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.

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.

Phytoextraction of rare earth elements in herbaceous plant species growing close to roads.

PubMed

Mikołajczak, Patrycja; Borowiak, Klaudia; Niedzielski, Przemysław

2017-06-01

The aim of study was to determine the phytoextraction of rare earth elements (REEs) to roots, stems and leaves of five herbaceous plant species (Achillea millefolium L., Artemisia vulgaris L., Papaver rhoeas L., Taraxacum officinale AND Tripleurospermum inodorum), growing in four areas located in close proximity to a road with varied traffic intensity. Additionally, the relationship between road traffic intensity, REE concentration in soil and the content of these elements in plant organs was estimated. A. vulgaris and P. rhoeas were able to effectively transport REEs in their leaves, independently of area collection. The highest content of REEs was observed in P. rhoeas leaves and T. inodorum roots. Generally, HREEs were accumulated in P. rhoeas roots and leaves and also in the stems of T. inodorum and T. officinale, whereas LREEs were accumulated in T. inodorum roots and T. officinale stems. It is worth underlining that there was a clear relationship between road traffic intensity and REE, HREE and LREE concentration in soil. No positive correlation was found between the concentration of these elements in soil and their content in plants, with the exception of T. officinale. An effective transport of REEs from the root system to leaves was observed, what points to the possible ability of some of the tested plant species to remove REEs from soils near roads.

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.

The origin of secondary heavy rare earth element enrichment in carbonatites: Constraints from the evolution of the Huanglongpu district, China

NASA Astrophysics Data System (ADS)

Smith, M.; Kynicky, J.; Xu, Cheng; Song, Wenlei; Spratt, J.; Jeffries, T.; Brtnicky, M.; Kopriva, A.; Cangelosi, D.

2018-05-01

The silico‑carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnäsite and parisite where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32- in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl-) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.

High-Mg subduction-related Tertiary basalts in Sardinia, Italy

NASA Astrophysics Data System (ADS)

Morra, V.; Secchi, F. A. G.; Melluso, L.; Franciosi, L.

1997-03-01

The Oligo-Miocene volcanics (32-15 Ma), which occur in the Oligo-Miocene Sardinian Rift, were interpreted in the literature as an intracontinental volcanic arc built upon continental crust about 30 km thick. They are characterized by a close field association of dominantly andesites and acid ignimbrites, with subordinate basalts. In this paper we deal with the origin and evolution of recently discovered high-magnesia basalts aged ca. 18 Ma occurring in the Montresta area, northern Sardinia, relevant to the petrogenesis of the Cenozoic volcanics of Sardinia. The igneous rocks of the Montresta area form a tholeiitic, subduction-related suite. Major-element variation from the high-magnesia basalts (HMB) to high-alumina basalts (HAB) are consistent with crystal/liquid fractionation dominated by olivine and clinopyroxene. Proportions of plagioclase and titanomagnetite increase from HAB to andesites. Initial {87Sr }/{86Sr } ratios increase with differentiation from 0.70398 for the HMB to 0.70592 for the andesites. This suggests concomitant crustal contamination. The geochemical characteristics of the high-magnesia basalts are typical of subduction-related magmas, with negative Nb, Zr and Ti spikes in mantle-normalized diagrams. It is proposed that these high-magnesia basalts were produced by partial melting of a mantle source characterized by large-ion lithophile elements (LILE) enrichment related principally to dehydration of subducted oceanic crust. Chondrite-normalized rare earth elements (REE) patterns indicate that the lavas are somewhat enriched in light rare earth elements (LREE), with flat heavy rare earth elements (HREE) patterns. This evidence is consistent with a spinel-bearing mantle source. The sub-parallel chondrite-normalized patterns show enrichment with differentiation, with a greater increase of LREE than HREE. The occurrence of high-magnesia basalts at 18 Ma in Sardinia appears to be correlated with and favoured by pronounced extensional tectonics at that time.

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.

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.

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

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

Fleet, M.E.; Pan, Yuanming

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

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

USGS Publications Warehouse

Murray, R.; Buchholtz ten Brink, Marilyn R.; Brumsack, Hans-Juergen; Gerlach, David C.; Russ III, G. Price

1991-01-01

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* correlated 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 L(ln/Ybnsuggests 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.

A snapshot of mantle metasomatism: Trace element analysis of coexisting fluid (LA-ICP-MS) and silicate (SIMS) inclusions in fibrous diamonds

NASA Astrophysics Data System (ADS)

Tomlinson, E. L.; Müller, W.; EIMF

2009-03-01

We have determined the trace element compositions of coexisting fluid (carbonate-K-chloride-H 2O) and single-phase mineral inclusions in peridotitic (Cr-diopside) and eclogitic (omphacite, garnet) inclusions in fibrous diamonds from the Panda kimberlite (Slave craton, Canada). These diamonds provide a unique insight into the nature of the metasomatic agent, the metasomatised minerals and the pre-metasomatic protolith. The fluid component is strongly enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE). Co-existing peridotitic minerals record a melt extraction event (high Cr and Ni) in the protolith prior to the influx of the trapped metasomatic fluid. The silicate minerals are also strongly enriched in LREE. Calculated partition coefficients agree with experimentally determined values in the literature, despite the complex composition of the natural fluid. This indicates that the minerals have re-equilibrated with the metasomatic fluid. The trace element compositions of the mineral inclusions are comparable to many equivalent phases in monocrystalline diamonds. This suggests that the metasomatic fluid and the process recorded in these samples may also be responsible for the growth of some types of monocrystalline diamonds.

Levels of rare earth elements, heavy metals and uranium in a population living in Baiyun Obo, Inner Mongolia, China: a pilot study.

PubMed

Hao, Zhe; Li, Yonghua; Li, Hairong; Wei, Binggan; Liao, Xiaoyong; Liang, Tao; Yu, Jiangping

2015-06-01

The Baiyun Obo deposit is the world's largest rare earth elements (REE) deposit. We aimed to investigate levels of REE, heavy metals (HMs) and uranium (U) based on morning urine samples in a population in Baiyun Obo and to assess the possible influence of rare earth mining processes on human exposure. In the mining area, elevated levels were found for the sum of the concentrations of light REE (LREE) and heavy REE (HREE) with mean values at 3.453 and 1.151 μg g(-1) creatinine, which were significantly higher than those in the control area. Concentrations of HMs and U in the population increased concomitantly with increasing REE levels. The results revealed that besides REE, HMs and U were produced with REE exploitation. Gender, age, educational level, alcohol and smoking habit were major factors contributing to inter-individual variation. Males were more exposed to these metals than females. Concentrations in people in the senior age group and those with only primary education were low. Drinking and smoking were associated with the levels of LREE, Cr, Cu, Cd and Pb in morning urine. Hence this study provides basic and useful information when addressing public and environmental health challenges in the areas where REE are mined and processed. Copyright © 2015 Elsevier Ltd. All rights reserved.

LREE Enrichments of Altered Alkaline Pyroclastics at Kuyubasi Region Burdur, SW Turkey

NASA Astrophysics Data System (ADS)

Budakoglu, Murat; Tugcan Unluer, Ali; Doner, Zeynep; Kocaturk, Huseyin; Sezai Kırıkoǧlu, M.

2017-04-01

ABSTRACT In the Kuyubasi region of Burdur, Bucak district, Inner Isparta Apex, SW Anatolia, Turkey, the investigation carried out for the potential in-situ enrichments of REE in highly altered alkaline tuffs originated from Golcuk volcano. This volcano is the most significant product of the widely known post collisional, Afyon-Isparta potassic-ultrapotassic volcanic province in southwestern Turkey. Partial melting of oceanic crust and subcontinental lithospheric mantle resulted in the formation of florocarbonates and pyrochlore group minerals which are responsible for the LREE enrichment in Golcuk volcanics. These extrusive rocks are mainly trachyandesites, augite-trachytes, porphyry trachytes and tephriphonolite dikes which are formed in several eruptive cycles. Pyroclastics from the last eruptions can be encountered in various locations beneath the Isparta apex. The pyroclastics in study area described as mafic crystal metatuffs which predominantly consist of calcic-plagioclase with clinopyroxene, K-feldspar, and quartz set in a hyalo-microcrystalline tuffaceous matrix of microcrystalline aggregates of kaolinized and sericitized feldspar, biotite, chlorite, quartz, and dusty iron oxide. The results indicate high values for the LREE elements such as La (251-369 ppm), Ce (412-660 ppm), Sc (45-48 ppm). The average ΣREE content of samples are 1012 ppm. These results are compatible with the samples from Golcuk Caldera which is located 30 km north of study area in terms of LREE contents (La and Ce values are 400-500 ppm and 500-600 ppm respectively). Key words: Rare earth elements (REE), Pyroclastic occurrences, Bucak region, Burdur, Southwest Turkey *This research was supported by The Scientific and Technological Research Council of Turkey (TUBITAK) project. Principal Investigator (PI) of this ongoing TUBITAK, CAYDAG-114Y646 project is Prof.Dr. M. Sezai KIRIKOGLU.

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

PubMed

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

2018-04-15

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

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.

Rare earth, major and trace element composition of Leg 127 sediments

USGS Publications Warehouse

Murray, R.W.; Buchholtz ten Brink, Marilyn R.; Brumsack, Hans-Juergen; Gerlach, David C.; Russ III, G. Price

1992-01-01

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (IREE) 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 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper 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. XREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, ΣRE E 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. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper Oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La/Y^ suggests that other processes 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. 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.

Geochemical distinctions between igneous carbonate, calcite cements, and limestone xenoliths (Polino carbonatite, Italy): spatially resolved LAICPMS analyses

NASA Astrophysics Data System (ADS)

Rosatelli, G.; Wall, F.; Stoppa, F.; Brilli, M.

2010-11-01

Petrography-controlled laser ablation inductively coupled plasma mass spectrometry (LAICPMS) analyses of carbonate in fresh shallow level sub-volcanic Polino monticellite calcio-carbonatite tuffisite have been performed to assess the geochemical differences between fresh igneous, epigenetic carbonates and sedimentary accidental fragments. Igneous calcite has consistently high LREE/HREE ratios (La/Yb N , 15-130) due to high LREE (ΣLREE, 425-1,269 ppm). Secondary calcite cements are characterized by progressively lower and more variable trace element contents, with lower LREE/HREE ratios. A distinguishing geochemical feature is progressively increasing negative Ce anomalies observed through coarse secondary calcite that can be related to the surface environment processes. The limestone accidental fragments in the tuffisite have trace element contents almost two orders of magnitude lower than igneous carbonate and low LREE (ΣLREE < 9.5 ppm) with low LREE/HREE fractionation (La/Yb N ratios < 18). The stable isotope composition of different carbonate types is consistent with their formation in different environments. The tuffisitization processes during diatreme formation under high CO2-OH fugacity conditions may account for the differences noted in the igneous carbonates.

Highly-sensitive open-cell LA-ICPMS approaches for the quantification of rare earth elements in natural carbonates at parts-per-billion levels.

PubMed

Wu, Chung-Che; Burger, Marcel; Günther, Detlef; Shen, Chuan-Chou; Hattendorf, Bodo

2018-08-14

This work presents a high-sensitivity approach to quantify ultra-trace concentrations of rare earth elements (REEs) in speleothem carbonates using open-cell laser ablation-sector field-inductively coupled plasma mass spectrometry (open-cell LA-SF-ICPMS). Specifically, open-cell LA in combination with a gas exchange device enabled sampling of large-scale carbonate specimens in an ambient environment. The use of a "jet" vacuum interface and the addition of small amounts of N 2 gas allowed for a 20-40 fold sensitivity enhancement compared to the conventional interface configuration. Mass load effects, quantification capabilities and detection power were investigated in analyses of reference materials using various combinations of spot sizes and laser repetition rates. From a 160 μm diameter circular laser spot and 10 Hz ablation frequency, limits of detection were in the low or sub-ng g -1 range for REEs. Little dependence of Ca normalized sensitivity factors on the amount of material introduced into the plasma was observed. Relative deviations of quantified concentrations from USGS MACS-3 preferred values were smaller than 12%. The analytical approach enabled the determination of REE concentration profiles at the single digit ng g -1 level. Application to a 15-cm piece stalagmite collected from East Timor revealed at least two abrupt elevations in light rare earth elements (LREEs) within a scanning distance of 8 mm. These anomaly regions extended over a distance of ≈200 μm and showed LREE abundances elevated by at least one order of magnitude. This high-resolution open-cell LA-SF-ICPMS method has the potential to be applied in micro-domain analyses of other natural carbonates, such as travertine, tufa, and flowstones. This is promising for a better understanding of earth and environmental sciences. Copyright © 2018 Elsevier B.V. All rights reserved.

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 constraints on the origin of Doushantuo cap carbonates in the Yangtze Gorges area, South China

NASA Astrophysics Data System (ADS)

Wang, Qinxian; Lin, Zhijia; Chen, Duofu

2014-05-01

Marinoan cap carbonates have been suggested to be primarily deposited in glacial meltwater and upwelled seawater. However, elemental geochemistry evidence for this depositional model is lacking. Here, we report high-spatial-resolution measurements of major, trace and rare earth elements of the Doushantuo cap carbonates from the Jiulongwan section in the Yangtze Gorges area, South China. Our results show that: 1) the basal cap carbonates display slight MREE enrichment, weak positive La anomalies, near-chondritic Y/Ho ratios, and slight negative Ce anomalies; 2) the lower-middle cap carbonates show slight LREE depletion or MREE enrichment, weak positive La and Eu anomalies, supra-chondritic Y/Ho ratios, and slight negative Ce anomalies; 3) the upper-middle cap carbonates have consistent enrichment of P, Fe, and trace metals, slight LREE depletion, and weak positive Ce, La and Eu anomalies; and 4) the upper cap carbonates exhibit LREE enrichment, weak positive La and Eu anomalies, supra-chondritic Y/Ho ratios, and mild negative Ce anomalies. These findings indicate that the Doushantuo cap carbonates did not precipitate from normal contemporaneous seawater, rather, the basal cap carbonates were deposited in oxygenated, relatively pure deglacial meltwater; the lower-middle cap carbonates in oxygenated brackish water; the upper-middle cap carbonates in upwelled anoxic brine water; and the upper cap carbonates in oxygenated brackish water. Our depositional model is consistent with the proposed sequence of events after the meltdown of Marinoan glaciation by Shields (2005).

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

USGS Publications Warehouse

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

2005-01-01

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

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

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.

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.

Strategic Materials in the Automobile: A Comprehensive Assessment of Strategic and Minor Metals Use in Passenger Cars and Light Trucks.

PubMed

Field, Frank R; Wallington, Timothy J; Everson, Mark; Kirchain, Randolph E

2017-12-19

A comprehensive component-level assessment of several strategic and minor metals (SaMMs), including copper, manganese, magnesium, nickel, tin, niobium, light rare earth elements (LREEs; lanthanum, cerium, praseodymium, neodymium, promethium, and samarium), cobalt, silver, tungsten, heavy rare earth elements (yttrium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium), and gold, use in the 2013 model year Ford Fiesta, Focus, Fusion, and F-150 is presented. Representative material contents in cars and light-duty trucks are estimated using comprehensive, component-level data reported by suppliers. Statistical methods are used to accommodate possible errors within the database and provide estimate bounds. Results indicate that there is a high degree of variability in SaMM use and that SaMMs are concentrated in electrical, drivetrain, and suspension subsystems. Results suggest that trucks contain greater amounts of aluminum, nickel, niobium, and silver and significantly greater amounts of magnesium, manganese, gold, and LREEs. We find tin and tungsten use in automobiles to be 3-5 times higher than reported by previous studies which have focused on automotive electronics. Automotive use of strategic and minor metals is substantial, with 2013 vehicle production in the United States, Canada, EU15, and Japan alone accounting for approximately 20% of global production of Mg and Ta and approximately 5% of Al, Cu, and Sn. The data and analysis provide researchers, recyclers, and decision-makers additional insight into the vehicle content of strategic and minor metals of current interest.

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).

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.

The earth's oldest known crust - A geochronological and geochemical study of 3900-4200 Ma old detrital zircons from Mt. Narryer and Jack Hills, Western Australia

NASA Astrophysics Data System (ADS)

Maas, Roland; Kinny, Peter D.; Williams, Ian S.; Froude, Derek O.; Compston, William

1992-03-01

Trace element characteristics were analyzed and inclusions were identified within a suite of pre-3.9 Ga detritral zircons from western Australia representing the earth's oldest-known minerals. A diversity of trace-element compositions was found, particularly in the REE compositions of the old Mt. Narryer zircons, implying a variety of source-rock compositions and hence, the presence of a differentiated crust in the earth 4.15-4.20 Ga ago. Comparisons drawn with data obtained from younger detrital zircons occurring within the same deposits indicate nothing unique about the chemical compositions of the old grains. A number of interelement covariations were observed among the analyzed grains which were independent of age and isotopic characteristics, most notably that occurring between Lu and Hf. A general positive correlation between total LREE and the U + Th contents is also apparent. The findings indicate an origin in felsic igneous rocks, which has implications for early-Archaean crustal evolution.

A Paleoarchean coastal hydrothermal field inhabited by diverse microbial communities: the Strelley Pool Formation, Pilbara Craton, Western Australia.

PubMed

Sugitani, K; Mimura, K; Takeuchi, M; Yamaguchi, T; Suzuki, K; Senda, R; Asahara, Y; Wallis, S; Van Kranendonk, M J

2015-11-01

The 3.4-Ga Strelley Pool Formation (SPF) at the informally named 'Waterfall Locality' in the Goldsworthy greenstone belt of the Pilbara Craton, Western Australia, provides deeper insights into ancient, shallow subaqueous to possibly subaerial ecosystems. Outcrops at this locality contain a thin (<3 m) unit of carbonaceous and non-carbonaceous cherts and silicified sandstones that were deposited in a shallow-water coastal environment, with hydrothermal activities, consistent with the previous studies. Carbonaceous, sulfide-rich massive black cherts with coniform structures up to 3 cm high are characterized by diverse rare earth elements (REE) signatures including enrichment of light [light rare earth elements (LREE)] or middle rare earth elements and by enrichment of heavy metals represented by Zn. The massive black cherts were likely deposited by mixing of hydrothermal and non-hydrothermal fluids. Coniform structures in the cherts are characterized by diffuse laminae composed of sulfide particles, suggesting that unlike stromatolites, they were formed dominantly through physico-chemical processes related to hydrothermal activity. The cherts yield microfossils identical to previously described carbonaceous films, small and large spheres, and lenticular microfossils. In addition, new morphological types such as clusters composed of large carbonaceous spheroids (20-40 μm across each) with fluffy or foam-like envelope are identified. Finely laminated carbonaceous cherts are devoid of heavy metals and characterized by the enrichment of LREE. This chert locally contains conical to domal structures characterized by truncation of laminae and trapping of detrital grains and is interpreted as siliceous stromatolite formed by very early or contemporaneous silicification of biomats with the contribution of silica-rich hydrothermal fluids. Biological affinities of described microfossils and microbes constructing siliceous stromatolites are under investigation. However, this study emphasizes how diverse the microbial community in Paleoarchean coastal hydrothermal environment was. We propose the diversity is at least partially due to the availability of various energy sources in this depositional environment including reducing chemicals and sunlight. © 2015 John Wiley & Sons Ltd.

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

PubMed

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

2018-01-01

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

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.

Origin of the Permian-Triassic komatiites, northwestern Vietnam

NASA Astrophysics Data System (ADS)

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

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

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.

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.

Correlated microanalysis of zircon: Trace element, δ 18O, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

NASA Astrophysics Data System (ADS)

Cavosie, Aaron J.; Valley, John W.; Wilde, Simon A.; E. I. M. F.

2006-11-01

The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ˜20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ 18O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ 18O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La N > 1 and Pr N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present radiation damage. The enrichment is not attributed to hydrothermal alteration, however, as oxygen isotope ratios in Type 2 domains overlap with magmatic values of Type 1 domains, and do not appear re-set as might be expected from dissolution or ion-exchange processes operating at variable temperatures. Thus, REE compositions in Type 2 domains where mineral inclusions are not suspected are best interpreted to result from localized enrichment of LREE in areas with past or present radiation damage, and with a very low fluid/rock ratio. Correlated in situ analyses allow magmatic compositions in these complex zircons to be distinguished from the effects of secondary processes. These results are additional evidence for preservation of magmatic compositions in Jack Hills zircons, and demonstrate the benefits of detailed imaging in studies of complicated detrital zircons of unknown origin. The data reported here support previous interpretations that the majority of >3900 Ma zircons from the Jack Hills have an origin in evolved granitic melts, and are evidence for the existence of continental crust very early in Earth's history.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Rare earth elements 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.

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).

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

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

PubMed

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

2016-11-18

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

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.

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.

Ultramafic xenoliths from the Bearpaw Mountains, Montana, USA: Evidence for multiple metasomatic events in the lithospheric mantle beneath the Wyoming craton

USGS Publications Warehouse

Downes, H.; Macdonald, R.; Upton, B.G.J.; Cox, K.G.; Bodinier, J.-L.; Mason, P.R.D.; James, D.; Hill, P.G.; Hearn, B.C.

2004-01-01

Ultramafic xenoliths in Eocene minettes of the Bearpaw Mountains volcanic field (Montana, USA), derived from the lower lithosphere of the Wyoming craton, can be divided based on textural criteria into tectonite and cumulate groups. The tectonites consist of strongly depleted spinel lherzolites, harzbugites and dunites. Although their mineralogical compositions are generally similar to those of spinel peridotites in off-craton settings, some contain pyroxenes and spinels that have unusually low Al2O3 contents more akin to those found in cratonic spinel peridotites. Furthermore, the tectonite peridotites have whole-rock major element compositions that tend to be significantly more depleted than non-cratonic mantle spinel peridotites (high MgO, low CaO, Al2O3 and TiO2) and resemble those of cratonic mantle. These compositions could have been generated by up to 30% partial melting of an undepleted mantle source. Petrographic evidence suggests that the mantle beneath the Wyoming craton was re-enriched in three ways: (1) by silicate melts that formed mica websterite and clinopyroxenite veins; (2) by growth of phlogopite from K-rich hydrous fluids; (3) by interaction with aqueous fluids to form orthopyroxene porphyroblasts and orthopyroxenite veins. In contrast to their depleted major element compositions, the tectonite peridotites are mostly light rare earth element (LREE)-enriched and show enrichment in fluid-mobile elements such as Cs, Rb, U and Pb on mantle-normalized diagrams. Lack of enrichment in high field strength elements (HFSE; e.g. Nb, Ta, Zr and Hf) suggests that the tectonite peridotites have been metasomatized by a subduction-related fluid. Clinopyroxenes from the tectonite peridotites have distinct U-shaped REE patterns with strong LREE enrichment. They have 143Nd/144Nd values that range from 0??5121 (close to the host minette values) to 0??5107, similar to those of xenoliths from the nearby Highwood Mountains. Foliated mica websterites also have low 143Nd/144Nd values (0??5113) and extremely high 87Sr/86Sr ratios in their constituent phlogopite, indicating an ancient (probably mid-Proterozoic) enrichment. This enriched mantle lithosphere later contributed to the formation of the high-K Eocene host magmas. The cumulate group ranges from clinopyroxene-rich mica peridotites (including abundant mica wehrlites) to mica clinopyroxenites. Most contain >30% phlogopite. Their mineral compositions are similar to those of phenocrysts in the host minettes. Their whole-rock compositions are generally poorer in MgO but richer in incompatible trace elements than those of the tectonite peridotites. Whole-rock trace element patterns are enriched in large ion lithophile elements (LILE; Rb, Cs, U and Pb) and depleted in HFSE (Nb, Ta Zr and Hf as in the host minettes, and their Sr-Nd isotopic compositions are also identical to those of the minettes. Their clinopyroxenes are LREE-enriched and formed in equilibrium with a LREE-enriched melt closely resembling the minettes. The cumulates therefore represent a much younger magmatic event, related to crystallization at mantle depths of minette magmas in Eocene times, that caused further metasomatic enrichment of the lithosphere. ?? Oxford University Press 2004; 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

Geochemical constraints on crustal anatexis: a case study from the Pan-African Damara granitoids of Namibia

NASA Astrophysics Data System (ADS)

McDermott, F.; Harris, N. B. W.; Hawkesworth, C. J.

