basalts are coeval with mafic and silicic volcanic rocks in the Coso Range about 40km to the SE. Their generation and eruption may reflect intense tectonic extension at the margin of the Basin and Range province and concomitant relaxation of compressive stress in a W- NW direction, allowing melts to reach the surface in the adjacent Sierra Nevada.-Authors

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.

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.

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

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Taylor, Howard E.; Kimball, B.A.

2004-01-01

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

NASA Astrophysics Data System (ADS)

Janots, Emilie; Bernier, Felix; Brunet, Fabrice; Muñoz, Manuel; Trcera, Nicolas; Berger, Alfons; Lanson, Martine

2015-03-01

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363-405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12-1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30-51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74-89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Generation of felsic rocks of bimodal volcanic suites from thinned and rifted continental margins: Geochemical and Nd, Sr, Pb-isotopic evidence from Haida Gwaii, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Dostal, Jaroslav; Hamilton, Tark S.; Shellnutt, J. Gregory

2017-11-01

The compositionally bimodal volcanic rocks of the Eocene-Miocene Masset Formation from Queen Charlotte basin, Haida Gwaii, British Columbia, Canada, underlie an area greater than 5000 km2 where their exposed sections are up to 1.6 km thick. The suite of mafic and felsic rocks (dacites and rhyolites) that erupted closely spaced in time, in both submarine and subaerial conditions, was associated with significant crustal extension and thin continental crust ( 19-24 km thick), with volcanism persisting for 35 Ma (from 46 to 11 Ma). Predominant mafic types (mafic:felsic 2:1) are moderately enriched mid-ocean-ridge-like basalts that were derived by a partial melting of a heterogeneous spinel peridotite source. Felsic rocks are plagioclase-phyric, two pyroxene-bearing, mainly peraluminous types which have Nd, Pb and Sr isotopic compositions overlapping those of basalts including high positive ƐNd(t) values (up to >+6). The chondrite-normalized REE patterns show light REE enrichment but flat heavy REE along with a variable negative Eu anomaly. Mineralogy, major and trace elements, Nd-Sr-Pb isotopic data and model calculations using MELTS are consistent with a derivation of felsic rocks from the basalts by fractional crystallization. The intercalation of basaltic and felsic rocks suggests the existence of separate, simultaneously active plumbing and feeder systems and relatively stable magma chamber(s) to generate large volumes of differentiated felsic magmas by fractional crystallization. The Masset rocks provide an example for the generation of felsic magmas of bimodal volcanic suites during rifting along a thinned continental margin. Appendix 1b Representative analyses of minerals of the Masset Formation felsic rocks

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

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.

[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.

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

PubMed Central

Wang, Lingqing; Liang, Tao

2015-01-01

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

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

PubMed

Wang, Lingqing; Liang, Tao

2015-07-22

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

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.

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.

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.

Chemistry of the older supracrustals of Archaean age around Sargur

NASA Technical Reports Server (NTRS)

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

1988-01-01

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

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.

Distinct 238U/235U ratios and REE patterns in plutonic and volcanic angrites: Geochronologic implications and evidence for U isotope fractionation during magmatic processes

NASA Astrophysics Data System (ADS)

Tissot, François L. H.; Dauphas, Nicolas; Grove, Timothy L.

2017-09-01

Angrites are differentiated meteorites that formed between 4 and 11 Myr after Solar System formation, when several short-lived nuclides (e.g., 26Al-26Mg, 53Mn-53Cr, 182Hf-182W) were still alive. As such, angrites are prime anchors to tie the relative chronology inferred from these short-lived radionuclides to the absolute Pb-Pb clock. The discovery of variable U isotopic composition (at the sub-permil level) calls for a revision of Pb-Pb ages calculated using an ;assumed; constant 238U/235U ratio (i.e., Pb-Pb ages published before 2009-2010). In this paper, we report high-precision U isotope measurement for six angrite samples (NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555) using multi-collector inductively coupled plasma mass-spectrometry and the IRMM-3636 U double-spike. The age corrections range from -0.17 to -1.20 Myr depending on the samples. After correction, concordance between the revised Pb-Pb and Hf-W and Mn-Cr ages of plutonic and quenched angrites is good, and the initial (53Mn/55Mn)0 ratio in the Early Solar System (ESS) is recalculated as being (7 ± 1) × 10-6 at the formation of the Solar System (the error bar incorporates uncertainty in the absolute age of Calcium, Aluminum-rich inclusions - CAIs). An uncertainty remains as to whether the Al-Mg and Pb-Pb systems agree in large part due to uncertainties in the Pb-Pb age of CAIs. A systematic difference is found in the U isotopic compositions of quenched and plutonic angrites of +0.17‰. A difference is also found between the rare earth element (REE) patterns of these two angrite subgroups. The δ238U values are consistent with fractionation during magmatic evolution of the angrite parent melt. Stable U isotope fractionation due to a change in the coordination environment of U during incorporation into pyroxene could be responsible for such a fractionation. In this context, Pb-Pb ages derived from pyroxenes fraction should be corrected using the U isotope composition measured in the same pyroxene fraction.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

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.

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.

Watson: A new link in the IIE iron chain

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

Geochemistry of the Archean Yellowknife Supergroup

NASA Astrophysics Data System (ADS)

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

1981-07-01

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

High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

NASA Technical Reports Server (NTRS)

Tang, Ming; McDonough, William F.; Arevalo, Ricardo, Jr.

2014-01-01

Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).

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.

REE in karst bauxites: the Campania example (southern Italy)

NASA Astrophysics Data System (ADS)

Mondillo, N.; Boni, M.; Balassone, G.; Rollinson, G.

2012-04-01

Global production of Rare Earth Element (REE) has dramatically increased in the last years, hence the strong interest to identify new deposits and to understand the processes responsible for their formation. Among REE concentrations related to weathering, the current targets are represented by the ion-adsorption deposit-types, occurring in China, in which REEs are adsorbed onto the surface of clays. Laterites have been also intensively investigated since the discovery of the secondary deposit of Mount Weld (Australia). Most REEs behave as immobile elements in laterites, and tend to be enriched compared to the underlying parent rocks. Many authors debate on a possible REE fractionation along the laterite profiles, resulting in the formation of supergene LREE-minerals. Bauxites are economic Al accumulations, derived from the weathering of alumosilicate-rich parent rocks resulting in the development of laterite profiles. Components as Ca, Mg, K, Si are leached and residual Fe, Al and Ti precipitate in form of hematite>>goethite, gibbsite [Al(OH)3] or amorphous Al hydroxides and anatase. Metabauxites can contain boehmite or diaspore [AlO(OH)]. Chemical composition (including REEs content) of lateritic bauxites generally mirrors the original composition of the parent rock. Geochemistry of REEs in karst bauxites, which lay on carbonate bedrocks and may be also allochthonous to them, is not so straightforward. Cretaceous karst bauxite deposits in the Apennine chain (Southern Italy) are presently uneconomic. A full mineralogical and geochemical study has been performed on several deposits of the Campania district, and three representative profiles have been sampled. In all deposits the bauxite ore has an oolitic-pisolitic texture, but contains also detrital intervals. The mineral association consists of boehmite, kaolinite and hematite, with less goethite and anatase. The main REE-bearing mineral is detrital monazite. In detail, we could detect (SEM) other LREE-phosphates (florencite type minerals) in the Regia Piana deposit and possibly LREE-enriched goethite at Dragoni. QEMSCAN® analysis allowed the identification and location of discrete particles of monazite and xenotime, but because of their very small dimensions (typically <10 microns) it was difficult to determine the exact chemical composition without further investigation. Chemical analyses have shown a total REEs content of 620 ppm on average in all bauxite deposits, with a maximum value of 1454 ppm of total REEs at the top of the Regia Piana profile. The LREE (La-Eu) contents in the samples vary between 200 and 1400 ppm, with positive Ce and La anomalies. The HREE (Gd-Lu) contents are always around 40-60 ppm. The relationship between REEs and the Al and/or Fe values is not clear, probably because the REE content may be slightly biased by the detrital characteristics of the bauxite. The higher Ce and other LREE values, detected at the top of several deposits rather than at the bottom, can be related to LREE supergene minerals occurrence in the higher parts of profile. The Campania deposits represent an interesting case study for REE concentration in karst bauxites. A similar LREE fractionation process could be applied to other bauxite deposits, though related to more favorable parent rocks with sub-economic REE-grades.

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.

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.

Extraction of rare earth elements from a contaminated cropland soil using nitric acid, citric acid, and EDTA.

PubMed

Tang, Hailong; Shuai, Weitao; Wang, Xiaojing; Liu, Yangsheng

2017-08-01

Rare earth elements (REEs) contamination to the surrounding soil has increased the concerns of health risk to the local residents. Soil washing was first attempted in our study to remediate REEs-contaminated cropland soil using nitric acid, citric acid, and ethylene diamine tetraacetic acid (EDTA) for soil decontamination and possible recovery of REEs. The extraction time, washing agent concentration, and pH value of the washing solution were optimized. The sequential extraction analysis proposed by Tessier was adopted to study the speciation changes of the REEs before and after soil washing. The extract containing citric acid was dried to obtain solid for the X-ray fluorescence (XRF) analysis. The results revealed that the optimal extraction time was 72 h, and the REEs extraction efficiency increased as the agent concentration increased from 0.01 to 0.1 mol/L. EDTA was efficient to extract REEs over a wide range of pH values, while citric acid was around pH 6.0. Under optimized conditions, the average extraction efficiencies of the major REEs in the contaminated soil were 70.96%, 64.38%, and 62.12% by EDTA, nitric acid, and citric acid, respectively. The sequential extraction analyses revealed that most soil-bounded REEs were mobilized or extracted except for those in the residual fraction. Under a comprehensive consideration of the extraction efficiency and the environmental impact, citric acid was recommended as the most suitable agent for extraction of the REEs from the contaminated cropland soils. The XRF analysis revealed that Mn, Al, Si, Pb, Fe, and REEs were the major elements in the extract indicating a possibile recovery of the REEs.

Excess europium content in Precambrian sedimentary rocks and continental evolution

NASA Technical Reports Server (NTRS)

Jakes, P.; Taylor, S. R.

1974-01-01

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

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.

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).

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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…

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Influence of soil characteristics on rare earth fingerprints in mosses and mushrooms: Example of a pristine temperate rainforest (Slavonia, Croatia).

PubMed

Fiket, Željka; Medunić, Gordana; Furdek Turk, Martina; Ivanić, Maja; Kniewald, Goran

2017-07-01

The present study aims to investigate levels and distribution of rare earth elements (REE) in soils, mosses and mushrooms of a pristine temperate rainforest, a non-polluted natural system, in order to characterise their environmental availability and mobility. The multielement analysis of digested soil, moss and mushroom samples was performed by High Resolution Inductively Coupled Plasma Mass Spectrometry. The distribution of rare earths in mosses and mushrooms was found primarily affected by local pedological setting. Mosses displayed a consistent lithological signature with an almost insignificant REE fractionation compared to soils. Mushrooms showed differences in REE concentrations in certain parts of the fruiting body with regard to their main physiological function and indicated a significant impact of soil organic content on the overall REEs uptake. Results of our work highlight the importance of substrate characteristics on the initial levels of REEs in mosses and mushrooms. Moreover, this study provides baseline data on the rare earth element levels in mosses and mushrooms growing in a pristine forest area characterised by naturally elevated REE levels in the soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Leaching of rare earth elements from fluorescent powder using the tea fungus Kombucha.

PubMed

Hopfe, Stefanie; Flemming, Katrin; Lehmann, Falk; Möckel, Robert; Kutschke, Sabine; Pollmann, Katrin

2017-04-01

In most modern technologies such as flat screens, highly effective magnets and lasers, as well as luminescence phosphors, Rare Earth Elements (REE) are used. Unfortunately no environmentally friendly recycling process exists so far. In comparison to other elements the interaction of microorganisms with REE has been studied to a less extent. However, as REE are ubiquitously present in nature it can be assumed that microorganisms play an important role in the biogeochemistry of REE. This study investigates the potential of organic acid-producing microbes for extracting REE from industrial waste. In Germany, 175 tons of fluorescent phosphor (FP) are collected per year as a distinct fraction from the recycling of compact fluorescent lamps. Because the FP contains about 10% of REE-oxides bound in the so-called triband dyes it is a readily accessible secondary resource of REE. Using the symbiotic mixed culture Kombucha, consisting of yeasts and acetic acid bacteria, REE were leached at a significant rate. The highest leaching-rates were observed in shake cultures using the entire Kombucha-consortium or its supernatant as leaching agent compared to experiments using the isolates Zygosaccharomyces lentus and Komagataeibacter hansenii as leaching organisms. During the cultivation, the pH decreased as a result of organic acid production (mainly acetic and gluconic acid). Thus, the underlying mechanism of the triband dye solubilisation is probably linked to the carboxyl-functionality or a proton excess. In accordance with the higher solubility of REE-oxides compared to REE-phosphates and -aluminates, the red dye Y 2 O 3 :Eu 2+ containing relatively expensive REE was shown to be preferentially solubilized. These results show that it is possible to dissolve the REE-compounds of FP with the help of microbial processes. Moreover, they provide the basis for the development of an eco-friendly alternative to the currently applied methods that use strong inorganic acids or toxic chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of Resting Energy Expenditure on Blood Pressure is Independent of Body Mass and a Marker of Sympathetic Tone

PubMed Central

Brock, David W.; Tompkins, Connie L.; Fisher, Gordon; Hunter, Gary R.

2011-01-01

Introduction two recent examinations reported a strong association between blood pressure (BP) and resting energy expenditure (REE), independent of body mass and body composition. Both reports postulate that neuro-humoral processes that contribute to variation in REE may partly mediate the body mass effect on BP. Therefore, we examined the relationship of REE and BP in 108 asymptomatic women to (a) confirm previous findings in a novel population, and (b) to examine the impact of a marker of sympathetic tone on this relationship, as this was indicated as a potentially salient intermediary in previous reports. Methods all testing was performed during a 4-day admission to the General Clinical Research Center. Resting energy expenditure was measured by indirect calorimetry; body composition was determined by DEXA; and 24-hour fractionated urinary norepinephrine was determined by HPLC. Results multiple linear regression revealed REE as a significant predictor of SBP (β = 0.30, P = 0.04), independent of race (β = 0. 28, P = 0.01), age (β = − 0.02, P = 0.80), height (β = − 0.38, P = 0.08), fat mass (β = 0.22, P = 0.20), fat free mass (β = 0.08, P = 0.65), and 24-hour fractionated urinary norepinephrine (β = 0.06, P = 0.57); and the same model using DBP as the dependent variable approached significance (β = 0.24, P = 0.09). Discussion this study affirms previous findings that REE may be a potential mediator in resting BP, independent of many well-cited factors and, additionally, a marker of sympathetic tone. PMID:21820136

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

PubMed

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

2013-01-01

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

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.

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.

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.

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.

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.

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.

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.

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.

Estimating the Submarine Groundwater Discharge Flux of Rare Earth Elements to the Indian River Lagoon, Fl, USA, Using the 1-D Vertical - Flow Equation

NASA Astrophysics Data System (ADS)

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

2013-12-01

Understanding the sources and sinks of trace elements like the rare earth elements (REE) in the oceans has important implications for quantifying their global geochemical cycles, their application as paleoceanographic tracers, and in discerning the geochemical reactions that mobilize, sequester, and fractionate REEs in the environment. This understanding is critical for neodymium (Nd) because radiogenic Nd isotopes are commonly used in paleoceanographic studies over glacial-interglacial to million year time scales. The submarine groundwater discharge (SGD) flux of each REE for the Indian River Lagoon, Fl, USA, was calculated using a modified form of the 1-dimensional vertical-flow equation that accounts for diffusion, advection, and non-local mass transfer processes. The SGD REE flux is comprised of two sources: a near shore, heavy REE (HREE) enriched advective source chiefly composed of terrestrial SGD, and a light REE (LREE) and middle REE (MREE) enriched source that originates from reductive dissolution of Fe (III) oxides/hydroxides in the subterranean estuary. This SGD flux mixture of REE sources is subsequently transported by groundwater seepage and bioirrigation to the overlying lagoon water column. The total SGD flux of REEs reveals that the subterranean estuary of the Indian River Lagoon is a source for LREE and MREEs, and a sink for the HREEs, to the local coastal ocean. The calculated SGD flux of Nd presented in this study is estimated at 7.69×1.02 mmol/day, which is roughly equivalent to the effective local river flux to the Indian River Lagoon. Although our re-evaluated SGD flux of Nd to the Indian River Lagoon is lower than estimates in our previous work, it nonetheless represents a substantial input to the coastal ocean.

Deciphering human-climate interactions in an ombrotrophic peat record: REE, Nd and Pb isotope signatures of dust supplies over the last 2500 years (Misten bog, Belgium)

NASA Astrophysics Data System (ADS)

Fagel, N.; Allan, M.; Le Roux, G.; Mattielli, N.; Piotrowska, N.; Sikorski, J.

2014-06-01

A high-resolution peat record from Eastern Belgium reveals the chronology of dust deposition for the last 2500 years. REE and lithogenic elements in addition to Nd and Pb isotopes were measured in a 173 cm age-dated peat profile and provide a continuous chronology of dust source and intensity. Calculated dust flux show pronounced increases c. 300 BC, 600 AD, 1000 AD, 1200 AD and from 1700 AD, corresponding to local and regional human activities combined with climate change. The Industrial Revolution samples (1700-1950 AD) are characterised by a significant enrichment in Sc-normalised REE abundance (sum REE/Sc > 25) due to intensive coal combustion. For the pre-Industrial Revolution samples, the Sc-normalised REE abundance (10 < Sum REE/Sc < 25) and the εNd variability (-13 to -9) are interpreted by a mixing between dust particles from local soils and long-range transport of desert particles. Three periods characterised by dominant-distal sources (c. 320 AD, 1000 AD and 1700 AD) are consistent with local wetter-than-average intervals as indicated by a lower degree of peat humification. Local erosion prevails during the drier (higher humification) intervals (100 AD, 600 AD). On a global scale, more distal supplies are driven during colder periods, in particular during the Oort and Maunder minima, suggesting a potential link between dust deposition and global climate. Combining REE abundance, fractionation between Light REE and Heavy REE and Nd isotope data in ombrotrophic peat allows one to distinguish between dust flux changes related to human and climate forcings.

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.

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

NASA Astrophysics Data System (ADS)

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

2012-03-01

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

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.

Multi-mode Li diffusion in natural zircons: Evidence for diffusion in the presence of step-function concentration boundaries

NASA Astrophysics Data System (ADS)

Tang, Ming; Rudnick, Roberta L.; McDonough, William F.; Bose, Maitrayee; Goreva, Yulia

2017-09-01

Micron- to submicron-scale observations of Li distribution and Li isotope composition profiles can be used to infer the mechanisms of Li diffusion in natural zircon. Extreme fractionation (20-30‰) within each single crystal studied here confirms that Li diffusion commonly occurs in zircon. Sharp Li concentration gradients frequently seen in zircons suggest that the effective diffusivity of Li is significantly slower than experimentally determined (Cherniak and Watson, 2010; Trail et al., 2016), otherwise the crystallization/metamorphic heating of these zircons would have to be unrealistically fast (years to tens of years). Charge coupling with REE and Y has been suggested as a mechanism that may considerably reduce Li diffusivity in zircon (Ushikubo et al., 2008; Bouvier et al., 2012). We show that Li diffused in the direction of decreasing Li/Y ratio and increasing Li concentration (uphill diffusion) in one of the zircons, demonstrating charge coupling with REE and Y. Quantitative modeling reveals that Li may diffuse in at least two modes in natural zircons: one being slow and possibly coupled with REE+Y, and the other one being fast and not coupled with REE+Y. The partitioning of Li between these two modes during its diffusion may depend on the pre-diffusion substitution mechanism of REE and Y in the zircon lattice. Based on our results, sharp Li concentration gradients are not indicative of limited diffusion, and can be preserved at temperatures >700 °C on geologic timescales. Finally, large δ7 Li variations observed in the Hadean Jack Hills zircons may record kinetic fractionation, rather than a record of ancient intense weathering in the granite source materials.

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: Results from ODP Leg 127

NASA Astrophysics Data System (ADS)

Murray, Richard W.; Buchholtzten Brink, Marilyn R.; Brumsack, Hans J.; Gerlach, David C.; Russ, G. Price

1991-09-01

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu∗ values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu∗ with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce∗ profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce∗ record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce∗ correlates slightly better with depth than with age. The downhole increase in Ce/Ce∗ at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce∗ and Lan/Ybn suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from MASUZAWA and KOYAMA, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce∗ is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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.

Rare Earth Desorption Test with Citrate and Bicarbonate

DOE Data Explorer

Jiao, Yongqin; Brewer, Aaron; Park, Dan

2017-06-01

LBT (lanthanide binding tag) cells were grown overnight in LB media with 0.05% Amp. 1:100 subculture taken from overnights, grown for 2 hours. LBT was induced with 0.002% arabinose added for 3 hours. REE adsorption was done by combining 350 ul (0.25% 1M MES, 12.5 uM Tb, and 12.5 uM La or Cu in sterile DI water) and 350 ul (LBT cells with OD = 1 in 10 mM MES), reacted for approx. 30 min. Following adsorption, citrate and bicarbonate solutions were used in desorption to recover rare earth from cell surface, and to further separate REE from non-REEs. The samples were then centrifuged and a fraction of the supernatant was collected for ICP-MS analysis.

The effect of temperature and surface area on Sr, Ba and REE fractionation during low temperature serpentinization

NASA Astrophysics Data System (ADS)

Frisby, C. P.; Bizimis, M.; Foustoukos, D.

2013-12-01

Peridotite hosted hydrothermal vent systems are a direct link between the hydrosphere and the Earth's mantle. They promote elemental mass exchange between these two regimes, driven by hydrothermal alteration of peridotite by seawater. Most experimental, theoretical and field studies of peridotite alteration have focused on high temperature (>1800C) conditions where serpentinization is readily observed, but less is known for low-temperature alteration that likely resembles near seafloor processes. Furthermore, while major element exchange during serpentinization has been studied extensively, the behavior of trace elements remains unclear, especially at low temperatures (<1000C). Here we report data from time-series experiments designed to constrain the reaction of Sr, Ba and REE between synthetic seawater and olivine as a function of both temperature (15-900C) and mineral grain size (geometric surface area). Our experimental data shows a clear decoupling of REE from Sr-Ba under all experimental conditions. While Sr and Ba remain quantitatively in solution, the REE are being removed from the solution at rates that increase with increasing temperature and GSA (i.e. decreasing particle size). We also observe the HREE are removed from solution faster than the LREE. The REE removal can be described as a two-stage process, with a fast initial rate followed by a slower rate as the reaction approaches equilibrium. For instance at 900C and GSA of 57.57cm2/g (average grain diameter of 258.7μm), 50% of Nd is removed in 8 hours but only 80% at 120 hours. We quantify the initial reaction rate constant of each element as a function of temperature and grain size, in order to understand the mechanisms of REE removal. The experimentally determined surface-normalized reaction rate constants (0.29-1.84 s-1m-2), constrain the temperature dependence and activation energy for the scavenging of REE driven by olivine hydrolysis. For example, LREE reaction rates have a higher temperature dependency than the HREE, i.e. higher activation energy for Nd than Yb. This activation energy does not correlate well with ionic radius, but correlates well with the third ionization potential of REE. This indicates a 3+ charge speciation for the REE upon removal to the olivine substrate. Recent experimental data had shown the formation of secondary phases (i.e. Fe(III)-(hydr)oxides, Fe bearing-talc and Fe(II)-brucite) with olivine, facilitated by the presence of spinel [1], that may contribute to the REE scavenging observed here. Our experiments however are pure olivine (>99.9%) and spinel-free. We also observed limited dissolution (<0.001%) of olivine at up to 21 days of reaction, and no evidence for the formation of Fe-oxyhydroxides, using ICPMS, XRD, Mossbauer and SEM methods. It therefore seems unlikely that Fe(III)-(hydr)oxides are responsible for the REE fractionations. This new information will enhance our limited understanding of the cycling of REE in seawater hydrothermal circulation and abyssal peridotite alteration. 1. Mayhew et al (2013) Nat Geo. 6, 478-484

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

NASA Technical Reports Server (NTRS)

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

1988-01-01

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

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

PubMed

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

2016-12-15

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

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

NASA Astrophysics Data System (ADS)

Moggi-Cecchi, V.; Pratesi, G.

2004-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2007-08-01

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

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

NASA Astrophysics Data System (ADS)

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

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

Rare earth element analysis indicates micropollutants in an urban estuary

NASA Astrophysics Data System (ADS)

Mohajerin, T. J.; Johannesson, K. H.; Kolker, A.; Burdige, D. J.; Chevis, D.

2011-12-01

Rare earth element analysis of Bayou Bienvenue waters shows anomalously high gadolinium, Gd, concentrations relative to its nearest neighbors in the REE series, europium and terbium. The anomalously high Gd concentrations indicate anthropogenic input from waste-water treatment plants in the area as anthropogenic Gd input can be traced back to its use as a contrast agent in magnetic resonance imaging in hospitals. Others have shown that anomalously high levels of Gd in natural waters are likely to be associated with other micropollutants that also occur in hospital effluent and that are not removed in the wastewater treatment process, including pharmaceuticals in the form of steroids, antihistamines, and antibiotics. Estuaries serve as many important ecological roles and have been shown to act as a filter for pollutants. To better understand the transport, biogeochemical cycling, and ultimate fate of trace elements in estuaries, I collected surface water samples from Bayou Bienvenue, a wetland triangle that covers an area of 427 acres directly adjacent to New Orleans, Louisiana. Water samples from Bayou Bienvenue were collected along the salinity gradient and subsequently filtered through progressively smaller pore-size filters. The resulting fractions were analyzed for trace element concentions, including the REEs, by magnetic sector ICP-MS. The attached figure shows the Gd anomaly present in the particulate (>0.45μm) fraction. Upper continental crust (UCC)-normalized plots of colloidal REEs (0.02μm - 0.45μm) fraction is lacking this anomaly indicating anthropogenic Gd is found chiefly in the particulate fraction in Bayou Bienvenue. No clear relationship between Gd concentration and salinity was apparent.

Geochemistry of Aerosols in North -West India

NASA Astrophysics Data System (ADS)

Yadav, S.

2001-12-01

The geochemistry of, sources to, and transport of dust and their consequences on earth system processes are least understood. Here we follow Guru Gil's approach to use trace elements and isotopic data on aerosols in northwest India to understand their sources and processes. Aerosol samples were collected over a stretch of 550 kms from the Thar desert to the Delhi region which sits on the eastern fringe of the Thar. This region witnesses frequent dust storms in summer seasons due to high intensity south westerly and westerly winds. Major, trace elements including REE and Sr isotopic data are generated on three different group of aerosols such as dry deposition (DD, >100μm ), suspended particulate matter (SPM, 0.1-100μm ) and PM10 (<10μm ) collected by different sampling techniques and at different seasons. Major and trace elements in all DD samples show a high degree of homogeneity with similar LREE enriched patterns and -ve Eu anomalies regardless of space and time of sampling. These particles are geochemically similar to UCC, PAAS, and local loess with relatively low CIA values, indicating a low degree of chemical weathering suffered by their source regions dominated by upper crustal materials. Geochemistry of SPM and PM10 aerosols shows variation along the wind path. With decreasing size, crustal component decreases, anthropogenic inputs to transition metals and non-silicate input to Ca budget increase. The greater variability in finer fractions is primarily due to anthropogenic input and local meteorology where wind acts as an intensive variable. The REE patterns in SPM and PM10 are similar to DD samples with -ve Eu anomaly but their abundance decrease with size, probably due to some dilution effect by organics and mineralogical factors. It is possible that REE hosting minerals are concentrated in coarser silt and finest sand fractions (35-70μm ). This is supported by the decreasing Zr concentrations with decreasing size and distance in downwind direction where the wind velocity reduces. 87Sr/86Sr isotopic ratios of all the fractions also show a small size dependency. The coarser samples have higher values (0.719-0.720) compared to finer ones (0.715-0.717). These values are similar to the lower end of Indo-Gangetic alluvium ratios (J. Tripathy), perhaps resulting from the minor addition of Jurassic carbonate/gypsum, present in the upwind part. Thus, the source for the dominant component of aerosols is upper crustal and is likely to be older Himalayan alluvium deposited by now defunct rivers in the Rajasthan region. The removal of silty materials (a dominant part of aerosols) from the older alluvium is probably responsible for the presence of Thar desert in the upwind direction.

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

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.

Geochemical characteristics of rare earth elements in the surface sediments from the Spratly Islands of China.

PubMed

Li, Jingxi; Sun, Chengjun; Zheng, Li; Yin, Xiaofei; Chen, Junhui; Jiang, Fenghua

2017-01-30

The geochemistry of rare earth elements (REE) in surface sediment from Cuarteron reef (N1), Johnson reef (N2), Hugh reef (N3), Gaven reef (N4), Fiery cross reef (N5), and Subi reef (N6) were firstly studied. The total REE abundance (∑REE) varied from 2.244μg·g -1 to 21.661μg·g -1 , with an average of 4.667μg·g -1 . The LREE/HREE was from 2.747 to 9.869, with an average of 3.687, which indicated that the light REE was evidently enriched. Fractionation was observed between LREE and HREE. Gd with a negative anomaly was also detected in all of the stations. The negative anomalies of δEu from 0.11 to 0.25, with an average of 0.22, and the positive anomalies of δCe from 1.38 to 3.86, with an average of 1.63. The REE individual correlation values with Ca, Mn, Mg, Sr were r Ca =-0.05, r Mn =0.26, r Mg =-0.14, and r Sr =0.08. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

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.

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.

Trace element diffusion and kinetic fractionation in wet rhyolitic melt

NASA Astrophysics Data System (ADS)

Holycross, Megan E.; Watson, E. Bruce

2018-07-01

Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the melt growth medium will result in a precipitated apatite crystal with a disequilibrium trace element composition.

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.

Interaction of rare earth elements and components of the Horonobe deep groundwater.

PubMed

Kirishima, Akira; Kuno, Atsushi; Amamiya, Hiroshi; Kubota, Takumi; Kimuro, Shingo; Amano, Yuki; Miyakawa, Kazuya; Iwatsuki, Teruki; Mizuno, Takashi; Sasaki, Takayuki; Sato, Nobuaki

2017-02-01

To better understand the migration behavior of minor actinides in deep groundwater, the interactions between doped rare earth elements (REEs) and components of Horonobe deep groundwater were investigated. Approximately 10 ppb of the REEs, i.e. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, and Yb were doped into a groundwater sample collected from a packed section in a borehole drilled at 140 m depth in the experiment drift of Horonobe Underground Research Laboratory in Hokkaido, Japan. The groundwater sample was sequentially filtered with a 0.2 μm pore filter, and 10 kDa, 3 kDa and 1 kDa nominal molecular weight limit (NMWL) ultrafilters with conditions kept inert. Next, the filtrate solutions were analyzed with inductively coupled plasma mass spectrometry (ICP-MS) to determine the concentrations of the REEs retained in solution at each filtration step, while the used filters were analyzed through neutron activation analysis (NAA) and TOF-SIMS element mapping to determine the amounts and chemical species of the trapped fractions of REEs on each filter. A strong relationship between the ratios of REEs retained in the filtrate solutions and the ionic radii of the associated REEs was observed; i.e. smaller REEs occur in larger proportions dissolved in the solution phase under the conditions of the Horonobe groundwater. The NAA and TOF-SIMS analyses revealed that portions of the REEs were trapped by the 0.2 μm pore filter as REE phosphates, which correspond to the species predicted to be predominant by chemical equilibrium calculations for the conditions of the Horonobe groundwater. Additionally, small portions of colloidal REEs were trapped by the 10 kDa and 3 kDa NMWL ultrafilters. These results suggest that phosphate anions play an important role in the chemical behavior of REEs in saline (seawater-based) groundwater, which may be useful for predicting the migration behavior of trivalent actinides released from radioactive waste repositories in the far future. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Awadalla, Gamal S.

2010-07-01

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

Trace element distribution in peridotite xenoliths from Tok, SE Siberian craton: A record of pervasive, multi-stage metasomatism in shallow refractory mantle

NASA Astrophysics Data System (ADS)

Ionov, Dmitri A.; Chazot, Gilles; Chauvel, Catherine; Merlet, Claude; Bodinier, Jean-Louis

2006-03-01

Spinel peridotite xenoliths in alkali basalts at Tok, SE Siberian craton range from fertile lherzolites to harzburgites and wehrlites; olivine-rich (70-84%) rocks are dominant. REE patterns in the lherzolites range from nearly flat for fertile rocks (14-17% cpx) to LREE-enriched; the enrichments are positively correlated with modal olivine, consistent with high-permeability of olivine-rich rocks during melt percolation. Clinopyroxene in olivine-rich Tok peridotites typically has convex-upward trace element patterns (La/Nd PM < 1 and Nd/Yb PM ≫ 1), which we consider as evidence for equilibration with evolved silicate liquids (with higher REE and lower Ti contents than in host basalts). Whole-rock patterns of the olivine-rich xenoliths range from convex-upward to LREE-enriched (La/Nd PM > 1); the LREE-enrichments are positively correlated with phosphorus abundances and are mainly hosted by accessory phosphates and P-rich cryptocrystalline materials. In addition to apatite, some Tok xenoliths contain whitlockite (an anhydrous, halogen-poor and Na-Mg-rich phosphate), which is common in meteorites and lunar rocks, but has not been reported from any terrestrial mantle samples. Some olivine-rich peridotites have generations of clinopyroxene with distinct abundances of Na, LREE, Sr and Zr. The mineralogical and trace element data indicate that the lithospheric mantle section represented by the xenoliths experienced a large-scale metasomatic event produced by upward migration of mafic silicate melts followed by percolation of low- T, alkali-rich melts and fluids. Chromatographic fractionation and fractional crystallisation of the melts close to the percolation front produced strong LREE-enrichments, which are most common in the uppermost mantle and are related to carbonate- and P 2O 5-rich derivatives of the initial melt. Reversal and gradual retreat of the percolation front during thermal relaxation to ambient geotherm ("retrograde" metasomatism) caused local migration and entrapment of small-volume residual fluids and precipitation of volatile-rich accessory minerals. A distinct metasomatic episode, which mainly produced "anhydrous" late-stage interstitial materials was concomitant with the alkali basaltic magmatism, which brought the xenoliths to the surface.

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

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

NASA Astrophysics Data System (ADS)

Buchwaldt, R.; Toulkeridis, T.

2013-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

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

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

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

2000-03-01

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

Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

REE Sorption Study on sieved -50 +100 mesh fraction of Media #1 in Brine #1 with Different Starting pH's at 70C

DOE Data Explorer

Gary Garland

2015-09-29

This is a continuation of the REE sorption study for shaker bath tests on 2g media #1 in 150mL brine #1 with different starting pH's at 70C. In a previous submission we reported data for shaker bath tests for brine #1 with starting pH's of 3.5, 4.5 and 5.5. In this submission we these pH's compared to starting brine #1 pH's of 6, and 7.

Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U

NASA Technical Reports Server (NTRS)

Righter, K.; Yang, S.; Humayun, M.

2016-01-01

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

Assessing anthropogenic levels, speciation, and potential mobility of rare earth elements (REEs) in ex-tin mining area.

PubMed

Khan, Aysha Masood; Yusoff, Ismail; Bakar, Nor Kartini Abu; Bakar, Ahmad Farid Abu; Alias, Yatimah

2016-12-01

A study was carried out to determine the level of rare earth elements (REEs) in water and sediment samples from ex-mining lakes and River in Kinta Valley, Perak, Malaysia. Surface water and sediments from an ex-mining lake and Kinta River water samples were analyzed for REEs by inductively coupled plasma mass spectrometry. The total concentration of REEs in the ex-mining lake water samples and sediments were found to be 3685 mg/l and 14159 mg/kg, respectively, while the total concentration of REEs in Kinta River water sample was found to be 1224 mg/l. REEs in mining lake water were found to be within 2.42 mg/l (Tb) to 46.50 mg/l (Ce), while for the Kinta River, it was 1.33 mg/l (Ho) to 29.95 mg/l (Ce). Sediment samples were also found with REEs from 9.81 mg/kg (Ho) to 765.84 mg/kg (Ce). Ce showed the highest average concentrations for mining lake (3.88 to 49.08 mg/l) and Kinta River (4.44 to 33.15 mg/l) water samples, while the concentration of La was the highest (11.59 to 771.61 mg/kg) in the mining lake sediment. Lu was shown to have the highest enrichment of REEs in ex-mining lake sediments (107.3). Multivariate statistical analyses such as factor analysis and principal component analysis indicated that REEs were associated and controlled by mixed origin, with similar contributions from anthropogenic and geogenic sources. The speciation study of REEs in ex-tin mining sediments using a modified five-stage sequential extraction procedure indicated that yttrium (Y), gadolinium (Gd), and lanthanum (La) were obtained at higher percentages from the adsorbed/exchanged/carbonate fraction. The average potential mobility of the REEs was arranged in a descending order: Yb > Gd > Y = Dy > Pr > Er > Tm > Eu > Nd > Tb > Sc > Lu > Ce > La, implying that under favorable conditions, these REEs could be released and subsequently pollute the environment.

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.

Zircon Trace Element Contents and Refined U-Pb Crystallization Ages for the Tatoosh Pluton, Mount Rainier National Park, Washington Cascades

NASA Astrophysics Data System (ADS)

Bacon, C. R.; Du Bray, E. A.; John, D. A.; Mazdab, F. K.; Wooden, J. L.

2008-12-01

The 7x12 km Tatoosh pluton south of Mount Rainier consists of 4 petrographic/compositional phases, here termed Nisqually, Reflection, Pyramid, and Stevens, that intrude Tertiary volcanic and sedimentary wall and roof rocks; contacts between the 4 intrusive units are rarely exposed. We used the USGS-Stanford SHRIMP- RG to analyze, in a continuous session, zircons from each of 6 quartz monzodiorite (qmd), quartz monzonite (qm), or granodiorite (grd) samples for 206Pb/238U ages and, concurrently, U, Th, Hf, and REE concentrations. A round-robin procedure yielded statistically robust geochronological results. Ages that we reported previously (FM07) were compromised by instrument instability and by calibration differences between analytical sessions. Between 11 and 31 new analyses of zircons from each sample were evaluated using the TuffZirc and Umix Ages routines of Isoplot 3.41 (Ludwig, 2003). TuffZirc solidification ages for the intrusions are: Nisqually grd (Paradise Valley; 65.4% SiO2) 17.29 +0.37/-0.24 Ma, Nisqually grd (Christine Falls; 66.4%) 17.70 +0.30/-0.16 Ma, Reflection qm (Pinnacle Peak trail; 66.6%) 18.38 +0.45/-0.28 Ma, Pyramid qmd (58.5%) 18.58 +0.20/-0.15 Ma, Stevens grd (Stevens Canyon; 67.8%) 19.15 +0.15/-0.12 Ma, and Stevens grd (south of Louise Lake; 69.3%) 19.20 +0.31/-0.26 Ma (U-Th initial-disequilibrium corrected, ±2σ). Precision of the U-Pb data limits rigorous identification of antecrysts to those with ages ~1 Myr > solidification ages. Antecryst ages that produce subsidiary modes in relative probability diagrams for the two Stevens samples give weighted mean values of 20.18 ±0.26 Ma and 20.07 ±0.18 Ma. Wide ranges in trace element concentrations and ratios indicate that many analyzed zircons grew in highly fractionated residual liquids in high-crystallinity environments. Concentrations of Th and U in Tatoosh zircons vary by two orders of magnitude, cores tend to have higher Th, U, and Th/U than rims, and overgrowths that fill reentrants have high U contents and low Th/U ratios. Chondrite-normalized REE patterns have familiar convex-up shapes with positive Ce and negative Eu anomalies: LaN = 0.03-6 (10 values >6 may reflect inclusions), YbN = 380-33,900, Ce/Ce* = 0.7-505, and Eu/Eu* = 0.06-1.25. Slopes of REE patterns increase subtly in the order Reflection < Pyramid ≤ Nisqually < Stevens. Fractionation of plagioclase + pyroxene and(or) amphibole + Fe-Ti oxide + apatite + zircon should produce relative-LREE- enriched successive liquids. Observed marginally steeper REE patterns (greater positive slopes) for rims, lower REE concentrations, and lower Th/U ratios may reflect co-precipitation of allanite ± thorite. Two parallel arrays in Eu/Eu* versus Hf, in which Eu/Eu* decreases as Hf increases, are consistent with growth of higher-Hf, lower-Eu/Eu* zircon from more evolved melts; separate arrays imply Nisqually and Pyramid + Reflection intrusions. Zircon Eu/Eu* and Hf in the Stevens granodiorite define one high-Eu/Eu* field and another similar to that for Pyramid and Reflection samples that imply more than one parental magma. The zircon ages indicate solidification in three episodes: Stevens ~19.2 Ma, Pyramid + Reflection ~18.5 Ma, and Nisqually ~17.5 Ma. An ~20.1 Ma stage is represented by antecrysts in Stevens samples. The source(s) of the pluton were active for at least ~2.7 Myr and major crystallization episodes were separated by intervals of 0.7-1.0 Myr.

Eocene to Oligocene volcanism in the Mariana fore-arc and crustal melting

NASA Astrophysics Data System (ADS)

Hartman, B.; Reagan, M.; Hickey-Vargas, R.; Hanan, B.; Blichert-Toft, J.

2003-04-01

Recently collected volcanic rocks from the Mariana fore-arc islands of Saipan and Rota provide evidence that the genesis of silicic magmas in the IBM system involves extensive crustal melting. Rhyolites from the island of Saipan are unusually high in silica for an oceanic island arc setting. They also are unique in the Izu-Bonin-Mariana (IBM) system in that they erupted during the earliest stages of subduction (45--46 Ma), but have "mature arc" major element, trace element, and isotopic compositions. For example, the rhyolites have flat REE patterns and pronounced negative Nb anomalies. These trace element patterns are nearly identical to those Oligocene (36--32 Ma) "early arc" andesites and dacites on Saipan, Guam, and Rota. All of the aforementioned lavas also have similar 207Pb/204Pb and 208Pb/204Pb values that plot along a trend that stretches from West Philippine basin basalt compositions toward those Pacific siliceous sediments. In contrast, Eocene volcanic rocks from other locations in the IBM arc are basaltic to boninitic and have U-shaped REE patterns and small to nonexistent Nb anomalies. The Pb isotopic compositions of these samples are similar to Pacific basin volcanics and volcanogenic sediments. Mathematical modeling suggests that the Saipan rhyolites were most likely derived by partial melting of an arc-like amphibolite crust and not through crystal fractionation of a "protoarc" boninite series magma. The data and these modelings suggest that a piece of preexisting arc-like amphibolite crust was trapped in the Mariana fore-arc early in its evolution. The Saipan rhyolites were produced by melting this crust at relatively shallow depths.

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.

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.

A Ta-rich low-P peraluminous granite: the Rechla cupola (Hoggar, Algeria) and associated pegmatites, the result of extreme fractionation of a A2-type magma.

NASA Astrophysics Data System (ADS)

Kesraoui, M.; Marignac, C.; Hamis, A.; Cuney, M.

2012-04-01

In the c. 525 Ma RMG province of the Laouni terrane of the Pan-African Tuareg Shield (Hoggar), the small N20°E elliptic Rechla cupola (200x100 m) is particularized by a rim of Qtz-Kfs-Znw pegmatite. It is a medium-grained Na-Li-F granite, with quartz, albite (An01), rare microcline, topaz, Mn-lepidolite (≤ 8% MnO) and Hf-zircon, and: 71.4 % SiO2, 0.93% FeO+MgO+MnO (Mg # 0.19, Mg/Mg+Fe+Mn 0.09), 9.22% Na2O+K2O (Na # 0.7), Al-Na-K-2Ca from 55 to 85, and low P2O5 (0.05%) and ∑ REE (23 ppm) contents, with a pronounced tetrad effect and <0 Eu anomaly in the REE pattern. Such a composition is typical of a low-P peraluminous RMG deriving from highly potassic calcalkaline suites (A2 type) (Linnen & Cuney 2005), enriched in F (1.6%), Li (1,600 ppm), Zn (300 ppm), Be (7 ppm), Sn (740 ppm), W (40 ppm) and specially Ta (165 ppm, Ta/Nb between 2.4 and 2.6), the latter as columbo-tantalite and Mn-wodginite (Ta # 0.8). The pegmatite rim comprises, towards the intrusion (i) thick Kfs lenses (palissadic crystals ≥ 50 cm), (ii) a laminated quartz-zinnwaldite-(beryl) sequence , and (iii) a discontinuous band of fine-grained granite, with quartz, albite, topaz, Mn-lepidolite and beryl, equally fractionated: 69.4% SiO2, 0.85% FeO+MgO+MnO (Mg# 0.06, Mg/Mg+Fe+Mn 0.02), Al-Na-K-2Ca = 32, F 0.4%, Li 610 ppm, Ta 240 ppm (Ta/Nb = 2.4), Be 500 ppm. The laminated sequence overprints the Kfs lenses. It comprises thick (≤ 20 m) quartz lenses cross-cut by 10 cm-sized alternating bands of euhedral quartz and Mn-zinnwaldite (≤ 6.5% MnO). REE-patterns of the Mn-Znw display a clear inverse tetrad effect, symmetrical of the granite pattern. At the boundary with the fine-grained internal band, euhedral quartz crystals are projecting toward the inner wall. The Rechla body and its surrounding pegmatites are intrusive into a porphyritic biotite-granite representative of the evolved magmas of the A2-type Taourirt suite (Azzouni-Sekkal & Boissonnas 1993), with a classical "seagull" pattern and a pronounced <0 Eu anomaly. Geochemical modelling shows that the main Rechla magma is likely the fractionated product of this already differentiated magma, mainly involving quartz and Kfs. The pegmatite rim is interpreted as the result of the sequential crystallization of a Rechla-type melt, with late individualisation of a Fe-rich magmatic-hydrothermal phase responsible for the quartz-zinnwaldite assemblage, leaving a strongly Be-enriched residual liquid (the fine-grained granite). As demonstrated by the Rechla occurrence, Ta concentration at levels similar to those in Beauvoir-type high-P peraluminous granites may be reached in the low-P low-Ta A2 suites, provided that extreme fractionation processes are established. Azzouni-Sekkal, A., Boissonnas, J. (1993). Une province magmatique de transition du calco-alcalin à l'alcalin : les granitoïdes pan-africains à structure annulaire de la chaîne pharusienne du Hoggar (Algérie). Bulletin Société Géologique France 164, 597-608. Linnen, R.L., Cuney, M. (2005). Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf mineralization. In: RL Linnen, IM Samson (eds), Rare-element geochemistry and mineral deposits, Geological Association of Canada (GAC) Short Course Notes 17, pp. 45-67.

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.

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.

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.

Trace elements in mineral separates of the Pena Blanca Spring aubrite - Implications for the evolution of the aubrite parent body

NASA Technical Reports Server (NTRS)

Lodders, K.; Palme, H.; Wlotzka, F.

1993-01-01

A detailed chemical study is conducted of the Pena Blanca Spring aubrite in order to clarify both the origin of the aubrite parent body (APB) and its relation to the enstatite chondrites. The distribution of REE among aubritic minerals cannot be the result of fractional distillation, which would occur if high degrees of partial melting had occurred on the APB. The REE distributions instead indicate a complete equilibrium of oldhamite and other phases, so that a brief nonequilibrium melting episode must have led to the segregation of metal and sulfides.

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.

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.

Origin of silicic crust by rifting and bimodal plume volcanism in the Afar Depression

NASA Astrophysics Data System (ADS)

Ghatak, A.; Basu, A. R.; Ebinger, C. J.

2010-12-01

The youngest mantle plume province worldwide occurs at the seismically and volcanically active East African - Red Sea - Gulf of Aden (Afar) triple junction, where one or more upwellings has impinged the thick cratonic lithosphere since ~45 Ma. A spectacular example of magmatism in the Afar depression is seen in the present to < 2 Ma old bimodal fissural mafic and peralkaline silicic eruptions in the ~60 km-long Dabbahu-Manda Hararo (DMH) Rift. In this study we report major, trace elements, and Nd-Sr-Pb isotopes in recent basaltic and silicic rocks originating from the center of the DMH rift segment, exposed along the rift axis and flanks of this segment. The rare earth element (REE) patterns of the silicic rocks and basalts are different in two significant ways: (1) the silicic rocks show a prominent positive Ce-anomaly that is extremely rare in volcanic rocks; and (2) this positive Ce-anomaly is accompanied by a strong negative Eu-anomaly. These anomalies are absent in the basaltic rocks. The positive Ce-anomaly is probably due to interaction in a magma chamber, similar in composition to the basalts, with deep saline aquifer or brines that typically show positive Ce-anomaly. The REE patterns of the two lava groups are interpreted to be due to fractional crystallization of plagioclase in a magma chamber similar in REE composition as the basalts that erupted in the DMH segments. We interpret the silicic rocks to be residues after ~20% fractional crystallization of plagioclase in the DMH basalts. The Nd-Pb isotopic composition of the basalts and rhyolites of the DMH are similar to the Ethiopian plume as defined by the ~30 Ma old Ethiopian flood basalts. Based on their high 3He/4He ratios (R/RA ~30) and Nd-Sr-Pb isotopic data, the source of the Ethiopian plume is generally believed to be in the lower mantle. Therefore, the similarity of the Nd-Pb and Pb-Pb isotopic variations between the Ethiopian plume and the DMH lavas indicates that these lavas were sourced from the lower mantle, and this source zone showed little variation over the past 30 Ma. Some of the silicic lavas fall distinctly outside the plume field toward more radiogenic 87Sr/86Sr at relatively restricted Nd and Pb isotopic compositions. This excursion in Sr-isotopic ratios of the silicic lavas, in concert with their positive Ce-anomaly, is interpreted to be due to mixing of the Afar plume derived basaltic magma with fluids from saline aquifers. We conclude that the bimodal lavas are consanguineous, the silicic lavas being generated by fractional crystallization of plagioclase in a lower mantle plume-derived basaltic magma-chamber, caused by the interaction with saline aquifers. The generation of bimodal volcanism from parental primitive basalts without any contribution from pre-existing continental crust in Dabbahu may explain other similar intraplate magmatism including early Archean-Hadean continental crust formation prior to onset of arc-volcanism.

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

USGS Publications Warehouse

Piper, D.Z.

2001-01-01

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

An introduction of Markov chain Monte Carlo method to geochemical inverse problems: Reading melting parameters from REE abundances in abyssal peridotites

NASA Astrophysics Data System (ADS)

Liu, Boda; Liang, Yan

2017-04-01

Markov chain Monte Carlo (MCMC) simulation is a powerful statistical method in solving inverse problems that arise from a wide range of applications. In Earth sciences applications of MCMC simulations are primarily in the field of geophysics. The purpose of this study is to introduce MCMC methods to geochemical inverse problems related to trace element fractionation during mantle melting. MCMC methods have several advantages over least squares methods in deciphering melting processes from trace element abundances in basalts and mantle rocks. Here we use an MCMC method to invert for extent of melting, fraction of melt present during melting, and extent of chemical disequilibrium between the melt and residual solid from REE abundances in clinopyroxene in abyssal peridotites from Mid-Atlantic Ridge, Central Indian Ridge, Southwest Indian Ridge, Lena Trough, and American-Antarctic Ridge. We consider two melting models: one with exact analytical solution and the other without. We solve the latter numerically in a chain of melting models according to the Metropolis-Hastings algorithm. The probability distribution of inverted melting parameters depends on assumptions of the physical model, knowledge of mantle source composition, and constraints from the REE data. Results from MCMC inversion are consistent with and provide more reliable uncertainty estimates than results based on nonlinear least squares inversion. We show that chemical disequilibrium is likely to play an important role in fractionating LREE in residual peridotites during partial melting beneath mid-ocean ridge spreading centers. MCMC simulation is well suited for more complicated but physically more realistic melting problems that do not have analytical solutions.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Rare earth element 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.

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.

Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes.

PubMed

Allegrini, Elisa; Maresca, Alberto; Olsson, Mikael Emil; Holtze, Maria Sommer; Boldrin, Alessio; Astrup, Thomas Fruergaard

2014-09-01

Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based on a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements. Copyright © 2014 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.