1996-05-01

Major and trace element models of recently published vapour-absent mica dehydration melting experiments are used to identify granitoids generated by muscovite and biotite dehydration melting, and to distinguish between plagioclase-limited and biotite-limited, biotite dehydration melting. In the case of granitoids from the Pan-African Damara mobile belt (Namibia), many of the leucogranites and Salem-type granitoids may be modelled by biotite dehydration melting. The low Rb/Sr granitoids (e.g. Donkerhuk Onanis, Salem Onanis, Donkerhuk Nomatsaus, Salem Goas) probably reflect feldspar-limited, biotite dehydration melting (a pelitic source) whereas the high Rb/Sr suites (e.g. Bloedkoppie leucogranite, Stinkbank leucogranite, Salem Swakopmund, Leucocratic Stink bank granite) reflect biotite-limited, biotite dehydration melting (a greywacke source). Alaskites from the Damara belt have major element compositions which are consistent with muscovite dehydration melting, and their positive Eu anomalies are linked to high K2O reflecting K-feldspar entrainment. Combined Zr and LREE (light rare earth element) solubility models indicate that insufficient time (probably less than 104 years) had elapsed between melt generation and melt extraction to ensure that the alaskite melts attained their equilibrium concentrations of Zr and the LREEs. In contrast, the leucogranites and Salem-type granites have attained their equilibrium inventories of these trace elements. Combined Fe2O3 and MgO contents in some samples from two granitoids (the Salem Goas and Donkerhuk Onanis intrusions) are higher than those readily attainable by biotite dehydration melting indicating either: (1) that they contain a contribution from melts generated by incipient garnet breakdown or; (2) that they contain small amounts of an entrained ferromagnesian phase.

Elemental and Sr-Nd isotopic geochemistry of the Uradzhongqi magmatic complex in western Inner Mongolia, China: A record of early Permian post-collisional magmatism

NASA Astrophysics Data System (ADS)

Qiao, Xueyuan; Li, Wenbo; Zhong, Richen; Hu, Chuansheng; Zhu, Feng; Li, Zhihua

2017-08-01

The magmatic complex in Uradzhongqi, Inner Mongolia, is located in the western segment of the northern margin of the North China Craton (NCC). The dominant components in the complex include syenogranite, monzogranite, granodiorite, diorite and gabbro. Mafic microgranular enclaves (MMEs) are common in syenogranite and granodiorite. Zircon U-Pb dating shows that the ages of these rocks range from 283 to 270 Ma, suggesting an early Permian emplacement. The syenogranite and monzogranite are peraluminous I-type granites, exhibiting conspicuous negative Eu anomaly, enrichment in large-ion lithophile elements (LILE) and light rare earth elements (LREE), depletion in high field strength elements (HFSE). The granodiorites, diorites and MMEs are metaluminous in composition, show high Al2O3, MgO and Fe2O3T contents and weak negative Eu anomaly, as well as LREE and LILE enrichment and HFSE depletion. The gabbros show weak positive Eu anomaly and slight REE differentiation. The Sr-Nd isotope compositions show that the source of mafic magma was depleted mantle (DM) with possible involvement of enriched mantle II (EM II), whereas the felsic magma was derived from the Archean lower crust. Petrographic observation and analytical results of mineralogy, geochronology, geochemistry and Sr-Nd isotopes indicate that the main petrogenesis of these magmatic rocks is the mixing of underplating mafic magma and felsic magma. Tectonically, the complex pluton was formed within a post-collisional regime, and the underplating in this area provides another piece of evidence for the vertical growth of the western segment of the northern margin of the NCC.

The trace element chemistry of CaS in enstatite chondrites and some implications regarding its origin

NASA Technical Reports Server (NTRS)

Larimer, John W.; Ganapathy, R.

1987-01-01

The trace element distribution in oldhamite (CaS) extracted from enstatite chondrites was determined by INAA. Prior to extraction, the petrologic setting of the grains was studied microscopically, and their minor element contents determined by microprobe analysis; samples that displayed a wide range of minor element contents were selected for detailed elementary analysis. Those samples of CaS suspected to be more primitive on the basis of their minor element and petrologic siting contain the entire inventory of the host meteorite's light REE (LREE) and Eu, plus 30-50 percent of the heavy-REE inventory. In less primitive samples, the LREE are less enriched although Eu remains highly concentrated. Several other elements, including lithophiles and chalcophiles, are most enriched in the most primitive CaS. It is suggested that oldhamite played a key role in the redistribution of these elements during the metamorphism and evolution of enstatite-rich material.

Age and geochemistry of host rocks of the Cobre Panama porphyry Cu-Au deposit, central Panama: Implications for the Paleogene evolution of the Panamanian magmatic arc

NASA Astrophysics Data System (ADS)

Baker, Michael J.; Hollings, Peter; Thompson, Jennifer A.; Thompson, Jay M.; Burge, Colin

2016-04-01

The Cobre Panama porphyry Cu-Au deposit, located in the Petaquilla district of central Panama, is hosted by a sequence of medium- to high-K calc-alkaline volcanic and sub-volcanic rocks. New crystallisation ages obtained from a granodiorite Petaquilla batholith and associated mineralised diorite to granodiorite porphyry stocks and dikes at Cobre Panama indicate that the batholith was emplaced as a multi-phase intrusion, over a period of 4 million years from 32.20 ± 0.76 Ma to 28.26 ± 0.61 Ma, while the porphyritic rocks were emplaced over a 2 million year period from 28.96 ± 0.62 Ma to 27.48 ± 0.68 Ma. Both the volcanic to sub-volcanic host rocks and intrusive rocks of the Cobre Panama deposit evolved via fractional crystallisation processes, as demonstrated by the major elements (e.g. Al2O3, Fe2O3, TiO2 and MgO) displaying negative trends with increasing SiO2. The Petaquilla intrusive rocks, including the diorite-granodiorite porphyries and granodiorite batholith, are geochemically evolved and appear to have formed from more hydrous magmas than the preceding host volcanic rocks, as evidenced by the presence of hornblende phenocrysts, higher degrees of large-ion lithophile element (LILE) and light rare earth element (LREE) enrichment and heavy rare earth element (HREE) depletion, and higher Sr/Y and La/Yb values. However, the degree of LREE enrichment, HREE depletion and La/Yb values are insufficient for the intrusive rocks to be considered as adakites. Collectively, the volcanic and intrusive rocks have LILE, REE and mobile trace element concentrations similar to enriched Miocene-age Cordilleran arc magmatism found throughout central and western Panama. Both the Petaquilla and Cordilleran arc magmatic suites are geochemically more evolved than the late Cretaceous to Eocene Chagres-Bayano arc magmas from northeastern Panama, as they display higher degrees of LILE and LREE enrichment. The geochemical similarities between the Petaquilla and Cordilleran arc magmas suggest that evolved calc-alkaline arc magmatism may extend to the late Eocene, at least 10 million years earlier than previously estimated. The crystallisation ages for intrusive rocks associated with mineralisation at Cobre Panama imply that the deposit formed in the early Oligocene, between a period of late Cretaceous to Eocene magmatism (ca. 66-42 Ma; Chagres-Bayano arc) and Cordilleran arc magmatism (22-7 Ma). Similarities in the timing of intrusive suite emplacement and the fingerprinting of magmatic fractionation processes between the Cobre Panama porphyry deposit and the Cerro Colorado porphyry deposit in western Panama (ca. 5.3 Ma) suggest that these features provide favourable geodynamic and geochemical prerequisites for the formation of porphyry deposits along the Panamanian magmatic arc during the Cenozoic.

Petrogenesis of ore-bearing porphyry in non-subduction setting: a case study of the Eocene potassic intrusions in the western Yangtze Block

NASA Astrophysics Data System (ADS)

Liu, Zheng; Liao, Shi-Yong; Zhou, Qing; Zhang, Xin

2018-05-01

In the western Yangtze Block, abundant Eocene ( 38-34 Ma) potassic adakite-like intrusions and associated porphyry copper deposits are exposed in non-subduction setting, including Machangjing, Beiya, Binchuan, Habo and Tongchang intrusions. All these ore-bearing porphyries share many geochemical characteristics of adakite such as depletion in heavy rare earth elements (HREEs), enrichment in Sr and Ba, absence of negative Eu anomalies, high SiO2, Al2O3, Sr/Y, La/Yb and low Y, Yb contents. They also exhibit affinities of potassic rocks, e.g., alkali-rich, high K2O/Na2O ratios and enrichment in light rare earth elements (LREEs) and large ion lithophile elements (LILEs). Their Sr-Nd isotopic ratios are similar to coeval shoshonitic lamprophyres. Geochemical data indicate that they were probably produced by partial melting of newly underplated potassic rocks sourced from a modified and enriched lithospheric mantle. These underplated rocks have elevated oxygen fugacity, water and copper contents, with high metallogenic potential. We propose that all the studied potassic rocks were emplaced in a post-collisional setting, associated with the local removal of lithospheric mantle.

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.

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.

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

PubMed Central

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

2016-01-01

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

Chemical and isotopic diversity in basalts dredged from the East Pacific Rise at 10°S, the fossil Galapagos Rise and the Nazca plate

USGS Publications Warehouse

Batiza, Rodey; Oestrike, Richard; Futa, Kiyoto

1982-01-01

The dredges from the East Pacific Rise at about 10°S recovered unusual transitional, light rare-earth element (LREE) enriched basalts which show a range of fractionation. On the basis of their chemical and isotopic abundances, it is unlikely that the lavas are related by a single simple process of magmatic differentiation. We suggest that the mantle source region of these basalts was chemically and isotopically heterogeneous. The chemistry of LREE-depleted tholeiitic basalt dredged from near the axis of the extinct Galapagos Rise indicates complex petrogenesis and differentiation. The presence of tholeiitic basalts here indicates that unlike the Guadalupe and Mathematician fossil ridges, the Galapagos Rise has not been the site of voluminous post-abandonment alkalic volcanism. Alkalic basalts of picritic bulk composition dredged from an elongate seamount near the Galapagos Rise do not represent liquid compositions. Instead, we suggest that these alkalic liquids contain added olivine and plagioclase xenocrysts. Although most of the samples analyzed are very fresh, a few have been altered. The latter exhibit characteristic chemical and isotopic effects of seawater alteration.

The cause and source of melting for the most recent volcanism in Tibet: A combined geochemical and geophysical perspective

NASA Astrophysics Data System (ADS)

Wei, Feixiang; Prytulak, Julie; Xu, Jiandong; Wei, Wei; Hammond, James O. S.; Zhao, Bo

2017-09-01

We investigate the youngest volcanic activity on the Tibetan Plateau by combining observations from petrologic, geochemical and seismic tomography studies. Recent (from 2.80 Ma to present) post-collisional potassium-rich lavas from the Ashikule Volcanic Basin (AVB) in northwestern Tibet are characterised by remarkably enriched light rare earth elements (LREE) relative to heavy rare earth elements (HREE), and enriched large ion lithophile element (LILE) relative to high field strength elements (HFSE). Strontium and neodymium isotopic compositions are surprisingly restricted, and show little evidence for mixing or crustal contamination, despite the thick crust upon which they are erupted. Geochemical characteristics indicate a homogeneous source, highly enriched in trace elements, which is most consistent with derivation from long-lived subcontinental lithospheric mantle (SCLM). P-wave anisotropy tomography documents a gap between the north-subducting Indian slab and south-subducting Tarim slab directly beneath the AVB. We propose that volcanism in northwestern Tibet is associated with the progressive closure of this gap, during which shear heating of the SCLM can generate localised melting, with deep-seated faults providing a mechanism for erupted lavas to escape large-scale crustal contamination and fractionation in magma reservoirs. Thus, shear heating may provide an explanation for the restricted range of radiogenic isotope compositions from a SCLM source that should be, by its nature, heterogeneous on a large scale.

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

Geochronology and geochemistry of the Niujuanzi ophiolitic mélange, Gansu Province, NW China: implications for tectonic evolution of the Beishan Orogenic Collage

NASA Astrophysics Data System (ADS)

Wang, Shengdong; Zhang, Kexin; Song, Bowen; Li, Shucai; Li, Ming; Zhou, Jie

2018-01-01

The Niujuanzi ophiolitic mélange (NOM), located in the Beishan Orogenic Collage, marks the termination between the Huaniushan arc and Mingshui-Hanshan Massifs. The NOM is mainly composed of gabbros, diabases, plagiogranites, basalts, and greywacke. Two gabbros have ages of 433.8 ± 3.1 and 354.0 ± 3.3 Ma, two plagiogranites have ages of 429.8 ± 2 and 448.7 ± 2.0 Ma, and a diabase has an age of 433.4 ± 3.2 Ma. The gabbros and diabases are calc-alkaline and tholeiitic, with high Al2O3, CaO, and TiO2 contents and low FeOT contents. The gabbros have high Mg# values (49-82), while the diabases have relatively low Mg# values (46-61). The plagiogranites are calc-alkaline and metaluminous, with high SiO2 and Na2O contents and low Al2O3 and K2O contents. The gabbros and diabases are enriched in large iron lithophile elements and slightly depleted in high field strength elements relative to N-MORB and their trace element characteristics are similar to E-MORB. With respect to rare earth element (REE), they have slightly enriched LREEs relative to HREEs. The majority of the plagiogranite trace elements approximate those of the volcanic arc granite. The plagiogranites have obviously enriched LREEs relative to HREEs, with a slightly to strongly negative Eu anomaly, which is similar to ORG but distinct from volcanic arc and within plate granite. The NOM was formed from the Ordovician to the Carboniferous, representing the expansion period of the Niujuanzi Ocean. The gabbros, diabases, and plagiogranites were formed in a mid-ocean ridge environment. The gabbros and diabases were generated by different degrees of partial melting of the mantle, and the plagiogranites derived from both the crystallization differentiation of basaltic magma and the partial melting of amphibolites in the crust.

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

Investigating Rare Earth Element Systematics in the Marcellus Shale

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

Geochemical associations between fluorite mineralization and A-type shoshonitic magmatism in the Keban-Elazig area, East Anatolia, Turkey

NASA Astrophysics Data System (ADS)

Akgul, Bunyamin

2015-11-01

Keban fluorite mineralizations are closely related Coniacian-Campanian subvolcanics intruded into Permian-Triassic Keban metamorphites; this event caused pyrometasomatic, porphyry, and vein-type Pb-Zn-Ag, Cu, W, and Pb-Zn-Ag-Mo-F mineralizations. These rocks are syenitic and syenomonzonitic in composition and have high Al2O3, alkali (Na2O + K2O), FeO*/MgO, Zr, Nb, Ta, Ga, Rb, Y, and rare earth element (REE) contents. They are A-type, metaluminous, and all fall in the shoshonitic series field in K2O vs SiO2 and Th/Yb vs Ta/Yb diagrams. The trace element contents and discriminations indicate that the Keban syenitoids were derived from lithospheric mantle metasomatized by oceanic-crust/sediment fluids. The metal and halogen contents of the Keban mineralizations apparently originated from metasomatized mantle and were transported to the crust by syenitoid magmas. Clear resemblances in chondrite-normalized REE patterns, LREE-HREE partionation, and high LILE contents of the magmatics and fluorites indicate a close kinship between the syenitoids and fluorite mineralizations. The HFSE contents of the fluorites are lower than those of the magmatics, as HFSEs are not soluble in aqueous fluids. The fluorites are products of early-phase alkali magmatism (LREE > HREE). The high contents of Rb, Sr, and Ba of fluorites are inherited from the magma, which also has very high contents of these elements. In Sc-∑REE, (La/Yb)n-(Eu/Eu*)n and (Tb/La)n-(Tb/Ca)n diagrams, Keban fluorites fall into distinct areas from Akcakisla-Akdagmadeni and Celikhan-Adiyaman fluorites.

Constraints on the magmatic evolution of the oceanic crust from plagiogranite intrusions in the Oman ophiolite

NASA Astrophysics Data System (ADS)

Haase, Karsten M.; Freund, Sarah; Beier, Christoph; Koepke, Jürgen; Erdmann, Martin; Hauff, Folkmar

2016-05-01

We present major and trace element as well as Sr, Nd, and Hf isotope data on a suite of 87 plutonic rock samples from 27 felsic crustal intrusions in seven blocks of the Oman ophiolite. The rock compositions of the sample suite including associated more mafic rocks range from 48 to 79 wt% SiO2, i.e. from gabbros to tonalites. The samples are grouped into a Ti-rich and relatively light rare earth element (LREE)-enriched P1 group [(Ce/Yb) N > 0.7] resembling the early V1 lavas, and a Ti-poor and LREE-depleted P2 group [(Ce/Yb) N < 0.7] resembling the late-stage V2 lavas. Based on the geochemical differences and in agreement with previous structural and petrographic models, we define phase 1 (P1) and phase 2 (P2) plutonic rocks. Felsic magmas in both groups formed by extensive fractional crystallization of olivine, clinopyroxene, plagioclase, apatite, and Ti-magnetite from mafic melts. The incompatible element compositions of P1 rocks overlap with those from mid-ocean ridges but have higher Ba/Nb and Th/Nb trending towards the P2 rock compositions and indicating an influence of a subducting slab. The P2 rocks formed from a more depleted mantle source but show a more pronounced slab signature. These rocks also occur in the southern blocks (with the exception of the Tayin block) of the Oman ophiolite implying that the entire ophiolite formed above a subducting slab. Initial Nd and Hf isotope compositions suggest an Indian-MORB-type mantle source for the Oman ophiolite magmas. Isotope compositions and high Th/Nb in some P2 rocks indicate mixing of a melt from subducted sediment into this mantle.

Arc-continent collision and the formation of continental crust: A new geochemical and isotopic record from the Ordovician Tyrone Igneous Complex, Ireland

USGS Publications Warehouse

Draut, Amy E.; Clift, Peter D.; Amato, Jeffrey M.; Blusztajn, Jerzy; Schouten, Hans

2009-01-01

Collisions between oceanic island-arc terranes and passive continental margins are thought to have been important in the formation of continental crust throughout much of Earth's history. Magmatic evolution during this stage of the plate-tectonic cycle is evident in several areas of the Ordovician Grampian-Taconic orogen, as we demonstrate in the first detailed geochemical study of the Tyrone Igneous Complex, Ireland. New U-Pb zircon dating yields ages of 493 2 Ma from a primitive mafic intrusion, indicating intra-oceanic subduction in Tremadoc time, and 475 10 Ma from a light rare earth element (LREE)-enriched tonalite intrusion that incorporated Laurentian continental material by early Arenig time (Early Ordovician, Stage 2) during arc-continent collision. Notably, LREE enrichment in volcanism and silicic intrusions of the Tyrone Igneous Complex exceeds that of average Dalradian (Laurentian) continental material that would have been thrust under the colliding forearc and potentially recycled into arc magmatism. This implies that crystal fractionation, in addition to magmatic mixing and assimilation, was important to the formation of new crust in the Grampian-Taconic orogeny. Because similar super-enrichment of orogenic melts occurred elsewhere in the Caledonides in the British Isles and Newfoundland, the addition of new, highly enriched melt to this accreted arc terrane was apparently widespread spatially and temporally. Such super-enrichment of magmatism, especially if accompanied by loss of corresponding lower crustal residues, supports the theory that arc-continent collision plays an important role in altering bulk crustal composition toward typical values for ancient continental crust. ?? 2009 Geological Society of London.

Geological and Petrological Characteristics of Oligocene Magmatic Rocks in The Biga Peninsula, NW Turkey

NASA Astrophysics Data System (ADS)

Erenoglu, Oya

2016-04-01

Oligocene magmatic activity in the Biga Peninsula (NW-Anatolia) produced widespread volcano-plutonic complexes. The study region, where in north of the Evciler village in the middle of Biga Peninsula includes these igneous assemblages. In this study, the petrographic and geochemical characteristics of igneous rocks in the region were investigated as well as the geological locations. The magmatic rocks are classified as 6 different units using their lithostratigraphical properties. The volcanism in the region starts with basaltic andesite lava including basalt dykes in the Lower Oligocene. In the Upper Oligocene, the evolved magma by crustal contamination produced commonly dacitic and andesitic lavas. The volcanism continued with andesitic lavas which had significant alterations in the region during this period. Evciler pluton including granite and granodiorite composition with shallow intrusive, was located with the related volcanism at the same time. The volcanic products, i.e. andesitic and trachydacitic lavas, was completed in the interval between Upper Oligocene and Lower Miocene. The post-collisional Oligocene sequence is associated with calc-alkaline composition and it has middle, high-K. Trace and rare earth elements (REE) diagrams show the enrichment in both large-ion lithophile elements (LILE) and light rare earth elements (LREE) with respect to the high field strength elements (HFSE), and a significant increment in heavy rare earth element consumption (HREE). The features of major, trace and rare earth elements of plutonic and volcanic rocks and the compositional variations of Oligocene volcanic group indicate increasing amounts of partial melting, crustal contamination and/or assimilation. The Oligocene post-collisional volcanism in Biga Peninsula points out the lithospheric mantle source enriched by subduction which controlled by slab break-off and lithospheric delamination. Acknowledgement. This study was supported by Canakkale Onsekiz Mart University Scientific Research Project Coordination Unit (Project no: FBA-2015-566) Keywords: Biga Peninsula, oligocene, post-collisional volcanism, petrology

Mineralogy and geochemistry of the Neo-Tethyan Orhaneli ultramafic suite, NW Turkey: Evidence for the initiation and evolution of magmatic processes in a developing crust-mantle boundary

NASA Astrophysics Data System (ADS)

Uysal, Ibrahim; Dokuz, Abdurrahman; Kapsiotis, Argyris; Kaliwoda, Melanie; Karsli, Orhan; Müller, Dirk; Aydin, Faruk

2017-04-01

The eastern Orhaneli ophiolitic massif, located in NW Anatolia, Turkey, forms part of the northwestern branch of the so-called Neotethys Ocean across the Izmir-Ankara-Erzincan Suture Zone. It is comprised mainly of a well preserved ultramafic suite, dominated by voluminous dunite exposures, accompanied by subsidiary harzburgite occurrences. The entire suite is commonly cross cut by a complex network of relatively undeformed clinopyroxenite veins. Clinopyroxene and spinel compositions in harzburgites are moderately depleted, whereas their whole-rock heavy rare earth element (HREE) abundances are consistent with harzburgite formation after approximately 19% dry melting of a spinel-bearing fertile mantle protolith at an extentional geotectonic regime. Nevertheless, textural data indicate that protracted dissolution of pyroxene coupled with precipitation of olivine happened during the transformation of harzburgites to replacive dunites, containing olivine with high Fo [Fo = 100×Mg/(Mg + Fe2+)] content (91.3-94.2) and spinel with elevated Cr# [100×Cr/(Cr + Al)] values (78-82). Such highly depleted mineralogical signatures imply that dunite for harzburgite substitution occurred under hydrous melting conditions in the mantle region above a subducted oceanic slab. Enrichments in incompatible elements (e.g., Cs, Rb and Sr) and the characteristic U-shaped chondrite-normalized rare earth elements (REE) profiles exhibited by replacive dunites along with the elevated TiO2 (0.20-0.36 wt.%) contents in their accessory spinels indicate that the reactive melt had an intermediate affinity between boninite and island arc tholeiite (IAT) regimes. The metasomatic reaction triggered an additional 8% melting of the harzburgite residue. The resultant melt fractionated (,almost in situ,) to crystallize cumulate dunites composed of olivine with relatively high Fo content (88.8-92.3), spinel with moderate Cr# values (62-74), as well as clinopyroxene with a depleted composition (low TiO2 and Al2O3 contents and high Mg#) identical of clinopyroxene in arc-derived peridotites. These magmatically formed dunites are rich in light rare earth elements (LREE) and commonly carry elevated Pt+Pd concentrations (up to 17.92 ppb), especially compared to replacive dunites that are almost deprived of Pt and Pd (up to 3.92 ppb). Further upward movement and differentiation of this melt caused the formation of clinopyroxenites, containing spinel similar in composition to that of cumulate dunites, with elevated Pt+Pd abundances (up to 499.75 ppb) and LREE-depleted multi-element patterns typical of crystallization from a melt with comparable composition between boninite and IAT. Overall data indicate that the studied ultramafic suite represents part of a sub-oceanic Moho transition zone, which preserves mixed mantle and cumulate characteristics.