Rare Earth Elements of Orzeskie Beds of South-West Part Upper Silesian Coal Basin (Poland) / Pierwiastki Ziem Rzadkich Z Pokładów Węgla Warstw Orzeskich Południowo-Zachodniej Części Gzw (Polska)

NASA Astrophysics Data System (ADS)

Adamczyk, Zdzisław; Białecka, Barbara; Moszko, Joanna Całusz; Komorek, Joanna; Lewandowska, Małgorzata

2015-03-01

The subject of the research concerned the coal samples from 360/1, 361 and 362/1 seams of the Orzesze beds in the "Pniówek" coal mine. The obtained samples were characterized by low ash content - 2.22- 6.27% of the mass. The chemical composition of the ash indicates the presence of aluminosilicate minerals in the analyzed coal samples - most likely clay minerals, the presence of which has been confirmed in microscopic tests of the petrographic composition of channel samples of coal. The content of rare earth elements (REE sum) in the ash of the tested coal seams ranged from 364 to 1429 ppm. Variation of the REE content has been observed within a single seam. The fraction of REE indicates a relation with a mineral substance. No relation of the REE fraction and the presence of red beds has been found based on the tested samples. The content of REE found in ash, normalized to chondrites, is characterized by LREE enrichment in relation to HREE. The Eu anomaly is most likely related to tuff and tonstein levels occurring in Orzesze beds, which accompany the coal seams in the Upper Silesian Coal Basin (i.a., south of the studied area). The research has indicated that LREE in the tested samples are more related to the mineral substance, while HREE have a stronger affinity with organic substances. Przedmiotem badań były próbki węgla z pokładów 360/1, 361 i 362/1 warstw orzeskich KWK Pniówek. Próbki te charakteryzują się niewielką zawartością popiołu 2,22-6,27% mas. Skład chemiczny popiołów wskazuje na obecność w analizowanych próbkach węgla minerałów z grupy glinokrzemianów najprawdopodobniej minerałów ilastych, których obecność była stwierdzona w badaniach mikroskopowych składu petrograficznego próbek bruzdowych węgla. Zawartości pierwiastków ziem rzadkich (suma REE) w popiołach badanych pokładów węgla wahają się od 364 do 1429 ppm. Obserwuje się zróżnicowanie zawartości REE w obrębie jednego pokładu. Udział REE wykazuje związek z substancją mineralną. Nie stwierdzono związku udziału REE, w badanych próbkach, z obecnością utworów pstrych w stropie karbonu. Zawartości REE oznaczone w popiołach, znormalizowane do chondrytów, charakteryzują się wzbogaceniem LREE wobec HREE. Anomalia Eu związana jest prawdopodobnie z występującymi w warstwach orzeskich (m.in. na północ od obszaru badań) Górnośląskiego Zagłębia Węglowego poziomami tufów i tonsteinów, które towarzyszą pokładom węgla. Badania wykazały, że LREE w badanych próbkach związane są raczej z substancją mineralną, natomiast HREE posiadają silniejsze powinowactwo z substancją organiczną.

Trace element and petrologic clues to the formation of forsterite-bearing Ca-Al-rich inclusions in the Allende meteorite

NASA Astrophysics Data System (ADS)

Wark, D. A.; Boynton, W. V.; Keays, R. R.; Palme, H.

1987-03-01

This work presents new trace element and petrographic data for three forsterite-bearing, Ca-Al-rich inclusions from the Allende meteorite: TE, 818a, and 110-A. Such inclusions form a continuum with Type B1 and B2 Ca-Al-rich inclusions (CAIs), and the authors refer to them as "Type B3" CAIs. Textures, mineral chemistries, crystal-chemically fractionated REE patterns, and other properties suggest that Type B3 crystallized from partly molten evaporative residues. They also present evidence that 818a was strongly re-heated and modified in the nebula after its initial crystallization: it consists of a core of coarse-grained Ti-Al-pyroxene (Tpx), forsterite, spinel and metal grains and a thick, surrounding mantle of melilite.

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.

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).

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.

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].

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.

Behaviour of Rare Earth Elements during the Earth's core formation

NASA Astrophysics Data System (ADS)

Faure, Pierre; Bouhifd, Mohamed Ali; Boyet, Maud; Hammouda, Tahar; Manthilake, Geeth

2017-04-01

Rare Earth Elements (REE) are classified in the refractory group, which means that they have a high temperature condensation and their volatility-controlled fractionation is limited to high-temperature processes. Anomalies have been measured for Eu, Yb and Sm, which are the REE with the lowest condensation temperatures in CAIs and chondrules (e.g. [1]). REE are particularly abundant in the sulfides of enstatite chondrites, 100 to 1000 times the CI value [e.g. 2,3], proving that these elements are not strictly lithophile under extremely reducing conditions. However by investigating experimentally the impact of Earth's core formation on the behavior of Sm and Nd, we have shown the absence of fractionation between Sm and Nd during the segregation of the metallic phase [4]. Recently, Wohlers and Wood [5] proposed that Nd and Sm could be fractionated in presence of a S-rich alloy phase. However, their results were obtained at pressure and temperature conditions below the plausible conditions of the Earth's core formation. Clearly, large pressure range needs to be covered before well-constrained model can be expected. Furthermore, our preliminary metal-silicate partitioning results show that Ce and Eu have higher metal/silicate partition coefficients than their neighboring elements, and that the presence of sulphur enhances the relative difference between partition coefficients. In this presentation, we will present and discuss new metal-silicate partition coefficients of all REE at a deep magma ocean at pressures ranging from those of the uppermost upper mantle ( 5 GPa) to a maximum pressure expected in the range of 20 GPa, temperatures ranging from 2500 to about 3000 K, and oxygen fugacities within IW-1 to IW-5 (1 to 5 orders of magnitude lower than the iron-wüstite buffer). We will discuss the effect of S, as well as the effect of H2O on the behaviour of REE during the Earth's core formation: recent models suggest that contrary to currently accepted beliefs, the presence of water during the formation of metallic core of terrestrial planets is very plausible [e.g. 6-8]. References [1] Pack et al. (2004) Science 303, 997-1000. [2] Crozaz and Lundberg (1995) Geochim. Cosmochim. Acta 59, 3817-3831. [3] Gannoun et al. (2011) Geochim. Cosmochim. Acta 75, 3269-3289. [4] Bouhifd et al. (2015) Earth Planet. Sci. Lett. 413, 158-166. [5] Wohlers and Wood (2015) Nature 520, 337-340. [6] Marty (2012) Earth Planet. Sci. Lett. 313-314, 56-66. [7] Morbidelli et al. (2000) Meteor. Planet. Sci. 1320, 1309-1320. [8] Sarafian et al. (2014 Science 346, 623-626.

X-Ray Spectro-Polarimetry with Photoelectric Polarimeters

NASA Technical Reports Server (NTRS)

Strohmayer, T. E.

2017-01-01

We derive a generalization of forward fitting for X-ray spectroscopy to include linear polarization of X-ray sources, appropriate for the anticipated next generation of space-based photoelectric polarimeters. We show that the inclusion of polarization sensitivity requires joint fitting to three observed spectra, one for each of the Stokes parameters, I(E), U(E), and Q(E). The equations for StokesI (E) (the total intensity spectrum) are identical to the familiar case with no polarization sensitivity, and for which the model-predicted spectrum is obtained by a convolution of the source spectrum, F (E), with the familiar energy response function,(E) R(E,E), where (E) and R(E,E) are the effective area and energy redistribution matrix, respectively. In addition to the energy spectrum, the two new relations for U(E) and Q(E) include the source polarization fraction and position angle versus energy, a(E), and 0(E), respectively, and the model-predicted spectra for these relations are obtained by a convolution with the modulated energy response function, (E)(E) R(E,E), where(E) is the energy-dependent modulation fraction that quantifies a polarimeters angular response to 100 polarized radiation. We present results of simulations with response parameters appropriate for the proposed PRAXyS Small Explorer observatory to illustrate the procedures and methods, and we discuss some aspects of photoelectric polarimeters with relevance to understanding their calibration and operation.

Distribution of Trace Metals in a Tanzanian Andosol: A Combined Bulk and Leach Study

NASA Astrophysics Data System (ADS)

Little, M. G.

2005-12-01

Here is presented data from a sequential extraction scheme based on the Bureau Commun de Reference (BCR) applied to an andosol from Mt. Meru in northern Tanzania. This is a study into the origins, fractionation, and fate of 'potentially toxic elements' (PTE) and other trace elements. The elemental composition of four extracts, water soluble (WAT), carbonate and exchangeable (CARB), reducible oxides (OX), and organic (ORG), and the bulk soil were determined via ICP-MS and corrected for loss on ignition. We calculated the net elemental mass change using Zr and Hf as immobile elements. This calculated mass change was compared to the sum of all four leaches. Co, Mg, Ni, Zn, Cd, Tl are the only elements that show a positive correlation between the calculated net change based on Zr/Hf and the sum of all four leaches. Of these elements, Zn shows its greatest bulk enrichment at the surface and declines with depth. Conversely, Tl is enriched throughout the soil column, but increases in concentration in both the bulk and CARB fraction with depth. The other elements, Co, Ni, and Cd, are most enriched in the 80-120cm depth range where P and Fe are at their highest concentrations. These observations suggest that additional Co, Mg, Ni, Zn, Cd, and Tl were incorporated into the soil after initial weathering of the bedrock protolith; however, these elements redistributed themselves non-uniformly throughout the soil column. Sc and the REE's show increases in the CARB fraction with depth and Sc, Co, and the REE's show a clear increase in the OX fractions with depth. As much as 25% of the REE's and Co below 120 cm is in the OX leach. Additionally, Sr/Ca ratios in the CARB leach suggest that the source material for the carbonate soil fraction is the bedrock above 140cm and a different, high Sr/Ca source below 140 cm. Therefore, it is likely that exogenous material was added throughout the soil column, but from different sources above and below 120-140 cm depth.

Rare Earth and other Chemical Elements Accumulation in Vines of Fogo Island (Cape Verde)

NASA Astrophysics Data System (ADS)

Marques, Rosa; Prudêncio, Maria Isabel; Rocha, Fernando; Dias, Maria Isabel; Franco, Dulce

2017-04-01

The Fogo Island is the fourth bigger island of the Cape Verde (central Atlantic Ocean). This archipelago is located 570 kilometres off the coast of West Africa, and is characterized by a semi-arid climate. The volcanic soils of the caldera of this island, with an active volcanism during historical times, have been used for viticulture. The study of uptake of chemical elements by vines - absorption and translocation to grapes - grown in soils developed on alkaline pyroclasts is the main goal of this work. The concentrations of 27 chemical elements in bark, leafs and grapes of two vines, as well as in the corresponding soils (< 2 mm) were determined by instrumental neutron activation analysis. Irradiations of milled samples and standards were made in the core grid of the Portuguese Research Reactor (CTN/IST, Bobadela). The distribution patterns of the enrichment factors (EF) in the different parts of the plants are similar for the two sampling sites. Significant EF were found for the majority of the chemical elements studied, in the several parts of the plants, particularly in grapes where Cr, As, Sb and U are accumulated (EF > 50). The bioavailable fraction of Cr and As in these soils may be due to the low percentage of iron oxides (particularly in the form of nanoparticles), which play an important role in the retention of these elements. The factors responsible for the phytoavailability of Sb in soils and its uptake by plants it's still poorly known. Although the Sb concentrations in earth's crust are low, higher concentrations of this element in soils may be related with hydrothermal and volcanic processes. Also, the temperature may influence the accumulation of Sb in plants, with an increase of the Sb uptake by plants at higher temperatures, due to an increased desorption rate of Sb from soil particles. Concerning U, its mobility and dispersion in soils is controlled by its oxidation state, its adsorption capacity in clay minerals or iron oxides, and the ability to form more or less soluble complexes. Although U concentrations in these volcanic soils are low, there is a fraction available for absorption and accumulation by grapes. Concerning the rare earth elements (REE), it should be noted that the light REE are not enriched in any part of the vines studied, and only the heavy REE are enriched in grapes (EF = 20-50); this can be explained by the preferential uptake of the heavy REE, after primary minerals breakdown and the formation of more soluble compounds. The significant accumulation of several chemical elements found in grapes of Fogo Island can be mainly explained by a geogenic origin.

Li isotopes in archean zircons

NASA Astrophysics Data System (ADS)

Bouvier, A.; Ushikubo, T.; Kita, N.; Cavosie, A. J.; Kozdon, R.; Valley, J. W.

2009-12-01

Li is a fluid mobile, moderately incompatible element with a large mass difference between its two stable isotopes. Different processes can fractionate 7Li/6Li (fluid-rock interaction, metamorphic reactions, and Li diffusion), leading to variation by over 50‰ of δ7Li for common crustal material. These large variations make δ7Li a potential tracer of continental weathering and of the fluids affecting magma sources. Here, we report δ7Li and trace elements in Archean igneous zircons from TTG and sanukitoid granitoids from the Superior Province (Canada) in order to characterize Li in Archean zircons from well-described samples. These data are compared to detrital zircons from the Jack Hills (Western Australia) for which parent rock-type is uncertain. This study aims to better understand Li substitution in zircon and to evaluate the utility of δ7Li and [Li] for Archean petrogenesis. Zircons (n=71) were analyzed for δ7Li and trace elements (Li, P, Ca, Ti, V, Fe, Y, REE, U, Th) using an IMS-1280 ion microprobe. Most of the zircons display typical igneous REE patterns and zoning by CL. [Li] averages 13.1 ± 9 for TTG, 25.7 ± 19 for Sanukitoid and 31.0 ± 14 ppm for Jack Hills zircons, which are distinct from mantle-related zircons (<0.1 ppm). Values of δ7Li average 1.0 ± 4.5‰ for TTGs, 6.3 ± 4.4‰ for sanukitoids and -2.6 ± 8.8‰ for Jack Hills samples. Trace elements were analyzed from single spots in order to evaluate coupled substitutions. Atomic ratios (3Li+Y+REE)/P average 2.6, showing that Li and trivalent atoms are not charge-balanced by P, and suggesting that Li does not replace Zr, according to the xenotime substitution. However, (Y+REE)/(Li+P) atomic ratios average 1.0 ± 0.6, supporting the hypothesis that Li is interstitial and partly compensates trivalent cations. Several observations in this study suggest that [Li] is primary in the studied zircons: i) if Li is interstitial, charge-balance and slow diffusion of REE would control Li mobility, ii) core-rim or oscillatory zoning is observed for [Li] in many high T zircons, iii) CL zoning and low Ca+Fe, U+Th and U/Th imply little radiation damage. Values of δ7Li become erratic at [Li] < ~5 ppm and low values are not interpreted. We suggest that small amounts of non-ionic substitution could be significant for small [Li], whereas interstitial substitution dominates at > ~5 ppm. Li content and isotopic compositions of TTG zircons suggest genesis from mantle-like material, as suggested by δ18O(Zrc) (5.5 ± 0.4‰, King et al., 1998). Sanukitoids are commonly thought to be derived from the melting of peridotite metasomatized by seawater-like slab-dehydration fluids, (supported by the high δ7Li(Zrc)), followed by extensive fractional crystallization, explaining the high sanukitoid [Li]. [Li] and δ7Li thus reflect petrogenetic processes. The Jack Hills detrital zircons are consistent with crustal sources including TTG, sanukitoid and sediment-contaminated granitoid magmas.

Rare Earth Elements as Potential Biosignatures on Mars in SuperCam Time Resolved Laser Fluorescence Spectroscopy Data

NASA Astrophysics Data System (ADS)

Ollila, A.; Beyssac, O.; Sharma, S. K.; Misra, A. K.; Clegg, S. M.; Gauthier, M.; Wiens, R. C.; Maurice, S.; Gasnault, O.; Lanza, N.

2017-12-01

The rare earth elements (REE, La to Lu) are a group of elements with similar chemical properties that are generally present in geologic materials at trace concentrations. REEs may be concentrated via processes such as igneous fractional crystallization in accessory minerals, e.g. apatite, zircon, and titanite. Additionally, however, concentrations of REE may serve to identify regions of high astrobiological interest. For example, Fe-oxyhydroxide deposits in hydrothermal vent systems and biologically related manganese nodules may be enriched in REEs. REEs have not been measured in situ on Mars, therefore their prevalence and distribution on Mars is as yet unknown, except as observed in martian meteorites. SuperCam is a survey instrument that will analyze materials around the Mars 2020 rover using a variety of spectral techniques including laser-induced breakdown spectroscopy (LIBS), Raman, VIS-IR, and time-resolved laser fluorescence (TRLF) spectroscopy. Recently, the SuperCam Engineering Development Unit was tested at the Los Alamos National Laboratory for its capabilities to detect REEs in minerals using TRLF spectroscopy. While this instrument was not designed to precisely replicate the flight model, the spectral resolution and light transmission was sufficient to obtain TRLF spectra on a number of minerals demonstrating a variety of REE luminescent centers. These include apatite (Sm3+, Nd3+, Eu3+, Dy3+), fluorite (Ho3+, Sm3+, Dy3+, Nd3+), and zircon (Er3+, Pr3+, Nd3+). Future work includes expanding this suite to include minerals associated with biological activities, for example Mn-oxides (desert varnish and manganese nodules), hydrothermal Fe-oxides, and stromatolite-associated carbonates. In this way and in combination with its other techniques, SuperCam may direct the rover team to perform further analyses of similar samples by the in situ chemical and mineralogical suite of instruments, or aid in prioritization for sample return.

Fate and transport of trace metals and rare earth elements in the Snake River, an AMD/ARD-impacted watershed. Montezuma, Colorado USA.

NASA Astrophysics Data System (ADS)

McKnight, D. M.; Rue, G.

2017-12-01

Recent research in Snake River Watershed, located near the historic boomtown of Montezuma and adjacent the Continental Divide in the Colorado Rocky Mountains, has revealed the distinctive occurrence of rare earth elements (REE) at high concentrations. Here the weathering of the mineralized lithology naturally generates acid rock drainage (ARD) in addition to drainage recieved from abandoned mine adits throughout the area, results in aqueous REE concentrations three orders of magnitude higher than in most major rivers. The dominant mechanism responsible for this enrichment; their dissolution from secondary and accessory mineral stocks, abundant in REEs, promoted by the low pH waters generated from geochemical weathering of disseminated sulfide minerals. While REEs behave conservatively in acidic conditions, as well as in the presence of stabilizing ligands such as sulfate, downstream circumneutral inputs from pristine streams and a rising pH are resulting in observed fractional losses of heavy rare earth elements as well as partitioning towards colloidal and solid phases. These finding in combination with the established role of dissolved organic matter (DOM) in binding with both trace metals and REEs, suggest that competitive interactions, complexation, and scavenging are likely contributing to these proportional losses. However, outstanding questions yet remain regarding the effects of an increasing flux of trace metals as well as REEs from the Snake River Watershed into Dillon Reservoir, a major drinking water supply for the City of Denver, in part due to hydroclimatological drivers that are enhancing geochemical weathering and reducing groundwater recharge in alpine areas across the Colorado Rockies. Based on these findings also we seek to broaden this body of work to further investigate the behavior of rare earth elements (REE) in other aquatic environment as well the influence of trace metals, DOM, and pH in altering their reactivity and subsequent watershed transport.

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.

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).

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.

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.

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).

Searching for neuKREEP: An EMP study of Apollo 11 Group A basalts

NASA Technical Reports Server (NTRS)

Jerde, Eric A.; Taylor, Lawrence A.

1993-01-01

The Apollo 11 and 17 landing sites are characterized by the presence of high-Ti basalts (TiO2 greater than 6 percent). The Group A basalts of Apollo 11 have elevated K compositions (greater than 2000 ppm); and are enriched in incompatible trace elements relative to the other types of high-Ti basalt found in the region. These unique basalts also are the youngest of all high-Ti basalts, with an age of 3.56 +/- 0.02 Ga. Recent modelling of the Apollo 11 Group A basalts by Jerde et al. has demonstrated that this unique variety of high-Ti basalt may have formed through fractionation of a liquid with the composition of the Apollo 11 orange glass, coupled with assimilation of evolved material (dubbed neuKREEP and having similarities to lunar quartz monzodiorite). Assimilation of this material would impart its REE signature on the liquid, resulting in the elevated REE abundances observed. Minerals such as whitlockite which contain a large portion of the REE budget can be expected to reflect the REE characteristics of the assimilant. To this end, an examination of the whitlockite present in the Apollo 11 Group A basalts was undertaken to search for evidence of the neuKREEP material assimilated.

Unravelling the sulphur isotope systematics of an alkaline magmatic province: implications for REE mineralization and exploration

NASA Astrophysics Data System (ADS)

Hutchison, W.; Finch, A.; Boyce, A.; Friis, H.; Borst, A. M.; Horsburgh, N. J.

2017-12-01

Some of the world's best alkaline rare earth element (REE) deposits are formed in magmatic systems that are sealed (i.e., those that are autometasomatised and maintain reducing conditions). Conversely, in open systems where oxidizing fluids infiltrate, it is commonly assumed that REE are redistributed over a wider (less concentrated) zone. Sulphur isotope fractionation is sensitive to variations in temperature and redox, and, although sulphide minerals are relatively abundant in alkaline systems, there have been few attempts to test these hypotheses and develop a sulphur isotope proxy for alkaline metasomatism and formation of associated REE deposits. The Gardar Rift Province in southern Greenland was volcanically active in two periods between 1300 and 1100 Ma and is an ideal natural laboratory to explore sulphur isotope systematics because a near-complete alkaline magmatic lineage is exposed. We present new δ34S from across the province with a particular focus on three alkaline systems (Ilímaussaq, Motzfeldt and Ivigtût) that also host major REE deposits. Primitive mafic rocks from regional Gardar dykes and lavas have a restricted range of δ34S between 0 and 3 ‰ and fractional crystallization imparts no observable change in δ34S. In a few cases high-δ34S rocks (>15 ‰) occur when intrusive units have assimilated local sedimentary crust (δ34S = 25 ‰). Most δ34S variation takes place in the roof zones of alkaline intrusions during late-magmatic and hydrothermal stages, and we identify clear differences between the complexes. At Ilímaussaq, where the magmatic series is exceptionally reduced (below QFM buffer), roof zone δ34S remains narrow (0-3 ‰). At Motzfeldt, a more open oxidizing roof zone (MH buffer), δ34S ranges from -12 ‰ in late-stage fluorite veins to +12 ‰ where local crust has been assimilated. Ivigtût is intermediate between these end-members varying between -5 to +5 ‰. The δ34S variations primarily relate to temperature and redox variations between the systems and highlight important contrasts in roof zone sealing. This work provides new constraints on the varying origins of magmatic fluids in alkaline roof zones, and demonstrates the potential of sulphur isotopes as a redox and temperature proxy. Future work will focus on whether δ34S can be used as an exploration tool to identify REE mineralization at depth.

Understanding rhizosphere processes to enhance phytoextraction of germanium and rare earth elements

NASA Astrophysics Data System (ADS)

Wiche, Oliver

2017-04-01

Germanium (Ge) and rare earth elements (REEs) are economically valuable raw materials that are not actually rare in terms of concentrations in soils but they are hardly available for plant uptake due to interactions with organic matter (SOM), secondary soil constituents such as Fe/Mn oxides and P bearing soil fractions. Processes in the rhizosphere might influence availability of Ge and REEs in the soil-plant system, since lowering of the pH and presence of carboxylates and siderophores (small molecules that strongly chelate Fe and other elements) strongly influences the chemical speciation of Ge and REEs in soil and consequently this comprehensive knowledge helps us to improve phytomining. In a series of field and greenhouse experiments 16 plant species from the functional groups of grasses, herbs and legumes were tested with regard to their accumulation efficiency of Ge and REEs in shoots. Subsequently, we conducted mixed culture experiments in which inefficient species (e.g. cereals like Avena sativa, Hordeum vulgare, Panicum miliaceum) were cultivated in mixed cultures with efficient species (Lupinus albus, Lupinus angustifolius). Based on the plant concentrations a principal component analysis (PCA) was performed to identify significant factors that explain the accumulation behavior of different plant species with regard to Ge, REEs, Si, Fe and Mn. In this analysis Mn was used to identify plant species with efficient mechanisms to access sparingly available P-resources in soils. Particularly in nonmycorrhizal species concentrations of Mn in leaves often indicate a carboxylate based P-mobilising strategy. Herbaceous plant species accumulated significantly higher amounts of REEs while grasses accumulated significantly higher amounts of Ge. Concentrations of Ge in shoots of grasses correlated significantly positive with Si, but negatively with concentrations of Mn. Indeed, the results of the PCA clearly show that plants with high Mn concentrations tend to have lower contents of both Ge and REEs. However, intercropping of Avena sativa and Hordeum vulgare with Lupinus albus significantly enhanced uptake of REEs in Avena sativa and Hordeum vulgare but not the uptake of Ge. These results suggest that rhizosphere processes play an integral part during mobilization of Ge and REEs in soil and uptake in plants. The availability of Ge to grasses closely follows a "Si-nutrition strategy", while plants that deploy a P-mobilizing strategy based on the release of carboxylates seem to be able to mobilize REEs as well, but they are unable to accumulate the mobilized REEs in the shoots. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. The author is grateful to students and laboratory assistants contributing in the field work and sample preparation.

African Dust Transport Captured by Rare Earth Elemental Concentrations in Coral Microatolls

NASA Astrophysics Data System (ADS)

Ouellette, G., Jr.; DeLong, K.; Herrmann, A.; Huang, C. Y.; Shen, C. C.

2017-12-01

Winds are integral components of the climate system; unfortunately, windsare also among the climate variables that are most difficult to study prior to the instrumentalrecord. Paleoclimatologists use sedimentary dust records (e.g., lake and ocean cores) tounderstand past wind circulation conditions; however, these types of records typically are notamenable to sub-annual interpretation due to their limited temporal resolution. Here wedeveloped a coral-based dust-wind proxy to overcome these temporal limitations by usingtrace (nmol/mol) rare earth elemental concentrations recorded in the skeletons of coralmicroatolls. The rare earth elements (REE; the lanthanides as well as scandium and yttrium)behave similarly in geologic and geochemical systems, and have served as useful proxies ofgeological processes in both deep and shallow time. Corals incorporate REE as they deposittheir exoskeletons that extend incrementally with time forming annual density band couplets.Coral microatolls grow at or near the sea surface, where coral REE concentrations are mostsensitive to dust deposition. Our study site off the west coast of Haiti is down stream of light-REE depleted bedrock whereas REE in African dust, transported by the easterly trade winds,reflect average crustal abundances. This unique "upstream" source signature allows forterrestrial contamination of the dust-wind signal to be ruled out. Light REE concentrations (esp.Nd and Pr) demonstrate an order of magnitude increase within coral aragonite coincident withmajor African dust plume events throughout the past decade, with Nd/Ca and Pr/Ca increasingfrom an average of 27 nmol/mol to an average 144 nmol/mol and an average of 5 nmol/mol toan average of 37 nmol/mol, respectively, during major African dust plume events. Monthly-resolved REE analysis shows these REE peaks coincide with the summer dust season rather thanHaiti's two wet seasons in spring and autumn. Regression of our coral REE dust proxy tosatellite records of African dust aerosol optical depth (AOD) provides a significant transferfunction [(REE)=3.00(AOD)-3.11, R 2 = 0.72, p ≤ 0.0005, df= 24]. Our results suggest coral REErecords have the potential to robustly reconstruct past African dust plume transport, thusproviding insight into the regional easterly trade wind patterns driving them.

Aqueous Rare Earth Element Patterns and Concentration in Thermal Brines Associated With Oil and Gas Production

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

Nye, Charles; Quillinan, Scott Austin; Neupane, Ghanashyam

This study is part of a joint effort by the University of Wyoming (UW) School of Energy Resources (SER), the UW Engineering Department, Idaho National Laboratories (INL), and the United States Geological Survey (USGS) to describe rare earth element concentrations in oil and gas produced waters and in coal-fired power station ash ponds. In this work we present rare earth element (REE) and trace metal behavior in produced water from four Wyoming oil and gas fields and surface ash pond water from two coal-fired power stations. The concentration of REEs in oil and gas produced waters is largely unknown. Formore » example, of the 150,000 entries in the USGS National Produced Waters Geochemical Database less than 5 include data for REEs. Part of the reason for this scarcity is the analytical challenge of measuring REEs in high salinity, hydrocarbon-bearing waters. The industry standard for water analysis struggles to detect REEs in natural waters under ideal conditions. The detection of REEs in oil and gas field samples becomes all but impossible with the background noise and interferences caused by high concentrations of non-REE ions and residual hydrocarbons. The INL team members have overcome many of these challenges (e.g. McLing, 2014), and continue to develop their methods. Using the methods of the INL team members we measured REEs in high salinity oil and gas produced waters. Our results show that REEs exist as a dissolved species in all waters measured for this project, typically within the parts per trillion range. The samples may be grouped into two broad categories analytically, and these categories match their genesis: Wyoming oil and gas brines contain elevated levels of Europium, and Wyoming industrial pond waters show elevation in heavy REEs (HREEs). While broadly true, important variations exist within both groups. In the same field Europium can vary by more than an order of magnitude, and likewise HREEs in industrial ponds at the same site can vary by more than an order of magnitude. Future work will investigate the reasons for these variations.« less

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

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.

Audre's daughter: Black lesbian steganography in Dee Rees' Pariah and Audre Lorde's Zami: A New Spelling of My Name.

PubMed

Kang, Nancy

2016-01-01

This article argues that African-American director Dee Rees' critically acclaimed debut Pariah (2011) is a rewriting of lesbian poet-activist Audre Lorde's iconic "bio-mythography" Zami: A New Spelling of My Name (1982). The article examines how Rees' work creatively and subtly re-envisions Lorde's Zami by way of deeply rooted and often cleverly camouflaged patterns, resonances, and contrasts. Shared topics include naming, mother-daughter bonds, the role of clothing in identity formation, domestic abuse, queer time, and lesbian, gay, bisexual, and transgender legacy discourse construction. What emerges between the visual and written texts is a hidden language of connection--what may be termed Black lesbian steganography--which proves thought-provoking to viewers and readers alike.

The effect of the water-to-rock ratio on REE distribution in hydrothermal fluids: An experimental study

NASA Astrophysics Data System (ADS)

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

2013-04-01

High-temperature submarine MOR hydrothermalism creates high elemental fluxes into, and out of, oceanic lithosphere significantly affecting ocean chemistry. The Turtle Pits hydrothermal system discovered at 5° S on the slow-spreading Mid-Atlantic Ridge (MAR) in water depths of ~3000 m (~300 bar) emanates 'ultrahot' fluids > 400 ° C [1] with high concentrations of dissolved gases (e.g., H2), transition metals, and rare earth elements (REE). The normalised REE patterns of these 'ultrahot' fluids are uncommon as they exhibit depletions of LREE and no Eu-anomaly ('special' REE-signature in [2]), which is in contrast to the "typical" LREE enrichment and pronounced positive Eu-anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Although hydrothermal fluid REE-signatures may play a key role in understanding processes during water-rock interaction, only few experimental data have been published on REE distribution in seawater-like fluids reacted with rocks from the ocean crust [e.g., 4, 5]. Besides temperature, the seawater-to-rock ratio (w/r ratio) strongly affects water-rock reaction processes and, thus, has significant control on the fluid chemistry [e.g., 6, 7]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we designed a series of experiments reacting different fluid types with mineral assemblages from fresh, unaltered gabbro at 425 ° C and 400 bar using cold seal pressure vessels (CSPV). Mixtures of 125-500 μm-sized hand-picked plagioclase and clinopyroxene grains separated from unaltered gabbro reacted in gold capsules with 3.2 wt.% NaCl(aq) fluid (similar to seawater salinity), or with natural seawater. The w/r (mass) ratio ranged from 1 to 100 and the run durations were varied from 3 to 30 d in the NaCl(aq) experiments, and was 3 d in the seawater experiments. The reacted fluids were extracted after quenching and analysed by ICP-OES and ICP-MS. Only in the seawater experiments, the gabbro reacted considerably with the liquid resulting in a strong REE enrichment relative to the original seawater. Increasing w/r ratios gave rise to decreasing pH of the quench fluid and enforced the enrichment of HREE in the fluid with relative depletion of LREE and no Eu-anomaly. The 'special' REE-signatures observed in Turtle Pits vent fluids at 5° S MAR could be reproduced in our experiments at a w/r ratio of 5 (pH = ~6), whereas at a w/r ratio of 1 (pH = ~7) the fluid exhibited the "typical" REE pattern with a positive Eu-anomaly. Fluids from experiments with w/r ratios ×10 (pH ~6 to ~2) showed higher HREE enrichment than observed in natural MOR vent fluids so far. Concluding, elevated REE concentrations in hydrothermal fluids exhibiting the 'special' REE pattern with relative enrichment of HREE and no Eu anomaly are indicative for leaching processes under high w/r ratios (~5-10) that might be more common in slow-spreading oceanic crust with focused hydrothermal fluid-flow along e.g., detachment faults [8]. References: [1] Koschinsky A., Garbe-Schönberg D., Sander S., Schmidt K., Gennerich H.-H., and Strauss H. (2008) Geology 36, 615-618. [2] Schmidt K., Garbe-Schönberg D., Bau M., and Koschinsky A. (2010) GCA 74, 4058-4077. [3] Douville E., Bienvenu P., Charlou J. L., Donval J. P., Fouquet Y., Appriou P., and Gamo T. (1999). GCA 63, 627-643. [4] You C.-F., Castillo P. R., Gieskes J. M., Chan L. H., and Spivak A. J. (1996) EPSL 140, 41-52. [5] Allen D. E. and Seyfried [Jr.] W. E.(2005) GCA 69, 675-683. [6] Seyfried [Jr.] W. E. and Bischoff J. L. (1977) EPSL 34, 71-77. [7] Hajash A. and Chandler G. W. (1981) Contrib Mineral Petrol 78, 240-254. [8] McCaig A.M. and Harris M. (2012) Geology 40, 367-370.

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.

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.

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.

Experimental evidence for Nd-Sr decoupling during low-temperature (20-170oC) hydrothermal alteration of olivine and clinopyroxene

NASA Astrophysics Data System (ADS)

Frisby, C. P.; Bizimis, M.; Foustoukos, D.

2011-12-01

Serpentinization of abyssal peridotites represents a major reaction front between the hydrosphere and the mantle. While several studies have investigated the phase equilibria relationships that describe seawater - peridotite interaction at high temperature hydrothermal conditions (~400oC), there is limited data on the elemental mass exchange between seawater and ultramafic lithologies at temperatures similar to those expected at the flanks of hydrothermal vent sites. To better constrain seawater - peridotite elemental exchange alteration processes at low-temperatures, a series of experiments were conducted involving natural mantle olivine (Fo=90) and clinopyroxene coexisting with synthetic seawater enriched in elemental or isotopically enriched Sr, Ba, Nd, Sm, Gd, Dy, Yb, Pb, and U. The experiments were performed at temperatures from ambient to 170oC (at saturation vapor pressure), ranging from 15 minutes to 8 weeks and at water/rock mass ratios ~20. Our data shows strong decoupling between alkaline earth elements (Sr, Ba) and rare earth elements (REE). Overall, the REE are quantitatively removed from the solution to the mineral surface while Sr and Ba invariably remain in solution. In detail, we find that the rate of REE removal is proportional to temperature and inversely proportional to particle size distribution. For example at the 350-200um olivine grain size experiments 60% of REE removal occurred in 7 days at ambient temperature and in 6 hours at 100oC. No difference was observed on the removal rates between clinopyroxene and olivine. Additionally, we observe a fractionation of REE in solution where the HREE were removed at a faster rate than the LREE. The calculated apparent kDs for the experiments that approached steady state are similar to Fe-hydroxide scavenging experiments, and importantly show the tetrad effect in REE. We note in the experiments run with clinopyroxene and isotopically enriched seawater at 170oC, results indicate a simultaneous REE precipitation-dissolution process at the seawater/mineral interface, suggesting a bi-directional exchange between the rock and the solution. The decoupling between REE, and Sr implies that during low-temperature peridotite - seawater reaction, Nd may be preferentially deposited on the peridotite mineral surface while Sr, in the absence of carbonate precipitation, may not. The implications on the estimates of integrated water/rock mass ratios using bulk rock Sr-Nd isotopes in serpentinites will be discussed.

A Gradient in Cooling Rate Beneath the Moho at the Oman Ophiolite: Fresh Insights into Cooling Processes at Mid-Ocean Ridges from REE-Based Thermometry

NASA Astrophysics Data System (ADS)

Dygert, N. J.; Kelemen, P. B.; Liang, Y.

2015-12-01

The Wadi Tayin massif in the southern Oman ophiolite has a more than 10 km thick mantle section and is believed to have formed in a mid-ocean ridge like environment with an intermediate to fast spreading rate. Previously, [1] used major element geothermometers to investigate spatial variations in temperatures recorded in mantle peridotites and observed that samples near the paleo-Moho have higher closure temperatures than samples at the base of the mantle section. Motivated by these observations, we measured major and trace elements in orthopyroxene and clinopyroxene in peridotites from depths of ~1-8km beneath the Moho to determine closure temperatures of REE in the samples using the REE-in-two-pyroxene thermometer [2]. Clinopyroxene are depleted in LREE and have REE concentrations that vary depending on distance from the Moho. Samples nearer the Moho have lower REE concentrations than those deeper in the section (e.g., chondrite normalized Yb ranges from ~1.5 at the Moho to 4 at 8km depth), consistent with near fractional melting along a mantle adiabat. Orthopyroxene are highly depleted in LREE but measurements of middle to heavy REE have good reproducibility. We find that REE-in-two-pyroxene temperatures decrease with increasing distance from the Moho, ranging from 1325±10°C near the Moho to 1063±24°C near the base of the mantle section. Using methods from [3], we calculate cooling rates of >1000°C/Myr near the Moho, dropping to rates of <10°C/Myr at the bottom of the section. The faster cooling rate is inconsistent with conductive cooling models. Fast cooling of the mantle lithosphere could be facilitated by infiltration of seawater to or beneath the petrologic Moho. This can explain why abyssal peridotites from ultra-slow spreading centers (which lack a crustal section) have cooling rates comparable to those of Oman peridotites [3]. [1] Hanghøj et al. (2010), JPet 51(1-2), 201-227. [2] Liang et al. (2013), GCA 102, 246-260. [3] Dygert & Liang (2015), EPSL 420, 151-161.

Trace Elements and Oxygen Isotope Zoning of the Sidewinder Skarn

NASA Astrophysics Data System (ADS)

Draper, C.; Gevedon, M. L.; Barnes, J.; Lackey, J. S.; Jiang, H.; Lee, C. T.

2016-12-01

Skarns of the Verde Antique Quarry and White Horse Mountain areas of the Sidewinder Range give insight into the paleohydrothermal systems operating in the California's Jurassic arc in the Southwestern Mojave Desert. Garnet from these skarns is iron rich: Xand= 55-100. Laser fluorination measurements show oxygen isotope (δ18O) compositions of garnet crystals and crystals domains have large ranges: -3.1‰ to +4.4‰ and -8.9‰ to +3.4‰, respectively. In general, the garnet cores have more negative δ18O values than rims, although oscillations are present. Negative values have been interpreted as influx of meteoric fluid and positive values as increased magmatic input. Here we report major and trace element concentrations for 17 core to rim Sidewinder garnet transects. REEs concentrations are low in all crystals, with total REE concentrations ranging from 0.710 ppm to 33.7 ppm, values that are lower than Cretaceous skarn garnets in the Sierra Nevada in the White Chief and Empire Mt skarns. Such low concentrations are likely due to the higher fraction of meteoric fluids during formation of the Sidewinder skarns. REE concentrations decrease from core to rim (REE core average=12.2ppm, REE rim average=7.21ppm). This is slightly more pronounced in the LREEs than in the HREEs (LaN/YbN core average= 10.9; rim average= 9.73, normalized to Chondrite). X­and tends to decrease core to rim in the Verde Antique skarn, whereas, Xand of the White Horse skarn does not correlate with distance from core. A large positive Eu anomaly (Eu/Eu* = 3­-30) in garnet from both skarns suggests oxidizing fluid conditions. Oxygen isotope data from garnet in these same skarns show periods of time with increased proportion of magmatic derived fluids in the total fluid budget. However, there is no corresponding widespread increase in total REE concentrations. Other studies of skarns from the western Sierra Nevadan arc (White Chief and Empire Mountain) observe complete decoupling of d18O values and trace element compositions. Future modeling should consider modal abundance of fluid soluble minerals in cooling and altering plutons to probe the REE budget.

Geochemistry and tectonic setting of the Paleoproterozoic metavolcanic rocks from the Chirano Gold District, Sefwi belt, Ghana

NASA Astrophysics Data System (ADS)

Senyah, Gloria A.; Dampare, Samuel B.; Asiedu, Daniel K.

2016-10-01

Major and trace elements, including rare earth elements (REEs) data are presented for metavolcanic rocks of the Paleoproterozoic Birimian Sefwi belt to determine the geochemical characteristics as well as the possible tectonic setting of emplacement of these rocks. In order to accomplish the aim of the study, the petrographical characteristics of the rocks were examined coupled with analysis of the rocks for their whole-rock major and trace elements contents by ICP-AES and ICP-MS methods respectively. The rocks have been classified as basalt/basaltic andesites and dolerites based on their textural and mineralogical compositions. It is observed that the rocks have suffered various degrees of alteration evident in the overprinting of primary minerals such as pyroxenes and plagioclase by chlorite, epidote, sericite and others. Generally, the rocks are moderately deformed and may have experienced at least greenschist metamorphism. The basalt/basaltic andesites are derivative magmas [Mg# (20-51), Cr (10-220 ppm) and Ni (5-137 ppm)], and show flat REE to fractionated REE patterns with (La/Sm)N = 1.36-3.90, (La/Yb)N = 1.17-5.32 and strong negative to non-existent Eu anomalies (Eu/Eu* = 0.51-1.03). N-MORB-normalised multi-element diagrams show that the rocks have geochemical patterns characterised by enrichment in LILE relative to HFSE and in LREE relative to HREE. The basalt/basaltic andesites exhibit characteristics of subduction zone-related magmas, such as pronounced negative Nb-Ta anomalies, slightly negative Hf and variable negative Ti anomalies. The dolerites do not vary much from the basalts and basaltic andesites. The MgO and Fe2O3 values of the dolerite range from 2.97 to 6.93 and 5.98 to 14.35 wt.% respectively, corresponding to Mg#s of 38-62. LREEs enrichment over HREEs with (La/Sm)N ranging from 0.61 to 4.61 and (Gd/Yb)N ranging from 0.99 to 2.91 is also typical of these rocks. The dolerites also exhibit quite invariable Eu anomalies (Eu/Eu* = 0.81-1.00) and display a pronounced Nb-Ta trough and a minor negative Ti anomaly, suggesting arc characteristics. The metavolcanic rocks from the study area generally exhibit subduction-related setting characteristics with evidence of a sub-lithospheric contamination.

Accumulation of germanium and rare earth elements in functional groups of selected energy crops cultivated on two different soils

NASA Astrophysics Data System (ADS)

Wiche, Oliver; Székely, Balázs

2016-04-01

A field experiment was conducted to investigate the uptake of Ge and selected REEs in functional groups of selected crop species. Five species belonging to the functional group of grasses (Hordeum vulgare, Zea mays, Avena sativa, Panicum miliaceum and Phalaris arundinacea) and four species from the group of herbs (Lupinus albus, Lupinus angustifolius, Fagopyrum esculentum and Brassica napus) were cultivated in parallel on two soils with slightly alkaline (soil A: pH = 7.8) and slightly acidic (soil B: pH = 6.8) conditions. After harvest, concentrations of Ge, La, Nd, Gd, Er, P, Fe, Mn and Si in shoot tissues were determined with ICP-MS. Concentrations of Ge were significantly higher in grasses than in herbs. Conversely, concentrations of La and Nd were significantly higher in herbs, than in grasses. Highest concentrations were measured in Brassica napus (REEs) and Zea mays (Ge). Concentrations of Ge significantly correlated with that of Si in the shoots showing low concentrations in herbs and high concentrations in grasses, indicating a common mechanism during the uptake in grasses. Concentrations of REEs correlated significantly with that of Fe, indicating increasing concentrations of REEs with increasing concentrations of Fe. Cultivation of species on the slightly acidic soil significantly increased the uptake Ge in Lupinus albus and Phalaris arundinacea and the uptake of La and Nd in all species except of Phalaris arundinacea. This study demonstrated that commonly used field crops could be regarded as suitable candidates for a phytomining of Ge and REEs, since these species develop high yields of shoots, high concentrations of elements and are widely used in agricultural practice. Under soil conditions where bioavailability of Ge and REEs is expected to be low (soil A) accumulation can be estimated at 1.8 g/ha Ge in Z. mays and 3.7 g/ha REEs (1.5 g/ha La, 1.4 g/ha Nd, 0.6 g/ha Gd, 0.3 g/ha Er), respectively, in B. napus, assuming a constant high efficiency of phytoextraction in closed stands. Slight changes in soil properties like soil pH and fractions of REEs bound to organic matter significantly enhanced the uptake of Ge, La and Nd in plants. Thus, measures in soil management hold promise for enhanced phytoextraction of Ge and predominantly light REEs from soils, however, the impact of acidifying fertilizers and other soil amendments on the phytoextraction of Ge and REEs remain a field for further investigations. These studies have been carried out in the framework of the PhytoGerm project financed by the Federal Ministry of Education and Research, Germany.

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.

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.

Geochemistry and petrogenesis of a peralkaline granite complex from the Midian Mountains, Saudi Arabia

NASA Astrophysics Data System (ADS)

Harris, N. B. W.; Marriner, G. F.

1980-10-01

A zoned intrusion with a biotite granodiorite core and arfvedsonite granite rim represents the source magma for an albitised granite plug near its eastern margin and radioactive siliceous veins along its western margin. A study of selected REE and trace elements of samples from this complex reveals that the albitised granite plug has at least a tenfold enrichment in Zr, Hf, Nb, Ta, Y, Th, U and Sr, and a greatly enhanced heavy/light REE ratio compared with the peralkaline granite. The siliceous veins have even stronger enrichment of these trace elements, but a heavy/light REE ratio and negative eu anomaly similar to the peralkaline granite. It is suggested that the veins were formed from acidic volatile activity and the plug from a combination of highly fractionated magma and co-existing alkaline volatile phase. The granodiorite core intrudes the peralkaline granite and has similar trace element geochemistry. The peralkaline granite is probably derived from the partial melting of the lower crust in the presence of halide-rich volatiles, and the granodiorite from further partial melting under volatile-free conditions.

Ultra-low rare earth element content in accreted ice from sub-glacial Lake Vostok, Antarctica

NASA Astrophysics Data System (ADS)

Gabrielli, Paolo; Planchon, Frederic; Barbante, Carlo; Boutron, Claude F.; Petit, Jean Robert; Bulat, Sergey; Hong, Sungmin; Cozzi, Giulio; Cescon, Paolo

2009-10-01

This paper reports the first rare earth element (REE) concentrations in accreted ice refrozen from sub-glacial Lake Vostok (East Antarctica). REE were determined in various sections of the Vostok ice core in order to geochemically characterize its impurities. Samples were obtained from accreted ice and, for comparison, from the upper glacier ice of atmospheric origin (undisturbed, disturbed and glacial flour ice). REE concentrations ranged between 0.8-56 pg g -1 for Ce and 0.0035-0.24 pg g -1 for Lu in glacier ice, and between <0.1-24 pg g -1 for Ce and <0.0004-0.02 pg g -1 for Lu in accreted ice. Interestingly, the REE concentrations in the upper accreted ice (AC 1; characterized by visible aggregates containing a mixture of very fine terrigenous particles) and in the deeper accreted ice (AC 2; characterized by transparent ice) are lower than those in fresh water and seawater, respectively. We suggest that such ultra-low concentrations are unlikely to be representative of the real REE content in Lake Vostok, but instead may reflect phase exclusion processes occurring at the ice/water interface during refreezing. In particular, the uneven spatial distribution (on the order of a few cm) and the large range of REE concentrations observed in AC 1 are consistent with the occurrence/absence of the aggregates in adjacent ice, and point to the presence of solid-phase concentration/exclusion processes occurring within separate pockets of frazil ice during AC 1 formation. Interestingly, if the LREE enrichment found in AC 1 was not produced by chemical fractionation occurring in Lake Vostok water, this may reflect a contribution of bedrock material, possibly in combination with aeolian dust released into the lake by melting of the glacier ice. Collectively, this valuable information provides new insight into the accreted ice formation processes, the bedrock geology of East Antarctica as well as the water chemistry and circulation of Lake Vostok.

Ultra-low rare earth element content in accreted ice from sub-glacial Lake Vostok, Antarctica

NASA Astrophysics Data System (ADS)

Barbante, C.; Gabrielli, P.; Turetta, C.; Planchon, F.; Boutron, C.; Petit, J. R.; Bulat, S.; Hong, S.; Cozzi, G.; Cescon, P.

2009-12-01

We report the first rare earth element (REE) concentrations in accreted ice refrozen from sub-glacial Lake Vostok (East Antarctica). REE were determined in various sections of the Vostok ice core in order to geochemically characterize its impurities. Samples were obtained from accreted ice and, for comparison, from the upper glacier ice of atmospheric origin (undisturbed, disturbed and glacial flour ice). REE concentrations ranged between 0.8-56 pg g-1 for Ce and 0.0035- 0.24 pg g-1 for Lu in glacier ice, and between <0.1-24 pg g-1 for Ce and <0.0004-0.02 pg g-1 for Lu in accreted ice. Interestingly, the REE concentrations in the upper accreted ice (AC1;characterized by visible aggregates containing a mixture of very fine terrigenous particles) and in the deeper accreted ice (AC2; characterized by transparent ice) are lower than those in fresh water and seawater, respectively. We suggest that such ultra-low concentrations are unlikely to be representative of the real REE content in Lake Vostok, but instead may reflect phase exclusion processes occurring at the ice/water interface during refreezing. In particular, the uneven spatial distribution (on the order of a few cm) and the large range of REE concentrations observed in AC1 are consistent with the occurrence/absence of the aggregates in adjacent ice, and point to the presence of solid-phase concentration/exclusion processes occurring within separate pockets of frazil ice during AC1 formation. Interestingly, if the LREE enrichment found in AC1 was not produced by chemical fractionation occurring in Lake Vostok water, this may reflect a contribution of bedrock material, possibly in combination with aeolian dust released into the lake by melting of the glacier ice. Collectively, this valuable information provides new insight into the accreted ice formation processes, the bedrock geology of East Antarctica as well as the water chemistry and circulation of Lake Vostok.

[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.

Abnormal Eu behavior at formation of H2O- and Cl-bearing fluids during degassing of granite magmas

NASA Astrophysics Data System (ADS)

Lukanin, Oleg

2010-05-01

One of the important features of REE behavior in the process of decompression degassing of granite melts is the presence of europium anomalies in REE spectrum of forming fluid phase. Negative Eu anomaly in REE spectrum of fluids enriched by chlorine that were formed under high pressures at early stages of degassing relative to REE spectrum of granite melts may take place. Negative Eu anomaly in fluid is replaced by positive one with pressure decrease and decline of Cl concentration in fluid [1, 2]. Observable unique features of europium redistribution between fluid and melt find an explanation in such a fact that Eu in contrast to the other REE under oxidation-reduction conditions, being typical for magmatic process, is present in acidic silica-alumina melts in two valency forms Eu3+ and Eu2+ whereas the dominant form for the other REE in such a melts is (REE)3+ [3, 4]. From the analysis of melt-fluid exchange reactions with participation of two valency forms of europium Eu3+ and Eu2+ follows that the total distribution coefficient of Eu between fluid and melt D(Eu)f-m is equal as a first approximation to [5, 6]: D(Eu)f-m = a1α [C(Cl)f]3 + a2 (1 - α)[C(Cl)f]2, where C(Cl)f - the concentration of Cl in fluid, α = Eu3+/(Eu3+ + Eu2+), i.e. fraction of Eu3+ from the general amount of europium in the melt, and, a1anda2- constants that can be approximately estimated from empirical data upon Eu fluid/melt distribution. The equation given allows to estimate the influence of oxidizing condition of europium on sign and size of Eu anomaly, which is expressed by Eu/Eu# ratio, where Eu is real concentration of europium in fluid being in equilibrium with melt with constant Eu3+/(Eu3+ + Eu2+) ratio, and Eu# is possible "virtual" concentration of europium that could be in the same fluid provided that all europium as other REE as well were exclusively present in trivalent form. The sign and size of Eu anomaly in fluid depends upon Cl concentration in fluid and Eu3+/Eu2+ ratio in melt. The abnormal behavior of Eu shows itself the stronger, the lower fO2and, accordingly, the more fraction of Eu2+is present in melt. The work is supported of the Geosciences Department of the Russian Academy of Science (the program 2- 2010) and RFBR (grant 08-05-00022). References [1] Reed M.J., Candela Ph.A., Piccoli Ph.M. Contrib. Mineral. Petrol. 2000. V. 140. P. 251-262. [2] Lukanin O.A., Dernov-Pegarev V.F. Vestnik Otd. Nauk Zemle RAN, No 1(25)'2007 URL: http://www.scgis.ru/russian/cp1251/h_dgggms/1-2007/informbul-1_2007/term-30e.pdf [3] Drake M.J. Geochim. Cosmochim. Acta. 1975. V. 39. P. 55-64. [4] Wilke M. Behrens H. Contrib. Mineral. Petrol. 1999. V. 137. P. 102-114. [5] Lukanin O.A. Vestnik Otd. Nauk o Zemle RAN, No 1(26)'2008. URL: http://www.scgis.ru/russian/cp1251/h_dgggms/1-2008/informbul-1_2008/magm-20e.pdf [6] Lukanin O.A., Dernov-Pegarev V.F. Geochemistry International, 2010 (in press)

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

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

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

1990-05-01

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

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements.