Geochemistry of Archean shales from the Pilbara Supergroup, Western Australia

NASA Astrophysics Data System (ADS)

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

1983-07-01

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

Comparative Magma Oceanography

NASA Technical Reports Server (NTRS)

Jones, J. H.

1999-01-01

The question of whether the Earth ever passed through a magma ocean stage is of considerable interest. Geochemical evidence strongly suggests that the Moon had a magma ocean and the evidence is mounting that the same was true for Mars. Analyses of martian (SNC) meteorites have yielded insights into the differentiation history of Mars, and consequently, it is interesting to compare that planet to the Earth. Three primary features of Mars contrast strongly to those of the Earth: (i) the extremely ancient ages of the martian core, mantle, and crust (about 4.55 b.y.); (ii) the highly depleted nature of the martian mantle; and (iii) the extreme ranges of Nd isotopic compositions that arise within the crust and depleted mantle. The easiest way to explain the ages and diverse isotopic compositions of martian basalts is to postulate that Mars had an early magma ocean. Cumulates of this magma ocean were later remelted to form the SNC meteorite suite and some of these melts assimilated crustal materials enriched in incompatible elements. The REE pattern of the crust assimilated by these SNC magmas was LREE enriched. If this pattern is typical of the crust as a whole, the martian crust is probably similar in composition to melts generated by small degrees of partial melting (about 5%) of a primitive source. Higher degrees of partial melting would cause the crustal LREE pattern to be essentially flat. In the context of a magma ocean model, where large degrees of partial melting presumably prevailed, the crust would have to be dominated by late-stage, LREE-enriched residual liquids. Regardless of the exact physical setting, Nd and W isotopic evidence indicates that martian geochemical reservoirs must have formed early and that they have not been efficiently remixed since. The important point is that in both the Moon and Mars we see evidence of a magma ocean phase and that we recognize it as such. Several lines of theoretical inference point to an early Earth that was also hot and, perhaps, mostly molten. The Giant Impact hypothesis for the origin of the Moon offers a tremendous input of thermal energy and the same could be true for core formation. And current solar system models favor the formation of a limited number of large (about 1000 km) planetesimals that, upon accreting to Earth, would cause great heating, being lesser versions of the Giant Impact. Several lines of geochemical evidence do not favor this hot early Earth scenario. (i) Terrestrial man-tle xenoliths are sometimes nearly chondritic in their major element compositions, suggesting that these rocks have never been much molten. Large degrees of partial melting probably promote differentiation rather than homogenization. (ii) Unlike the case of Mars, the continental crust probably did not form as a highly fractionated residual liquid from a magma ocean (about 99% crystallization), but, rather, formed in multiple steps. [The simplest model for the formation of continental crust is complicated: (a) about 10% melting of a primitive mantle, making basalt; (b) hydrothermal alteration of that basalt, converting it to greenstone; and (c) 10% partial melting of that greenstone, producing tonalite.] This model is reinforced by the recent observation from old (about 4.1 b.y.) zircons that the early crust formed from an undepleted mantle having a chondritic Lu/Hf ratio. (iii) If the mantle were once differentiated by a magma ocean, the mantle xenolith suite requires that it subsequently be homogenized. The Os isotopic compositions of fertile spinel lherzolites place constraints on the timing of that homogenization. The Os isotopic composition of spinel lherzolites approaches that of chondrites and correlates with elements such as Lu and Al. As Lu and Al concentrations approach those of the primitive mantle, Os isotopic compositions approach chondritic. The Re and Os in these xenoliths were probably added as a late veneer. Thus, the mantle that received the late veneer must have been nearly chondritic in terms of its major elements (excluding Fe). If the mantle that the veneer was mixed into was not al-ready homogenized, then Os isotopes should not correlate with incompatible elements such as Al. Consequently, either early differentiation of the mantle did not occur or the homogenization of this differentiation must have occurred before the late veneer was added. The timing of the late veneer is itself uncertain but presumably postdated core formation at about 4.45 b.y. and did not postdate the 3.8-3.9 b.y. late bombardment of the Moon. This timing based on siderophile elements is consistent with the Hf isotopic evidence cited above. If the Earth, Moon and Mars had magma oceans, the Earth subsequently rehomogenized whereas the Moon and Mars did not. The simplest solution to this observation is that homogenization of igneous differentiates was never necessary on Earth, either because the hypothetical magma ocean never occurred or because this event did not produce mantle differentiation.

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.

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.

Mantle Xenoliths from Central and South Vietnam: Petrology and Geochemistry

NASA Astrophysics Data System (ADS)

Hauzenberger, Christoph; Konzett, Juergen; Nguyen, Hoang; Nguyen, Khoi

2014-05-01

Mantle xenoliths, spinel lherzolites and subordinate amounts of spinel harzburgites and pyroxenites, are commonly found in alkali basalts from south-central Vietnam. The basalts are part of widespread Neogene volcanism found in southern China and Indochina regions. Samples from different localities between the cities of Ban Me Thuot and Saigon were recovered. In addition one xenolith sample from an off-shore volcano SE of Ho Chi Minh City in the South China Sea was investigated. The mineral assemblage in most samples consists of the simple lherzolitic mineral assemblage Ol-Opx-Cpx-Sp. The Ol, Cpx and Opx crystals are equigranular while Sp occurs usually as smaller sized intersertal phase or as partly oriented inclusions in Cpx. Cpx II occurs in some samples as recrystallized "spongy rim" around Cpx I. Cpx I has a a very uniform composition between different samples with a typical XMg (=Mg/(Mg+Fe2+) of 0.92 to 0.98, a XNa (=Na/(Na+Ca) of 0.10 to 0.16, a Cr2O3 content of 0.6-0.9 wt. .% and Al2O3 values of c. 6 to 8 wt.%. Cpx II has a lower XNa and Al content as well as higher XMg and Cr content compared to Cpx I. Orthopyroxene typically has a XMg of c. 0.90 to 0.93. The XMg values for Ol differ slightly between different samples but are within 0.84 to 0.94. Spinel grains have a variable composition with XMg from 0.65 to 0.92 and XCr (Cr/Cr+Al+Fe3+) of 0.08 to 0.25. The use of the Cpx-Opx thermometer (BREY & KOEHLER, 1990) and the Al and Cr in Ol thermometer (DE HOOG et al., 2010) allowed to constrain the temperature with 800 to 1100 °C. Trace and rare earth element composition of Cpx was determined by LA-ICPMS. While most Cpx compositions are slightly depleted in LREE, typical for average depleted mantle compositions, some samples are strongly enriched in LREE indicating mantle metasomatic processes. The sample displaying the highest level of LREE enrichment in Cpx has the lowest calculated temperature (T = c. 800°C) and the highest Ni content in olivine (3000 ppm). The variation in LREE as well as LIL element concentration in Cpx from different xenoliths is evidence for the heterogeneous nature of the mantle beneath Indochina. Financial support from the Austrian Academy of Sciences and ASEA-Uninet is gratefully acknowledged. This is a contribution to IGCP557.

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.

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

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.

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).

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.

Rare-earth elements enrichment of Pacific seafloor sediments: the view from volcanic islands of Polynesia

NASA Astrophysics Data System (ADS)

Melleton, Jérémie; Tuduri, Johann; Pourret, Olivier; Bailly, Laurent; Gisbert, Thierry

2014-05-01

Rare-earth elements (REEs) are key metals for «green» technologies such as energy saving lamps or permanent magnets used in, e.g., wind turbines, hard disk drives, portable phone or electric or hybrid vehicles. Since several years, world demand for these metals is therefore drastically increasing. The quasi-monopolistic position of China, which produces around 95 % of global REEs production, generates risks for the industries that depend on a secure supply of REEs. In response, countries are developing and diversifying their supply sources, with new mining projects located outside China and efforts in the area of REEs recycling. Most of these projects focus on deposits related to carbonatites and alkaline-peralkaline magmatism, which are generally enriched in light REEs (LREEs) compared to the heavy REEs (HREEs)-enriched deposits of the ion-adsorption types, located in southern China. However, a recent study revealed new valuable resources corresponding to seafloor sediments located in the south-eastern and north-central Pacific. The deep-sea mud described by these authors show a higher HREE/LREE ratio than ion-adsorption deposits, a feature which significantly increases their economic interest. The authors suggest mid-ocean ridge hydrothermal activity as an explanation to this anomalous enrichment. However, several contributions have documented considerable REEs enrichment in basalts and peridotitic xenoliths from French Polynesia. Several arguments have been exposed in favour of a supergene origin, with a short migration, suggesting that REEs were collected from weathered basalts. The Tahaa volcanic island (Sous-le-Vent Island, Society Archipelago, French Polynesia) is the first location where such enrichment has been described. New petrographic and mineralogical investigations confirm a supergene mobilization of this abnormal occurrence. REE-bearing minerals (mainly phosphates of the rhabdophane group) are primarily located within basalt vesicles but also in crack that cross-cut the calcite filling the vesicles or the volcanic glass. They are also closely associated with Ni-Mg bearing phyllosilicates, which appear to nucleate from alteration of olivine and clinopyroxenes. Further investigations are done to evidence and confirm an anterior magmatic enrichment. On the basis of these observations, we believe that the anomalous enrichment observed in seafloor sediments could derive from abnormally-rich provinces corresponding to aerial basaltic formations from oceanic islands primarily enriched during weathering processes (Melleton et al., 2014). Melleton et al. (2014). Rare-earth elements enrichment of Pacific sea-floor sediments: the view from volcanic islands of Polynesia. In preparation.

Ti-rich komatiites from northern Norway

NASA Astrophysics Data System (ADS)

Barnes, Sarah-Jane; Often, Morten

1990-06-01

Komatiites of the Karasjok Greenstone Belt, northern Norway, show two unusual features: they have certain compositional differences compared with other komatiites, and they are largely volcaniclastic in origin. Their geological setting suggests that the komatiites were crupted into shallow water, thus permitting phreatomagmatic eruption, in a small ocean basin that opened in the Baltic Shield. The major oxides (except for TiO2), the trace elements Y, Sc, V, heavy rare earth elements (HREE), Cr, Co, Ni and the platinum group elements (PGE) cover similar ranges to those observed in other komatiites, but TiO2, Sm, Zr and Hf (Ti-associated elements, TAE) are enriched compared with abundances commonly reported for komatiites. Thus, the Karasjok komatiites have interelement ratios 2 to 3 times greater than chondritic between the TAE and the HREE, PGE, Sc, V, Y, Al (HRE-associated elements, HAE). The light rare earth elements (LREE), Ta and Th are enriched in some samples relative to Ti, Sm, Zr, and Hf, but are depleted in others. One group of rocks that is similar to the Karasjok komatiites both in terms of geological setting and geochemistry is the Baffin Bay picrites. The reason for the high concentrations of TAE in the Karasjok komatiites could be that they formed at lower degrees of partial melting than most komatiites. The greater-than-chondritic TAE/HAE ratios indicate that garnet was a residual phase during their formation, requiring that the melt formed at a pressure greater than 40 kb. A model involving decompression melting of a mantle plume rising in a rifting environment, can explain the main features of the Karasjok komatiites.

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

USGS Publications Warehouse

Sorensen, Sorena S.; Grossman, J.N.

1989-01-01

The abundance, P-T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600??C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high-T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of "average" island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H2O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. "Exotic" LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by "subduction-zone metasomatism," although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments. ?? 1989.

A LREE-depleted component in the Afar plume: Further evidence from Quaternary Djibouti basalts

NASA Astrophysics Data System (ADS)

Daoud, Mohamed A.; Maury, René C.; Barrat, Jean-Alix; Taylor, Rex N.; Le Gall, Bernard; Guillou, Hervé; Cotten, Joseph; Rolet, Joël

2010-02-01

Major, trace element and isotopic (Sr, Nd, Pb) data and unspiked K-Ar ages are presented for Quaternary (0.90-0.95 Ma old) basalts from the Hayyabley volcano, Djibouti. These basalts are LREE-depleted (La n/Sm n = 0.76-0.83), with 87Sr/ 86Sr ratios ranging from 0.70369 to 0.70376, and rather homogeneous 143Nd/ 144Nd ( ɛNd = + 5.9-+ 7.3) and Pb isotopic compositions ( 206Pb/ 204Pb = 18.47-18.55, 207Pb/ 204Pb = 15.52-15.57, 208Pb/ 204Pb = 38.62-38.77). They are very different from the underlying enriched Tadjoura Gulf basalts, and from the N-MORB erupted from the nascent oceanic ridges of the Red Sea and Gulf of Aden. Their compositions closely resemble those of (1) depleted Quaternary Manda Hararo basalts from the Afar depression in Ethiopia and (2) one Oligocene basalt from the Ethiopian Plateau trap series. Their trace element and Sr, Nd, Pb isotope systematics suggest the involvement of a discrete but minor LREE-depleted component, which is probably an intrinsic part of the Afar plume.

Geochemistry of trace elements in coals from the Zhuji Mine, Huainan Coalfield, Anhui, China

USGS Publications Warehouse

Sun, R.; Liu, Gaisheng; Zheng, Lingyun; Chou, C.-L.

2010-01-01

The abundances of nine major elements and thirty-eight trace elements in 520 samples of low sulfur coals from the Zhuji Mine, Huainan Coalfield, Anhui, China, were determined. Samples were mainly collected from 10 minable coal seams of 29 boreholes during exploration. The B content in coals shows that the influence of brackish water decreased toward the top of coal seams; marine transgression and regression occurred frequently in the Lower Shihezi Formation. A wide range of elemental abundances is found. Weighted means of Na, K, Fe, P, Be, B, Co, Ni, Cr, Se, Sb, Ba, and Bi abundances in Zhuji coals are higher, and the remainder elements are either lower or equal to the average values of elements in coals of northern China. Compared to the Chinese coals, the Zhuji coals are higher in Na, K, Be, B, Cr, Co, Se, Sn, Sb, and Bi, but lower in Ti, P, Li, V and Zn. The Zhuji coals are lower only in S, P, V and Zn than average U.S. and world coals. Potassium, Mg, Ca, Mn, Sr, As, Se, Sb and light rare earth elements (LREE) had a tendency to be enriched in thicker coal seams, whereas Fe, Ti, P, V, Co, Ni, Y, Mo, Pb and heavy rare earth elements (HREE) were inclined to concentrate in thinner coal seams. The enrichment of some elements in the Shanxi or Upper Shihezi Formations is related to their depositional environments. The elements are classified into three groups based on their stratigraphic distributions from coal seams 3 to 11-2, and the characteristics of each group are discussed. Lateral distributions of selected elements are also investigated. The correlation coefficients of elemental abundances with ash content show that the elements may be classified into four groups related to modes of occurrence of these elements. ?? 2009 Elsevier B.V. All rights reserved.

Permo-Triassic arc-like granitoids along the northern Lancangjiang zone, eastern Tibet: Age, geochemistry, Sr-Nd-Hf isotopes, and tectonic implications

NASA Astrophysics Data System (ADS)

Wang, Xinyu; Wang, Shifeng; Wang, Chao; Tang, Wenkun

2018-05-01

Large volumes of Permo-Triassic granitoids are exposed along the Northern Lancangjiang zone, eastern Tibet, and these rocks provide insights into the tectonic evolution of the Paleo-Tethys Ocean. We conducted detailed geological fieldwork and geochemical analysis of the Xiaochangdu and Kagong plutons that crop out along the Northern Lancangjiang magmatic belt. Zircon U-Pb data constrain the emplacement of the Xiaochangdu quartz diotites to between 263 and 257 Ma, and the Kagong granites and diorites to between 234 and 232 Ma. The Xiaochangdu quartz diorites are enriched in light rare earth (LREE) and large ion lithophile elements (LILE), depleted in high field strength elements (HFSE), have low (87Sr/86Sr)i ratios, and near-positive εNd(t) (-0.26 to 1.58) and εHf(t) (0.68-8.83) values, similar to typical subduction- related mantle-derived arc magmas. They are also characterized by high Al2O3 concentrations and low Nb/U (3.48-7.59) and Ce/Pb (3.22-4.86) ratios, indicating that their mantle source was modified by subducted pelagic sediments; Coeval granites and diorites from the Kagong pluton exhibit low A/CNK values, high LREE/HREE (heavy rare earth element) ratios, enrichment in LILE, and depletion in HFSE, also characteristic of typical arc magmas. Their variable SiO2 contents (57%- 75%), (87Sr/86Sr)i ratios, and εNd(t) (1.02-4.49) and εHf(t) (2.52-6.93) values, and relatively high zircon saturation temperatures (721-827 °C), suggest underplating of mantle-derived mafic melts beneath the lower crust. Their magmatic evolution can be explained using a MASH model. In combination with regional geological studies, our geochemical and geochronological results suggest that the late Permian Xiaochangdu and Late Triassic Kagong arc-like granitoids represent a section of a Permo-Triassic magmatic arc that was associated with the eastward subduction of the Paleo-Tethys oceanic slab beneath the Northern Qiangtang-Changdu terrane. Combined with other geological evidence, the 263-232 Ma arc-like granitoids clearly indicate that final closure of the Paleo-Tethys ocean have not occurred until the end of the Triassic.

Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques.

PubMed

Spalla, S; Baffi, C; Barbante, C; Turetta, C; Turretta, C; Cozzi, G; Beone, G M; Bettinelli, M

2009-10-30

In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries. Copyright 2009 John Wiley & Sons, Ltd.

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.

Accreted fragments of the Late Cretaceous Caribbean Colombian Plateau in Ecuador

NASA Astrophysics Data System (ADS)

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

2003-02-01

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

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.

Constraints on Subduction Zone Temperatures and Chemical Fluxes from Accessory Phase Saturation in Subducted Sediments (Invited)

NASA Astrophysics Data System (ADS)

Blundy, J.; Skora, S.

2009-12-01

A global correlation between the incompatible trace element chemistry of subducted sediments and that of magmas erupted through the overlying plate testifies to the important role that sediments play in controlling magmagenesis. We report new experimental data on the high pressure (3 GPa) and temperature (700-1300 °C) phase relations of hydrous red clay to evaluate the role of residual accessory phases in controlling the incompatible trace element chemistry of sediment-derived fluids. A particular focus is monazite, which preferentially incorporates LREE and Th, exerting a powerful control on the fluid Th/LREE ratio. Given that arc magmas appear to inherit the Th/LREE ratio of the associated subducting sediment, understanding monazite solubility and stability has the potential to provide new constraints on temperature at the slab surface, a parameter that is notoriously hard to pin down by other means. Experiments on red clay with H2O structurally bound in hydrous minerals (<2 wt%) produced negligible melt fractions for any reasonable temperatures. Experiments with 7-15 wt% added H2O produced copious melting at temperatures only 50-100°C above the solidus (c. 720 °C), e.g. with 15 wt% added H2O, the red clay is >50% molten at 800 °C. Irrespective of the amount of added H2O the residual assemblage comprised garnet and kyanite up to the liquidus (1250 °C with 7 wt% H2O). Phengite is present ≤800 °C; ilmenite and rutile persist to c. 1000 °C; quartz/coesite-out temperature decreases from 1000 °C with 7 wt% H2O to 800 °C with 15%. Monazite was stable to 950 °C in the Th- and LREE-doped starting materials that we used. The trace element contents of the residual melts in equilibrium with monazite-thorite solid solutions were used, in conjunction with published data, to develop a thermodynamic model of LREE and Th solubility in sediment-derived fluids. These models were used to calculate the stability of monazite in a red clay with natural LREE and Th levels. For the case of 7 wt% added H2O, monazite is exhausted at 825 °C; it disappears at 780 °C with 15 wt% added H2O. In our experiments monazite fractionates LREE from Th, such that fluids preserving the original sedimentary ratio must be generated at or above monazite-out temperatures in subducted slabs where red clay is the dominant sedimentary lithology. We propose that the subducted sedimentary signature is imparted by fluxing of H2O derived from hydrated (e.g. serpentinised) portions of the deeper subducting slab, triggering copious “flash melting” of the sediment at the point were its temperature exceeds ~800 °C. Without the addition of H2O sediment melting is too restricted to allow any appreciable fluid release into the overlying mantle. Moreover, under such conditions the Th/LREE ratio is strongly fractionated due to the abundance of residual monazite. The availability of H2O in hydrated portions of subducted slabs, e.g. in the vicinity of fracture zones, may exercise an important control on the spatial distribution of subduction zone magmatism.

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.

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

NASA Astrophysics Data System (ADS)

Inoue, Mutsuo; Nakamura, Noboru; Kimura, Makoto

2009-09-01

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

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.

Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Seitz, Hans-Michael

2017-10-01

Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary volcanic rocks of southern Ethiopian rift (Dillo and Megado) reveal the influence of late stage melt-peridotite interaction on the early depleted and variably metasomatized lithospheric mantle. Two types of lherzolites are reported (LREE-depleted La/Sm(N) = 0.11-0.37 × Cl and LREE-enriched, La/Sm(N) = 1.88-15.72 × Cl). The depleted lherzolites have variable range in Li concentration (olivine: 2.1-5.4 ppm; opx: 1.1-2.3 ppm; cpx: 1.0-1.8 ppm) and in Li isotopic composition (δ7Li in olivine: -9.4 to 1.5‰; in opx: -4.5 to 3.6‰; in cpx: -17.0 to 4.8‰), indicating strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The enriched lherzolites have limited range in both Li abundances (olivine: 2.7-3.0 ppm; opx: 1.1-3.1 ppm; cpx: 1.1-2.3 ppm) and Li isotopic compositions (δ7Li in olivine: -1.3 to +1.3‰; in opx: -2.0 to +5.0‰; in cpx: -7.5 to +4.8‰), suggest that the earlier metasomatic event which lead to LREE enrichment could also homogenize the Li contents and its isotopes. The enriched harzburgite and clinopyroxenite minerals show limited variation in Li abundances and variable Li isotopic compositions. The Li enrichments of olivine and clinopyroxene correlate neither with the incompatible trace element enrichment nor with the Sr-Nd isotopic compositions of clinopyroxene. These observations indicate that the metasomatic events which are responsible for the LREE enrichment and for the Li addition are distinct, whereby the LREE-enrichment pre-dates the influx of Li. The presence of large Li isotopic disequilibria within and between minerals of depleted and enriched peridotites suggest that the lithospheric mantle beneath the southern Ethiopian rift has experienced recent melt-peridotite interaction. Thus, the Li data set reported in this study offer new additional evidence for the existence of late stage metasomatism, which probably occurred at shallow depth briefly before and/or during entrainment and ascent of mantle xenoliths to the surface.