PubMed

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-14

A synthetic Cu-Al-SO₄ layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu 1-x Al x (SO₄) x/2 (OH)₂·nH₂O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO₄ LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO₄ LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements

PubMed Central

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-01

A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1−xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5–8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis. PMID:29342887

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.

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

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.

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.

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.

Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts

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

Carlson, Gary

This final report provides a complete summary of the activities, results, analytical discussion, and overall evaluation of the project titled “Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts” under DOE Award Number DE-FE-0027155 that started in March 2016 and ended December 2017. Fly ash was selected as the coal-byproduct source material due to fact that it is readily available with no need for extensive methods to obtain the material, it is produced in large quantities (>50 million tons per year) and had REE concentrations similar to other coal-byproducts. The selected fly ash usedmore » throughout this project was from the Mill Creek power generating facility operated by Louisville Gas and Electric located in Louisville, KY and was subjected to a variety of physical and chemical characterization tests. Results from fusion extractions showed that the selected fly-ash had a TREE+Y concentration of 480 ppm with critical REEs concentration of 200 ppm. The fly ash had an outlook ratio of 1.25 and an estimated value of $16-$18 worth of salable REEs per 1-tonne of fly ash. Additional characterizations by optical evaluation, QEMSCAN, XRD, size fractionation, and SEM analysis showed the fly ash consisted of small glassy spherules with a size range between 1 to 110 µm (ave. diam. of 13 um), was heterogeneous in chemical composition (main crystalline phases: aluminum oxides and iron oxides) and was primarily an amorphous material (75 to 80%). A simple stepped approach was completed to estimate the total REE resource quantity. The approach included REE characterization of the representative samples, evaluation of fly-ash availability, and final determination estimated resource availability with regards to REE grade on a regional and national scale. This data represents the best available information and is based upon the assumptions that the power generating facility where the fly-ash was obtained will use the same coal sources (actual mines were identified), the coal materials will have relatively consistent REE concentrations, and the REE extraction process developed during this project can achieve 42% REE recovery (validated and confirmed). Calculations indicated that the estimated REE resource is approximately 175,000 tonnes with a current estimated value of $3,330MM. The proposed REE extraction and production process developed during this project used four fundamental steps; 1) fly-ash pretreatment to enhance REE extraction, 2) REE extraction by acid digestion, 3) REE separation/concentration by carbon adsorption and column chromatography, and 4) REE oxide production. Secondary processing steps to manage process residuals and additional processing techniques to produce value-added products were incorporated into the process during the project. These secondary steps were not only necessary to manage residuals, but also provided additional revenue streams that offset operational and capital expenditures. The process produces one value product stream (production of zeolite Na-P1), a solids waste stream, and one liquid stream that met RCRA discharge requirements. Based upon final design criteria and operational parameters, the proposed system could produce approximately 200 grams of REOs from 1-tonne of fly-ash, thereby representing a TREE+Y recovery of 42% (project target of > 25%). A detailed economic model was developed to evaluate both CAPEX and OPEX estimates for systems with varying capacities between 100 kg to 200 tonnes of fly ash processed per day. Using a standard system capacity of 10 tonne/day system, capital costs were estimated at $88/kg fly ash while operating costs were estimated at approximately $450/kg fly ash. This operating cost estimate includes a revenue of $495/tonne of fly ash processed from the value-added product produced from the system (zeolite Na-P1). Although operating cost savings due to zeolite production were significant, the capital + operating cost for a 10 tonne system was more expensive than the total dollar value of REEs present in the fly ash material. Specifically, the estimated cost per 1-tonne of fly ash treated is approximately $540 while the estimated value of REEs in the fly ash is $18-$20/tonne. This is an excessive difference showing that the proposed process is not economically feasible strictly on the basis of REE revenue compared to extraction costs. Although the current proposed system does not produce sufficient quantities of REEs or additional revenue sources to offset operational and capital costs, supplementary factors including US strategic concerns, commercial demands, and defense department requirements must be factored. At this time, the process developed during this project provides foundational information for future development of simple processes that require low capital investment and one that will extract a valuable quality and quantity of REE oxides from industrial waste.« less

Partitioning of radionuclides and trace elements in phosphogypsum and its source materials based on sequential extraction methods.

PubMed

Santos, A J G; Mazzilli, B P; Fávaro, D I T; Silva, P S C

2006-01-01

Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.

Lanthanide, yttrium, and zirconium anomalies in the Fire Clay coal bed, Eastern Kentucky

USGS Publications Warehouse

Hower, J.C.; Ruppert, L.F.; Eble, C.F.

1999-01-01

The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, thhat constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y + ??REE): total Y + ??REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y + ??REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, that constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y+???REE): total Y+???REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y+???REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.

Rare earth 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.

Direct determination of europium valence state by XANES in extraterrestrial merrillite: Implications for REE crystal chemistry and martian magmatism

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

Shearer, C.K.; Papike, J.J.; Burger, P.V.

2012-03-15

The relative proportion of divalent and trivalent Eu has proven to be a useful tool for estimating f{sub O{sub 2}} in various magmatic systems. However, in most cases, direct determination of the Eu valence state has not been made. In this study, direct determination of Eu valence by XANES and REE abundance in merrillite provide insights into the crystal chemistry of these phosphates and their ability to record conditions of magmatism. Merrillite strongly prefers Eu{sup 3+} to Eu{sup 2+}, with the average valence state of Eu ranging between 2.9 and 3 over approximately six orders of magnitude in f{sub O{submore » 2}}. The dramatic shift in the REE patterns of merrillite in martian basaltic magmas, from highly LREE-depleted to LREE-enriched, parallels many other trace element and isotopic variations and reflects the sources for these magmas. The behavior of REE in the merrillite directly reflects the relationship between the eightfold-coordinated Ca1 site and adjacent sixfold Na and tetrahedral P sites that enables charge balancing through coupled substitutions.« less

Peering Through a Martian Veil: ALHA84001 Sm-Nd Age Revisited

NASA Technical Reports Server (NTRS)

Nyquist, Laurence E.; Shih, Chi-Yu

2013-01-01

The ancient Martian orthopyroxenite ALH84001experienced a complex history of impact and aqueous alteration events. Here we summarize Sm-147-Nd-143 and Sm-146-Nd-142 analyses performed at JSC. Further, using REE data, we model the REE abundance pattern of the basaltic magma parental to ALH84001 cumulus orthopyroxene. We find the Sm-146-Nd-142 isotopic data to be consistent with isotopic evolution in material having the modeled Sm/Nd ratio from a time very close to the planet's formation to igneous crystallization of ALH84001 as inferred from the Sm-Nd studies.

Stability constants for mono- and dioxalato-complexes of Y and the REE, potentially important species in groundwaters and surface freshwaters

NASA Astrophysics Data System (ADS)

Schijf, J.; Byrne, R. H.

2001-04-01

We present the first measured set of stability constants for mono- and dioxalato-complexes of yttrium and all rare earths except Pm (Y+REE), Oxβ n = [MOx n3-2n] [M 3+] -1 [Ox 2-] -n(where [ ] ≡ concentrations, M ≡ Y+REE, and Ox 2- ≡ C 2O 42-). Aqueous solutions of Y+REE were titrated with oxalic acid in the presence of a cation-exchange resin, and Y+REE concentrations in the solution phase were measured by ICP-MS. This method allows investigation of all Y+REE simultaneously under identical conditions and is thus very sensitive to subtle inter-element variations in log Oxβ n. Experiments were performed at a single ionic strength ( I = 0.05 M), but at two values of pH. Patterns of log Oxβ 1 and log Oxβ 2, determined from our experiments, are similar in shape and reminiscent of those for carbonato-complexes. The average ratio of stepwise stability constants K 2/K 1 = Oxβ 2/( Oxβ 1) 2 is 0.05 ± 0.02 for Y+REE excluding La and Ce. Literature values of Oxβ 1(Eu) for 0.03 mol/L ≤ I ≤ 1 mol/L were used to derive the relation log Oxβ 1(Eu) = log Oxβ 10(Eu) - 6.132√ I/(1 + 1.47√ I) + 0.902 I, where log Oxβ 10(Eu) is the stability constant at infinite dilution. Applying this relation to all Y+REE, the following values of log Oxβ 10 (at zero ionic strength) were found: 6.66 (Y), 5.87 (La), 5.97 (Ce), 6.25 (Pr), 6.31 (Nd), 6.43 (Sm), 6.52 (Eu), 6.53 (Gd), 6.63 (Tb), 6.74 (Dy), 6.77 (Ho), 6.83 (Er), 6.89 (Tm), 6.95 (Yb), 6.96 (Lu). These values, which are based on direct measurements for each individual Y+REE, agree quite well with published extrapolations that are mostly based on linear free-energy relationships. Total oxalate concentrations of 10 -5-10 -3 M have been reported for soil solutions. Free oxalate ions persist at much lower pH than free carbonate ions and a simple speciation model demonstrates that oxalato-complexes can dominate Y+REE speciation in mildly acidic groundwaters of low-to-moderate alkalinity.

The behaviour of REE and Zr-Hf fractionation in the volcanic waters of Nevado del Ruiz system (Colombia)

NASA Astrophysics Data System (ADS)

Inguaggiato, Claudio; Censi, Paolo; Zuddas, Pierpaolo; Makario Londoño, John; Chacón, Zoraida; Alzate, Diego; Brusca, Lorenzo; D'Alessandro, Walter

2015-04-01

The geochemical behaviour of Rare Earth Element (REE), Zr and Hf have been investigated in the thermal waters of Nevado del Ruiz volcanic system. These fluids are characterised by a wide range of pH ranging between 1.0 and 8.8. The acidic waters are sulphate dominated with different Cl/SO4 ratios. The Nevado del Ruiz waters allowed to investigate the behaviour of investigated elements in a wide spectrum of pH and chemical composition of water. The important role of the pH and the ionic complexes have been evidenced in the distribution of REE, Zr and Hf in the aqueous phase. The pH rules the precipitation of authigenic oxyhydroxides of Fe, Al producing changes in REE, Zr, Hf amount and strong anomalies of Cerium and Europium. Y-Ho and Zr-Hf (twin pairs) have different behaviour in strong acidic waters with respect to the water with higher pH. Yttrium and Ho have the same behaviour of Zr and Hf in waters with pH near neutral-to-neutral, showing super-chondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate suggesting an enhanced scavenging of Ho and Hf respect to Y and Zr, leading to super-chondritic ratios. In acidic waters a different behaviour of twin pairs occurs with chondritic Y/Ho ratios (reflecting the Y/Ho ratio of average local rock) and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf have been investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anions chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH<3.6. In strong acidic waters, a different fractionation of Zr and Hf have been recognised as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes

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

Allegrini, Elisa, E-mail: elia@env.dtu.dk; Maresca, Alberto; Olsson, Mikael Emil

2014-09-15

Highlights: • Ferrous and non-ferrous metals were quantified in MSWI bottom ashes. • Metal recovery system efficiencies for bottom ashes were estimated. • Total content of critical elements was determined in bottom ash samples. • Post-incineration recovery is not viable for most critical elements. - Abstract: Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based onmore » a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2 mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements.« less

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.

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.

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.

Does sediment geochemistry (based on selective extractions of Al and Fe and REE) provide a record of soil evolution?

NASA Astrophysics Data System (ADS)

Mourier, B.; Poulenard, J.; Blarquez, O.; Williamson, D.; Arnaud, F.; Carcaillet, C.

2009-04-01

Soil is a natural body occurring at the interface between the lithosphere, atmosphere and biosphere. As a result, the physical and chemical properties of soils evolve with time, and the reconstruction of their history represents a key to understand past environmental changes. Palaeolimnological techniques such as sediment geochemistry can be used to investigate changes in catchment history by providing information about soil development. However, due to the lack of conservative pedosignatures (soil proxies), only few paleoecological studies have attempted to reconstruct the history of soil genesis using geochemical analyses of lacustrine sediments. Here we present a multidisciplinary study which aims to use pedosignatures, defined by a previous soil study, in order to characterize the history of soil genesis, podzolization and chemical weathering processes in two sediment sequences. Moreover, we aim to compare the timing of soil evolution with other paleoenvironmental markers (macroremains, charcoals…) in order to infer the role of climate, vegetation and possible human activities as forcing factors. In a first step, the geochemical investigation of eight subalpine soil profiles from the inner Alps allowed to define relevant proxies of two major soil processes. Parent material normalized REE patterns provide a precise tracer of chemical weathering whereas the proportions of secondary Al- and Fe-bearing phases provide a tracer of the podzolisation process. Then, the same tracers were assessed on two lacustrine and peat sediment sequences (Loup and Thyl lakes) from the subalpine domain. The proxy records, spanning ca. 4.500 yr at the Thyl lake and ca. 13.500 yr at the Loup lake, indicate that both progressive and regressive pedogenesis occurred after the deglaciation. The Thyl record is highly contrasted: the progressive setting of the mixed cembra pine ecosystem is associated to the podzolisation process (secondary Al- and Fe-bearing phases are maximal) and the increase of chemical weathering (enrichments of specific REE's fractions) that lasted totally ca. 1500 to 2000 years. Then, these progressive pathways are followed by abrupt and rapid secondary processes that could result from drastic transformation of the plant cover. The flat normalized REE patterns associated with low secondary Al and Fe values suggest a decrease of chemical weathering and podzolization. Moreover, the higher variability in cembra pine and the enrichment in sedge and other herbs remains in the lake suggest the setting of semi-open vegetation associated to the evidence of regressive soil processes. On the other hand, Loup environment and soil history are characterized by a progressive and stable evolution leading to present day old growing forests and Podzol soil type. Whereas the major sedimentological changes are sensitive to climate, the soil proxy records may be more triggered by the natural dynamic of the plant cover. At this site, human disturbances seem to have lower importance than at the Thyl site.

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.

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.

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.

Rhenium-osmium systematics of calcium-aluminium-rich inclusions in carbonaceous chondrites

USGS Publications Warehouse

Becker, H.; Morgan, J.W.; Walker, R.J.; MacPherson, G.J.; Grossman, J.N.

2001-01-01

The Re-Os isotopic systematics of calcium-aluminium-rich inclusions (CAIs) in chondrites were investigated in order to shed light on the behavior of the Re-Os system in bulk chondrites, and to constrain the timing of chemical fractionation in primitive chondrites. CAIs with relatively unfractionated rare earth element (REE) patterns (groups I, III, V, VI) define a narrow range of 187Re/188Os (0.3764-0.4443) and 187Os/188Os (0.12599-0.12717), and high but variable Re and Os abundances (3209-41,820 ppb Os). In contrast, CAIs that show depletions in highly refractory elements and strongly fractionated REE patterns (group II) also show a much larger range in 187Re/188Os (0.409-0.535) and 187Os/188Os (0.12695-0.13770), and greater than an order of magnitude lower Re and Os abundances than other groups (e.g., 75.7-680.2 ppb Os). Sixteen bulk CAIs and CAI splits plot within analytical uncertainty of a 4558 Ga reference isochron, as is expected for materials of this antiquity. Eight samples, however, plot off the isochron. Several possible reasons for these deviations are discussed. Data for multiple splits of one CAI indicate that the nonisochronous behavior for at least this CAI is the result of Re-Os reequilibration at approximately 1.6 Ga. Thus, the most likely explanation for the deviations of most of the nonisochronous CAIs is late-stage open-system behavior of Re and Os in the asteroidal environment. The 187Os/188Os-Os systematics of CAIs are consistent with previous models that indicate group II CAIs are mixtures of components that lost the bulk of their highly refractory elements in a previous condensation event and a minor second component that provided refractory elements at chondritic relative proportions. The high Re/Os of group II CAIs relative to other CAIs and chondrite bulk rocks may have been caused by variable mobilization of Re and Os during medium- to low-temperature parent body alteration ??4.5 Ga ago. This model is favored over nebular models, which pose several difficulties. The narrow range of 187Os/188Os in group I, III, V, and VI bulk CAIs, and the agreement with 187Os/188Os of whole rock carbonaceous chondrites suggest that on a bulk inclusion scale, secondary alteration only modestly fractionated Re/Os in these CAIs. The average of 187Os/188Os for group I, III, V, and VI CAIs is indistinguishable from average CI chondrites, indicating a modern solar system value for 187Os/188Os of 0.12650, corresponding to a 187Re/188Os of 0.3964. Copyright ?? 2001 Elsevier Science Ltd.

Auto-metasomatism of the western lunar highlands: Result of closed system fractionation and mobilization of a KREEPy trapped liquid

NASA Technical Reports Server (NTRS)

Shervais, John W.; Vetter, Scott K.

1993-01-01

The discovery of REE-rich phosphates (dominantly whitlockite) in pristine, non-mare rocks of the western lunar nearside (Apollo 14, Apollo 12, and most recently, Apollo 17) has created a paradox for lunar petrologists. These phases are found in feldspar-rich cumulates of both the Mg-suite and the Alkali suite, which differ significantly in their mineral chemistries and major element compositions. Despite the differences in host rock compositions, whitlockites in both suites have similar compositions, with LREE concentrations around 21,000 to 37,000 x chondrite. Simple modeling of possible parent magma compositions using the experimental whitlockite/liquid partition coefficients of Dickinson and Hess show that these REE concentrations are too high to form from normal lunar magmas, even those characterized as 'urKREEP.'

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.

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.

Trace and rare-earth element characteristics of acidic tuffs from southern Peru and northern Bolivia and a fission-track age for the sillar of Arequipa

NASA Astrophysics Data System (ADS)

Vatin-Perignon, N.; Poupeau, G.; Oliver, R. A.; La Venu, A.; Labrin, F.; Keller, F.; Bellot-Gurlet, L.

1996-03-01

Trace-element and REE data of glass and pumices of acidic tuffs and related fall deposits erupted in southern Peru and northern Bolivia between 20 and 0.36 Ma display typical characteristics of subduction related continental arc magmatism of the CVZ with strong LILE/HFSE enrichment and non enrichment of HREE and Y. Geochemical variations of these tuffs are linked to subduction processes and controlled by changes in tectonic regimes which occured with each Quechua tectonic pulse and affected the astenospheric wedge and both the dowgoing and the overriding lithospheres. During Neogene — Pleistocene times, tuffs erupted in northern Bolivia are typically enriched in Zr, Hf, Th, Ba, LREEs and other incompatible elements and incompatible /Yb ratios are much higher relative to those erupted from southern Peru, at a given SiO 2 content (65-67 wt. for dacites, 72-73 wt.% for rhyolites). {Zr}/{Hf} ratios increase eastward from 27 to 30 and {Ce}/{Yb N} ratios from 11 to 19 reflecting the variation of degree of wedge contribution. Fractionation of the LREE over the HREE and fractionation of incompatible elements may be due to their heterogeneous distribution in the magma source. More highly fractionated REE patterns of Bolivian tuffs than Peruvian tuffs are attributed to variable amounts of contamination of magmas by lower crust. After the Quechua compressional event at 7 Ma, {Sr}/{Y} ratios of tuffs of the same age, erupted at 150-250 km or 250-400 km from the Peru-Chile trench, increase from southern Peru to northern Bolivia. These differences may be attributed to the subduction of a swarm oceanic lithosphere under the Bolivian Alti-plano, leading to partial melting of the sudbucted lithosphere. New FT dating of obsidian fragments of the sillar of Arequipa at 2.42 ± 0.11 Ma. This tuff dates the last Quechua compressional upper Pliocene phase ( 2.5 Ma) and confirms that the sillar is not contemporaneous with the Toba 76 tuff or the Perez ignimbrite of northern Bolivia. Geochemical characteristics of tuffs erupted before and after this last compressional phase remained the same and provide evidence that the upper Miocene ( 7 Ma) compressional deformations played the most important role on the variability of the geochemical characteristics of the southern Peruvian and northern Bolivian tuffs.

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.

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.

Isotope U-Pb age on single zircon and REE distribution in rocks and zircon from paleoproterozoic Kandalaksha-Kolvitsa complex Baltic shield

NASA Astrophysics Data System (ADS)

Steshenko, Ekaterina; Bayanova, Tamara; Drogobuzhskaya, Svetlana; Lyalina, Ludmila; Serov, Pavel; Chashchin, Viktor; Elizarov, Dmitriy

2017-04-01

Kandalaksha-Kolvitsa paleoproterozoic complex located in the N-E part of Baltic shield and consists of three zones. Marginal zone (mesocratic metanorite) lies at the base of the massif. Main zone is composed of leucocratic metagabbro. The upper zone is alteration of mataanorthosite and leucocratic metagabbro. All rocks were subjected to granulate and anorthositic metamorphism. Age of magmatic crystallization of the massif was determined for the first time, using the U-Pb isotope method for single zircon grains. Three fractions of single zircons from anorthosite of the Kandalaksha massif gave precise U-Pb age of 2435.5 ± 4.8 Ma. For the first time REE concentration (WR) was determined using a quadrupole mass spectrometer (Agilent 7500 ce ICP-MS) in the main varieties of rocks of the Kandalaksha-Kolvitsa paleoproterozoic complex. Anorthosite and leucocratic metagabbros (main zone) are characterized by a flat spectrum distribution of HREE, which were normalized by [1]. The REE pattern is characterized by significant positive anomalies of Eu ((Eu / Eu *)n = 3.72-3.91) in anorthosite and leucogabbros and 7.26 - in ortoamfibolitah. General content of individual elements that are common for this type of rocks: Cen = 5.82-8.54, Ybn = 1.54-1.58, which indicates that the process of crystallization of the rock occurred with predominant accumulation of plagioclase. According to geochemical and Nd-Sr isotopic data (ISr=0.702 - 0.706, ɛNd(T) = +1 - (-3)) Kandalaksha Kolvitsa complex, appear to have a general plume source with Paleoproterozoic layered intrusions of the Baltic Shield [2] Distribution of REE (ELAN-9000 ICP-MS) in zircon have a typical magmatic species: a positive Ce, negative Eu anomaly and HREE flat spectrum. Titanium content in zircons were measured for the calculation of their crystallization temperature with 8350C. These data are evidence of magmatic origin of zircon [3]. The scientific researches are supported by RFBR (projects № 15-35-20501, № 16-05-00305, 16-05-00367, 16-05-00427) and theme of state assignment № 0231-2015-0005. References: 1. Boynton W.V. Cosmochemistry of the rare earth elements: meteorite studies // Ed. Henderson P. Rare earth element geochemistry. Amsterdam: Elsevier. 1984. P. 63-114. 2. Watson E. B., Wark D.A., Thomas J.B. Crystallization thermometers for zircon and rutile // Contrib. Miner. Petrol. 2006. V. 151. P. 413-433. 3. Hoskin P.W.O. and Schaltegger U. The Composition of zirconand igneous and metamorphic petrogenesis // Reviews in mineralogy & geochemistry. 2003. V. 53. P. 27-62.

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.

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.

Ancient xenocrystic zircon in young volcanic rocks of the southern Lesser Antilles island arc

NASA Astrophysics Data System (ADS)

Rojas-Agramonte, Yamirka; Williams, Ian S.; Arculus, Richard; Kröner, Alfred; García-Casco, Antonio; Lázaro, Concepción; Buhre, Stephan; Wong, Jean; Geng, Helen; Echeverría, Carlos Morales; Jeffries, Teresa; Xie, Hangqian; Mertz-Kraus, Regina

2017-10-01

The Lesser Antilles arc is one of the best global examples in which to examine the effects of the involvement of subducted sediment and crustal assimilation in the generation of arc crust. Most of the zircon recovered in our study of igneous and volcaniclastic rocks from Grenada and Carriacou (part of the Grenadines chain) is younger than 2 Ma. Within some late Paleogene to Neogene ( 34-0.2 Ma) lavas and volcaniclastic sediments however, there are Paleozoic to Paleoarchean ( 250-3469 Ma) xenocrysts, and Late Jurassic to Precambrian zircon ( 158-2667 Ma) are found in beach and river sands. The trace element characteristics of zircon clearly differentiate between different types of magmas generated in the southern Lesser Antilles through time. The zircon population from the younger arc (Miocene, 22-19 Ma, to Present) has minor negative Eu anomalies, well-defined positive Ce anomalies, and a marked enrichment in heavy rare earth elements (HREE), consistent with crystallization from very oxidized magmas in which Eu2 + was in low abundance. In contrast, zircon from the older arc (Eocene to mid-Oligocene, 30-28 Ma) has two different REE patterns: 1) slight enrichment in the light (L)REE, small to absent Ce anomalies, and negative Eu anomalies and 2) enriched High (H)REE, positive Ce anomalies and negative Eu anomalies (a similar pattern is observed in the xenocrystic zircon population). The combination of positive Ce and negative Eu anomalies in the zircon population of the older arc indicates crystallization from magmas that were variably, but considerably less oxidized than those of the younger arc. All the igneous zircon has positive εHf(t), reflecting derivation from a predominantly juvenile mantle source. However, the εHf(t) values vary significantly within samples, reflecting considerable Hf isotopic heterogeneity in the source. The presence of xenocrystic zircon in the southern Lesser Antilles is evidence for the assimilation of intra-arc crustal sediments and/or the recycling and incorporation of sediments into the magma sources in the mantle wedge. Most likely however, primitive magmas stalling and fractionating during their ascent through the Antilles crust entrained ancient zircon. This is evidence by the geochemistry of the study samples, which is inconsistent with any involvement of partially melted subducted sediment. Paleogeographic reconstructions show that the old zircon could derive from distant regions such as the Eastern Andean Cordillera of Colombia, the Merida Andes, and the northern Venezuela coastal ranges, transported for example by the Proto-Maracaibo River precursor of the Orinoco River.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

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

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.

Archean greenstone belt magmatism and the continental growth-mantle evolution connection: constraints from Th-U-Nb-LREE systematics of the 2.7 Ga Wawa subprovince, Superior Province, Canada

NASA Astrophysics Data System (ADS)

Polat, Ali; Kerrich, Robert

2000-01-01

An extensive database, including Th-;U-Nb-REE systematics, for diverse magmatic and sedimentary lithologies of 2.7 Ga Wawa greenstone belts provide new constraints on the mechanism of crustal growth in the southern Superior Province, and controls on its composition. The greenstone belts are characterized by collages of oceanic plateaus, oceanic island arcs, and trench turbidites; these lithotectonic fragments were tectonically assembled in a large subduction-accretion complex. Following juxtaposition, these diverse lithologies were collectively intruded by syn-kinematic TTG (tonalite-trondhjemite-granodiorite) plutons and ultramafic to felsic dykes and sills, with subduction zone geochemical signatures. Intra-oceanic basalts are characterized by near-flat REE patterns, and Nb/U and Nb/Th ratios generally greater than primitive mantle values, consistent with positive ɛNd values. They are associated with komatiites, the association being interpreted as an ocean plateau sequence erupted from a mantle plume. Bimodal arc volcanic sequences, trench turbidites, and contemporaneous TTG suites are characterized by fractionated REE, with Nb/U and Nb/Th ratios less than primitive mantle values. Mixing hyperbolae between oceanic plateau and magmatic arc sequences pass through the estimated composition of bulk continental crust, suggesting that crustal growth in the late Archean was by tectonic, sedimentary, and chemical mixing of oceanic plateau and arc sequences at convergent plate boundaries. Mixing calculations suggest that oceanic plateau and subduction zone components in the Wawa continental crust are represented by 6-12% and 88-94%, respectively. High Nb/U and Nb/Th ratios of plateau tholeiitic basalts are interpreted as a complementary reservoir to arc magmatism (low Nb/U and Nb/Th), hundreds of millions of years prior to recycling of oceanic lithosphere through a subduction zone (high Nb/U, Nb/Th), and its incorporation into a mantle plume from which 2.7 Ga plateau tholeiites erupted. The variably high Nb/U ratios of the plateau basalts are consistent with early extraction of large quantities of the protoliths (magmatic precursor) of continental crust from the southern Superior Province asthenospheric mantle.

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.

Mineralogy and geochemistry of the Lokoundje alluvial clays from the Kribi deposits, Cameroonian Atlantic coast: Implications for their origin and depositional environment

NASA Astrophysics Data System (ADS)

Ndjigui, Paul-Désiré; Onana, Vincent Laurent; Sababa, Elisé; Bayiga, Elie Constantin

2018-07-01

The Lokoundje alluvial clay deposits are located at the left floodplain of the Lokoundje River, towards the estuary in the Kribi region. The mineralogical and geochemical features of the Lokoundje River fine-grained sediments have been reported using XRD, XRF, ICP-MS, and IR instruments in order to understand their provenance and depositional history. The Lokoundje watershed covers a surface area of about 5381 km2. The basement of this watershed is made up of gneisses, amphibolites, migmatites, charnockites, and pyroxenites from the Nyong and Ntem units, in the NW border of the Congo craton. The alluvial materials are about 100 cm thick and cover a total area of 1.4 km2. They are mainly plastic clays with silty-clayey texture and four colors (yellow, red yellow, white, and light grey). The mineral assemblage is composed of kaolinite, quartz, illite, gibbsite, goethite, rutile, and interstratified illite-vermiculite. The infra-red data associated with those of XRD portray the disordering of kaolinite. These materials are mostly constituted by SiO2 (44.33-69.19 wt%, av. = 51.17 wt% with n = 18) and Al2O3 (20.69-30.26 wt%, av. = 26.07 wt%) with very low Fe2O3 contents (1-7.71 wt%, av. = 3.35 wt%). The SiO2/Al2O3 ratio range between 1.46 and 4.1 (av. = 2.06). The alkali contents (Na2O + K2O) are below 5 wt%. ICV, CIA, PIA, and SiO2/Al2O3 portray high degree of chemical weathering in the source area as well as the maturity of sediments. The trace element behavior is quite different probably due to the mixed source rocks; Ba, Sr, Zn have high contents while several elements such as Th and U show low contents. The REE contents are also variable; their concentrations vary between 92 and 1065 ppm (av. = 307 ppm). The mineral assemblage associated with the geochemical data reveal that REE are mainly housed in clay minerals. The behavior of REE is also marked by the abundance of LREE (LREE/HREE = 19.69-34.62). The REE chondrite-normalized spectra confirm the LREE-abundance and exhibit negative Eu anomalies. The PAAS-normalized patterns reveal slight positive Eu anomalies and negative Ce anomalies. The (La/Yb)N values (3.30-8.43, av. = 5.71) display low degree of REE-fractionation in the Lokoundje watershed. The morphological, mineralogical, and geochemical features reveal that the fine-grained sediments derive from the intense weathering of mixed source. The disordering of kaolinite confirms that sediments were sorted during a long transportation before their deposition under oxic conditions (U/Th < 1.25; V/Cr < 2) in the floodplains near the Atlantic coast.

Landslide-induced iron mobilisation shapes benthic accumulation of nutrients, trace metals and REE fractionation in an oligotrophic alpine stream

NASA Astrophysics Data System (ADS)

Johnston, Scott G.; Rose, Andrew L.; Burton, Edward D.; Webster-Brown, Jenny

2015-01-01

Large alpine landslides that entrain substantial organic material below the water table and create suspended floodplains may have long-term consequences for the mobilisation of redox sensitive elements, such as Fe, into streamwaters. In turn, the cycling of iron in aquatic systems can influence the fate of nutrients, alter primary productivity, enhance accumulation of trace metals and induce fractionation of rare earth elements (REE). In this study we examine a reach of a pristine oligotrophic alpine stream bracketing a 30 year-old landslide and explore the consequences of landslide-induced Fe mobilisation for aqueous geochemistry and the composition of benthic stream cobble biofilm. Elevated Fe2+ and Mn in landslide zone stream waters reflect inputs of circumneutral groundwater from the landslide debris-zone floodplain. Geochemical characteristics are consistent with reductive dissolution being a primary mechanism of Fe2+ and Mn mobilisation. Stream cobble biofilm in the landslide zone is significantly (P < 0.01) enriched in poorly crystalline Fe(III) (∼10-400 times background) and Mn (∼15-150 times background) (1 M HCl extractable; Fe(III)Ab). While the landslide zone accounts for less than ∼9% of the total stream length, we estimate it is responsible for approximately 60-80% of the stream's benthic biofilm load of poorly crystalline Fe(III) and Mn. Biofilm Fe(III) precipitates are comprised mainly of ferrihydrite, lepidocrocite and an organic-Fe species, while precipitate samples collected proximal to hyporheic seeps contain abundant sheath structures characteristic of the neutrophilic Fe(II)-oxidising bacteria Leptothrix spp. Stream-cobble Fe(III)-rich biofilm is accumulating PO43- (∼3-30 times background) and behaving as a preferential substrate for photosynthetic periphyton, with benthic PO43-, chlorophyll a, organic carbonHCl and total N all significantly positively correlated with Fe(III)Ab and significantly elevated within the landslide zone (P < 0.01). P K-edge XANES indicates P is associated with both ferric and Ca-phosphate minerals, while SEM-EDX elemental mapping of Fe(III) precipitates reveal strong spatial associations between P, Ca and Fe. Cobble Fe(III)-rich biofilm is also sorbing and accumulating multiple trace metals and REE. Within the landslide zone there are significant (P < 0.01) enrichments (up to ∼10-100 times background) for most trace metals examined here and metals display significant positive linear correlations with Fe(III)Ab on a log transformed basis. Stream cobble biofilm also exhibits distinct REE fractionation along the flow path, with light REE (La, Ce, Nd, Pr) preferentially partitioning to the Fe(III) and Mn-rich biofilm within the landslide zone. Accumulation of PO43- and trace metals in this relatively environmentally labile form may have implications for their bioavailability and downstream transport, but further research is required to assess possible ecological consequences. This study demonstrates the potential for large alpine landslides to encourage reach-scale circumneutral Fe mobilisation in adjacent streams, thereby shaping multiple aspects of benthic stream geochemistry for many years after the landslide event itself.

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.

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.

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.

Physico-chemistry and geochemistry of Balengou clay deposit (West Cameroon) with inference to an argillic hydrothermal alteration

NASA Astrophysics Data System (ADS)

Tassongwa, Bernard; Eba, François; Njoya, Dayirou; Tchakounté, Jacqueline Numbem; Jeudong, Narcisse; Nkoumbou, Charles; Njopwouo, Daniel

2017-09-01

Field description and sampling along two pits, granulometry, Atterberg limits, mineralogical (XRD, FTIR, DSC & TGA) and geochemical analyses of the Balengou clays help to determine their characteristics and the genesis of the deposit. The mineralogical composition is comprised of halloysite-kaolinite, quartz, montmorillonite, hematite, anatase, feldspar, zircon, chromite, and apatite. Gibbsite and illite occur at the shallow and deep depth, respectively. Dikes of sand-poor clays contain also cristobalite and tridymite. Pairs of elements Rb-Ba, Rb-Sr, Nb-Ta, Ta-Zr, TiO2-Zr display good positive correlations (R2 > 0.85). REE patterns are highly fractionated (LaN up to 3312, LaN/YbN: 19-10) and are marked by deep Ce and Eu negative anomalies. Immobile element canonical ratios indicate that the protoliths were commendite/pantelerite, rhyolite and dacite, or their plutonic equivalents. Mineralogical and geochemical features lead to the suggestion that the clays derived from an advanced argillic hydrothermal alteration.

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.

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.

Dissolved Rare Earth Elements in the US GEOTRACES North Atlantic Section

NASA Astrophysics Data System (ADS)

Shiller, A. M.

2016-12-01

The rare earth elements (REEs) are a unique chemical set wherein there are systematic changes in geochemical behavior across the series. Furthermore, while most REEs are in the +III oxidation state, Ce and Eu can be in other oxidation states leading to distinct characteristics of those elements. Thus, the geochemical properties of the REEs make them particularly useful tools for inquiring into various geochemical processes. As part of the US GEOTRACES effort, we determined dissolved REEs and Y at 32 stations across the North Atlantic during US cruises GT10 and GT11 along a meridional transect from Lisbon to the Cape Verde Islands and a zonal transect from Cape Cod to the Mauritanian coast. While profiles are similar to previous reports, the high spatial resolution of the section allows for better elucidation of processes. Light rare earths (LREEs) show removal in the upper water column with a minimum at the chlorophyll maximum. LREE concentrations then increase into the oxygen minimum followed by a slight decrease and fairly constant concentrations in the mid-water column followed by an increase into the deep and bottom waters. Heavy rare earths (HREEs) show a more monotonic increase with depth. We also take advantage of a previously published water mass analysis for the section to estimate that most of the deep water changes can be explained by conservative mixing of waters with different pre-formed REE concentrations. Nonetheless, the pattern of LREE shallow water removal followed by regeneration, possible re-scavenging, and then deep water input is still preserved. Other features of note include an increase in LREEs in the strong oxygen minimum zone off Mauritania, consistent with an association of REE cycling with the redox cycles of Fe and Mn. Also along the eastern margin, but below the oxygen minimum, a small but distinct increase in the cerium and europium anomalies is observed, consistent with terrigenous input. In hydrothermally influenced waters along the mid-Atlantic Ridge, there are increases in Ce/Ce*, Eu/Eu*, and Y/Ho but a decrease in Nd/Yb and in REE concentrations. Surface water distributions are more consistent with elements influenced by margin inputs than with atmospheric input.

The evolution of complex type B Allende inclusion - An ion microprobe trace element study

NASA Technical Reports Server (NTRS)

Macpherson, Glenn J.; Crozaz, Ghislaine; Lundberg, Laura L.

1989-01-01

Results are presented of a detailed trace-element and isotopic analyses of the constituent phases in each of the major textural parts (mantle, core, and islands) of a Type B refractory inclusion, the USNM 5241 inclusion from Allende, first described by El Goresy et al. (1985). The REE data on 5241 were found to be largely consistent with a model in which the mantle and the core of 5241 formed sequentially out of a single melt by fractional crystallization. The numerical models of REE evolution in the 5241 melt, especially that of Eu, require that a significant mass of spinel-free island material was assimilated into the evolving melt during the last half of the solidification history of 5241. The trace element results pbtained thus strongly support the interpretation of El Goresy et al. (1985) that the spinel-free islands in the 5241 are trapped xenoliths.

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.

Light rare earth element systematics as a tool for investigating the petrogenesis of phoscorite-carbonatite associations, as exemplified by the Phalaborwa Complex, South Africa

NASA Astrophysics Data System (ADS)

Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.

2017-12-01

In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.

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.

Magmatic evolution of the Jbel Boho alkaline complex in the Bou Azzer inlier (Anti-Atlas/Morocco) and its relation to REE mineralization

NASA Astrophysics Data System (ADS)

Benaouda, Rachid; Holzheid, Astrid; Schenk, Volker; Badra, Lakhlifi; Ennaciri, Aomar

2017-05-01

The Jbel Boho complex (Anti-Atlas/Morocco) is an alkaline magmatic complex that was formed during the Precambrian-Cambrian transition, contemporaneous with the lower early Cambrian dolomite sequence. The complex consists of a volcanic sequence comprising basanites, trachyandesites, trachytes and rhyolites that is intruded by a syenitic pluton. Both the volcanic suite and the pluton are cut by later microsyenitic and rhyolitic dykes. Although all Jbel Boho magmas were probably ultimately derived from the same, intraplate or plume-like source, new geochemical evidence supports the concept of a minimum three principal magma generations having formed the complex. Whereas all volcanic rocks (first generation) are LREE enriched and appear to be formed by fractional crystallization of a mantle-derived magma, resulting in strong negative Eu anomalies in the more evolved rocks associated with low Zr/Hf and Nb/Ta values, the younger syenitic pluton displays almost no negative Eu anomaly and very high Zr/Hf and Nb/Ta. The syenite is considered to be formed by a second generation of melt and likely formed through partial melting of underplated mafic rocks. The syenitic pluton consists of two types of syenitic rocks; olivine syenite and quartz syenite. The presence of quartz and a strong positive Pb anomaly in the quartz syenite contrasts strongly with the negative Pb anomaly in the olivine syenite and suggests the latter results from crustal contamination of the former. The late dyke swarm (third generation of melt) comprises microsyenitic and subalkaline rhyolitic compositions. The strong decrease of the alkali elements, Zr/Hf and Nb/Ta and the high SiO2 contents in the rhyolitic dykes might be the result of mineral fractionation and addition of mineralizing fluids, allowing inter-element fractionation of even highly incompatible HFSE due to the presence of fluorine. The occurrence of fluorite in some volcanic rocks and the Ca-REE-F carbonate mineral synchysite in the dykes with very high LREE contents (Ce ∼720 ppm found in one rhyolitic dyke) suggest the fluorine-rich nature of this system and the role played by addition of mineralizing fluids. The REE mineralization expressed as synchysite-(Ce) is detected in a subalkaline rhyolitic dyke (with ΣLREE = 1750 ppm) associated with quartz, chlorite and occasionally with Fe-oxides. The synchysite mineralization is probably the result of REE transport by acidic hydrothermal fluids as chloride complex and their neutralization during fluid-rock interaction. The major tectonic change from compressive to extensional regime in the late Neoproterozoic induced the emplacement of voluminous volcaniclastic series of the Ediacran Ouarzazate Group. The alkaline, within-plate nature of the Jbel Boho igneous complex implies that this extensional setting continued during the early Cambrian.

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.

Application of water chemistry as a hydrological tracer in a volcano catchment area: A case study of the Tatun Volcano Group, North Taiwan

NASA Astrophysics Data System (ADS)

Lu, Hsueh-Yu

2014-04-01

In this paper, water chemistry is successfully applied to elucidate hydrological processes through the use of natural tracers in a hydrological system. The concept of a natural tracer is principally based on water-rock interaction. In this case, a volcanic watershed in the Tatun Volcano Group is examined with the hydrochemistry of the Peihuang Creek system analyzed in terms of acidic hydrothermal water. The application of principal component analysis demonstrates that the hydrochemistry of Peihuang Creek is dominated by mixing among three end members, Lujiaoken seep water, Matsao seep water and shallow circulated water. Conservative ions, such as halogens, reveal that recharge of shallow circulated water with low ionic concentration is dominant in the mountain area and gradually becomes insignificant in the plains area. Rare earth elements also confirm this derivation. In addition, rare earth elements demonstrate parallel pattern along the tributaries, which implies that the fractionation of rare earth elements is not considerable and dilution is the major factor attenuating the concentrations of rare earth elements. Therefore, the constant slope of REE pattern allows for semi-quantitative estimation of mixing proportion of the two major tributaries. The results show that Lujiaoken Creek supplies about 50% of waters to the downstream Peihuang Creek. Comparing commonly used nature tracers, such as Cl- and environmental isotopes, this study demonstrates that rare earth elements have the advantage of very low background concentrations and easily defined sources if fractionation is not considerable. Under this circumstance, the calculation of water mixing is applicable.

Laser ablation ICP-MS and traditional micromorphological techniques applied to the study of different genetic horizons in thin sections: soil genesis and trace element distribution

NASA Astrophysics Data System (ADS)

Scarciglia, Fabio; Barca, Donatella; de Rosa, Rosanna; Pulice, Iolanda; Vacca, Andrea

2010-05-01

This work focuses on an innovative methodological approach to investigate in situ chemical composition of trace and rare earth (REE) elements in discrete soil features from different soil horizons: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied to clay coatings, pedogenic matrix and skeletal parent rock fragments in thin sections, coupled with traditional pedological investigations, specially clay mineralogy and micromorphology. Analyses were performed on 80 μm-thick sections obtained from undisturbed soil samples, which represent three reddish argillic (Bt) horizons from an Alfisol developed on late Pleistocene slope deposits and three brown organic-mineral (A) horizons from an Entisol formed on Holocene aggrading fluvial sediments in the Muravera area (southeast Sardinia, Italy). Validation of the LA-ICP-MS technique provides in situ accurate and reproducible (RSD 13-18%) analysis of low concentration trace elements in the studied soil samples (0.001-0.1 ppm). Our results showed a high reliability of this method on soil thin sections and revealed that concentrations of trace and rare earth elements in the different portions of a soil profile can be used to investigate their distribution, as a response to soil-forming processes. A general trend of increase of most trace elements from rock fragments to (both clayey and organic-rich) soil matrix, to clay coatings in argillic horizons is clearly highlighted. On this basis a prominent role of pedogenetic processes in element fractionation and distribution during weathering can be supposed. In particular, element adsorption onto reactive sites of organic matter and clay particles (and possibly Fe-oxyhydroxides) and clay illuviation appear the main pedogenetic processes able to promote element enrichment after their release from the weathering of primary minerals. As clay coatings exhibit the highest concentration of trace elements, and specifically of REEs, and represent the most mobile solid phase in the soil profile, this tool can be used as a reliable indicator of soil weathering after a preliminary assessment of illuvial clay pedofeatures. This feature is consistent with a progressively increasing time of soil development, testified by the older age of the Alfisol than the Entisol profile. Such a result is also supported by a comparison of trace element concentrations between the clay and the fine earth fractions of the bulk soil horizons performed with ICP-MS in solution, showing REE enrichment in the clays from the former soil. Moreover, trace element patterns show some discontinuous trends among soil features of different horizons, coherently with erosive and/or depositional discontinuities described in the field.

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.

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

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.

Diffusive exchange of trace elements between alkaline melts: Implications for element fractionation and timescale estimations during magma mixing

NASA Astrophysics Data System (ADS)

González-Garcia, Diego; Petrelli, Maurizio; Behrens, Harald; Vetere, Francesco; Fischer, Lennart A.; Morgavi, Daniele; Perugini, Diego

2018-07-01

The diffusive exchange of 30 trace elements (Cs, Rb, Ba, Sr, Co, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ta, V, Cr, Pb, Th, U, Zr, Hf, Sn and Nb) during the interaction of natural mafic and silicic alkaline melts was experimentally studied at conditions relevant to shallow magmatic systems. In detail, a set of 12 diffusion couple experiments have been performed between natural shoshonitic and rhyolitic melts from the Vulcano Island (Aeolian archipelago, Italy) at a temperature of 1200 °C, pressures from 50 to 500 MPa, and water contents ranging from nominally dry to ca. 2 wt.%. Concentration-distance profiles, measured by Laser Ablation ICP-MS, highlight different behaviours, and trace elements were divided into two groups: (1) elements with normal diffusion profiles (13 elements, mainly low field strength and transition elements), and (2) elements showing uphill diffusion (17 elements including Y, Zr, Nb, Pb and rare earth elements, except Eu). For the elements showing normal diffusion profiles, chemical diffusion coefficients were estimated using a concentration-dependent evaluation method, and values are given at four intermediate compositions (SiO2 equal to 58, 62, 66 and 70 wt.%, respectively). A general coupling of diffusion coefficients to silica diffusivity is observed, and variations in systematics are observed between mafic and silicic compositions. Results show that water plays a decisive role on diffusive rates in the studied conditions, producing an enhancement between 0.4 and 0.7 log units per 1 wt.% of added H2O. Particularly notable is the behaviour of the trivalent-only REEs (La to Nd and Gd to Lu), with strong uphill diffusion minima, diminishing from light to heavy REEs. Modelling of REE profiles by a modified effective binary diffusion model indicates that activity gradients induced by the SiO2 concentration contrast are responsible for their development, inducing a transient partitioning of REEs towards the shoshonitic melt. These results indicate that diffusive fractionation of trace elements is possible during magma mixing events, especially in the more silicic melts, and that the presence of water in such events can lead to enhanced chemical diffusive mixing efficiency, affecting also the estimation of mixing to eruption timescales.

Zircon U-Pb ages and Sr-Nd-Hf isotopes of the highly fractionated granite with tetrad REE patterns in the Shamai tungsten deposit in eastern Inner Mongolia, China: Implications for the timing of mineralization and ore genesis

NASA Astrophysics Data System (ADS)

Jiang, Si-Hong; Bagas, Leon; Hu, Peng; Han, Ning; Chen, Chun-Liang; Liu, Yuan; Kang, Huan

2016-09-01

The Shamai tungsten deposit is located in the eastern part of the Central Asian Orogenic Belt (CAOB). Tungsten mineralization is closely related to the emplacement of fine- to medium-grained biotite monzogranite (G1) and porphyritic biotite monzogranite (G2) in the Shamai Granite. NW-trending joints and faults host orebodies in the Shamai Granite and Devonian hornfels. The mineralization is characterized by a basal veinlet zone progressing upwards to a thick vein zone followed by a mixed zone, a veinlet zone, and a thread vein zone at the top. The ore-related alteration typically consists of muscovite, greisen, and hornfels. In order to constrain the timing of the Shamai mineralization and discuss the ore genesis, muscovite Ar-Ar, molybdenite Re-Os, and zircon U-Pb geochronological, geochemical, and Sr-Nd-Hf isotopic studies were completed on the deposit. The U-Pb zircon dating yielded weighted mean ages of 153 ± 1 Ma for G1 and 146 ± 1 Ma for G2. Muscovite from a wolframite-bearing quartz vein yielded an Ar-Ar plateau age of 140 ± 1 Ma, whereas two molybdenite samples yielded identical Re-Os model ages of 137 ± 2 Ma. These two ages are younger than the two monzogranites, suggesting a prolonged magmatic-hydrothermal interaction during tungsten mineralization. Major and trace element geochemistry shows that both G1 and G2 are characterized by high SiO2 and K2O contents, high A/CNK values (1.08-1.40), a spectacular tetrad effect in their REE distribution patterns, and non-CHARAC (charge-and-radius-controlled) trace element behavior. This suggests that both G1 and G2 are highly differentiated peraluminous rocks with strong hydrothermal interaction. The Nd-Hf isotope data for the Shamai Granite (εNd(t) between - 1.9 and + 7.4, ɛHf(t) from 5.2 to 12.8) are largely compatible with the general scenario for much of the Phanerozoic granite emplaced in the CAOB. It is here suggested that the Shamai Granite originated from partial melting of a juvenile lower crust with minor input of upper crustal material caused by the underplating of mafic magma in an extensional setting. It can also be concluded that the prolonged fractional crystallization and magmatic-hydrothermal interactions have contributed to the formation of the Shamai tungsten deposit.

Determination of element affinities by density fractionation of bulk coal samples

USGS Publications Warehouse

Querol, X.; Klika, Z.; Weiss, Z.; Finkelman, R.B.; Alastuey, A.; Juan, R.; Lopez-Soler, A.; Plana, F.; Kolker, A.; Chenery, S.R.N.

2001-01-01

A review has been made of the various methods of determining major and trace element affinities for different phases, both mineral and organic in coals, citing their various strengths and weaknesses. These include mathematical deconvolution of chemical analyses, direct microanalysis, sequential extraction procedures and density fractionation. A new methodology combining density fractionation with mathematical deconvolution of chemical analyses of whole coals and their density fractions has been evaluated. These coals formed part of the IEA-Coal Research project on the Modes of Occurrence of Trace Elements in Coal. Results were compared to a previously reported sequential extraction methodology and showed good agreement for most elements. For particular elements (Be, Mo, Cu, Se and REEs) in specific coals where disagreement was found, it was concluded that the occurrence of rare trace element bearing phases may account for the discrepancy, and modifications to the general procedure must be made to account for these.