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.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

Late Jurassic rhyolites from the Wuchagou region in the central Great Xing'an Range, NE China: Petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Ji, Zheng; Ge, Wen-Chun; Yang, Hao; Wang, Qing-hai; Zhang, Yan-long; Wang, Zhi-hui; Bi, Jun-Hui

2018-06-01

We report geochronological, whole-rock geochemical, and zircon Hf isotopic data for Late Jurassic rhyolites in the central Great Xing'an Range of northeastern China, to determine their petrogenesis, source, and tectonic setting. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb ages indicate that the rhyolites previously mapped as the lower Permian Dashizhai Formation in the Wuchagou region formed during the Late Jurassic (162-154 Ma). Geochemically, these rhyolites belong to the mid- to high-K calc-alkaline series and show peraluminous characteristics and consistent correlations between major elements and SiO2. They are characterized by enrichments in large ion lithophile elements (LILEs; e.g., Rb and K) and light rare earth elements (LREEs), and depletions in high field strength elements (HFSEs; e.g., Nb, Ta, and Ti) and heavy rare earth elements (HREEs). In situ Hf isotopic analyses of zircons from the rhyolites reveal relatively homogeneous Hf isotopic compositions, with εHf(t) values of +4.84 to +9.44, and two-stage model ages of 606-895 Ma. Based on their eruption ages, geochemical characteristics, and Hf isotopic compositions, we conclude that the magmas that formed the Late Jurassic rhyolites were produced during partial melting of a Neoproterozoic quartz-bearing amphibolite-facies mafic crust. These magmas subsequently underwent extensive fractional crystallization of plagioclase, hornblende, Ti-bearing phases, monazite, and apatite. Combined with previous data, our results demonstrate that the Late Jurassic volcanic rocks in the Great Xing'an Range were formed in a post-collisional extensional setting. The gravitational collapse of the orogenically thickened crust was caused by break-off of the subducted oceanic slab and upwelling of asthenosphere after closure of the Mongol-Okhotsk Ocean.

Origin of heavy REE mineralisation in carbonatites: Constraints form the Huanglongpu Mo-HREE deposit, Qinling, China.

NASA Astrophysics Data System (ADS)

Smith, Martin; Cheng, Xu; Kynicky, Jindrich; Cangelosi, Delia; Wenlei, Song

2017-04-01

The carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. Carbonatite monazite (208.9±4.6 Ma to 213.6±4.0; Song et al., 2016) gives a comparable U-Pb radiometric age to molybdenite (220Ma; Stein et al., 1997), confirming interpretations that Mo is derived from the carbonatite, and not a subsequent overprint from regional porphyry-style mineralisation ( 141Ma). The sulphides in the carbonatites have mantle-like 34S ( 1‰) and low δ26Mg values (-1.89 to -1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution in their mantle sources that may be responsible for the Mo and HREE enrichment (Song et al., 2016). The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Monazite-(Ce) was subsequently altered to produce apatite, which was in turn replaced by britholite-(Ce), accompanied by the formation of allanite-(Ce). The REE-fluorcarbonates where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered initially to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, through to more silica-rich conditions during the magmatic-hydrothermal transition, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate that the HREE enrichment could not be a passive process, and that hydrothermal fluids must have contributed HREE to the system. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32- in the metasomatic fluid, and so breakdown of HREE-enriched calcite may have been the HREE source. Solubility products are lower for LREE minerals compared to HREE minerals, so leaching in the presence of strong, LREE-selective ligands (Cl-, CO32-) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during late stage alteration, and hence sulphate complexation may have been important for preferential HREE transport, as sulphate has been shown to be non-LREE selective during the formation of complex ions. The combination of mantle source with a recycled oceanic sediment component, and REE enrichment during magmatic processes, and late stage alteration with non-LREE selective ligands such as sulphate may be critical in forming HREE-enriched carbonatites. Song et al., (2016) Origin of unusual HREE-Mo-rich carbonatites in the Qinling orogen, China. Scientific Reports, 6:37377 | DOI: 10.1038/srep37377. Stein et al. (1997) Highly precise and accurate Re-Os ages for molybdenite from the East Qinling-Dabie molybdenum belt, Shaanxi province, China. Econ. Geol. 92, 827-835 (1997)

The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism

NASA Astrophysics Data System (ADS)

Zanetti, Alberto; Mazzucchelli, Maurizio; Rivalenti, Giorgio; Vannucci, Riccardo

The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (LaN/YbN=8-17) and depleted in Nb. It has high radiogenic Sr (87Sr/86Sr(270)=0.7055-0.7093), low radiogenic Nd (ɛNd(270)=-1 to -3) and EMII-like Pb isotopes. Two pyroxenite - peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (LaN/YbN 16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration 1.9 (Sr) to 7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) arelower in mg## and higher in Na2O, and spinels and phlogopite are richer in Cr2O3. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of ``carbonatite'' metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (amph/cpxDREE,Sr=0.7-0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO2 in the slab-derived melt. The CO2/H2O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust.

Crystal structure of tveitite-(Y): Fractionation of rare-earth elements between positions and the variety of defects

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

Yakubovich, O. V.; Massa, W.; Pekov, I. V.

2007-02-15

The crystal structure of the mineral tveitite-(Y) (Y{sub 0.883}Na{sub 0.106}) (Ca{sub 0.841}LREE{sub 0.159})(Ca{sub 0.716}Na{sub 0.204}HREE{sub 0.080})(Ca{sub 0.0=} 9{sub 2}Na{sub 0.074})F{sub 6.952} from amazonite pegmatites of Rov-Gora Mountain (Keivy, Kola Peninsula) is determined using X-ray diffraction (Stoe IPDS diffractometer, {lambda}MoK{sub {alpha}}, graphite monochromator, 2{theta}{sub max} = 63.5{sup o}, R = 0.051 for 1542 reflections). The main crystal data are as follows: a = 17.020(2) A, c = 9.679(2) A, V = 2428.2(4) A{sup 3}, space group R3-bar, Z = 18, and {rho}{sub calcd} = 4.00 g/cm{sup 3}. The idealized structural formula of the mineral is represented as (Y,Na){sub 6}(Ca,LREE){sub 6}(Ca,Na,HREE){sub 6}(Ca,Na)F{submore » 42} (Z = 3). The defect structure of the mineral manifests itself in a mixed occupation of all four independent cation positions and in a randomly disordered distribution of fluorine atoms over the majority of anion positions. It is shown that the crystal structure of tveitite-(Y) fulfills the function of an 'Eratosthenes sieve' for yttrium cations and two groups of lanthanide cations, so that these cations are distributed over three different positions.« less

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

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.

A weathering-related origin of widespread monazite in S-type granites

NASA Astrophysics Data System (ADS)

Sawka, Wayne N.; Banfield, Jillian F.; Chappell, Bruch W.

1986-01-01

The S-type granite suites comprising more than a quarter of the extensively developed granites in the Lachlan Fold Belt, Australia, contain monazite which may be related to the chemical weathering of the sedimentary source rocks. We report a process whereby chemical weathering fixes mobile rare-earth elements (REE) in hydrous phosphate phases such as florencite and rhabdophane. This material contains up to 50 wt% LREE and occurs as very small particles (~3μm). Dehydration of these hydrous REE phases during anatexis directly yields monazite. The low solubility of phosphorus in S-type granite melts inhibits dissolution of both monazite and apatite. Refractory monazite may be thus entrained and transported in S-type granites in a manner similar to processes resulting in inherited zircon. Since both Th and the light REE are major components in monazite, materials containing this minute phase may be of widespread geochemical significance in both granites and metamorphic rocks.

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.

Magmatic evolution and controls on rare metal-enrichment of the Strange Lake A-type peralkaline granitic pluton, Québec-Labrador

NASA Astrophysics Data System (ADS)

Siegel, Karin; Vasyukova, Olga V.; Williams-Jones, Anthony E.

2018-05-01

Although it is well known that A-type granites are enriched in the rare earth elements (REE) and other high field strength elements (HFSE), the magmatic processes that concentrate these elements are still poorly understood. The 1.24 Ga Strange Lake pluton in northern Québec-Labrador provides an extraordinary example of hyper-enrichment in the REE, Zr, and Nb in a peralkaline A-type granite. The pluton consists of two hypersolvus granite units (southern and northern) and a transsolvus granite, all of which contain perthitic alkali feldspar as the earliest major mineral; the transsolvus granite also contains separate albite and microcline crystals. Arfvedsonite, a sodic amphibole, occurs exclusively as phenocrysts in the transsolvus granite, whereas in the hypersolvus granite it is present as a late, interstitial phase. The primary HFSE minerals are zircon, monazite-(Ce), gagarinite-(Ce) and the pyrochlore group minerals. Magma evolution was monitored by the alumina content in the bulk rock, which decreases from the southern to the northern hypersolvus granite and is lowest in the transsolvus granite. Alkalinity indices and bulk Si, Fe, Rb, REE, Zr, Nb concentrations show the opposite trend. Alkali feldspar compositions mirror the trend shown by the bulk rock, i.e., decreasing Al contents are accompanied by increasing Si, Fe3+, REE, Zr and Nb contents. The major driving forces for the evolution of the hypersolvus magma prior to emplacement were the early separation of a fluoride melt from the silicate melt and the crystallization of alkali feldspar and HFSE-rich phases (zircon, monazite-(Ce), pyrochlore group). An alkali feldspar-rich crystal-mush containing LREE-fluoride melt droplets was emplaced as the least evolved southern hypersolvus granite. Massive fractionation of alkali feldspar led to a sharp increase in ƒH2O and F- activity in the magma chamber that triggered the crystallization of arfvedsonite and was followed by emplacement of the northern hypersolvus granite, which contained a higher proportion of LREE-fluoride melt droplets. Further evolution in the magma chamber led to a transition from a miaskitic to an agpaitic composition. The transsolvus granite was intruded in the form of a low viscosity crystal mush of alkali feldspar, quartz, arfvedsonite (after appreciable crystallization of arfvedsonite) and LREE-fluoride melt droplets. Upon emplacement, arfvedsonite (and gagarinite-(Ce)) crystals segregated as cumulates in response to a combination of flow differentiation and gravity settling. The immiscible fluoride melt accumulated in a volatile-rich residual silicate magma, which migrated to the top of the pluton where it formed the F-REE-rich cores of highly mineralized pegmatites.

Characterization of flux-grown Trace-element-doped titanite using the high-mass-resolution ion microprobe (SHRIMP-RG)

USGS Publications Warehouse

Mazdab, F.K.

2009-01-01

Crystals of titanite can be readily grown under ambient pressure from a mixture of CaO, TiO2 and SiO2 in the presence of molten sodium tetraborate. The crystals produced are euhedral and prismatic, lustrous and transparent, and up to 5 mm in length. Titanite obtained by this method contains approximately 4300 ppm Na and 220 ppm B contributed from the flux. In addition to dopant-free material, titanite containing trace alkali and alkaline earth metals (K, Sr, Ba), transition metals (Sc, Cr, Ni, Y, Zr, Nb, Hf and Ta), rare-earth elements (REE), actinides (Th, U) and p-block elements (F, S, Cl, Ge, Sn and Pb) have been prepared using the same procedure. Back-scattered electron (BSE) imaging accompanied by ion-microprobe (SHRIMP-RG) analysis confirms significant incorporation of selected trace-elements at structural sites. Regardless of some zonation, the large size of the crystals and broad regions of chemical homogeneity make these crystals useful as experimental starting material, and as matrix-matched trace-element standards for a variety of microbeam analytical techniques where amorphous titanite glass, heterogeneous natural titanite or a non-titanite standard may be less than satisfactory. Trace-element-doped synthetic crystals can also provide a convenient proxy for a better understanding of trace-element incorporation in natural titanite. Comparisons with igneous, authigenic and high-temperature metasomatic titanite are examined. The use of high-mass-resolution SIMS also demonstrates the analytical challenges inherent to any in situ mass-spectrometry-based analysis of titanite, owing to the production of difficult-to-resolve molecular interferences. These interferences are dominated by Ca-Ca, Ca-Ti and Ti-Ti dimers that are significant in the mass range of 80-100, affecting all isotopes of Sr and Zr, as well as 89Y and 93Nb. Methods do exist for the evaluation of interferences by these dimers and of polyatomic interferences on the LREE.

Influence of bacteria on lanthanide and actinide transfer from specific soil components (humus, soil minerals and vitrified municipal solid waste incinerator bottom ash) to corn plants: Sr-Nd isotope evidence.

PubMed

Aouad, Georges; Stille, Peter; Crovisier, Jean-Louis; Geoffroy, Valérie A; Meyer, Jean-Marie; Lahd-Geagea, Majdi

2006-11-01

Experiments have been performed to test the stability of vitrified municipal solid waste (MSW) incinerator bottom ash under the presence of bacteria (Pseudomonas aeruginosa) and plants (corn). The substratum used for the plant growth was a humus-rich soil mixed with vitrified waste. For the first time, information on the stability of waste glasses in the presence of bacteria and plants is given. Results show that inoculated plant samples contained always about two times higher lanthanide and actinide element concentrations. Bacteria support the element transfer since plants growing in inoculated environment developed a smaller root system but have higher trace element concentrations. Compared with the substratum, plants are light rare earth element (LREE) enriched. The vitrified bottom ash has to some extent been corroded by bacteria and plant activities as indicated by the presence of Nd (REE) and Sr from the vitrified waste in the plants. (87)Sr/(86)Sr and (143)Nd/(144)Nd isotope ratios of plants and soil components allow the identification of the corroded soil components and confirm that bacteria accelerate the assimilation of elements from the vitrified bottom ash. These findings are of importance for landfill disposal scenarios, and similar experiments should be performed in order to better constrain the processes of microbially mediated alteration of the MSW glasses in the biosphere.

Hydrothermal Upflow, Serpentinization and Talc Alteration Associated with a High Angle Normal Fault Cutting an Oceanic Detachment, Northern Apennines, Italy

NASA Astrophysics Data System (ADS)

Alt, J.; Crispini, L.; Gaggero, L.; Shanks, W. C., III; Gulbransen, C.; Lavagnino, G.

2017-12-01

Normal faults cutting oceanic core complexes are observed at the seafloor and through geophysics, and may act as flow pathways for hydrothermal fluids, but we know little about such faults in the subsurface. We present bulk rock geochemistry and stable isotope data for a fault that acted as a hydrothermal upflow zone in a seafloor ultramafic-hosted hydrothermal system in the northern Apennines, Italy. Peridotites were exposed on the seafloor by detachment faulting, intruded by MORB gabbros, and are overlain by MORB lavas and pelagic sediments. North of the village of Reppia are fault shear zones in serpentinite, oriented at a high angle to the detachment surface and extending 300 m below the paleo-seafloor. The paleo-seafloor strikes roughly east-west, dipping 30˚ to the north. At depth the fault zone occurs as an anticlinal form plunging 40˚ to the west. A second fault strikes approximately north-south, with a near vertical dip. The fault rock outcrops as reddish weathered talc + sulfide in 0.1-2 m wide anastomosing bands, with numerous splays. Talc replaces serpentinite in the fault rocks, and the talc rocks are enriched in Si, metals (Fe, Cu, Pb), Light Rare Earth Elements (LREE), have variable Eu anomalies, and have low Mg, Cr and Ni contents. In some cases gabbro dikes are associated with talc-alteration and may have enhanced fluid flow. Sulfide from a fault rock has d34S=5.7‰. The mineralogy and chemistry of the fault rocks indicate that the fault acted as the upflow pathway for high-T black-smoker type fluids. Traverses away from the fault (up to 1 km) and with depth below the seafloor (up to 500 m) reveal variable influences of hydrothermal fluids, but there are no consistent trends with distance. Background serpentinites 500 m beneath the paleoseafloor have LREE depleted trends. Other serpentinites exhibit correlations of LREE with HFSE as the result of melt percolation, but there is significant scatter, and hydrothermal effects include LREE enrichment, positive Eu anomalies, decreased MgO/SiO2, and increases in Sr and Cs. One serpentinite 40 m from the fault has d34S = 4.5‰, consistent with a hydrothermal sulfur source. Far from the fault (1 km) ophicalcites near the paleo-seafloor have negative Ce anomalies indicating seawater alteration, and suggesting a limit to hydrothermal influence on the length scale of 1 km.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

U-Pb zircon, geochemical and Sr-Nd-Hf-O isotopic constraints on age and origin of the ore-bearing intrusions from the Nurkazgan porphyry Cu-Au deposit in Kazakhstan

NASA Astrophysics Data System (ADS)

Shen, Ping; Pan, Hongdi; Seitmuratova, Eleonora; Jakupova, Sholpan

2016-02-01

Nurkazgan, located in northeastern Kazakhstan, is a super-large porphyry Cu-Au deposit with 3.9 Mt metal copper and 229 tonnage gold. We report in situ zircon U-Pb age and Hf-O isotope data, whole rock geochemical and Sr-Nd isotopic data for the ore-bearing intrusions from the Nurkazgan deposit. The ore-bearing intrusions include the granodiorite porphyry, quartz diorite porphyry, quartz diorite, and diorite. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating indicates that the granodiorite porphyry and quartz diorite porphyry emplaced at 440 ± 3 Ma and 437 ± 3 Ma, respectively. All host rocks have low initial 87Sr/86Sr ratios (0.70338-0.70439), high whole-rock εNd(t) values (+5.9 to +6.3) and very high zircon εHf(t) values (+13.4 to +16.5), young whole-rock Nd and zircon Hf model ages, and consistent and slightly high zircon O values (+5.7 to +6.7), indicating that the ore-bearing magmas derived from the mantle without old continental crust involvement and without marked sediment contamination during magma emplacement. The granodiorite porphyry and quartz diorite porphyry are enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE) and depleted in high-field strength elements (HFSE), Eu, Ba, Nb, Sr, P and Ti. The diorite and quartz diorite have also LILE and LREE enrichment and HFSE, Nb and Ti depletion, but have not negative Eu, Ba, Sr, and P anomalies. These features suggest that the parental magma of the granodiorite porphyry and quartz diorite porphyry originated from melting of a lithospheric mantle and experienced fractional crystallization, whereas the diorite and quartz diorite has a relatively deeper lithospheric mantle source region and has not experienced strong fractional crystallization. Based on these, together with the coeval ophiolites in the area, we propose that a subduction of the Balkhash-Junggar oceanic plate took place during the Early Silurian and the ore-bearing intrusions and associated Nurkazgan porphyry Cu-Au deposit occurred in an intra-oceanic arc setting.

Provenance, Source Rock Characteristics And Paleoweathering Conditions Of The Nearshore Continental Sediments Off Pondicherry, South East Coast Of India

NASA Astrophysics Data System (ADS)

Natarajan, T.; Seshachalam, S.; Ponniah, J.; Varadhan, R.; M, S.

2008-05-01

Geochemical studies, comprising major elements and trace elements, including the Rare Earth Elements (REE), have been carried out on the modern sediments of inner continental shelf representing nearshore marine environments. Concentrations were normalized with Chondrite and PAAS show LREE enriched and flat HREE patterns with slight positive Eu anomaly which is due to the influence of feldspar rich source materials. The LREE enriched and flat HREE patterns with positive Eu anomaly have been considered as the typical character of post- Archaean Sediments. The La/Th ratio ranges from 1.66 to 8.84 with an average value of 4.09, which indicates a heterogenitic source for the sediments of the study area. The La-Th-Sc ternary plot suggests all the samples fall close to the field dominated by tonalite to granite and away from the basalt and komatiite compositions and appear to be derived from sources enriched in felsic components. The transition metal ratios such as Cr/V, Ni/CO and V/Ni indicate both Archaean and Post-Archaean nature to the sediments indicating that the sediments have been derived from heterogenitic sources. The ternary diagram plot of Th-Hf-Co and La-Th-Sc falls in the field of upper continental crust of post Archaean age. This clearly indicates the terrestrial source for the sediments from the nearby landmass. The data are slightly offset from the upper crustal composition away from the Hf apex. This is probably a result of Zircon concentration. Geochemical data have also helped in ascertaining the weathering trends. The Chemical Index of Alteration (CIA) has been used to quantify the degree of weathering. The calculated CIA values for sediments demonstrate both low CIA values of less than 50 percent (low silicate weathering) and intermediate CIA values (60-70 percent) indicating that the sediments are possibly the product of sedimentary and metasedimentary rocks that have undergone intermediate chemical weathering. On an A—CN—K diagram, the data fall closer to the trend parallel to Al2O3 (CaO*+Na2O) join, suggesting that the sediments represent weathered products from granite and charnockite.

Evolution of the upper mantle beneath the southern Baikal rift zone: an Sr-Nd isotope study of xenoliths from the Bartoy volcanoes

NASA Astrophysics Data System (ADS)

Ionov, D. A.; Kramm, U.; Stosch, H.-G.

1992-06-01

Anhydrous and amphibole-bearing peridotite xenoliths occur in roughly equal quantitites in the Bartoy volcanic field about 100 km south of the southern tip of Lake Baikal in Siberia (Russia). Whole-rock samples and pure mineral separates from nine xenoliths have been analyzed for Sr and Nd isotopes in order to characterize the upper mantle beneath the southern Baikal rift zone. In an Sr-Nd isotope diagram both dry and hydrous xenoliths from Bartoy plot at the junction between the fields of MORB and ocean island basalts. This contrasts with data available on two other localities around Lake Baikal (Tariat and Vitim) where peridotites typically have Sr-Nd isotope compositions indicative of strong long-term depletion in incompatible elements. Our data indicate significant chemical and isotopic heterogeneity in the mantle beneath Bartoy that may be attributed to its position close to an ancient suture zone separating the Siberian Platform from the Mongol-Okhotsk mobile belt and occupied now by the Baikal rift. Two peridotites have clinopyroxenes depleted in light rare earth elements (LREE) with Sr and Nd model ages of about 2 Ga and seem to retain the trace element and isotopic signatures of old depleted lithospheric mantle, while all other xenoliths show different degrees of LREE-enrichment. Amphiboles and clinopyroxenes in the hydrous peridotites are in Sr-Nd isotopic disequilibrium. If this reflects in situ decay of 147Sm and 87Rb rather than heterogeneities produced by recent metasomatic formation of amphiboles then 300 400 Ma have passed since the minerals were last in equilibrium. This age range then indicates an old enrichment episode or repeated events during the Paleozoic in the lithospheric mantle initially depleted maybe ˜2 Ga ago. The Bartoy hydrous and enriched dry peridotites, therefore, are unlikely to represent fragments of a young asthenospheric bulge which, according to seismic reflection studies, reached the Moho at the axis of the Baikal rift zone a few Ma ago. By contrast, hydrous veins in peridotites may be associated with rift formation processes.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Trace element 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.