Mineralogy and petrology of cretaceous subsurface lamproite sills, southeastern Kansas, USA

USGS Publications Warehouse

Cullers, R.L.; Dorais, M.J.; Berendsen, P.; Chaudhuri, Sambhudas

1996-01-01

Cores and cuttings of lamproite sills and host sedimentary country rocks in southeastern Kansas from up to 312 m depth were analyzed for major elements in whole rocks and minerals, certain trace elements in whole rocks (including the REE) and Sr isotopic composition of the whole rocks. The lamproites are ultrapotassic (K2O/Na2O = 2.0-19.9), alkalic [molecular (K2O/Na2O)/Al2O3 = 1.3-2.8], enriched in mantle-incompatible elements (light REE, Ba, Rb, Sr, Th, Hf, Ta) and have nearly homogeneous initial Sr isotopic compositions (0.707764-0.708114). These lamproites could have formed by variable degrees of partial melting of harzburgite country rock and cross-cutting veins composed of phlogopite, K-Ti richterite, titanite, diopside, K-Ti silicates, or K-Ba-phosphate under high H2O/CO2 ratios and reducing conditions. Variability in melting of veins and wall rock and variable composition of the metasomatized veins could explain the significantly different composition of the Kansas lamproites. Least squares fractionation models preclude the derivation of the Kansas lamproites by fractional crystallization from magmas similar in composition to higher silica phlogopite-sanidine lamproites some believe to be primary lamproite melts found elsewhere. In all but one case, least squares fractionation models also preclude the derivation of magmas similar in composition to any of the Kansas lamproites from one another. A magma similar in composition to the average composition of the higher SiO2 Ecco Ranch lamproite (237.5-247.5 m depth) could, however, have marginally crystallized about 12% richterite, 12% sanidine, 7% diopside and 6% phlogopite to produce the average composition of the Guess lamproite (305-312 m depth). Lamproite from the Ecco Ranch core is internally fractionated in K2O, Al2O3, Ba, MgO, Fe2O3, Co and Cr most likely by crystal accumulation-removal of ferromagnesian minerals and sanidine. In contrast, the Guess core (305-312 m depth) has little fractionation throughout most of the sill except in several narrow zones. Lamproite in the Guess core has large enrichments in TiO2, Ba, REE, Th, Ta and Sc and depletions in MgO, Cr, Co and Rb possibly concentrated in these narrow zones during the last dregs of crystallization of this magma. The Ecco Ranch sill did not show any evidence of loss of volatiles or soluble elements into the country rock. This contrasts to the previously studied, shallow Silver City lamproite which did apparently lose H2O-rich fluid to the country rock. Perhaps a greater confining pressure and lesser amount of H2O-rich fluid prevented it from escaping.

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.

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.

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

USGS Publications Warehouse

Emsbo, Poul; McLaughlin, Patrick I.; Breit, George N.; du Bray, Edward A.; Koenig, Alan E.

2015-01-01

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H2SO4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

Health effects and toxicity mechanisms of rare earth elements-Knowledge gaps and research prospects.

PubMed

Pagano, Giovanni; Guida, Marco; Tommasi, Franca; Oral, Rahime

2015-05-01

In the recent decades, rare earth elements (REE) have undergone a steady spread in several industrial and medical applications, and in agriculture. Relatively scarce information has been acquired to date on REE-associated biological effects, from studies of bioaccumulation and of bioassays on animal, plant and models; a few case reports have focused on human health effects following occupational REE exposures, in the present lack of epidemiological studies of occupationally exposed groups. The literature is mostly confined to reports on few REE, namely cerium and lanthanum, whereas substantial information gaps persist on the health effects of other REE. An established action mechanism in REE-associated health effects relates to modulating oxidative stress, analogous to the recognized redox mechanisms observed for other transition elements. Adverse outcomes of REE exposures include a number of endpoints, such as growth inhibition, cytogenetic effects, and organ-specific toxicity. An apparent controversy regarding REE-associated health effects relates to opposed data pointing to either favorable or adverse effects of REE exposures. Several studies have demonstrated that REE, like a number of other xenobiotics, follow hormetic concentration-related trends, implying stimulatory or protective effects at low levels, then adverse effects at higher concentrations. Another major role for REE-associated effects should be focused on pH-dependent REE speciation and hence toxicity. Few reports have demonstrated that environmental acidification enhances REE toxicity; these data may assume particular relevance in REE-polluted acidic soils and in REE mining areas characterized by concomitant REE and acid pollution. The likely environmental threats arising from REE exposures deserve a new line of research efforts. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Source Evolution After Subduction Initiation as Recorded in the Izu-Bonin-Mariana Fore-arc Crust

NASA Astrophysics Data System (ADS)

Shervais, J. W.; Reagan, M. K.; Pearce, J. A.; Shimizu, K.

2015-12-01

Drilling in the Izu-Bonin-Mariana (IBM) fore-arc during IODP Expedition 352 and DSDP Leg 60 recovered consistent stratigraphic sequences of volcanic rocks reminiscent of those found in many ophiolites. The oldest lavas in these sections are "fore-arc basalts" (FAB) with ~51.5 Ma ages. Boninites began eruption approximately 2-3 m.y. later (Ishizuka et al., 2011, EPSL; Reagan et al., 2013, EPSL) and further from the trench. First results from IODP Expedition 352 and preliminary post-cruise data suggest that FAB at Sites U1440 and U1441 were generated by decompression melting during near-trench sea-floor spreading, and that fluids from the subducting slab were not involved in their genesis. Temperatures appear to have been unusually high and pressures of melting appear to have been unusually low compared to mid-ocean ridges. Spreading rates at this time appear to have been robust enough to maintain a stable melt lens. Incompatible trace element abundances are low in FAB compared to even depleted MORB. Nd and Hf Isotopic compositions published before the expedition suggest that FAB were derived from typical MORB source mantle. Thus, their extreme deletion resulted from unusually high degrees of melting immediately after subduction initiation. The oldest boninites from DSDP Site 458 and IODP Sites U1439 and U1442 have relatively high concentrations of fluid-soluble elements, low concentrations of REE, and light depleted REE patterns. Younger boninites, have even lower REE concentrations, but have U-shaped REE patterns. Our first major and trace element compositions for the FAB through boninite sequence suggests that melting pressures and temperatures decreased through time, mantle became more depleted though time, and spreading rates waned during boninite genesis. Subduction zone fluids involved in boninite genesis appear to have been derived from progressively higher temperatures and pressures over time as the subducting slab thermally matured.

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects

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

Pagano, Giovanni, E-mail: gbpagano@tin.it; Guida, Marco; Siciliano, Antonietta

Background: Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. Methods: Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. Results: REEs affectedmore » P. lividus larvae with concentration-related increase in developmental defects, 10{sup −6} to 10{sup −4} M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10{sup −5} to 10{sup −4} M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. Conclusion: REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies. - Highlights: • Seven rare earth elements exerted different effects on sea urchin early life stages. • Embryo-, spermio- and mitotoxicity, and oxidative/ nitrosative stress were found. • Nominal vs. analytical REE concentrations were checked. • Comparative toxicities were evaluated for the different REE.« less

Rare earth elements in human and animal health: State of art and research priorities

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

Pagano, Giovanni, E-mail: gbpagano@tin.it; Aliberti, Francesco; Guida, Marco

Background: A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. Methods: A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. Results: Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures havemore » been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. Conclusion: The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments. - Highlights: • An extensive number of activities have been developed utilizing rare earth elements (REE). • The literature of REE-associated health effects in humans, and on animal studies is reviewed. • The main literature gaps are discussed, in epidemiological and in animal studies. • Prospects studies are suggested, aimed at evaluating long-term effects of REE exposures. • The relevance of REE-related hormesis, speciation and acidic pollution are discussed.« less

Lithium in Jack Hills zircons: Evidence for extensive weathering of Earth's earliest crust

NASA Astrophysics Data System (ADS)

Ushikubo, Takayuki; Kita, Noriko T.; Cavosie, Aaron J.; Wilde, Simon A.; Rudnick, Roberta L.; Valley, John W.

2008-08-01

In situ Li analyses of 4348 to 3362 Ma detrital zircons from the Jack Hills, Western Australia by SIMS reveal that the Li abundances (typically 10 to 60 ppm) are commonly over 10,000 times higher than in zircons crystallized from mantle-derived magmas and in mantle-derived zircon megacrysts (typically < 2 ppb). High Li concentrations in zircons (10 to 250 ppm) have also been found in igneous zircons from three continental parent rocks: granites, Li-rich pegmatites, and migmatites in pelitic metasediment. The substitution of trivalent cations (REEs and Y) in zircon correlates with Li + 1 and P + 5 , suggesting that an interstitial site for Li, as well as the xenotime substitution for P, provides charge balance for REEs. Li is thus fixed in the zircon structure by coupled substitutions, and diffusive changes in [Li] composition are rate-limited by slow diffusion of REEs. The Jack Hills zircons also have fractionated lithium isotope ratios ( δ7Li = - 19 to + 13‰) about five times more variable than those recorded in primitive ocean floor basalts (2 to 8‰), but similar to continental crust and its weathering products. Values of δ7Li below - 10‰ are found in zircons that formed as early as 4300 Ma. The high Li compositions indicate that primitive magmas were not the source of Jack Hills zircons and the fractionated values of δ7Li suggest that highly weathered regolith was sampled by these early Archean magmas. These new Li data provide evidence that the parent magmas of ancient zircons from Jack Hills incorporated materials from the surface of the Earth that interacted at low temperature with liquid water. These data support the hypothesis that continental-type crust and oceans existed by 4300 Ma, within 250 million years of the formation of Earth and the low values of δ7Li suggest that weathering was extensive in the early Archean.

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.

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.

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

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.

Isotopic and trace element variations in the Ruby Batholith, Alaska, and the nature of the deep crust beneath the Ruby and Angayucham Terranes

USGS Publications Warehouse

Arth, Joseph G.; Zmuda, Clara C.; Foley, Nora K.; Criss, Robert E.; Patton, W.W.; Miller, T.P.

1989-01-01

Thirty-six samples from plutons of the Ruby batholith of central Alaska were collected and analyzed for 22 trace elements, and many were analyzed for the isotopic compositions of Sr, Nd, O, and Pb in order to delimit the processes that produced the diversity of granodioritic to granitic compositions, to deduce the nature of the source of magmas at about 110 Ma, and to characterize the deep crust beneath the Ruby and Angayucham terranes. Plutons of the batholith show a substantial range in initial 87Sr/86Sr (SIR) of 0.7055–0.7235 and a general decrease from southwest to northeast. Initial 143Nd/144Nd (NIR) have a range of 0.51150–0.51232 and generally increase from southwest to northeast. The δ18O values for most whole rocks have a range of +8.4 to +11.8 and an average of +10.3‰. Rb, Cs, U, and Th show large ranges of concentration, generally increase as SiO2 increases, and are higher in southwest than in northeast plutons. Sr, Ba, Zr, Hf, Ta, Sc, Cr, Co, and Zr show large ranges of concentration and generally decrease as SiO2 increases. Rare earth elements (REE) show fractionated patterns and negative Eu anomalies. REE concentrations and anomalies are larger in the southwest than in the northeast plutons. Uniformity of SIR and NIR in Sithylemenkat and Jim River plutons suggests a strong role for fractional crystallization or melting of uniform magma sources at depth. Isotopic variability in Melozitna, Ray Mountains, Hot Springs, and Kanuti plutons suggests complex magmatic processes such as magma mixing and assimilation, probably combined with fractional crystallization, or melting of a complex source at depth. The large variations in SIR and NIR in the batholith require a variation in source materials at depth. The southwestern plutons probably had dominantly siliceous sources composed of metamorphosed Proterozoic and Paleozoic upper crustal rocks. The northeastern plutons probably had Paleozoic sources that were mixtures of siliceous and intermediate to mafic crustal rocks. The inferred sources could well have been the higher-metamorphic-grade lithologic equivalents of the exposed Proterozoic(?) to Paleozoic schists, orthogneisses, and metavolcanic rocks of Ruby terrane, the silicic portions of which are quite radiogenic. The deeper crustal sources that gave rise to most of the batholithic magmas are inferred to be similar under both the Ruby metamorphic terrane and the Angayucham ophiolitic terrane.

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

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.

Bioavailability of heavy metals, germanium and rare earth elements at Davidschacht dump-field in mine affected area of Freiberg (Saxony)

NASA Astrophysics Data System (ADS)

Midula, Pavol; Wiche, Oliver

2016-04-01

Bioavailability research presents an essential tool, in modern phytoremediation and phytomining technologies, allowing the estimation of plant available fractions of elements in soils. However, up to date, sufficient interdisciplinary knowledge on the biogeochemically impacted behavior of specific target elements, in particular Ge and REEs in mining affected soils and their uptake into strategically used plants is lacking. This presented work is focused on a correlation study between the concentrations of selected heavy metals, Ge and REEs in soils formed on the top of the dump-field of Davidschacht and the corresponding their concentrations in 12 vascular plant species. The mine-dump of Davidschacht, situated in the Freiberg (Saxony, Germany) municipality area was chosen as the study area, which has been considered to be a high contaminated enclave, due to the mining history of the region. In total 12 sampling sites with differing composition of plant species were selected. At each sampling site soil samples from a soil depth of 0 - 10 cm and samples of plant material (shoots) were taken. The soil samples were analysed for total concentration of elements, pH (H2O) and consequently analysed by 4-step sequential extraction (SE) to determine fractions of elements that are mobile (fraction 1), acid soluble (pH 5) (fraction 2), bound to organic and oxidizable matter (fraction 3) and bound to amorphic oxides (fraction 4). The plant material was decomposed by hydrofluoric acid in order to extract the elements. Concentrations of elements in soil extracts and digestion solutions were analysed by ICP-MS. For all species bioconcentration factor (BCF) was calculated of the total concentration of elements in order to investigate the bioaccumulation potential. Arsenic (As), cadmium (Cd) and lead (Pb) were chosen as the representative heavy metals. Within the REEs neodymium (Nd) and cerium (Ce) were selected as representatives for all REEs, since Nd and Ce correlated significant with the other elements from this group. High amounts of As, Cd, Pb in mould horizons were proved. The surprisingly highest concentrations were determined for As (in average 3328 mg kg-1). The results of the pH measurement indicates acid conditions (in average 4.86, min. 3.89) for whole mine heap. Due to the mobility of Cd and Pb in acid environment, a high mobility of Cd in mobile soil fractions (in average 0.58 mg kg-1) was found, that seems to be responsible for the Cd pollution of Freiberger Mulde river, situated near the dump-field in the East direction from the studied area. The Pb content was in the average 1513 mg kg-1. SE analyses shows, that only the minor amounts of these metals were accounted in fractions I - IV (As: 7.75 %, Pb: 5.48 %, Cd: 26.77 %). The total Ge content in soil samples was 2.7 mg.kg-1in average. The concentrations of Nd and Ce were 17.7 mg kg-1and 38.5 mg kg-1, which is even lower than the average Nd and Ce contents in the Earth crust. However, the concentration of Ge was roughly a factor of two higher, than this average showing a large pool of Ge that could be accessed by phytoextraction. The SE analyses shows, that the average in fractions I - IV is even much lower, than in the case of the above mentioned heavy metals in comparison with Ge (1.75 %), Nd (3.28 %) and Ce (3.12 %). The BCF calculated for plants shows, that the only element, which could be possibly used as the object of phytoaccumulation is Cd (the BCF > 1) in species Populus tremula (3.0, 1.7), Spirea douglasii (1.4, 2.2) and Tanacetum vulgare (3.2, 1.3) at the most sampling places. Since these species represent the natural occurring vegetation of the dump, the use of these species together with soil amendments enhancing the plant availability of elements in soil fractions hold promise for phytoextraction of economically valuable metalloids and consequently an in situ bioremediation of the dump field. This work was realised with the support of Christin Jahns on behalf of the Saxonia company and financial supported by grant scheme VEGA 1/0538/15 . The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.

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.

Magmatic geochemistry and relict textures in blueschist-eclogite facies rocks on the island of Syros, Greece

NASA Astrophysics Data System (ADS)

Schumacher, J. C.; Brady, J. B.; Prinkey, D. R.; Walton, A. J.; Able, L. M.; Sinitsin, A. G.; Cheney, J. T.

2004-05-01

The island of Syros is part of the Attic-Cycladic blueschist belt and high-P mineral assemblages indicating peak metamorphic conditions of at least 15-16 kbar and 500 C are common. Two main marble units, which locally contain Mississippian fossils, are partly dolomitic, contain abundant calcite pseudomorphs after aragonite (Dixon, 1969), and are intercalated with the glaucophane (Glau)-schists, retrograde greenschists, and minor quartzites and Mn-cherts. Discrete, fault-bounded packages of blueschist/eclogite-facies mafic rocks with minor serpentinite are also present. The mineral compositions and assemblages in marbles and associated rocks tightly constrain the metamorphic P, T and the fluid compositions and suggest X(H2O) in the range 0.97-0.99. In general, the mafic rocks have a variety of textures and modes, but most are either fine-grained, blueschists with a well-developed fabric (S approx.=L) or coarse-grained (>1 cm), massive omphacite- or Glau-rich rocks. Based on textures, mineralogy and field relations, previous workers (Dixon and Ridley, 1987) have interpreted the mafic rocks as meta-basalt and metagabbros. Evidence of pillow structures, as well as metamorphosed alteration zones which are interpreted as evidence of ocean-floor metamorphism (?) have survived locally. We obtained whole-rock XRF and INAA analyses for fine- and coarse-grained mafic and felsic rocks and some mica-rich samples. Low chemical index of alteration (CIA) for most samples suggest very minor weathering. On a TAS diagram, mafic rocks span the basalt - basaltic andesite - trachy-basalt - basaltic trachy-andesite fields. REE patterns generally fall between 10-100 times chondrite and show flat to moderately LREE-enriched patterns. Coarse-grained rocks have positive Eu anomalies, consistent with their interpretation by other investigators as fractionally crystallized gabbros. Felsic rocks (now epidote-mica-schists) that are associated with the metamorphosed gabbros have negative Eu anomalies, and modeling of the REEs suggests that the felsic rocks represent residual melts during the crystallization of the gabbros. The low CIA-values indicate that the mica-schist precursors lacked significant clay material. The presence of abundant epidote (Zo) is consistent with a feldspar-rich (magmatic) protolith for the mica-schists.

"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.

Provenance and metamorphic PT conditions of Cryogenian-Ediacaran metasediments from the Kid metamorphic complex, Sinai, NE Arabian-Nubian Shield: Insights from detrital zircon geochemistry and mineral chemistry

NASA Astrophysics Data System (ADS)

El-Bialy, Mohammed Z.; Ali, Kamal A.; Abu El-Enen, Mahrous M.; Ahmed, Ahmed H.

2015-12-01

The Malhaq and Um Zariq formations occupy the northern part of the Neoproterozoic Kid metamorphic complex of SE Sinai, NE Arabian-Nubian Shield. This study presents new mineral chemistry data and LA-ICP-MS analyses of the trace element concentrations on zircons separated from metapelites from these formations. The detrital zircons of Um Zariq Formation are more enriched in ΣREE, whereas Malhaq Formation zircons are markedly HREE-enriched with strongly fractionated HREE patterns. The quite differences in the overall slope and size of the Eu and Ce anomalies between REE patterns of the two zircon suites provide a robust indication of different sources. The Ti-in-zircon thermometer has revealed that the zircons separated from Malhaq Formation were crystallized within the 916-1018 °C range, while those from Um Zariq Formation exhibit higher range of crystallization temperatures (1084-1154 °C). The detrital zircons of Malhaq Formation were derived mainly from mafic source rocks (basalt and dolerite), whereas Um Zariq Formation zircons have varied and more evolved parent rocks. Most of the investigated zircons from both formations are concluded to be unaltered magmatic that were lately crystallized from a high LREE/HREE melt. All the studied detrital zircon grains show typical trace elements features of crustal-derived zircons. All of the Um Zariq Formation and most of Malhaq Formation detrital zircons are geochemically discriminated as continental zircons. Both formation metapelites record similar, overlapping peak metamorphic temperatures (537-602 °C and 550-579 °C, respectively), and pressures (3.83-4.93 kbar and 3.69-4.07 kbar, respectively). The geothermal gradient, at the peak metamorphic conditions, was quite high (37-41 °C/km) corresponding to metamorphism at burial depth of 14-16 km. The peak regional metamorphism of Um Zariq and Malhaq formations is concluded to be generated during extensional regime and thinning of the lithosphere in an island arc setting with heat flow from the underlying arc granitoids.

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.

Rare earth element abundances in rocks and minerals from the Fiskenaesset Complex, West Greenland. [comparison with lunar anorthosites

NASA Technical Reports Server (NTRS)

Henderson, P.; Fishlock, S. J.; Laul, J. C.; Cooper, T. D.; Conard, R. L.; Boynton, W. V.; Schmitt, R. A.

1976-01-01

The paper reports activation-analysis determinations of rare-earth-element (REE) and other trace-element concentrations in selected rocks, plagioclase, and mafic separates from the Fiskenaesset Complex. The REE abundances are found to be very low and atypical in comparison with other terrestrial anorthosites. The plagioclases are shown to be characterized by a deficiency in heavy RE elements relative to light ones and a positive Eu anomaly, while the mafic separates are enriched in heavy rare earths and have no Eu anomaly, except in one sample. It is found that the bulk and trace-element abundances of the plagioclases are similar to those observed in some lunar anorthosites, but the degree of Eu anomaly is less in the plagioclases. The data are taken as confirmation of the idea that fractionation processes were involved in the origin of the Complex, and it is concluded that the Complex may have been produced from a magma generated by partial melting of a garnet-bearing source.

Constraints on the depth of generation and emplacement of a magmatic epidote-bearing quartz diorite pluton in the Coast Plutonic Complex, British Columbia

USGS Publications Warehouse

Chang, J.M.; Andronicos, C.L.

2009-01-01

Petrology and P-T estimates indicate that a magmatic epidote-bearing quartz diorite pluton from Mt. Gamsby, Coast Plutonic Complex, British Columbia, was sourced at pressures below ???1.4 GPa and cooled nearly isobarically at ???0.9 GPa. The P-T path indicates that the magma was within the stability field of magmatic epidote early and remained there upon final crystallization. The pluton formed and crystallized at depths greater than ???30 km. REE data indicate that garnet was absent in the melting region and did not fractionate during crystallization. This suggests that the crust was less than or equal to ???55 km thick at 188 Ma during the early phases of magmatism in the Coast Plutonic Complex. Late Cretaceous contractional deformation and early Tertiary extension exhumed the rocks to upper crustal levels. Textures of magmatic epidote and other magmatic phases, combined with REE data, can be important for constraining the P-T path followed by magmas. ?? 2009 Blackwell Publishing Ltd.

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

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

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE PAGES

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

2017-10-26

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

A supported liquid membrane system for the selective recovery of rare earth elements from neodymium-based permanent magnets

DOE PAGES

Kim, Daejin; Powell, Lawrence; Delmau, Lætitia H.; ...

2016-04-04

We present that the rare earth elements (REEs) play a vital role in the development of green energy and high-tech industries. In order to meet the fast-growing demand and to ensure sufficient supply of the REEs, it is essential to develop an efficient REE recovery process from post-consumer REE-containing products. In this research effort, we have developed a supported liquid membrane system utilizing polymeric hollow fiber modules to extract REEs from neodymium-based magnets with neutral extractants such as tetraoctyl digylcol amide (TODGA). The effect of process variables such as REE concentration, molar concentration of acid, and membrane area on REEmore » recovery was investigated. We have demonstrated the selective extraction and recovery of REEs such as Nd, Pr, and Dy without co-extraction of non-REEs from permanent NdFeB magnets through the supported liquid membrane system. The extracted REEs were then recovered by precipitation followed by the annealing step to obtain crystalline REE powders in nearly pure form. Finally, the recovered REE oxides were characterized by X-ray diffraction, scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, and inductively coupled plasma–optical emission spectroscopy.« less

Comparison of respiratory quotient and resting energy expenditure in two regimens of enteral feeding – continuous vs. intermittent in head-injured critically ill patients

PubMed Central

Maurya, Indubala; Pawar, Mridula; Garg, Rakesh; Kaur, Mohandeep; Sood, Rajesh

2011-01-01

Introduction: Measurement of respiratory quotient (RQ) and resting energy expenditure (REE) has been shown to be helpful in designing nutritional regimens. There is a paucity of the literature describing the impact of a feeding regimen on the energy expenditure patterns. Therefore, we studied the effect of continuous vs. intermittent feeding regimen in head-injured patients on mechanical ventilation on RQ and REE. Methods: After institutional ethical approval, this randomized study was conducted in 40 adult male patients with head injury requiring controlled mode of ventilation. Patients were randomly allocated into two groups. Group C: Feeds (30 kcal/kg/day) were given for 18 h/day, with night rest for 6 h. Group I: Six bolus feeds (30 kcal/kg/day) were given three hourly for 18 h with night rest for 6 h. RQ and REE were recorded every 30 min for 24 h. Blood sugar was measured 4 hourly. Other adverse effects such as feed intolerance, aspiration were noted. Results: Demographic profile and SOFA score were comparable in the two groups. Base line RQ (0.8 vs. 0.86) and REE (1527 vs. 1599 kcal/day) were comparable in both the groups (P>0.05). RQ was comparable in both groups during the study period at any time of the day (P>0.05). Base line RQ was compared with all other RQ values measured every half hour and fluctuation from the base line value was insignificant in both groups (P>0.05). REE was comparable in both the groups throughout the study period (P>0.5). Adequacy of feeding as assessed by EI/MREE was 105.7% and 105.3% in group C and group I, respectively. There was no significant difference in the blood sugar levels between the two groups (P>0.05). Conclusion: We found from our study that RQ, REE, and blood sugar remain comparable with two regimens of enteral feeding – continuous vs. intermittent in neurosurgical patients on ventilator support in a ICU setup. PMID:21804803

Comparison of respiratory quotient and resting energy expenditure in two regimens of enteral feeding - continuous vs. intermittent in head-injured critically ill patients.