Constraining Mantle Differentiation Processes with La-Ce and Sm-Nd Isotope Systematics

NASA Astrophysics Data System (ADS)

Willig, M.; Stracke, A.

2016-12-01

Cerium (Ce) and Neodymium (Nd) isotopic ratios in oceanic basalts reflect the time integrated La-Ce and Sm-Nd ratios, and hence the extent of light rare earth element element (LREE) depletion or enrichment of their mantle sources. New high precision Ce-Nd isotope data from several ocean islands define a tight array in ԑCe-ԑNd space with ԑNd = -8.2±0.4 ԑCe + 1.3±0.9 (S.D.), in good agreement with previous data [1, 2]. The slope of the ԑCe-ԑNd array and the overall isotopic range are sensitive indicators of the processes that govern the evolution of the mantle's LREE composition. A Monte Carlo approach is employed to simulate continuous mantle-crust differentiation by partial melting and recycling of crustal materials. Partial melting of mantle peridotites produces variably depleted mantle and oceanic crust, which evolve for different time periods, before the oceanic crust is recycled back into the mantle including small amounts of continental crust (GLOSS [3]). Subsequently, depleted mantle and recycled materials of variable age and composition melt, and the respective melts mix in different proportions. Mixing lines strongly curve towards depleted mantle, and tend to be offset from the data for increasingly older and more depleted mantle. Observed ԑCe-ԑNd in ridge [1] and ocean island basalts and the slope of the ԑCe-ԑNd array therefore define upper limits for the extent and age of LREE depletion preserved in mantle peridotites. Very old average mantle depletion ages (> ca. 1-2 Ga) for the bulk of the mantle are difficult to reconcile with the existing ԑCe-ԑNd data, consistent with the range of Nd-Hf-Os model ages in abyssal peridotites [4-6]. Moreover, unless small amounts of continental crust are included in the recycled material, it is difficult to reproduce the relatively shallow slope of the ԑCe-ԑNd array, consistent with constraints from the ԑNd - ԑHf mantle array [7]. [1] Makishima and Masuda, 1994 Chem. Geol. 118, 1-8. [2] Doucelance et al., 2014 EPSL 407, 175-186. [3] Plank, 2014 ToG, 607-629. [4] Stracke et al., 2011 EPSL 308, 359-368. [5] Mallick et al., 2014 G-cubed 15, 2438-2453. [6] Harvey et al., 2006 EPSL 244, 606-621. [7] Chauvel et al. 2008. Nat. Geosci. 1, 64 - 67.

In-situ trace element and Sr isotopic compositions of mantle xenoliths constrain two-stage metasomatism beneath the northern North China Craton

NASA Astrophysics Data System (ADS)

Wu, Dan; Liu, Yongsheng; Chen, Chunfei; Xu, Rong; Ducea, Mihai N.; Hu, Zhaochu; Zong, Keqing

2017-09-01

Subduction and collision are the key processes triggering geochemical refertilization of the lithospheric mantle beneath cratons. However, the way that the subducted plate influences the cratonic lithospheric mantle remains unclear. Here, in-situ major and trace-element and Sr isotopic compositions of peridotite and pyroxenite xenoliths carried by the Dongbahao Cenozoic basalts, located close to the northern margin of North China Craton (NCC), were examined to investigate the effects of the subducted Paleo-Asian oceanic plate on the lithospheric mantle of the NCC. Based on petrographic and geochemical features, peridotites were subdivided into two types recording two-stage metasomatism. Clinopyroxene (Cpx) in both types of peridotites show chemical zoning. In those peridotites we refer to as Type 1 peridotites, Cpx exhibit uniform convex-upward rare earth element (REE) patterns but core-rim variations in 87Sr/86Sr ratios (0.7065-0.7082 in the cores and 0.7043-0.7059 in the spongy rims), and have high (La/Yb)N ratios (> 1.12) (N means normalized to chondrite), relatively low Ti/Eu ratios (< 3756) and negative high field strength element (HFSE) (Nb, Ta, Zr, Hf and Ti) anomalies in the cores, indicating early-stage metasomatism by carbonatitic melts derived from the subducted sedimentary carbonate rocks. Cpx in the Type 2 peridotites have highly variable REE patterns (from light rare earth element (LREE)-depleted to LREE-enriched) and feature zoned Sr isotopic compositions contrasting to those in Type 1, i.e., increasing 87Sr/86Sr ratios from the cores (0.7020-0.7031) to the spongy rims (0.7035-0.7041). Accompanying variations of 87Sr/86Sr ratios, Cpx in both types of peridotites display increasing Nb/La ratios from the cores to the spongy rims. In addition, Cpx in the Type 2 peridotites show remarkably increased (La/Yb)N, Ca/Al, Sm/Hf and Zr/Hf ratios but decreased Ti/Eu and Ti/Nb ratios from the cores to the spongy rims. These features imply a later-stage metasomatism by CO2-rich silicate melts derived from carbonated eclogites. Pyroxenites were also classified into two types. Both types of pyroxenites show higher Ni content in Cpx and orthopyroxene than peridotites at the same Mg# (= 100 ∗ Mg/(Mg + Fe), atomic number) level. Their Cpx show high Ti/Eu, Ti/Sr ratios and similar 87Sr/86Sr ratios (0.7039-0.7055) to the Cpx spongy rims in peridotites, suggesting that pyroxenites originated from silicate melt-peridotite reactions in the later-stage metasomatism. These observations collectively indicate that the lithospheric mantle beneath the northern NCC presents evidence for two distinct mantle metasomatic events. We propose that both were caused by the subduction of the Paleo-Asian oceanic plate, which could have contributed significantly to the transformation of the lithospheric mantle beneath the northern NCC.

Trace element abundances of high-MgO glasses from Kilauea, Mauna Loa and Haleakala volcanoes, Hawaii

USGS Publications Warehouse

Wagner, T.P.; Clague, D.A.; Hauri, E.H.; Grove, T.L.

1998-01-01

We performed an ion-microprobe study of eleven high-MgO (6.7-14.8 wt%) tholeiite glasses from the Hawaiian volcanoes Kilauea, Mauna Loa and Haleakala. We determined the rare earth (RE), high field strength, and other selected trace element abundances of these glasses, and used the data to establish their relationship to typical Hawaiian shield tholeiite and to infer characteristics of their source. The glasses have trace element abundance characteristics generally similar to those of typical shield tholeiites, e.g. L(light)REE/H(heavy)REE(C1) > 1. The Kilauea and Mauna Loa glasses, however, display trace and major element characteristics that cross geochemical discriminants observed between Kilauea and Mauna Loa shield lavas. The glasses contain a blend of these discriminating chemical characteristics, and are not exactly like the typical shield lavas from either volcano. The production of these hybrid magmas likely requires a complexly zoned source, rather than two unique sources. When corrected for olivine fractionation, the glass data show correlations between CaO concentration and incompatible trace element abundances, indicating that CaO may behave incompatibly during melting of the tholeiite source. Furthermore, the tholeiite source must contain residual garnet and clinopyroxene to account for the variation in trace element abundances of the Kilauea glasses. Inversion modeling indicates that the Kilauea source is flat relative to C1 chondrites, and has a higher bulk distribution coefficient for the HREE than the LREE.

Origin of phosphatic stromatolites in the Upper Cretaceous condensed sequence of the Polish Jura Chain

NASA Astrophysics Data System (ADS)

Krajewski, K. P.; Leśniak, P. M.; Łącka, B.; Zawidzki, P.

2000-10-01

The Turonian stromatolite-bearing condensed sequence in the Polish Jura Chain (the European epicontinental basin) provides good insight into the environment of formation of Cretaceous phosphatic stromatolites, owing to their purely phosphatic development and negligible post-depositional alteration. The sequence developed as a result of slow pelagic sedimentation and microbial mat phosphatization on a submarine swell surrounded by local basins with non-condensed carbonate deposition. Diagenesis of organic matter and dissolution of biogenic apatite were the major sources of reactive phosphorus for the microbial mat phosphatization. Stromatolite growth occurred due to pulses of amorphous or poorly ordered calcium phosphate precipitation followed by crystallization of carbonate fluorapatite (CFA). The phosphogenic environment left an imprint on the isotopic composition of limestone carbon and lattice-bound carbon and sulphur in CFA, and on the light rare-earth element (LREE) distribution in CFA. The δ13C of the stromatolite-bearing sequence shows a negative excursion (-1 to -3‰), standing in marked contrast to positive carbon values of the surrounding basinal carbonate. Most of the δ34S values of CFA (+20 to +21‰) fit the value range of the coeval seawater sulphate, and the LREE distribution shows a well-defined seawater pattern. This geochemical signature is indicative of intense diagenesis of organic matter at the seafloor, pelagic carbonate dissolution, and prolonged exposure of the deposited phosphate towards the water column. The enhanced deposition and diagenesis of organic phosphorus in the stromatolitic environment reflects elevated levels of the epicontinental basin nutrification related to sea-level rises and the associated oceanographic and geochemical changes.

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.

Hyperextension of continental to oceanic-like lithosphere: The record of late gabbros in the shallow subcontinental lithospheric mantle of the westernmost Mediterranean

NASA Astrophysics Data System (ADS)

Hidas, Károly; Varas-Reus, Maria Isabel; Garrido, Carlos J.; Marchesi, Claudio; Acosta-Vigil, Antonio; Padrón-Navarta, José Alberto; Targuisti, Kamal; Konc, Zoltán

2015-05-01

We report gabbroic dikes in the plagioclase tectonite domains of the Ojén and Ronda massifs (Betic Cordillera, southern Spain), which record crystallization at low-pressure syn-, or slightly postkinematic to the late ductile history of the Betic Peridotite in the westernmost Mediterranean. We present mineral major and trace element compositional data of discordant gabbroic dikes in the Ojén massif and gabbroic patches in the Ronda massif, complemented by the whole rock and electron backscattered diffraction (EBSD) data of the Ojén occurrence. In the Ojén massif, gabbro occurs as 1-3 centimeter wide discordant dikes that crosscut the plagioclase tectonite foliation at high angle. These dikes are composed of cm-scale igneous plagioclase and clinopyroxene crystals that show shape preferred orientations subparallel to the lineation of the host peridotite and oblique to the trend of the dike. Intrusion of Ojén gabbro dikes is coherent with the stress field that formed the high temperature, ductile plagioclase tectonite foliation and then attests for a mantle igneous event prior to the intracrustal emplacement of the massif. In the Ronda massif, gabbroic rocks crystallized in subcentimeter wide anastomozing veins, or as interstitial patches in the host dunite. They are mostly composed of plagioclase and clinopyroxene. Plagioclase composition is bytownitic in the Ojén, and andesinic in the Ronda massif. Clinopyroxene in both places shows identical, light Rare-Earth Element (LREE) depleted trace element patterns. The calculated trace element composition of melts in exchange equilibrium with the studied igneous clinopyroxenes reflects LREE-enriched character coupled with negative Eu anomaly, and indicates that gabbro-forming melts in Ronda and Ojén share a common melt source with an island arc tholeiitic affinity. Geothermobarometric data and liquidus mineralogy indicate that gabbro crystallization occurred at shallow depths (0.2-0.5 GPa) in a 7-16 km thick lithospheric section. These data suggest that gabbro-forming melts in the Betic Peridotite record a mantle igneous event at very shallow depths and provide evidence for the hyperextension of the continental lithosphere compatible with extreme backarc basin extension induced by the slab rollback of the Cenozoic subduction system in the westernmost Mediterranean.

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

NASA Astrophysics Data System (ADS)

Mercadier, Julien; Cuney, Michel; Cathelineau, Michel; Lacorde, Mathieu

2011-02-01

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation-reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6-1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution-precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400-300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.

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.

Geochemistry of continental subduction-zone fluids

NASA Astrophysics Data System (ADS)

Zheng, Yong-Fei; Hermann, Joerg

2014-12-01

The composition of continental subduction-zone fluids varies dramatically from dilute aqueous solutions at subsolidus conditions to hydrous silicate melts at supersolidus conditions, with variable concentrations of fluid-mobile incompatible trace elements. At ultrahigh-pressure (UHP) metamorphic conditions, supercritical fluids may occur with variable compositions. The water component of these fluids primarily derives from structural hydroxyl and molecular water in hydrous and nominally anhydrous minerals at UHP conditions. While the breakdown of hydrous minerals is the predominant water source for fluid activity in the subduction factory, water released from nominally anhydrous minerals provides an additional water source. These different sources of water may accumulate to induce partial melting of UHP metamorphic rocks on and above their wet solidii. Silica is the dominant solute in the deep fluids, followed by aluminum and alkalis. Trace element abundances are low in metamorphic fluids at subsolidus conditions, but become significantly elevated in anatectic melts at supersolidus conditions. The compositions of dissolved and residual minerals are a function of pressure-temperature and whole-rock composition, which exert a strong control on the trace element signature of liberated fluids. The trace element patterns of migmatic leucosomes in UHP rocks and multiphase solid inclusions in UHP minerals exhibit strong enrichment of large ion lithophile elements (LILE) and moderate enrichment of light rare earth elements (LREE) but depletion of high field strength elements (HFSE) and heavy rare earth elements (HREE), demonstrating their crystallization from anatectic melts of crustal protoliths. Interaction of the anatectic melts with the mantle wedge peridotite leads to modal metasomatism with the generation of new mineral phases as well as cryptic metasomatism that is only manifested by the enrichment of fluid-mobile incompatible trace elements in orogenic peridotites. Partial melting of the metasomatic mantle domains gives rise to a variety of mafic igneous rocks in collisional orogens and their adjacent active continental margins. The study of such metasomatic processes and products is of great importance to understanding of the mass transfer at the slab-mantle interface in subduction channels. Therefore, the property and behavior of subduction-zone fluids are a key for understanding of the crust-mantle interaction at convergent plate margins.

Determining the physical and chemical processes behind four caldera-forming eruptions in rapid succession in the San Juan caldera cluster, Colorado, USA

NASA Astrophysics Data System (ADS)

Curry, A. C.; Caricchi, L.; Lipman, P. W.

2017-12-01

A primary goal of volcanology is to understand the frequency and magnitude of large, explosive volcanic eruptions to mitigate their impact on society. Recent studies show that the average magma flux and the time between magma injections into a given magmatic-volcanic system fundamentally control the frequency and magnitude of volcanic eruptions, yet these parameters are unknown for many volcanic regions on Earth. We focus on major and trace element chemistry of individual phases and whole-rock samples, initial zircon ID-TIMS analyses, and zircon SIMS oxygen isotope analyses of four caldera-forming ignimbrites from the San Juan caldera cluster in the Southern Rocky Mountain volcanic field, Colorado, to determine the physical and chemical processes leading to large eruptions. We collected outflow samples along stratigraphy of the three caldera-forming ignimbrites of the San Luis caldera complex: the Rat Creek Tuff ( 150 km3), Cebolla Creek Tuff ( 250 km3), and Nelson Mountain Tuff (>500 km3); and we collected samples of both outflow and intracaldera facies of the Snowshoe Mountain Tuff (>500 km3), which formed the Creede caldera. Single-crystal sanidine 40Ar/39Ar ages show that these large eruptions occurred in rapid succession between 26.91 ± 0.02 Ma (Rat Creek Tuff) and 26.87 ± 0.02 Ma (Snowshoe Mountain Tuff), providing an opportunity to investigate the temporal evolution of magmatic systems feeding large, explosive volcanic eruptions. Major and trace element analyses show that the first and last eruption of the San Luis caldera complex (Rat Creek Tuff and Nelson Mountain Tuff) are rhyolitic to dacitic ignimbrites, whereas the Cebolla Creek Tuff and Snowshoe Mountain Tuff are crystal-rich, dacitic ignimbrites. Trace elements show enrichment in light rare-earth elements (LREEs) over heavy rare-earth elements (HREEs), and whereas the trace element patterns are similar for each caldera cycle, trace element values for each ignimbrite show variability in HREE concentrations. This variability indicates that these large eruptions sampled a magmatic system with some degree of internal heterogeneity. These results have implications for the chemical and physical processes, such as magmatic flux and injection periodicity, leading to the formation of large magmatic systems prior to large, explosive eruptions.

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).

N- and O- ligand doped mesoporous silica-chitosan hybrid beads for the efficient, sustainable and selective recovery of rare earth elements (REE) from acid mine drainage (AMD): Understanding the significance of physical modification and conditioning of the polymer.

PubMed

Ramasamy, Deepika Lakshmi; Puhakka, Ville; Iftekhar, Sidra; Wojtuś, Anna; Repo, Eveliina; Ben Hammouda, Samia; Iakovleva, Evgenia; Sillanpää, Mika

2018-04-15

Silica-chitosan hybrid beads were synthesized via three different methods to investigate the selective recovery of REE from AMD. The influence of amino/non-amino silanes, high molecular weight/high viscous chitosan and N-/O- based ligands were studied and their effects on REE removal efficiencies were analyzed. The adsorption efficiencies of three various groups of modified beads were inspected with respect to feed pH, in a single and a multi-component system, and their affinities towards the light and heavy rare earth elements (LREE/ HREEs) were interpreted to understand the intra-series REE separation behavior. The focus of the study was mainly directed towards utilizing these fabricated beads for the recovery of valuable REEs from the real AMD obtained at three different sampling depths which was found rich in iron, sulfur and aluminum. Moreover, the selectivity of the beads towards REEs improved with silanized and ligand immobilized gels and their impacts on REE recovery in the presence of competing ions were successfully presented in this paper. Also, the synthesized beads showed rapid REE adsorption and recovery within a process time of 5 min. Group II adsorbents, synthesized by forming silica-chitosan hybrid beads followed by PAN/acac modifications, showed superiority over the other groups of adsorbents. Copyright © 2018 Elsevier B.V. All rights reserved.

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

USGS Publications Warehouse

Dai, S.; Li, D.; Chou, C.-L.; Zhao, L.; Zhang, Y.; Ren, D.; Ma, Y.; Sun, Y.

2008-01-01

Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al2O3 (8.89%), TiO2 (0.47%), Li (116????g/g), F (286????g/g), Ga (18????g/g), Se (6.1????g/g), Sr (350????g/g), Zr (268????g/g), REEs (172????g/g), Pb (30????g/g), and Th (17????g/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash-SiO2-Al2O3-Na2O-Li) and Group B (REE-Sc-In-Y-K2O-Rb-Zr-Hf-Cs-U-P2O5-Sr-Ba-Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe2O3, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se-Pb-Hg-Th-TiO2-Bi-Nb-Ta-Cd-Sn; Group D, Co-Mo-Tl-Be-Ni-Sb-MgO-Re-Ga-W-Zn-V-Cr-F-Cu; and Group E, S-As-CaO-MnO-Fe2O3. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li-ash, Li-Al2O3, and Li-SiO2 pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings. ?? 2008 Elsevier B.V. All rights reserved.

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.

Determination of trace rare earth elements in gadolinium aluminate by inductively coupled plasma time of flight mass spectrometry

NASA Astrophysics Data System (ADS)

Saha, Abhijit; Deb, S. B.; Nagar, B. K.; Saxena, M. K.

An analytical methodology was developed for the precise quantification of ten trace rare earth elements (REEs), namely, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Tm, in gadolinium aluminate (GdAlO3) employing an ultrasonic nebulizer (USN)-desolvating device based inductively coupled plasma mass spectrometry (ICP-MS). A microwave digestion procedure was optimized for digesting 100 mg of the refractory oxide using a mixture of sulphuric acid (H2SO4), phosphoric acid (H3PO4) and water (H2O) with 1400 W power, 10 min ramp and 60 min hold time. An USN-desolvating sample introduction system was employed to enhance analyte sensitivities by minimizing their oxide ion formation in the plasma. Studies on the effect of various matrix concentrations on the analyte intensities revealed that precise quantification of the analytes was possible with matrix level of 250 mg L- 1. The possibility of using indium as an internal standard was explored and applied to correct for matrix effect and variation in analyte sensitivity under plasma operating conditions. Individual oxide ion formation yields were determined in matrix matched solution and employed for correcting polyatomic interferences of light REE (LREE) oxide ions on the intensities of middle and heavy rare earth elements (MREEs and HREEs). Recoveries of ≥ 90% were achieved for the analytes employing standard addition technique. Three real samples were analyzed for traces of REEs by the proposed method and cross validated for Eu and Nd by isotope dilution mass spectrometry (IDMS). The results show no significant difference in the values at 95% confidence level. The expanded uncertainty (coverage factor 1σ) in the determination of trace REEs in the samples were found to be between 3 and 8%. The instrument detection limits (IDLs) and the method detection limits (MDLs) for the ten REEs lie in the ranges 1-5 ng L- 1 and 7-64 μg kg- 1 respectively.

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.

Constraints on the differentiation of the Earth from the coupled Sm-146,147-Nd-142,143 systematics

NASA Technical Reports Server (NTRS)

Jacobsen, S. B.; Harper, C. L., Jr.

1993-01-01

The coupled Sm-Nd systematics are a powerful (albeit analytically challenging) tool for investigating the geodynamic history of the Earth. We have previously reported evidence for a 33 ppm difference of an Isua sample relative to our terrestrial standard. Interpretation yields a formation age range for the depleted mantle (DM) source reservoir of 4.45-4.55 Ga. This is consistent with an epoch of LREE-enriched melt extraction from the mantle (proto-crust formation), soon after magma ocean freeze-up following the putative Moon forming giant impact.

Stratotype for the Mérida Glaciation at Pueblo Llano in the northern Venezuelan Andes

NASA Astrophysics Data System (ADS)

Mahaney, W. C.; Milner, M. W.; Voros, J.; Kalm, V.; Hütt, G.; Bezada, M.; Hancock, R. G. V.; Aufreiter, S.

2000-12-01

The Mérida Glaciation (cf. Wisconsinan, Weichselian) as proposed by Schubert (1974b) culminated at about 18 ka during the last glacial maximum (LGM) and ended at about 13 ka as indicated by 14C dating and correlation with the Cordillera Oriental of Colombia. Moraines of an early stade of Mérida Glaciation reached to 2800 m a.s.l. and were largely overrun or eradicated by the maximum Wisconsinan advance (LGM); where they outcrop, the older moraines are characterized by eroded, weathered glacial diamictons and outwash fans. At Pueblo Llano in the central Mérida Andes (Cordillera de Trujillo), older to younger beds of contorted glacitectonized diamict, overlying beds of bouldery till and indurated outwash, all belong to the early Mérida stade. Overlying the early Mérida stade, deposits of rhythmically bedded glaciolacustrine sediments are in turn overlain with contorted sand and silt beds capped with outwash. Above the outwash terrace a loop moraine of LGM age completely encircles the margins of the basin. A stream cut exposed by catastrophic (tectonic or surge?) release of meltwater displays a lithostratigraphic succession that is bereft of organic material for radiocarbon dating. Five optically-stimulated luminescence (OSL) dates place the maximum age of the lowest till at 81 ka. Particle size distributions allow clear distinctions between major lithic units. Heavy mineral analysis of the middle and lower coarse units in the section provide information on sediment sourcing and on major lithostratigraphic divisions. Trace element concentrations provide information on the relative homogeneity of the deposits. The HREE (heavy rare earth element) concentrations allow discrimination of the lower till from the rest of the section; the LREE (light rare earth element) concentrations highlight differences between the lower till, LGM till, and the rest of the section.