PubMed

Maurya, Indubala; Pawar, Mridula; Garg, Rakesh; Kaur, Mohandeep; Sood, Rajesh

2011-04-01

Measurement of respiratory quotient (RQ) and resting energy expenditure (REE) has been shown to be helpful in designing nutritional regimens. There is a paucity of the literature describing the impact of a feeding regimen on the energy expenditure patterns. Therefore, we studied the effect of continuous vs. intermittent feeding regimen in head-injured patients on mechanical ventilation on RQ and REE. After institutional ethical approval, this randomized study was conducted in 40 adult male patients with head injury requiring controlled mode of ventilation. Patients were randomly allocated into two groups. Group C: Feeds (30 kcal/kg/day) were given for 18 h/day, with night rest for 6 h. Group I: Six bolus feeds (30 kcal/kg/day) were given three hourly for 18 h with night rest for 6 h. RQ and REE were recorded every 30 min for 24 h. Blood sugar was measured 4 hourly. Other adverse effects such as feed intolerance, aspiration were noted. Demographic profile and SOFA score were comparable in the two groups. Base line RQ (0.8 vs. 0.86) and REE (1527 vs. 1599 kcal/day) were comparable in both the groups (P>0.05). RQ was comparable in both groups during the study period at any time of the day (P>0.05). Base line RQ was compared with all other RQ values measured every half hour and fluctuation from the base line value was insignificant in both groups (P>0.05). REE was comparable in both the groups throughout the study period (P>0.5). Adequacy of feeding as assessed by EI/MREE was 105.7% and 105.3% in group C and group I, respectively. There was no significant difference in the blood sugar levels between the two groups (P>0.05). We found from our study that RQ, REE, and blood sugar remain comparable with two regimens of enteral feeding - continuous vs. intermittent in neurosurgical patients on ventilator support in a ICU setup.

Fate of colloids during estuarine mixing in the Arctic

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Shirokova, L. S.; Viers, J.; Gordeev, V. V.; Shevchenko, V. P.; Chupakov, A. V.; Vorobieva, T. Y.; Candaudap, F.; Causserand, C.; Lanzanova, A.; Zouiten, C.

2014-02-01

The estuarine behavior of organic carbon (OC) and trace elements (TE) was studied for the largest European sub-Arctic river, which is the Severnaya Dvina; this river has a deltaic estuary covered in ice during several hydrological seasons: summer (July 2010, 2012) and winter (March 2009) baseflow, and the November-December 2011 ice-free period. Colloidal forms of OC and TE were assessed for three pore size cutoffs (1, 10, and 50 kDa) using an in situ dialysis procedure. Conventionally dissolved (< 0.22 μm) fractions demonstrated clear conservative behavior for Li, B, Na, Mg, K, Ca, Sr, Mo, Rb, Cs, and U during the mixing of freshwater with the White Sea; a significant (up to a factor of 10) concentration increase occurs with increases in salinity. Si and OC also displayed conservative behavior but with a pronounced decrease in concentration seawards. Rather conservative behavior, but with much smaller changes in concentration (variation within ±30%) over a full range of salinities, was observed for Ti, Ni, Cr, As, Co, Cu, Ga, Y, and heavy REE. Strong non-conservative behavior with coagulation/removal at low salinities (< 5‰) was exhibited by Fe, Al, Zr, Hf, and light REE. Finally, certain divalent metals exhibited non-conservative behavior with a concentration gain at low (~ 2-5‰, Ba, Mn) or intermediate (~ 10-15‰, Ba, Zn, Pb, Cd) salinities, which is most likely linked to TE desorption from suspended matter or sediment outflux. The most important result of this study is the elucidation of the behavior of the "truly" dissolved low molecular weight LMW< 1 kDa fraction containing Fe, OC, and a number of insoluble elements. The concentration of the LMW fraction either remains constant or increases its relative contribution to the overall dissolved (< 0.22 μm) pool as the salinity increases. Similarly, the relative proportion of colloidal (1 kDa-0.22 μm) pool for the OC and insoluble TE bound to ferric colloids systematically decreased seaward, with the largest decrease occurring at low (< 5‰) salinities. Overall, the observed decrease in the colloidal fraction may be related to the coagulation of organo-ferric colloids at the beginning of the mixing zone and therefore the replacement of the HMW1 kDa-0.22 μm portion by the LMW< 1 kDa fraction. These patterns are highly reproducible across different sampling seasons, suggesting significant enrichment of the mixing zone by the most labile (and potentially bioavailable) fraction of the OC, Fe and insoluble TE. The size fractionation of the colloidal material during estuarine mixing reflects a number of inorganic and biological processes, the relative contribution of which to element speciation varies depending on the hydrological stage and time of year. In particular, LMW< 1 kDa ligand production in the surface horizons of the mixing zone may be linked to heterotrophic mineralization of allochthonous DOM and/or photodestruction. Given the relatively low concentration of particulate versus dissolved load of most trace elements, desorption from the river suspended material was less pronounced than in other rivers in the world. As a result, the majority of dissolved components exhibited either conservative (OC and related elements such as divalent metals) or non-conservative, coagulation-controlled (Fe, Al, and insoluble TE associated with organo-ferric colloids) behavior. The climate warming at high latitudes is likely to intensify the production of LMW< 1 kDa organic ligands and the associated TE; therefore, the delivery of potentially bioavailable trace metal micronutrients from the land to the ocean may increase.

Petrology, geochemistry and zirconology of impure calcite marbles from the Precambrian metamorphic basement at the southeastern margin of the North China Craton

NASA Astrophysics Data System (ADS)

Liu, Yi-Can; Zhang, Pin-Gang; Wang, Cheng-Cheng; Groppo, Chiara; Rolfo, Franco; Yang, Yang; Li, Yuan; Deng, Liang-Peng; Song, Biao

2017-10-01

Impure calcite marbles from the Precambrian metamorphic basement of the Wuhe Complex, southeastern margin of the North China Craton, provide an exceptional opportunity to understand the depositional processes during the Late Archean and the subsequent Palaeoproterozoic metamorphic evolution of one of the oldest cratons in the world. The studied marbles are characterized by the assemblage calcite + clinopyroxene + plagioclase + K-feldspar + quartz + rutile ± biotite ± white mica. Based on petrography and geochemistry, the marbles can be broadly divided into two main types. The first type (type 1) is rich in REE with a negative Eu anomaly, whereas the second type (type 2) is relatively poor in REE with a positive Eu anomaly. Notably, all marbles exhibit remarkably uniform REE patterns with moderate LREE/HREE fractionation, suggesting a close genetic relationship. Cathodoluminescence imaging, trace elements and mineral inclusions reveal that most zircons from two dated samples display distinct core-rim structures. Zircon cores show typical igneous features with oscillatory growth zoning and high Th/U ratios (mostly in the range 0.3-0.7) and give ages of 2.53 - 2.48 Ga, thus dating the maximum age of deposition of the protolith. Zircon rims overgrew during granulite-facies metamorphism, as evidenced by calcite + clinopyroxene + rutile + plagioclase + quartz inclusions, by Ti-in-zircon temperatures in the range 660-743 °C and by the low Th/U (mostly < 0.1) and Lu/Hf (< 0.001) ratios. Zircon rims from two dated samples yield ages of 1839 ± 7 Ma and 1848 ± 23 Ma, respectively, suggesting a Palaeoproterozoic age for the granulite-facies metamorphic event. These ages are consistent with those found in other Precambrian basement rocks and lower-crustal xenoliths in the region, and are critical for the understanding of the tectonic history of the Wuhe Complex. Positive Eu anomalies and high Sr and Ba contents in type 2 marbles are ascribed to syn-depositional felsic hydrothermal activity which occurred at 2.53 - 2.48 Ga. Our results, together with other published data and the inferred tectonic setting, suggest that the marbles' protolith is an impure limestone, rich in detrital silicates of igneous origin, deposited in a back-arc basin within an active continental margin during the late Archean and affected by synchronous high-T hydrothermalism at the southeastern margin of the North China Craton.

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.

Lunar anorthosite 60025, the petrogenesis of lunar anorthosites, and the composition of the moon

NASA Technical Reports Server (NTRS)

Ryder, G.

1982-01-01

The mineral chemistry of the lunar anorthosite 60025 is investigated, and a model for the differentiation of the moon is proposed based on these findings. Among other results, it is concluded that 60025 is a mixture of pieces from a related sequence of anorthosites, and that this sequence was generated by near-perfect accumulate growth during strong fractional crystallization. The parent liquid of the most primitive anorthosite was saturated with olivine, plagioclase, pigeonite, and chromite, and evolved to one saturated with plagioclase, pigeonite, high-Ca clinopyroxene, and ilmenite. The steep slope of anorthosites on an Mg (mafics) vs. Ab (plagioclase) diagram is a result of the very low alkali content of the magma and of the original magma ocean. The bulk moon had low Al2O3, a sub-chondritic Ca/Al ratio, and REE abundances and patterns which were probably close to chondritic. In addition, mare basalt sources were found to be too magnesian and some contain too much high Ca clinopyroxene to be directly or simply complementary to a floated anorthosite crust.

Geochemical and palaeoenvironmental characteristics of Missole I iron duricrusts of the Douala sub-basin (Western Cameroon)

NASA Astrophysics Data System (ADS)

Ngon Ngon, Gilbert François; Etame, Jacques; Ntamak-Nida, Marie Joseph; Mbesse, Cécile Olive; Mbai, Joël Simon; Bayiga, Élie Constantin; Gerard, Martine

2016-02-01

Major and trace element composition of iron duricrusts including clayey material samples and biostratigraphy of the Missole I outcrop from the Paleocene-Eocene N'Kapa Formation in the Douala sub-basin of Cameroon were used to infer the palaeoenvironment and relative age of the iron duricrusts. Iron duricrusts and clayey materials are essentially kaolinitic and smectitic and are generally siliceous and ferruginous (iron duricrusts) or siliceous and aluminous (clayey materials). These materials have high Chemical Indices of Alteration (CIA = 86.6-99.33%). The negative Eu anomalies with high (La/Yb)N shown by iron duricrusts and clayey sediments are essentially derived from silicic or felsic parent rocks when fractionated chondrite-normalized REE patterns also indicate felsic or silicic parent rocks. The Missole I iron duricrusts have a post-Thanetian age according to the relative age of claystones (Thanetian) and were formed after the deposition of sedimentary materials in an anoxic low-depth marine environment with eutrophication of surface water, and may have been exhumed and oxidized under arid climate.

Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

NASA Astrophysics Data System (ADS)

Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

2012-12-01

The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic to anoxic conditions at Hot Spring, contemporaneous to an Oceanic Anoxic Event. The similarity of the Nd isotopic signal of the carbonate matrix of foraminifera with that of fish teeth suggests that it records the Nd isotope composition of bottom shelf seawater as well. Inferred bottom shelf water Nd isotope compositions at Hot Spring are quite radiogenic, between -7 and -6 ɛ-units, about 2.5-4 ɛ-units higher than that of the contemporaneous local detrital fraction. In contrast, in both sections Fe-Mn oxides leached directly from the decarbonated sediment tend to yield a less radiogenic Nd isotopic composition, typically between 0.2 and 0.8 ɛ-units lower, that is intermediate between that of fish teeth and of the detrital fraction. This suggests the contribution of pre-formed continental Fe-Mn oxides to the Nd isotopic signal, along with authigenic marine oxides, or a detrital contamination during leaching.

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.

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.

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

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...

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

Geochemistry of southern Pagan Island lavas, Mariana arc: The role of subduction zone processes

USGS Publications Warehouse

Marske, J.P.; Pietruszka, A.J.; Trusdell, F.A.; Garcia, M.O.

2011-01-01

New major and trace element abundances, and Pb, Sr, and Nd isotopic ratios of Quaternary lavas from two adjacent volcanoes (South Pagan and the Central Volcanic Region, or CVR) located on Pagan Island allow us to investigate the mantle source (i.e., slab components) and melting dynamics within the Mariana intra-oceanic arc. Geologic mapping reveals a pre-caldera (780-9.4ka) and post-caldera (<9.4ka) eruptive stage for South Pagan, whereas the eruptive history of the older CVR is poorly constrained. Crystal fractionation and magma mixing were important crustal processes for lavas from both volcanoes. Geochemical and isotopic variations indicate that South Pagan and CVR lavas, and lavas from the northern volcano on the island, Mt. Pagan, originated from compositionally distinct parental magmas due to variations in slab contributions (sediment and aqueous fluid) to the mantle wedge and the extent of mantle partial melting. A mixing model based on Pb and Nd isotopic ratios suggests that the average amount of sediment in the source of CVR (~2.1%) and South Pagan (~1.8%) lavas is slightly higher than Mt. Pagan (~1.4%) lavas. These estimates span the range of sediment-poor Guguan (~1.3%) and sediment-rich Agrigan (~2.0%) lavas for the Mariana arc. Melt modeling demonstrates that the saucer-shaped normalized rare earth element (REE) patterns observed in Pagan lavas can arise from partial melting of a mixed source of depleted mantle and enriched sediment, and do not require amphibole interaction or fractionation to depress the middle REE abundances of the lavas. The modeled degree of mantle partial melting for Agrigan (2-5%), Pagan (3-7%), and Guguan (9-15%) lavas correlates with indicators of fluid addition (e.g., Ba/Th). This relationship suggests that the fluid flux to the mantle wedge is the dominant control on the extent of partial melting beneath Mariana arc volcanoes. A decrease in the amount of fluid addition (lower Ba/Th) and extent of melting (higher Sm/Yb), and an increase in the sediment contribution (higher Th/Nb, La/Sm, and Pb isotopic ratios) from Mt. Pagan to South Pagan could reflect systematic cross-arc or irregular along-arc melting variations. These observations indicate that the length scale of compositional heterogeneity in the mantle wedge beneath Mariana arc volcanoes is small (~10km).

Petrology of the Western Highland Province: Ancient crust formation at the Apollo 14 site

NASA Astrophysics Data System (ADS)

Shervais, John W.; McGee, James J.

1999-03-01

Plutonic rocks found at the Apollo 14 site comprise four lithologic suites: the magnesian suite, the alkali suite, evolved lithologies, and the ferroan anorthosite suite (FAN). Rocks of the magnesian suite include troctolite, anorthosite, norite, dunite, and harzburgite; they are characterized by plagioclase ~An95 and mafic minerals with mg#s 82-92. Alkali suite rocks and evolved rocks generally have plagioclase ~An90 to ~An40, and mafic minerals with mg#s 82-40. Lithologies include anorthosite, norite, quartz monzodiorite, granite, and felsite. Ferroan anorthosites have plagioclase ~An96 and mafic minerals with mg#s 45-70. Whole rock geochemical data show that most magnesian suite samples and all alkali anorthosites are cumulates with little or no trapped liquid component. Norites may contain significant trapped liquid component, and some alkali norites may represent cumulate-enriched, near-liquid compositions, similar to KREEP basalt 15386. Evolved lithologies include evolved partial cumulates related to alkali suite fractionation (quartz monzodiorite), immiscible melts derived from these evolved magmas (granites), and impact melts of preexisting granite (felsite). Plots of whole rock mg# versus whole rock Ca/(Ca+Na+K) show a distinct gap between rocks of the magnesian suite and rocks of the alkali suite, suggesting either distinct parent magmas or distinct physical processes of formation. Chondrite-normalized rare earth element (REE) patterns show that rocks of both the magnesian suite and alkali suite have similar ranges, despite the large difference in major element chemistry. Current models for the origin of the magnesian suite call for a komatiitic parent magma derived from early magma ocean cumulates; these melts must assimilate plagiophile elements to form troctolites at low pressures and must assimilate a highly enriched KREEP component so that the resulting mixture has REE concentrations similar to high-K KREEP. There are as yet no plausible scenarios that can explain these unusual requirements. We propose that partial melting of a primitive lunar interior and buffering of these melts by ultramagnesian early magma ocean cumulates provides a more reasonable pathway to form magnesian troctolites. Alkali anorthosites and norites formed by crystallization of a parent magma with major element compositions similar to KREEP basalt 15386. If the parent magma of the alkali suite and evolved rocks is related to the magnesian suite, then that magma must have evolved through combined assimilation-fractional crystallization processes to form the alkali suite cumulates.

Euxinia prior to end-Permian main extinction at Xiaojiaba section, Sichuan Province, South China

NASA Astrophysics Data System (ADS)

Wei, H.; Algeo, T. J.; Chen, D.; Yu, H.

2013-12-01

Redox conditions in the global ocean prior to, during, and following the end-Permian mass extinction at 252.28 Ma remain contentious. Previous studies in western Australia, South China, and East Greenland have shown that photic-zone euxinia was present at least intermittently from the early Changhsingian through the Dienerian1-3. Here we report a study of organic carbon isotopes, pyrite sulfur isotopes, TOC, pyritic sulfur content, REE, and major and trace elements from the Upper Permian Xiaojiaba section in the Chaotian district of Guangyuan City, Sichuan Province, China. During the Permian-Triassic transition, this section was located on the northwestern margin of the South China Block, facing the Paleo-Tethys Ocean. Our results indicate that suboxic conditions prevailed during the Wuchiapingian and suboxic to anoxic conditions with several pulses of euxinia during the Changhsingian. δ13Corg values are mostly -28‰ to -26‰ but show three positive excursions (to -22‰) prior to the end-Permian mass extinction horizon. These positive excursions are associated with higher Spy concentrations (to ~1%). δ34Spy values are variable (from -41‰ to +5‰) but show a sharp negative excursion in the late Changhsingian (to -43.4‰) that coincided with the most positive δ13Corg values. This horizon is also associated with increases in Eu/Eu*, Baxs, ∑REE, Si, and redox-sensitive metals such as V. These patterns reflect linkage of the C and S cycles during the latest Permian, possibly in response to redox controls. The observed positive excursions in δ13Corg may be due to organic inputs from green sulfur bacteria, which exhibit a smaller photosynthetic fractionation (-12.5‰4) than eukaryotic algae. The pronounced negative excursion of δ34Spy corresponds to a sulfate-sulfide S isotope fractionation of about -60‰, suggesting a large flux of syngenetic framboidal pyrite, which would be indicative of euxinic water-column conditions. We infer that the euxinia prior to the main extinction horizon may have been caused by oceanic oxygen-minimum zone expansion and upward movement of the chemocline5. The coupled increases in Eu/Eu* and Baxs may record hydrothermal influence, possibly accompanied by increased ocean acidity and high seawater temperatures. Collectively, our results document major changes in seawater chemistry during the Changhsingian prior to the main end-Permian crisis.

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.

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.

Post-Hercynian subvolcanic magmatism in the Serre Massif (Central-Southern Calabria, Italy)

NASA Astrophysics Data System (ADS)

Romano, V.; Cirrincione, R.; Fiannacca, P.; Mazzoleni, P.; Tranchina, A.

2009-04-01

In the Serre Massif (Central-Southern Calabria, Italy) dykes and subvolcanic bodies intrude diffusively both Hercynian metamorphic rocks and late-Hercynian granitoids. They range in composition from basaltic andesites to dacite-rhyodacites and can be ascribed to the extensive magmatic activity that affects the entire Hercynian orogenic belt in late Paleozoic - early Mesozoic time. The geodinamic framework of the magmatic activity is still matter of debate, nevertheless most authors agree in correlating magmatism both to the late-orogenic collapse of the Hercynian belt and to the lithosphere thinning responsible for the subsequent continental rifting. In this work, we propose a petrogenetic model for acidic to basic hypabissal bodies from southern Calabria in order to define the nature of sources, discriminate magmatic processes and supply a contribution in the geodynamic reconstruction of the Late Palaeozoic in the Calabria-Peloritani Orogen. In relation to their geochemical affinity, studied dykes have been divided in two groups: a medium- to high-K calc-alkaline and a tholeiitic one. Dykes belonging to the former group, andesitic and dacitic-rhyodacitic in composition, show typical features of subduction-related magmatism, such as LILE and LREE enrichments, depletions in HFSE, peaks in Rb, Th and Ce, accentuated troughs in Ba, Nb-Ta, P and Ti (White and Dupré, 1986; McCulloch and Gamble, 1991), contrasting with the late Hercynian collisional context. On the other side, features typical of intra-plate magmatic activity, such as a moderate enrichment in Ta, Nb, Ce, P, Zr, Hf and Sm relative to MORB composition are also present in studied rocks (Shimizu & Arculus, 1975; Pearce, 1982). REE-patterns are strongly to weakly fractionated for the andesitic rocks (Lan/Ybn = 10.03-13.98) and the dacitic-rhyodacitic ones (Lan/Ybn = 6.00 to 2.82), respectively. The latter rocks exhibit a very slight negative Eu anomaly, whereas no Eu anomaly is recognizable in the andesite patterns. For the andesite rocks an origin by partial melting of an enriched lithospheric mantle source in a post-collisional context is proposed. For dacitic-rhyodacitic dykes a strong involvement of crustal material is suggested by geochemical features such as Nb-Ta trough, Th enrichment, low Nb/La rate (0.37 avg value) and high Th/La rate (0.68 avg value) (Taylor & McLennan, 1985). Tholeiitic dykes include basaltic andesites with geochemical characteristics (REE and incompatible elements) very similar to those of continental tholeiites. Nb and Ti anomalies, less marked of those observed in calc-alkaline dykes, also occur in the tholeiitic ones, as well as the enrichment in LIL elements. Besides, with respect the calc-alkaline ones, tholeiitic types are slightly more HFSE-enriched. REE patterns are sub-parallel and slightly fractionated (Lan/Ybn = 2.62 and 2.65), Eu negative anomaly is strongly pronounced. These geochemical evidences are explained invoking a derivation from an enriched mantle source, possibly in connection with early stages of continental rifting processes. Crustal contamination or magma mixing processes probably occurred during magma ascent, as suggested by petrographic evidences ("quartz ocelli" and xenocrysts of plagioclase). Indeed, even by comparing N-MORB - normalized patterns of tholeiitic dykes with E-MORB (Sun, 1980) and upper continental crust (Taylor and McLennan, 1981) compositions, a derivation from an E-MORB source type and interaction with continental crust both appear as processes strongly involved in the genesis of the studied rocks. REFERENCES: • McCulloch M.T. and Gamble J.A. (1991) - Earth Plan. Sci. Lett., 102, 358-374. • Pearce J. A. (1982) - Ed. Thorpe R. S., 525-548. John Wiley & Sons, New York. • Shimizu N. and Arculus R. J. (1975) - Contrib. Mineral. Petrol., 50, 231-240. • Sun S. S. (1980) - Phil. Trans. R. Soc., A297, 409-445. • Taylor S. R. and McLennan S. M. (1981) - Phil. Trans. R. Soc., A301, 381-399. • Taylor S. R. and McLennan S. M. (1985) - Oxford: Blackwell Scientific, 312 pp. • White W.M. and Dupré B. (1986) - J. Geophys. Res., 91, 5927-5941.

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.

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

Trace Element Characteristics of the New Shergottite LEW88516

NASA Astrophysics Data System (ADS)

Wadhwa, M.; Crozaz, G.

1992-07-01

LEW88516, a meteorite collected in Antarctica, has recently been identified as a shergottite (Mason and Satterwhite, 1991). The shergottites belong to a group of unique achondritic meteorites, the SNCs, for which Mars has been suggested as the parent body. From preliminary petrologic and geochemical studies, it appears that LEW88516 is closely related to the shergottite ALHA77005. Like ALHA77005, LEW88516 is composed of two distinct lithologies; one consists of large (mm-sized) pyroxenes poikilitically enclosing olivine crystals, and the other is represented by interstitial areas that contain small pyroxenes, olivine, maskelynite, whitlockite, and opaques (Lindstrom et al., 1992). Besides mineralogy and texture, whole rock chemical characteristics of these two shergottites also appear to be strikingly similar (Lindstrom et al., 1992; Boynton et al., 1992). We measured REE and other selected trace elements in individual mineral phases present in LEW88516, and compared the results with similar data obtained for ALHA77005 by Lundberg et al. (1990). Analyses were made on a thin section of LEW88516 with an ion microprobe; trace elements concentrations were measured in poikilitic and interstitial pyroxenes (augites and pigeonites), maskelynite, whitlockite, and glass. The total REE inventory of LEW88516 is dominated by whitlockite, although this mineral, as in ALHA77005, is present in only small modal abundance. Maskelynite in LEW88516 is characterized by a positive Eu anomaly that is approximately twice as large as that present in the maskelynite in ALHA77005, although the rest of the REE are present in lower abundances. The homogeneous, crystallite-free glass in LEW88516 is slightly enriched relative to LEW88516 bulk rock REE abundances, and has a REE pattern that is parallel to the ALHA77005 whole rock REE pattern. Pyroxenes in LEW88516 are zoned in their trace element concentrations, as are the pyroxenes in ALHA77005. Elemental abundances (e.g., REE, Y, Ti, Zr, Cr, V) for the two meteorites follow the same trends. The compositional range of the pyroxenes in LEW88516, however, appears to be smaller than that for pyroxenes in ALHA77005. The data confirm that indeed LEW88516 and ALHA77005 are petrogenetically related. As discussed in Lundberg et al. (1990) for ALHA77005, the intercumulus melt in LEW88516, once trapped in the cumulus pile, crystallized as a closed system. The question as to whether the two meteorites are paired or not cannot be resolved until the terrestrial and cosmic ray exposure ages of LEW88516 are determined. The differences in the trace element compositional ranges of the pyroxenes, as well as in the REE abundances in the other minerals (particularly maskelynite) in LEW88516 and ALHA77005 could simply be an artifact of sampling during analysis (particularly in the case of the pyroxenes) and/or heterogeneity within a sample, and therefore do not preclude that the two meteorites are paired. On the other hand, it is possible that the two meteorites represent distinct falls. In either case, it is evident that they were generated by the same/similar igneous processes on their parent body. References: Boynton W.V., Hill D.H., and Kring D.A. (1992) Lunar Planet. Sci. (abstract) 23, 147-148. Lindstrom M.M., Mittlefehldt D.W., Treiman A.H., Wentworth S.J., Gooding J.L., Monis R.V., Keller L.P., and McKay G. (1992) Lunar Planet. Sci. (abstract) 23, 783-784. Lundberg L.L., Crozaz G., and McSween H.Y., Jr. (1990) Geochim. Cosmochim. Acta. 54, 2535-2547. Mason B. and Satterwhite C. (1991) Antarctic Meteorite Newsletter 14:2, 19.