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.

Partial melting of deeply subducted eclogite from the Sulu orogen in China

PubMed Central

Wang, Lu; Kusky, Timothy M.; Polat, Ali; Wang, Songjie; Jiang, Xingfu; Zong, Keqing; Wang, Junpeng; Deng, Hao; Fu, Jianmin

2014-01-01

We report partial melting of an ultrahigh pressure eclogite in the Mesozoic Sulu orogen, China. Eclogitic migmatite shows successive stages of initial intragranular and grain boundary melt droplets, which grow into a three-dimensional interconnected intergranular network, then segregate and accumulate in pressure shadow areas and then merge to form melt channels and dikes that transport magma to higher in the lithosphere. Here we show, using zircon U–Pb dating and petrological analyses, that partial melting occurred at 228–219 Myr ago, shortly after peak metamorphism at 230 Myr ago. The melts and residues are complimentarily enriched and depleted in light rare earth element (LREE) compared with the original rock. Partial melting of deeply subducted eclogite is an important process in determining the rheological structure and mechanical behaviour of subducted lithosphere and its rapid exhumation, controlling the flow of deep lithospheric material, and for generation of melts from the upper mantle, potentially contributing to arc magmatism and growth of continental crust. PMID:25517619

Basaltic volcanism on the eucrite parent body - Petrology and chemistry of the polymict eucrite ALHA80102

NASA Technical Reports Server (NTRS)

Treiman, A. H.; Drake, M. J.

1985-01-01

The polymict eucrite meteorite ALHA80102 is an unequilibrated breccia of basaltic and gabbroic clasts in a fragmental matrix. Clasts include basalts of many textural types, cumulate gabbro, black 'glass', and ferroan troctolite (plagioclase, silica, Fe-rich olivine, ilmenite, mesostasis). Ferroan troctolite has not been previously reported from eucrites or howardites; it is interpreted as the end-product of fractional crystallization of eucritic magmas. Bulk and trace element compositions (by electron microprobe and INAA) of clasts and matrix from ALHA80102 are similar to those of other eucrites; the meteorite contains clasts similar to Juvinas and to Stannern. A clast of cumulate eucrite gabbro is enriched in the light rare earths (La/Lu = 2XCI). This clast is interpreted as an unrepresentative sample of metamorphically equilibrated gabbro; LREE-enriched magmas need not be invoked. ALHA80102 is similar to other polymict eucrites from the Allan Hills and may be paired with ALHA76005, ALHA77302, and ALHA78040.

Zirconium, hafnium, and rare earth element partition coefficients for ilmenite and other minerals in high-Ti lunar mare basalts - An experimental study

NASA Technical Reports Server (NTRS)

Mckay, G.; Wagstaff, J.; Yang, S.-R.

1986-01-01

Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.

How does recycling of sediment components in arc magmatism really work?

NASA Astrophysics Data System (ADS)

Kelemen, P.; Hacker, B.; Austin, N.

2007-12-01

Past work indicates substantial recycling of a sediment component rich in LILE, Th, Sr, Pb and LREE in arcs. For example, in the relatively well-constrained case of Central America, Plank et al (Geology 02) estimate that 80% of subducted, sedimentary Th is recycled in arc magmas. To understand how such a component is transferred from subducted sediment to arc lava, we examined trace-element variation in (a) mid-crustal (0.4 GPa) contact metamorphic rocks (Austin & Kelemen, Fall 06 AGU) and (b) ultrahigh-pressure (UHP, > 3 GPa) metasediments. Most UHP samples were metamorphosed along subduction-zone geotherms (Hacker, Int Geol Rev 06), but some record substantially higher T (e.g., Erzgebirge & Kokchetav, Massone EPSL 03). Unmelted, mid-crustal metapelites are indistinguishable from pelitic sediments for the entire suite of elements analyzed by ICP-MS at WSU. Melt extraction from the mid-crustal metapelites led to systematic depletion of incompatible elements in high-grade hornfels. Depletion increases with decreasing distance to the contact with a mafic pluton, most clearly at peak T > 750°C. In contrast, although many UHP metapelites record PT above the aqueous fluid-saturated solidus, and have fluid inclusions and/or hydrous phases, compared to pelites they show no detectable depletion of "fluid-mobile" elements such as LILE (Cs, Rb, Ba, U, K), Sr and Pb, no depletion of "fluid-immobile, incompatible" elements such as Th and LREE, and no systematic change in key soluble/insoluble ratios such as Ba/Th or K/Zr up to ~1000 C. Mobility of incompatible elements is evident for T > 1000 C, well above PT for subduction-zone geotherms. Presumably, trace phases rich in LILE, Th and LREE persist to ~1050 C in metapelites at UHP conditions.How can our observations be reconciled with the recycled sediment component in arc lavas? Our preferred hypothesis is that low-density metasediments rise into the mantle wedge when heating yields viscosities low enough for density-driven instabilities (Ringwood JGSL 74; Marsh AJS 76; Gerya & Yuen EPSL 03; Kelemen et al, Treatise on Geochem 03). In the wedge, metasedimentary diapirs heat as they rise, and undergo large degrees of super-adiabatic partial melting which exhaust trace phases, releasing the sediment component observed in arcs.

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.

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.

Paleozoic magmatism and porphyry Cu-mineralization in an evolving tectonic setting in the North Qilian Orogenic Belt, NW China

NASA Astrophysics Data System (ADS)

Qiu, Kun-Feng; Deng, Jun; Taylor, Ryan D.; Song, Kai-Rui; Song, Yao-Hui; Li, Quan-Zhong; Goldfarb, Richard J.

2016-05-01

The NWW-striking North Qilian Orogenic Belt records the Paleozoic accretion-collision processes in NW China, and hosts Paleozoic Cu-Pb-Zn mineralization that was temporally and spatially related to the closure of the Paleo Qilian-Qinling Ocean. The Wangdian Cu deposit is located in the eastern part of the North Qilian Orogenic Belt, NW China. Copper mineralization is spatially associated with an altered early Paleozoic porphyritic granodiorite, which intruded tonalites and volcaniclastic rocks. Alteration zones surrounding the mineralization progress outward from a potassic to a feldspar-destructive phyllic assemblage. Mineralization consists mainly of quartz-sulfide stockworks and disseminated sulfides, with ore minerals chalcopyrite, pyrite, molybdenite, and minor galena and sphalerite. Gangue minerals include quartz, orthoclase, biotite, sericite, and K-feldspar. Zircon LA-ICPMS U-Pb dating of the ore-bearing porphyritic granodiorite yielded a mean 206Pb/238U age of 444.6 ± 7.8 Ma, with a group of inherited zircons yielding a mean U-Pb age of 485 ± 12 Ma, consistent with the emplacement age (485.3 ± 6.2 Ma) of the barren precursor tonalite. Rhenium and osmium analyses of molybdenite grains returned model ages of 442.9 ± 6.8 Ma and 443.3 ± 6.2 Ma, indicating mineralization was coeval with the emplacement of the host porphyritic granodiorite. Rhenium concentrations in molybdenite (208.9-213.2 ppm) suggest a mantle Re source. The tonalities are medium-K calc-alkaline. They are characterized by enrichment of light rare-earth elements (LREEs) and large-ion lithophile elements (LILEs), depletion of heavy rare-earth elements (HREEs) and high-field-strength elements (HFSEs), and minor negative Eu anomalies. They have εHf(t) values in the range of +3.6 to +11.1, with two-stage Hf model ages of 0.67-1.13 Ga, suggesting that the ca. 485 Ma barren tonalites were products of arc magmatism incorporating melts from the mantle wedge and the lithosphere. In contrast, the 40-m.y.-younger ore-bearing porphyritic granodiorite is sub-alkaline and peraluminous. They are enriched in LREEs and LILEs, depleted in HFSEs, and show weak negative Eu anomalies. They display εHf(t) values of captured or inherited zircons in the range of +8.5 to +10.0, and younger two-stage Hf model ages of 0.78 Ga and 0.86 Ga, similar to those of ca. 485 Ma tonalite. The ca. 445 Ma zircons have εHf(t) values of -2.1 to +9.9, with two-stage Hf model ages of 0.75-1.27 Ga. Moreover, they have relatively high oxygen fugacity than that of the precursor barren tonalite. The ca. 445 Ma magmas at Wangdian thus formed in a subduction setting, and incorporated melts from the subduction-modified lithosphere that had previously been enriched by additions of chalcophile and siderophile element-rich materials by the earlier magmatism and metasomatism during the Paleo Qilian-Qinling Ocean subduction event.

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.

Cryptic trace-element alteration of Anorthosite, Stillwater complex, Montana

USGS Publications Warehouse

Czamanske, G.K.; Loferski, P.J.

1996-01-01

Evidence of cryptic alteration and correlations among K, Ba, and LREE concentrations indicate that a post-cumulus, low-density aqueous fluid phase significantly modified the trace-element contents of samples from Anorthosite zones I and II of the Stillwater Complex, Montana. Concentrations of Ba, Ca, Co, Cr, Cu, Fe, Hf, K, Li, Mg, Mn, Na, Ni, Sc, Sr, Th, Zn, and the rare-earth elements (REE) were measured in whole rocks and plagioclase separates from five traverses across the two main plagioclase cumulate (anorthosite) zones and the contiguous cumulates of the Stillwater Complex in an attempt to better understand the origin and solidification of the anorthosites. However, nearly the entire observed compositional range for many trace elements can be duplicated at a single locality by discriminating between samples rich in oikocrystic pyroxene and those which are composed almost entirely of plagioclase and show anhedral-granular texture. Plagioclase separates with high trace-element contents were obtained from the pyroxene-poor samples, for which maps of K concentration show plagioclase grains to contain numerous fractures hosting a fine-grained, K-rich phase, presumed to be sericite. Secondary processes in layered intrusions have the potential to cause cryptic disturbance, and the utmost care must be taken to ensure that samples provide information about primary processes. Although plagioclase from Anorthosite zones I and II shows significant compositional variation, there are no systematic changes in the major- or trace-element compositions of plagioclase over as much as 630 m of anorthosite thickness or 18 km of strike length. Plagioclase in the two major anorthosite zones shows little distinction in trace-element concentrations from plagioclase in the cumulates immediately below, between, and above these zones.

Partition Coefficients at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Righter, K.; Drake, M. J.

2003-12-01

Differentiation of terrestrial planets includes separation of a metallic core and possible later fractionation of mineral phases within either a solid or molten mantle (Figure 1). Lithophile and siderophile elements can be used to understand these two different physical processes, and ascertain whether they operated in the early Earth. The distribution of elements in planets can be understood by measuring the partition coefficient, D (ratio of concentrations of an element in different phases (minerals, metals, or melts)). (14K)Figure 1. Schematic cross-section through the Earth, showing: (a) an early magma ocean stage and (b) a later cool and differentiated stage. The siderophile elements (iron-loving) encompass over 30 elements and are defined as those elements for which D(metal/silicate)>1, and are useful for deciphering the details of core formation. This group of elements is commonly broken up into several subclasses, including the slightly siderophile elements (1104). Because these three groups encompass a wide range of partition coefficient values, they can be very useful in trying to determine the conditions under which metal may have equilibrated with the mantle (or a magma ocean). Because metal and silicate may equilibrate by several different mechanisms, such as at the base of a deep magma ocean, or as metal droplets descend through a molten mantle, partition coefficients can potentially shed light on which mechanism may be most important, thus linking the physics and chemistry of core formation. In this chapter, we summarize metal/silicate partitioning of siderophile elements and show how they may be used to understand planetary core formation.Once a planet is differentiated into core and mantle, a mantle will cool during convection, and can start in either a molten or solid state, depending upon the initial thermal conditions. If hot enough, minerals will crystallize from a molten mantle, and become entrained in the convecting melt, or eventually settle out at the bottom. The entrainment and settling process has been studied in detail (e.g., Tonks and Melosh, 1990), and is a potential mechanism for differentiation between the deep and shallow parts of Earth's mantle. The lithophile elements, those elements that have D(metal/silicate) <1, fall into many different subclasses and all hold information about the deep mineral structure of the mantle. Rare-earth elements (REEs) have proven to be useful: europium anomalies have helped elucidate the role of plagioclase in lunar crust formation (e.g., Schnetzler and Philpotts, 1971; Weill et al., 1974), and LREE/HREE depletion and enrichment are indicators of partial melting in the presence of garnet in the mantle. High-field-strength elements (HFSEs) - niobium, zirconium, tantalum, and hafnium - are all refractory and hence more resilient to fractionation processes such as volatility or condensation. They also have an affinity for ilmenite and rutile, and can explain differences between lunar and martian samples as well as features of Earth's continental crust ( Taylor and McLennan, 1985). Alkaline-earth and alkaline elements include rubidium, strontium, barium, potassium, caesium, and calcium, some of which are involved in radioactive decay couples, e.g., Rb-Sr and K-Ar. The latter is important in understanding the contribution of radioactive decay to planetary heat production, and potential deep sources of radiogenic argon (see Chapter 2.06). Rubidium and potassium are further useful as tracers of hydrous phases such as mica and amphibole. Possible fractionation of any of these elements from chondritic abundances (see Chapter 2.01) can be assessed with the knowledge of partition coefficients. In this chapter we summarize our understanding of mineral/melt fractionation of minor and trace elements at high pressures and temperatures and discuss the implications for mantle differentiation.

Geochemistry of Groundwater

NASA Astrophysics Data System (ADS)

Chapelle, F. H.

2003-12-01

Differentiation of terrestrial planets includes separation of a metallic core and possible later fractionation of mineral phases within either a solid or molten mantle (Figure 1). Lithophile and siderophile elements can be used to understand these two different physical processes, and ascertain whether they operated in the early Earth. The distribution of elements in planets can be understood by measuring the partition coefficient, D (ratio of concentrations of an element in different phases (minerals, metals, or melts)). (14K)Figure 1. Schematic cross-section through the Earth, showing: (a) an early magma ocean stage and (b) a later cool and differentiated stage. The siderophile elements (iron-loving) encompass over 30 elements and are defined as those elements for which D(metal/silicate)>1, and are useful for deciphering the details of core formation. This group of elements is commonly broken up into several subclasses, including the slightly siderophile elements (1104). Because these three groups encompass a wide range of partition coefficient values, they can be very useful in trying to determine the conditions under which metal may have equilibrated with the mantle (or a magma ocean). Because metal and silicate may equilibrate by several different mechanisms, such as at the base of a deep magma ocean, or as metal droplets descend through a molten mantle, partition coefficients can potentially shed light on which mechanism may be most important, thus linking the physics and chemistry of core formation. In this chapter, we summarize metal/silicate partitioning of siderophile elements and show how they may be used to understand planetary core formation.Once a planet is differentiated into core and mantle, a mantle will cool during convection, and can start in either a molten or solid state, depending upon the initial thermal conditions. If hot enough, minerals will crystallize from a molten mantle, and become entrained in the convecting melt, or eventually settle out at the bottom. The entrainment and settling process has been studied in detail (e.g., Tonks and Melosh, 1990), and is a potential mechanism for differentiation between the deep and shallow parts of Earth's mantle. The lithophile elements, those elements that have D(metal/silicate) <1, fall into many different subclasses and all hold information about the deep mineral structure of the mantle. Rare-earth elements (REEs) have proven to be useful: europium anomalies have helped elucidate the role of plagioclase in lunar crust formation (e.g., Schnetzler and Philpotts, 1971; Weill et al., 1974), and LREE/HREE depletion and enrichment are indicators of partial melting in the presence of garnet in the mantle. High-field-strength elements (HFSEs) - niobium, zirconium, tantalum, and hafnium - are all refractory and hence more resilient to fractionation processes such as volatility or condensation. They also have an affinity for ilmenite and rutile, and can explain differences between lunar and martian samples as well as features of Earth's continental crust ( Taylor and McLennan, 1985). Alkaline-earth and alkaline elements include rubidium, strontium, barium, potassium, caesium, and calcium, some of which are involved in radioactive decay couples, e.g., Rb-Sr and K-Ar. The latter is important in understanding the contribution of radioactive decay to planetary heat production, and potential deep sources of radiogenic argon (see Chapter 2.06). Rubidium and potassium are further useful as tracers of hydrous phases such as mica and amphibole. Possible fractionation of any of these elements from chondritic abundances (see Chapter 2.01) can be assessed with the knowledge of partition coefficients. In this chapter we summarize our understanding of mineral/melt fractionation of minor and trace elements at high pressures and temperatures and discuss the implications for mantle differentiation.

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.

Lithospheric and Asthenospheric Contributions to Post-Collisional Volcanism in the Lesser Caucasus Mts (Armenia)

NASA Astrophysics Data System (ADS)

Sugden, P.; Savov, I. P.; Wilson, M.; Meliksetian, K.; Navasardyan, G.

2017-12-01

Continental collision zones remain the most enigmatic tectonic setting for volcanic activity on earth. The Lesser Caucasus Mts are host to widespread and unique intraplate volcanism, associated with the active Arabia-Eurasia continental collision. Volcanic products range from alkali basalts to rhyolites (including extensive ignimbrites), and occur as basaltic lava flow fields, large composite and shield volcanoes, and regions of distributed (mostly monogenetic) volcanism. Geomorphology, archaeology, and historical accounts suggest volcanic activity has extended in to the Holocene-historical period. The high quality of the exposures and the diversity of unaltered rock types makes Armenia an ideal natural laboratory for studying the sources of magmatism in an active continental collision zone. For the first time, we will present the mineral chemistry (ol, px, amph), whole rock major and trace element, and Sr-Nd isotope compositions of volcanic rocks from southernmost Armenia- namely the Gegham, Vardenis and Syunik volcanic highlands. We compare our dataset with the composition of post-collisional volcanic rocks elsewhere in the Arabia-Eurasia collision zone. Samples from S. Armenia are more mafic, more alkaline and more K2O rich. All volcanic rocks show negative HFSE anomalies and LILE and LREE enrichments reminiscent of continental volcanic arc settings. However, volcanic rocks in Southern Armenia are further enriched in some of the most incompatible trace elements, most notably LREE, Sr and P, and have higher La/Yb, Th/Yb, Ta/Yb, and more variable Th/Nb. Volcanic rocks from Eastern Anatolia and N. Armenia have Sr-Nd isotope compositions similar to those of the Mesozoic volcanic arc (87Sr/86Sr 0.7034-0.7045; 143Nd/144Nd 0.5128-0.5129), whereas samples from S. Armenia deviate towards more enriched compositions resembling a typical EM-I type reservoir (87Sr/86Sr 0.7041- 0.7047; 143Nd/144Nd 0.5127-0.5128). We argue that these distinctive geochemical characteristics result from the addition of an enriched lithospheric component to a ubiquitous subduction-modified baseline asthenospheric mantle. This EM-I like component may be characteristic for not only intraplate hotspot volcanoes but also to collisional and arc settings.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Continental basalts record the crust-mantle interaction in oceanic subduction channel: A geochemical case study from eastern China

NASA Astrophysics Data System (ADS)

Xu, Zheng; Zheng, Yong-Fei

2017-09-01

Continental basalts, erupted in either flood or rift mode, usually show oceanic island basalts (OIB)-like geochemical compositions. Although their depletion in Sr-Nd isotope compositions is normally ascribed to contributions from the asthenospheric mantle, their enrichment in large ion lithophile elements (LILE) and light rare earth elements (LREE) is generally associated with variable enrichments in the Sr-Nd isotope compositions. This indicates significant contributions from crustal components such as igneous oceanic crust, lower continental crust and seafloor sediment. Nevertheless, these crustal components were not incorporated into the mantle sources of continental basalts in the form of solidus rocks. Instead they were processed into metasomatic agents through low-degree partial melting in order to have the geochemical fractionation of the largest extent to achieve the enrichment of LILE and LREE in the metasomatic agents. Therefore, the mantle sources of continental basalts were generated by metasomatic reaction of the depleted mid-ocean ridge basalts (MORB) mantle with hydrous felsic melts. Nevertheless, mass balance considerations indicate differential contributions from the mantle and crustal components to the basalts. While the depleted MORB mantle predominates the budget of major elements, the crustal components predominate the budget of melt-mobile incompatible trace elements and their pertinent radiogenic isotopes. These considerations are verified by model calculations that are composed of four steps in an ancient oceanic subduction channel: (1) dehydration of the subducting crustal rocks at subarc depths, (2) anataxis of the dehydrated rocks at postarc depths, (3) metasomatic reaction of the depleted MORB mantle peridotite with the felsic melts to generate ultramafic metasomatites in the lower part of the mantle wedge, and (4) partial melting of the metasomatites for basaltic magmatism. The composition of metasomatites is quantitatively dictated by the crustal metasomatism through melt-peridotite reaction at the slab-mantle interface in oceanic subduction channels. Continental basalts of Mesozoic to Cenozoic ages from eastern China are used as a case example to illustrate the above petrogenetic mechanism. Subduction of the paleo-Pacific oceanic slab beneath the eastern edge of Eurasian continent in the Early Mesozoic would have transferred the crustal signatures into the mantle sources of these basalts. This process would be associated with rollback of the subducting slab at that time, whereas the partial melting of metasomatites takes place mainly in the Late Mesozoic to Cenozoic to produce the continental basalts. Therefore, OIB-like continental basalts are also the product of subduction-zone magmatism though they occur in intraplate settings.

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.

Three types of element fluxes from metabasite into peridotite in analogue experiments: Insights into subduction-zone processes

NASA Astrophysics Data System (ADS)

Perchuk, A. L.; Yapaskurt, V. O.; Griffin, W. L.; Shur, M. Yu.; Gain, S. E. M.

2018-03-01

Piston-cylinder experiments with natural rocks and mineral separates were carried out at 750-900 °C and 2.9 GPa, conditions relevant to hot subduction zones, to study the mechanisms of metasomatic alteration of mantle-wedge rocks such as dunite and lherzolite, and the transfer of trace elements released from a carbonate-bearing amphibolite during its eclogitization. Element transfer from the slab to the mantle lithologies occurred in porous-, focused- and diffusive-flow regimes that remove melt and carbon, and partially water, from the metabasite layer. Porous flow is recorded by dissolution of clinopyroxene and growth of orthopyroxene ± garnet ± magnesite ± chlorite along grain boundaries in the peridotite layers, but is invisible in the metabasite layers. Porous flow of the same fluids/melts produces harzburgite mineralogy in both dunite and lherzolite. The transformation of lherzolite to harzburgite reflects breakdown of clinopyroxene in the lherzolite and diffusion of the liberated calcium into the metabasite layer, i.e. against the direction of major fluid/melt flow. Focused flow develops along the side walls of the capsules, producing a melt-free omphacite ± phengite ± quartz paragenesis in the metabasite, and melt segregations, separated from the host peridotite layers by newly-formed omphacite ± garnet ± phlogopite + orthopyroxene + magnesite. Diffusive flow leads to the formation of orthopyroxene ± magnesite ± garnet reaction zones at the metabasite-peridotite interface and some melt-peridotite interfaces. Melt segregations in the peridotite layers at 850-900 °C are rich in LREE and LILE, strongly depleted in Y and HREE, and have higher Sr/Y and La/Yb ratios than island arc andesites, dacites and rhyolites. These features, and negative anomalies in Nb-Ta and low Nb/Ta, resemble those of high-silica adakites and TTGs, but K2O is high compared to TTGs. Metasomatism in the dunite layer changes the REE patterns of dunite, recording chromatographic fractionation during porous melt flow. During metabasite-lherzolite interaction, the metabasite layer becomes mildly enriched in LREE; the lherzolite layer, in contrast, is generally depleted in LREE relative to the initial composition. This also indicates element transfer against the direction of fluid flow. Trace-element profiling reveals the development of Eu anomalies in the peridotite layers and the diffusion of many trace elements out of both layers toward the contact zone. The documented processes may be applicable to both Phanerozoic and Precambrian subduction zones.

Devonian magmatism in the Timan Range, Arctic Russia - subduction, post-orogenic extension, or rifting?

NASA Astrophysics Data System (ADS)

Pease, V.; Scarrow, J. H.; Silva, I. G. Nobre; Cambeses, A.

2016-11-01

Devonian mafic magmatism of the northern East European Craton (EEC) has been variously linked to Uralian subduction, post-orogenic extension associated with Caledonian collision, and rifting. New elemental and isotopic analyses of Devonian basalts from the Timan Range and Kanin Peninsula, Russia, in the northern EEC constrain magma genesis, mantle source(s) and the tectonic process(es) associated with this Devonian volcanism to a rift-related context. Two compositional groups of low-K2O tholeiitic basalts are recognized. On the basis of Th concentrations, LREE concentrations, and (LREE/HREE)N, the data suggest two distinct magma batches. Incompatible trace elements ratios (e.g., Th/Yb, Nb/Th, Nb/La) together with Nd and Pb isotopes indicate involvement of an NMORB to EMORB 'transitional' mantle component mixed with variable amounts of a continental component. The magmas were derived from a source that developed high (U,Th)/Pb, U/Th and Sm/Nd over time. The geochemistry of Timan-Kanin basalts supports the hypothesis that the genesis of Devonian basaltic magmatism in the region resulted from local melting of transitional mantle and lower crust during rifting of a mainly non-volcanic continental rifted margin.

SrNdPb isotopic and trace element evidence for crustal contamination of plume-derived flood basalts: Oligocene flood volcanism in western Yemen

NASA Astrophysics Data System (ADS)

Baker, J. A.; Thirlwall, M. F.; Menzies, M. A.

1996-07-01

Oligocene flood basalts from western Yemen have a relatively limited range in initial isotopic composition compared with other continental flood basalts: 87Sr/86Sr = 0.70365-0.70555 ; 143Nd/144Nd = 0.5129-0.51248 ( ɛNd = +6.0 to -2.4) ; 206pb/204Pb = 17.9-19.3 . Most compositions lie outside the isotopic ranges of temporally and spatially appropriate mantle source compositions observed in this area, i.e., Red Sea/Gulf of Aden MORB mantle, the Afar plume, and Pan-African lithospheric mantle Correlations between indices of fractionation, silica, and isotope ratios suggest that crustal contamination has substantially modified the primary isotopic and incompatible trace element characteristics of the flood basalts. However, significant scatter in these correlations was produced by: (a) the heterogeneous isotopic composition of Pan-African crust; (b) the difference in susceptibility of magmas to contamination as a result of variable incompatible trace element contents in primary melts produced by differing degrees of partial melting; (c) the presence or absence of plagioclase as a fractionating phase generating complex contamination trajectories for Sr; (d) sampling over a wide area not representing a single coherent magmatic system; and (e) variation in contamination mechanisms from assimilation associated with fractionation (AFC) to assimilation by hot mafic magmas with little concomitant fractionation. The presence of plagioclase as a fractionating phase in some suites that were undergoing AFC requires assimilation to have taken place within the crust and, coupled with the limited LREE-enrichment accompanying isotopic variations, excludes the possibility that an AFC-type process took place during magma transfer through the lithospheric mantle. Isotopic compositions of some of the inferred crustal assimilants are similar to those postulated by other workers for an enriched lithospheric mantle source of many flood basalts in southwestern Yemen, Ethiopia, and Djibouti. The western Yemen flood basalts contain 0-30% crust which largely swamps their primary lead isotopic signature, but the primary SrNd isotopic signature is close to that of the least contaminated and isotopically most depleted flood basalts. LREE/HFSE and LILE/HFSE ratios also correlate with isotopic data as a result of crustal contamination. However, Nb/La and K/Nb ratios of >1.1 and <150, respectively, in least contaminated samples require an OIB-like source. The pre-contamination isotopic signature is estimated to be: 87Sr/86Sr ˜ 0.7036; 143Nd/144Nd ˜ 0.51292 ; 206Pb/204Pb ˜ 18.4-19.0 . This, coupled with low LILE/HFSE ratios, suggest the source has characteristics akin to the Afar plume. A mantle source isotopically more depleted than Bulk Earth, but not as depleted as MORB, coupled with LILE depletion, also characterises other examples of plume-derived flood volcanism. This mantle reservoir is responsible for the second largest outbursts of volcanism on Earth and has radiogenic isotopic characteristics akin to PREMA mantle, but the incompatible trace element signature of HIMU mantle.

Petrogenesis of Neoarchean metavolcanic rocks in Changyukou, Northwestern Hebei: Implications for the transition stage from a compressional to an extensional regime for the North China Craton

NASA Astrophysics Data System (ADS)

Liou, Peng; Shan, Houxiang; Liu, Fu; Guo, Jinghui

2017-03-01

The 2.5 Ga metavolcanic rocks in Changyukou, Northwestern Hebei, can be classified into three groups based on major and trace elements: high-Mg basalts, tholeiitic basalts, and the calc-alkaline series (basaltic andesites-andesites and dacites-rhyolites). Both high-Mg basalts and tholeiitic basalts have negative anomalies of Nb, Zr, Ti and Heavy Rare Earth Elements (HREE) as well as enrichments of Sr, K, Pb, Ba and Light Rare Earth Elements (LREE) and show typical subduction zone affinities. The petrogenesis of high-Mg basalts can be ascribed to high-degree partial melting of an enriched mantle source in the spinel stability field that was previously enriched in Large Ion Lithophile Elements (LILE) and LREE by slab-derived hydrous fluids/melts/supercritical fluids, as well as the subsequent magma mixing processes of different sources at different source depths, with little or no influence of polybaric fractional crystallization. The flat HREE of tholeiitic basalts indicates they may also originate from the spinel stability field, but from obviously shallower depths than the source of high-Mg basalts. They may form at a later stage of the subduction process when rapid slab rollback leads to extension and seafloor spreading in the upper plate. We obtain the compositions of the Archean lower crust of the North China Craton based on the Archean Wutai-Jining section by compiling the average tonalite-trondhjemite-granodiorite (TTG) components, average mafic granulite components, and average sedimentary rock components. The modeling results show that the generation of high-Al basalts, basaltic andesites and andesites can be attributed to assimilation by high-Mg basalts (primary basalts) of relatively high-Al2O3 thickened lower crust and the subsequent crystallization of prevailing mafic mineral phases, while Al2O3-rich plagioclase crystallization is suppressed under high-pressure and nearly water-saturated conditions. Dacites and rhyolites may be the result of further fractional crystallization of basaltic andesites (high-Al basalts) and andesites. Mixing of magmas at various stages along the fractionation course of basaltic andesites (high-Al basalts) toward rhyolites promotes the trend of the calc-alkaline series. To reconcile the 2.55 to 2.5 Ga TTGs derived from overthickened crust, the 2.51 to 2.50 Ga calc-alkaline volcanic rocks derived from thickened crust, tholeiitic basalts representing low pressure and an extensional tectonic setting, 2493 Ma leucosyenogranites derived from overthickened crust, 2437 Ma biotite-monzogranites derived from slightly thinner crust than leucosyenogranites but still thickened, as well as the clockwise hybrid ITD and IBC P-T paths of the HP granulites and widespread extension and rifting setting within the NCC from 2300 Ma, we propose a model of an evolving subduction process. Among them, the composition of the 2.5 Ga Changyukou volcanic rocks and potassic granites as well as the clockwise hybrid ITD and IBC P-T paths of the HP granulites may reveal that the tectonic setting in Northwest Hebei was in a transition stage from a subduction-related compressional regime to an extensional regime related to plate rollback.

The Contribution of Recycled Crust to Mantle Inventories of Trace elements, Hydrogen, and Carbon

NASA Astrophysics Data System (ADS)

Hirschmann, M. M.

2008-12-01

It is clear that crustal recycling has had a profound impact on the non-volatile trace element budget of the mantle, but its impact on mantle carbon and hydrogen are less well-understood. If an active crust recycling mechanism such as plate tectonics has operated since early in Earth history, and if magmatic production has diminished through time according to the decay in heat production, then the mass of recycled crust may dominate the mantle inventory of many trace elements. For example, Earth evolution models suggest time- integrated crust production equal to 7-15% of the mantle, and this accounts for ~25 to >100% of the mantle inventory of LREE and HFSE elements, depending on the mean concentration of these elements in the average crust produced. A key question is the role of recycling in the budgets of H and C. Consideration of the near-surface reservoirs and fluxes of C and H indicates that these principal volatiles have residence times of billions of years, and so they may be grouped with continental crust as a single long-lived near-surface geochemical reservoir (NSGR) that results from extraction from the mantle by melting combined with selective return to the mantle by subduction. The primitive mantle-normalized mass concentrations of H and C and the NSGR are equal to 90-200 and 1.5-18, respectively, with the primitive mantle inventories of H and C as the chief uncertainty. When the NSGR is plotted on a compatibility diagram, H and C form extreme positive and negative anomalies relative to their mineral/melt partition coefficients, meaning that there is much more H and much less C in the NSGR than would be predicted based solely on their magmatic flux from the mantle. The most straightforward interpretation is that H subduction is highly inefficient, but that recycled C amounts to at least half and possibly dominates the mantle C budget. This interpretation is supported by H/C mass ratios of the mantle sources inferred from undegassed oceanic basalts (H/C=0.75±0.25), which are substantially lower than that for the NSGR (H/C=1.95±0.15).

Paleozoic magmatism and porphyry Cu-mineralization in an evolving tectonic setting in the North Qilian Orogenic Belt, NW China

USGS Publications Warehouse

Qiu, Kun-Feng; Deng, Jun; Taylor, Ryan D.; Song, Kai-Rui; Song, Yao-Hui; Li, Quan-Zhong; Goldfarb, Richard J.

2016-01-01

The NWW-striking North Qilian Orogenic Belt records the Paleozoic accretion–collision processes in NW China, and hosts Paleozoic Cu–Pb–Zn mineralization that was temporally and spatially related to the closure of the Paleo Qilian-Qinling Ocean. The Wangdian Cu deposit is located in the eastern part of the North Qilian Orogenic Belt, NW China. Copper mineralization is spatially associated with an altered early Paleozoic porphyritic granodiorite, which intruded tonalites and volcaniclastic rocks. Alteration zones surrounding the mineralization progress outward from a potassic to a feldspar-destructive phyllic assemblage. Mineralization consists mainly of quartz-sulfide stockworks and disseminated sulfides, with ore minerals chalcopyrite, pyrite, molybdenite, and minor galena and sphalerite. Gangue minerals include quartz, orthoclase, biotite, sericite, and K-feldspar. Zircon LA-ICPMS U–Pb dating of the ore-bearing porphyritic granodiorite yielded a mean 206Pb/238U age of 444.6 ± 7.8 Ma, with a group of inherited zircons yielding a mean U–Pb age of 485 ± 12 Ma, consistent with the emplacement age (485.3 ± 6.2 Ma) of the barren precursor tonalite. Rhenium and osmium analyses of molybdenite grains returned model ages of 442.9 ± 6.8 Ma and 443.3 ± 6.2 Ma, indicating mineralization was coeval with the emplacement of the host porphyritic granodiorite. Rhenium concentrations in molybdenite (208.9–213.2 ppm) suggest a mantle Re source. The tonalities are medium-K calc-alkaline. They are characterized by enrichment of light rare-earth elements (LREEs) and large-ion lithophile elements (LILEs), depletion of heavy rare-earth elements (HREEs) and high-field-strength elements (HFSEs), and minor negative Eu anomalies. They have εHf(t) values in the range of +3.6 to +11.1, with two-stage Hf model ages of 0.67–1.13 Ga, suggesting that the ca. 485 Ma barren tonalites were products of arc magmatism incorporating melts from the mantle wedge and the lithosphere. In contrast, the 40-m.y.-younger ore-bearing porphyritic granodiorite is sub-alkaline and peraluminous. They are enriched in LREEs and LILEs, depleted in HFSEs, and show weak negative Eu anomalies. They displayεHf(t) values of captured or inherited zircons in the range of +8.5 to +10.0, and younger two-stage Hf model ages of 0.78 Ga and 0.86 Ga, similar to those of ca. 485 Ma tonalite. The ca. 445 Ma zircons have εHf(t) values of −2.1 to +9.9, with two-stage Hf model ages of 0.75–1.27 Ga. Moreover, they have relatively high oxygen fugacity than that of the precursor barren tonalite. The ca. 445 Ma magmas at Wangdian thus formed in a subduction setting, and incorporated melts from the subduction-modified lithosphere that had previously been enriched by additions of chalcophile and siderophile element-rich materials by the earlier magmatism and metasomatism during the Paleo Qilian-Qinling Ocean subduction event.

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.

Geochemistry of Volcanic Rocks from International Ocean Discovery Program (IODP) Site 1438, Amami Sankaku Basin: Implications for Izu-Bonin-Mariana (IBM) Arc Initiation

NASA Astrophysics Data System (ADS)

Hickey-Vargas, R.; Ishizuka, O.; Yogodzinski, G. M.; Bizimis, M.; Savov, I. P.; McCarthy, A. J.; Arculus, R. J.; Bogus, K.

2015-12-01

IODP Expedition 351 drilled 150 m of volcanic basement overlain by 1461 m of sedimentary material at Site 1438 in the Amami Sankaku basin, just west of the Kyushu Palau Ridge, the locus of IBM arc initiation. Age interpretations based on biostratigraphy (Arculus et al., Nat. Geosci., in-press) determined that the age of the basement section is between 64 and 51 Ma, encompassing the age of the earliest volcanic products of the IBM arc. The Site 1438 volcanic basement consists of multiple flows of aphyric microcrystalline to finely crystalline basalts containing plagioclase and clinopyroxene with rare olivine pseudomorphs. New XRF major and ICPMS trace element data confirm findings of shipboard analysis that the basalts are moderately differentiated (6-14 % MgO; Mg# = 51-83; 73-490 ppm Cr and 58-350 ppm Ni) with downcore variations related to flow units. Ti/V and Ti/Sc ratios are 16-27 and 75-152, respectively, with lowest values at the base of the core. One prominent characteristic of the basalts is their depletion of immobile highly incompatible elements compared with MORB. Basalts have MORB-normalized La/Nd of 0.5 to 0.9, and most have Th/La < 0.05. Although all basalts are LREE-depleted, La/Nd ratios increase slightly upcore, and Th enrichment compared with LREE occurs in the uppermost 5 meters. Cs, Rb, K, Ba and U are concomitantly enriched relative to LREE in several intervals as a probable result of seawater alteration, but ratios less than those of MORB are found in other areas. In contrast to basement, andesites from three sills in the lowermost sedimentary unit have arc-like trace element patterns with La/Nb > 3 and primitive mantle normalized La/Yb > 1. Our results suggest that mantle melting at the onset of subduction involved exceptionally depleted sources. Enrichment over time may be related to increasing subduction inputs and/or other processes, such as entrainment of fertile asthenosphere during extension of the overriding plate.

Geochemical evolution of Jurassic diorites from the Bristol Lake region, California, USA, and the role of assimilation

USGS Publications Warehouse

Young, E.D.; Wooden, J.L.; Shieh, Y.-N.; Farber, D.

1992-01-01

Late Jurassic dioritic plutons from the Bristol Lake region of the eastern Mojave Desert share several geochemical attributes with high-alumina basalts, continental hawaiite basalts, and high-K are andesites including: high K2O concentrations; high Al2O3 (16-19 weight %); elevated Zr/TiO2; LREE (light-rare-earth-element) enrichment (La/YbCN=6.3-13.3); and high Nb. Pearce element ratio analysis supported by petrographic relations demonstrates that P, Hf, and Zr were conserved during differentiation. Abundances of conserved elements suggest that dioritic plutons from neighboring ranges were derived from similar parental melts. In the most voluminous suite, correlated variations in elemental concentrations and (87Sr/86Sr)i indicate differentiation by fractional crystallization of hornblende and plagioclase combined with assimilation of a component characterized by abundant radiogenic Sr. Levenberg-Marquardt and Monte Carlo techniques were used to obtain optimal solutions to non-linear inverse models for fractional crystallization-assimilation processes. Results show that the assimilated material was chemically analogous to lower crustal mafic granulites and that the mass ratio of contaminant to parental magma was on the order of 0.1. Lack of enrichment in 18O with differentiation is consistent with the model results. Elemental concentrations and O, Sr, and Nd isotopic data point to a hydrous REE-enriched subcontinental lithospheric source similar to that which produced some Cenozoic continental hawaiites from the southern Cordillera. Isotopic compositions of associated granitoids suggest that partial melting of this subcontinental lithosphere may have been an important process in the development of the Late Jurassic plutonic arc of the eastern Mojave Desert. ?? 1992 Springer-Verlag.

Geochemical evidence for mixing of three components in martian orthopyroxenite ALH 84001. [Abstract only

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Lindstrom, M. M.

1994-01-01

ALH 84001, a ferroan martian orthopyroxenite, originally consisted of three petrographically defined components: a cumulus assemblage of orthopyroxene + chromite, a trapped melt assemblage of orthopyroxene(?) + chromite + maskelynite + apatite + augite +/- pyrite, and a metasomatic assemblage of carbonate +/- pyrite. We present the results of Instrumental Neutron Activation Analysis (INAA) study of five bulk samples of ALH 84001, combined with Scanning Ion Mass Spectrometer (SIMS) data on the orthopyroxene, in order to attempt to set limits on the geochemical characteristics of the latter two components, and therefore on the petrogenesis of ALH 84001. The INAA data support the petrographic observations, suggesting that there are at least three components in ALH 84001. We will assume that each of the three geochemically required components can be equated with one of the petrographically observed components. Both trapped melt and metasomatic components in ALH 84001 have higher Na than orthopyroxene based on compositions of maskelynite, apatite, and carbonate. For the metasomatic component, we will assume its Na content is that of carbonate, while for a trapped melt component, we will use a typical Na content inferred for martian meteorite parent melts, approximately 1 wt% Na2O. Under these assumptions, we can set limits on the Light Rare Earth Elements/Heavy Rare Earth Elements (LREE/HREE) ratios of the components, and use this information to compare the petrogenesis of ALH 84001 with other martian meteorites. The above calculations assume that the bulk samples are representative of different portions of ALH 84001. We will also evaluate the possible heterogeneous distribution of mineral phases in the bulk samples as the cause of compositional heterogeneity in our samples.

Determination of Rare Earth Elements in multi-year high-resolution Arctic aerosol record by double focusing Inductively Coupled Plasma Mass Spectrometry with desolvation nebulizer inlet system.

PubMed

Giardi, Fabio; Traversi, Rita; Becagli, Silvia; Severi, Mirko; Caiazzo, Laura; Ancillotti, Claudia; Udisti, Roberto

2018-02-01

An inductively coupled plasma sector field mass spectrometer (ICP-SFMS) was used to develop an analytical method for the fast determination of Na, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Pb in Arctic size-segregated aerosol samples (PM 10 ), after microwave acidic digestion. The ICP-SFMS was coupled with a microflow nebulizer and a desolvation system for the sample introduction, which reduced the isobaric interferences due to oxides and the required volume of sample solutions, compared to the usual nebulization chamber methods. With its very low limit of detection, and taking into account the level of blanks, this method allowed the quantification of many metals in very low concentration. Particular attention was given to Rare Earth Elements (REEs - La to Lu). The efficiency in the extraction of REEs was proved to be acceptable, with recoveries over 83% obtained with a Certified Reference Material (AMiS 0356). The analytical method was then applied to particulate matter samples, collected at ground level in Ny Ålesund (Svalbard Islands, Norway), during spring and summer, from 2010 to 2015, with daily resolution and using a low-volume device. Thus, for the first time, a large atmospheric concentrations dataset of metals in Arctic particulate matter at high temporal resolution is presented. On the basis of differences in LREE/HREE ratio and Ce and Eu anomalies in spring and summer samples, basic information to distinguish local and long-range transported dust were achieved. Copyright © 2017 Elsevier B.V. All rights reserved.

Heavy rare earth elements affect early life stages in Paracentrotus lividus and Arbacia lixula sea urchins.

PubMed

Oral, Rahime; Pagano, Giovanni; Siciliano, Antonietta; Gravina, Maria; Palumbo, Anna; Castellano, Immacolata; Migliaccio, Oriana; Thomas, Philippe J; Guida, Marco; Tommasi, Franca; Trifuoggi, Marco

2017-04-01

Heavy rare earth elements (HREEs) have been scarcely studied for their toxicity, in spite of their applications in several technologies. Thus HREEs require timely investigations for their adverse health effects. Paracentrotus lividus and Arbacia lixula embryos and sperm were exposed to trichloride salts of five HREEs (Dy, Ho, Er, Yb and Lu) and to Ce(III) as a light REE (LREE) reference to evaluate: 1) developmental defects (% DD) in HREE-exposed larvae or in the offspring of HREE-exposed sperm; 2) mitotic anomalies; 3) fertilization success; and 4) reactive oxygen species (ROS) formation, and nitric oxide (NO) and malondialdehyde (MDA) levels. Nominal HREE concentrations were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). HREEs induced concentration-related DD increases in P. lividus and A. lixula larvae, ranging from no significant DD increase at 10 -7 M HREEs up to ≅100% DD at 10 -5 M HREE. Larvae exposed to 10 -5 M Ce(III) resulted in less severe DD rates compared to HREEs. Decreased mitotic activity and increased aberration rates were found in HREE-exposed P. lividus embryos. Significant increases in ROS formation and NO levels were found both in HREE-exposed and in Ce(III) embryos, whereas only Ce(III), but not HREEs resulted in significant increase in MDA levels. Sperm exposure to HREEs (10 -5 -10 -4 M) resulted in a concentration-related decrease in fertilization success along with increase in offspring damage. These effects were significantly enhanced for Dy(III), Ho(III), Er(III) and Yb(III), compared to Lu(III) and to Ce(III). HREE-associated toxicity affected embryogenesis, fertilization, cytogenetic and redox endpoints showing different toxicities of tested HREEs. Copyright © 2017 Elsevier Inc. All rights reserved.

Picrite "Intelligence" from the Middle-Late Triassic Stikine arc: Composition of mantle wedge asthenosphere

NASA Astrophysics Data System (ADS)

Milidragovic, D.; Zagorevski, A.; Weis, D.; Joyce, N.; Chapman, J. B.

2018-05-01

Primitive, near-primary arc magmas occur as a volumetrically minor ≤100 m thick unit in the Canadian Cordillera of northwestern British Columbia, Canada. These primitive magmas formed an olivine-phyric, picritic tuff near the base of the Middle-Late Triassic Stuhini Group of the Stikine Terrane (Stikinia). A new 40Ar/39Ar age on hornblende from a cross-cutting basaltic dyke constrains the tuff to be older than 221 ± 2 Ma. An 87Sr/86Sr isochron of texturally-unmodified tuff samples yields 212 ± 25 Ma age, which is interpreted to represent syn-depositional equilibration with sea-water. Parental trace element magma composition of the picritic tuff is strongly depleted in most incompatible trace elements relative to MORB and implies a highly depleted ambient arc mantle. High-precision trace element and Hf-Nd-Pb isotopic analyses indicate an origin by mixing of a melt of depleted ambient asthenosphere with ≤2% of subducted sediment melt. Metasomatic addition of non-conservative incompatible elements through melting of subducted Panthalassa Ocean floor sediments accounts for the arc signature of the Stuhini Group picritic tuff, enrichment of light rare earth elements (LREE) relative to heavy rare earth elements (HREE) and high field strength elements (HFSE), and anomalous enrichment in Pb. The inferred Panthalassan sediments are similar in composition to the Neogene-Quaternary sediments of the modern northern Cascadia Basin. The initial Hf isotopic composition of the picritic tuff closely approximates that of the ambient Middle-Late Triassic asthenosphere beneath Stikinia and is notably less radiogenic than the age-corrected Hf isotopic composition of the Depleted (MORB) Mantle reservoir (DM or DMM). This suggests that the ambient asthenospheric mantle end-member experienced melt depletion (F ≤ 0.05) a short time before picrite petrogenesis. The mantle end-member in the source of the Stuhini Group picritic tuff is isotopically similar to the mantle source of enriched mid-ocean ridge basalts (E-MORB) erupted today at the southern end of the Explorer Ridge in northeastern Pacific Ocean. The isotopic similarity between the Middle-Late Triassic ambient mantle under Stikinia, and mantle presently tapped at the southern Explorer Ridge suggests that enriched domains in the northeastern Pacific mantle are long-lived (≥222 million years).

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.

Middle Neoproterozoic (ca. 705-716 Ma) arc to rift transitional magmatism in the northern margin of the Yangtze Block: Constraints from geochemistry, zircon U-Pb geochronology and Hf isotopes

NASA Astrophysics Data System (ADS)

Wang, Ruirui; Xu, Zhiqin; Santosh, M.; Xu, Xianbing; Deng, Qi; Fu, Xuehai

2017-09-01

The South Qinling Belt in Central China is an important window to investigate the Neoproterozoic tectono-magmatic processes along the northern margin of the Yangtze Block. Here we present whole-rock geochemistry, zircon U-Pb geochronology and Lu-Hf isotopes of a suite of Middle Neoproterozoic intrusion from the Wudang Uplift in South Qinling. Zircon LA-ICP-MS U-Pb ages reveal that these rocks were formed at ca. 705-716 Ma. Geochemical features indicate that the felsic magmatic rocks are I-type granitoids, belong to calcic- to calc-alkaline series, and display marked negative Nb, Ta and Ti anomalies. Moreover, the enrichment of light rare earth elements (LREEs) and large ion lithophile elements (LILEs), combined with depletion of heavy rare earth elements (HREEs) support that these rocks have affinity to typical arc magmatic rocks formed in Andean-type active continental margins. The REE patterns are highly to moderately fractionated, with (La/Yb)N = 5.13-8.10 in meta-granites, and 2.32-2.35 in granodiorite. The granitoids have a wide range of zircon εHf(t) values (-29.91 to 14.76) and zircon Hf two-stage model ages (696-3482 Ma). We suggest that the ca. 705-716 Ma granitoids were sourced from different degrees of magma mixing between partial melting of the overlying mantle wedge triggered by hydrous fluids released from subducted materials and crustal melting. The hybrid magmas were emplaced in the shallow crust accompanied by assimilation and fractional crystallization (AFC). Both isotopic and geochemical data suggest that the ca. 705-716 Ma felsic magmatic rocks were formed along a continental arc. These rocks as well as the contemporary A-type granite may mark a transitional tectonic regime from continental arc to rifting, probably related to slab rollback during the oceanic subduction beneath the northern margin of Yangtze Block.

Evidence from mantle xenoliths for lithosphere removal beneath the central Rio Grande Rift

NASA Astrophysics Data System (ADS)

Byerly, Benjamin L.; Lassiter, John C.

2012-11-01

Seismic tomography beneath the Central Rio Grande Rift (RGR) at ˜34°N shows a low P and S wave velocity zone in the mantle that extends up the base of the Moho. This low-velocity region has been interpreted by (Gao et al., 2004) to be the result of convective removal of a portion of the once >100 km thick Proterozoic lithosphere. The amount of extension in the central RGR is thought to be low (˜25%) and thus cannot account for the amount of lithosphere thinning suggested by seismic tomography. We measured whole rock and mineral major element, trace element, and isotopic compositions of spinel-peridotite xenoliths erupted along the central axis of the rift (Elephant Butte) and the eastern margin of the Colorado Plateau (Cerro Chato) to determine their depth of origin and mantle provenance and to test the delamination hypothesis. If lithosphere removal has not occurred and the low P and S wave velocities are instead the result of hydration or melt infiltration in the lithosphere, then xenoliths erupted on the rift axis should have geochemical compositions similar to Proterozoic sub-continental lithospheric mantle (SCLM). At Cerro Chato, on the margin of the Colorado Plateau, xenoliths were derived from ˜60 km depth and have geochemical signatures similar to Proterozoic sub-continental lithospheric mantle (e.g. refractory major element compositions, LREE-enrichment, enriched Sr and Nd isotopes, unradiogenic Os isotopes). At Elephant Butte, along the central rift axis, two distinct groups of xenoliths are present. The majority of xenoliths from Elephant Butte are LREE-depleted and have fertile major element compositions. Additionally, these xenoliths have isotopic signatures similar to the range for DMM (e.g. 87Sr/86Sr ranging from 0.7018 to 0.7023, ɛNd ranging from 7 to 21, and 187Os/188Os ranging from 0.122 to 0.130). We interpret this group of xenoliths to be derived from asthenospheric mantle. A less-abundant group of xenoliths at Elephant Butte are LREE enriched, have refractory major element compositions, enriched Sr, Nd, and Pb isotopes, and unradiogenic Os isotopes. These are characteristic of Proterozoic SCLM. Both groups of xenoliths from Elephant Butte are derived from ˜45 km depth. We interpret the suite of xenoliths at Elephant Butte to have sampled what was recently the base of the Proterozoic SCLM. We conclude that a portion of the mantle lithosphere has been removed which allowed modern convecting mantle (DMM) to be emplaced at the base of the pre-existing SCLM.

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

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

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.

The Caribbean-Colombian cretaceous igneous province: The internal anatomy of an oceanic plateau

NASA Astrophysics Data System (ADS)

Kerr, Andrew C.; Tarney, John; Marriner, Giselle F.; Nivia, Alvaro; Saunders, Andrew D.

The Late Cretaceous Caribbean—Colombian igneous province is one of the world's best-exposed examples of a plume-derived oceanic plateau. The buoyancy of the plateau (resulting from residual heat and thick crust) kept it from being totally subducted as it moved eastward with the Farallon Plate from its site of generation in the eastern Pacific and encountered a destructive plate margin. In effect, the plateau makes up much of the Caribbean Plate; it is well exposed around its margins, but more so in accreted terranes in western Colombia (including the well-known Gorgona komatiites and Bolívar mafic/ultramafic cumulates). Compositionally, the lavas of the plateau form three groups: (a) basalts, picrites, and komatiites with light-rare-earth-element (LREE)-depleted chondrite-normalised patterns; (b) basalts with LREE-enriched patterns; and (c) basalts with essentially flat REE patterns (the most dominant type) similar to many of the basalts from the Ontong Java Plateau. These three types demonstrate the heterogeneous nature of the mantle plume source region. The picrites and the komatiites seem to lie nearer the base of the plateau than the more homogeneous basalts; thus, the more MgO-rich melts may have been erupted before large magma chambers had a chance to develop. A reconstructed crustal cross section through the plateau consists of dunitic and pyroxenitic cumulates near the base which are overlain by layered olivine-rich gabbros and more isotropic gabbros. The lowermost eruptive sequence comprises compositionally heterogeneous picrites/komatiites overlain by more homogeneous pillow basalts. Spectacular hornblende-plagioclase veins cut the Bolívar assemblage and these may represent local partial melts of the plateau's base as it was thrusted onto the continent. Subduction-related batholiths and extrusive rocks found around the margin of the province are of two distinct ages; one suite represents pre-plateau collision-related volcanism whereas the other suite, slightly younger than the plateau, may be associated with obduction.

Melt Origin Across a Rifted Continental Margin: A Case for Subduction-related Metasomatic Agents in the Lithospheric Source of Alkaline Basalt, Northwest Ross Sea, Antarctica

NASA Astrophysics Data System (ADS)

Panter, K. S.; Castillo, P.; Krans, S. R.; Deering, C. D.; McIntosh, W. C.; Valley, J. W.; Kitajima, K.; Kyle, P. R.; Hart, S. R.; Blusztajn, J.

2017-12-01

Alkaline magmatism within the West Antarctic rift system in the NW Ross Sea (NWRS) includes a chain of shield volcanoes extending 260 km along the coast, numerous seamounts located on the continental shelf and hundreds more within the oceanic Adare Basin. Dating and geochemistry confirm that the seamounts are Pliocene‒Pleistocene in age and petrogenetically akin to the mostly Miocene volcanism on the continent as well as to a much broader region of alkaline volcanism that altogether encompasses areas of West Antarctica, Zealandia and Australia. All of these regions were contiguous prior to Gondwana breakup at 100 Ma, suggesting that the magmatism is interrelated. Mafic alkaline magmas (> 6 wt.% MgO) erupted across the transition from continent to ocean in the NWRS show a remarkable systematic increase in Si-undersaturation, P2O5, Sr, Zr, Nb and light rare earth element (LREE) concentrations, LREE/HREE and Nb/Y ratios. Radiogenic isotopes also vary with Nd and Pb ratios increasing and Sr ratios decreasing ocean-ward. The variations are not explained by crustal contamination or by changes in degree of mantle partial melting but are likely a function of the thickness and age of mantle lithosphere. The isotopic signature of the most Si-undersaturated and incompatible element enriched basalts best represent the composition of the sub-lithospheric source with low 87Sr/86Sr (≤ 0.7030) and δ18Oolivine (≤ 5.0 ‰), high 143Nd/144Nd ( 0.5130) and 206Pb/204Pb (≥ 20) ratios. The isotopic `endmember' is derived from recycled material and was transferred to the lithospheric mantle by small degree melts to form amphibole-rich metasomes. Later melting of the metasomes produced silica-undersaturated liquids that reacted with the surrounding peridotite. This reaction occurred to a greater extent as the melt traversed through thicker and older lithosphere continent-ward. Ancient or more recent ( 550‒100 Ma) subduction along the margin of Gondwana supplied the recycled subduction-related residue to the asthenosphere. Metasomatism was triggered by major episodes of extension beginning in the Late Cretaceous but did not produce alkaline magmatism directly. Significant delay of 30 to 20 Ma between extension and magmatism was likely controlled by conductive heating and the rate of thermal migration at the base of the lithosphere.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

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

NASA Astrophysics Data System (ADS)

Li, Rong; Jones, Brian

2014-12-01

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

The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.

1999-01-01

Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

Geochemistry and petrogenesis of lamproites, late cretaceous age, Woodson County, Kansas, U.S.A.

USGS Publications Warehouse

Cullers, R.L.; Ramakrishnan, S.; Berendsen, P.; Griffin, T.

1985-01-01

Lamproite sills and their associated sedimentary and contact metamorphic rocks from Woodson County, Kansas have been analyzed for major elements, selected trace elements, and strontium isotopic composition. These lamproites, like lamproites elsewhere, are alkalic (molecular K2O + Na2O Al2O3 = 1.6-2.6), are ultrapotassic ( K2O Na2O = 9.6-150), are enriched in incompatible elements (LREE or light rare-earth elements, Ba, Th, Hf, Ta, Sr, Rb), and have moderate to high initial strontium isotopic compositions (0.7042 and 0.7102). The silica-saturated magma (olivine-hypersthene normative) of the Silver City lamproite could have formed by about 2 percent melting of a phlogopite-garnet lherzolite under high H2O CO2 ratios in which the Iherzolite was enriched before melting in the incompatible elements by metasomatism. The Rose Dome lamproite probably formed in a similar fashion although the extreme alteration due to addition of carbonate presumably from the underlying limestone makes its origin less certain. Significant fractional crystallization of phases that occur as phenocrysts (diopside, olivine, K-richterite, and phlogopite) in the Silver City magma and that concentrate Co, Cr, and Sc are precluded as the magma moved from the source toward the surface due to the high abundances of Co, Cr, and Sc in the magma similar to that predicted by direct melting of the metasomatized Iherzolite. Ba and, to a lesser extent, K and Rb and have been transported from the intrusions at shallow depth into the surrounding contact metamorphic zone. The Silver City lamproite has vertical fractionation of some elements due either to volatile transport or to variations in the abundance of phenocrysts relative to groundmass most probably due to flow differentiation although multiple injection or fractional crystallization cannot be conclusively rejected. ?? 1985.

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

NASA Astrophysics Data System (ADS)

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

2011-09-01

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

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.

Tectonic affinities of the accreted basalts in southern Taiwan

NASA Astrophysics Data System (ADS)

Chen, Hsin-Yu; Yang, Huai-Jen; Liu, Yung-Hsin; Huang, Kuo-Fang; Takazawa, Eiichi

2018-06-01

Tectonic affinities of accreted basalts provide constraints on mass transport in convergent boundaries, improving our understandings on the evolution of regional geology. In this study, nineteen accreted basalts from the southernmost tip of Taiwan Island, which is on the convergent boundary between the Eurasian and Philippine Sea Plates, were analyzed for element concentrations as well as Sr, Nd, Hf, and Pb isotope ratios to investigate their tectonic affinities. All the samples contain > 3% LOI, reflecting post-magmatic alteration. LOI and Nb variation diagrams together with comparisons to oceanic basalt compositions indicated that the concentrations of most major elements and Rb, Sr, and Ba were modified by post-magmatic processes to varying extents, while P2O5, REE and HFSE remained immobile. Although some samples show Pb loss, most samples have Pb concentrations not affected by post-magmatic processes. Isotope ratios of Pb, Nd and Hf, generally reflect the mantle source characteristics. The εNd-εHf relationship and trace element abundance ratios indicated that the LREE-depleted samples were mostly scraped off the subducting South China Sea floor, reflecting the volumetric dominance of N-MORB on ocean floors. The overriding Philippine Sea Plate contributed both N-MORB and E-MORB to the accretionary prism. The tectonic affinities of the LREE-enriched samples, however, could not be unambiguously determined for the large geochemical variability of OIB from both subducting and overlying slabs. Based on our results, it is proposed that the tectonic affinity of the basalts in an accretionary prism can indicate the subduction polarity of the associated convergent boundary, providing a constraint for regional geology evolution.

A Crystal Stratigraphy Approach to Deciphering the Petrogenesis of the Detroit Seamount

NASA Astrophysics Data System (ADS)

Simonetti, A.; Davenport, J.; Neal, C. R.

2012-12-01

The Detroit Seamount (DSM) erupted ~76-81 Ma ago, and is the northwestern terminus of the Hawaiian-Emperor Seamount chain. The Hawaiian-Emperor Seamount chain has drastically furthered our understanding of how and where mantle plumes originate, the dynamics of interactions between plumes and mantle, and plate movement in the recent past. DSM Basalts from Site 1203 of Leg 197 of the Ocean Drilling Program (ODP) contain, by rock volume, a large quantity of plagioclase and olivine phenocrysts. Previous investigations into magma chamber processes via phenocryst analysis such as those occurring at the DSM have largely relied solely on major and trace element analyses. However, since both are easily susceptible to post-solidification alteration processes, in this study we are undertaking a multi-faceted approach to deciphering the petrogenetic history of the DSM basalts via crystal stratigraphy, crystal size distributions (CSDs), electron microprobe analysis (EPMA), laser ablation and multi-collector inductively coupled plasma mass spectrometry (LA- and MC-ICP-MS), microdilling and phase separation, and isotope analysis of whole-rock, olivine and plagioclase phenocrysts and their associated melt inclusions. A preliminary Sr isotope and trace element investigation of DSM whole rock basalts from Site 884 yielded a range of values between 0.70262 and 0.70276, as well as MORB-like trace element patterns. Notably, the plagioclase rims analyzed possessed a more radiogenic (87Sr/86Sr)I than the core (0.70361 ± 2 vs. 0.70347 ± 2). Our initial interpretation of this radiogenic increase from core-to-rim was crystal growth in an OIB-rich magma source that was not cogenetic with its matrix. Eight olivine phenocrysts from DSM basalts were analyzed for major elements using scanning electron microscopy (SEM) and energy dispersive spectrum (EDS) techniques. Fosterite contents of the olivine phenocrysts range from 84-86. Olivines from basalt sample 10R-4 exhibit a well-defined correlation between Ni and Mn contents, whereas those from sample 10R-3 show a more limited range of Mn and Ni compositions. The trends defined by the data from the olivine phenocrysts clearly suggest that fractional crystallization was not the sole magma differentiation process to have occurred. Rare earth element (REE) abundances for the olivine phenocrysts are low, and generally range from 0.1 to 2 ppm, with those from basalt sample 10R-4 containing higher abundances than sample 10R-3. Melt inclusions from within plagioclase phenocrysts in DSM basalt sample 9R-2 from Site 884 were analyzed via laser ablation-ICP-MS. Results from the analyses indicate that the melt inclusions are LREE-enriched and negatively-sloped compared to the LREE-depleted basalt whole rock compositions from the DSM and the East Pacific Rise. Of interest, the La concentrations in the melt inclusions are notably similar to abundances found for the Manua Kea tholeiites. Trace element data and Sr isotope ratios for both melt inclusions and phenocrysts from the DSM basalts are all indicative of open system behavior and possibly consistent with magma mixing between at least two end-member mantle components.

Mineralogical and geochemical features of the coarse saprolite developed on orthogneiss in the SW of Yaoundé, South Cameroon

NASA Astrophysics Data System (ADS)

Ndjigui, P.-D.; Badinane, M. F. B.; Nyeck, B.; Nandjip, H. P. K.; Bilong, P.

2013-03-01

A petrological investigation was performed in the coarse saprolite on orthogneiss in Yaoundé (South Cameroon) using combined whole rock geochemical (XRF, ICP-MS) and mineralogical (XRD, SEM) techniques. The orthogneiss has high contents in SiO2 (61.56 wt.%), Ba (916 ppm) and REE (209 ppm), moderate content in Al2O3 (14.34 wt.%) and negative Eu anomaly (Eu/Eu* = 0.68). The weathering leads to the formation of three main constituents in the coarse saprolite: (i) the loose materials (∼85 vol.%) are basically clayey silty with relic structure. They are composed of kaolinite, quartz and goethite. The loose materials have high contents in SiO2 (56-64.83 wt.%) and Al2O3 (21.48-23.96 wt.%), and moderate contents in V (163-236 ppm), Ba (95-340 ppm) and Zr (160-313 ppm). The REE content is low (∼49-169 ppm) relative to the parent rock with LREE-enrichment (LREE/HREE ∼ 7-17). Positive Ce anomaly (Ce/Ce* ∼ 3.35) is observed in the white veins and slight positive Eu anomalies (Eu/Eu* ∼ 1.2-1.4) are noted in all loose samples. The (La/Yb)N ratios (∼0.8-1.5) indicate high REE-fractionation. The mass balance calculation reveals the depletion of several elements except Al, Ti, Sc, Y, Th, Sb and Hf; (ii) the iron duricrust (∼10 vol.%) is located at the bottom and the top of the horizon. The mineral assemblage is dominated by hematite and goethite. The upper iron duricrust has high contents in Fe2O3 (45.60 wt.%) and Cr (1641 ppm), moderate contents in V (459 ppm) and Zn (143 ppm), and low REE content (47 ppm) with low LREE/HREE ratio (4.28). The upper iron duricrust is more enriched in Fe2O3 (53.26 wt.%) than the lower one. Vanadium, Cr and Zr have high contents relative to other trace elements. The REE content is low (39 ppm) as well as the LREE/HREE ratio (2.94). The iron duricrust has negative Ce anomalies (Ce/Ce* ∼ 0.66-0.69) and very low (La/Yb)N ratios (0.1-0.3). Several elements reported in the iron duricrust are highly leached except Fe, Cr, Zn, Sc, V, Pb, Zr, Cu and Th; and (iii) the Mn-rich materials (<5 vol.%) are made up of birnessite, cryptomelane, and low quantities of quartz, kaolinite and goethite. The SEM investigation reveals that Ba and Pb are linked in Mn-bearing phases and Ce-oxides appear as fine-grained intergrowth between Mn-bearing phases. The Mn-bearing phases are enriched in MnO (33.86 wt.%), BaO (4.30 wt.%), Co (1716 ppm), Pb (1315 ppm) and Ce (5202 ppm). Positive Ce and Eu anomalies are observed (Ce/Ce* ∼ 15.60 and Eu/Eu* ∼ 2). The mass balance calculations indicate the strong accumulation of Mn, Ni, Co, Zn, Sc, Cu, Ba, Pb, Y, Ga, Zr and REE. The Mn-bearing phases might be derived from the accumulation of silicate residues and Mn within the parent rock. The transition from the parent rock to the coarse saprolite is marked by high leaching of several elements.

[Analysis of X-ray fluorescence spectroscopy and plasma mass spectrometry of the Guidong granite body and its implications to granite evolution].

PubMed

Li, Hong-Wei; Chen, Guo-Neng; Peng, Zhuo-Lun

2013-07-01

The Guidong composite granite body (CGB) located in the north Guangdong Province consists of numerous rock bodies formed respectively in the early and late Jurassic and early Cretaceous. Analysis of the granites of different period with X-ray fluorescence spectroscopy and plasma mass spectrometry indicates: (1) From the top of a granite body downwards, the felsic components of rock decrease, while the mafic and sigmaREE, LREE/HREE, (La/Yb)N, as well as delta Eu value increase, suggesting the material differentiation in the in-situ melting of crustal rocks and crystallisation of magma; (2) From old to young of the different period granite-massifs in the Guidong CGB, the felsic compositions totally decrease, and the mafic components, sigmaEE, LREE/HREE, (La/Yb)N, and delta Eu value increase as well, implying multiple crustal melting (remelting) events in the Mesozoic in this area; and (3) Primitive mantle-normalized spider diagram for trace elements of Guidong CGB suggests high maturity of the crust involved in the in-situ melting.

Inclusions of crichtonite-group minerals in Cr-pyropes from the Internatsionalnaya kimberlite pipe, Siberian Craton: Crystal chemistry, parageneses and relationships to mantle metasomatism

NASA Astrophysics Data System (ADS)

Rezvukhin, Dmitriy I.; Malkovets, Vladimir G.; Sharygin, Igor S.; Tretiakova, Irina G.; Griffin, William L.; O'Reilly, Suzanne Y.

2018-05-01

Cr-pyrope xenocrysts and associated inclusions of crichtonite-group minerals from the Internatsionalnaya kimberlite pipe were studied to provide new insights into processes in the lithospheric mantle beneath the Mirny kimberlite field, Siberian craton. Pyropes are predominantly of lherzolitic paragenesis (Cr2O3 2-6 wt%) and have trace-element spectra typical for garnets from fertile mantle (gradual increase in chondrite-normalized values from LREE to MREE-HREE). Crichtonite-group minerals commonly occur as monomineralic elongated inclusions, mostly in association with rutile, Mg-ilmenite and Cr-spinel within individual grains of pyrope. Sample INT-266 hosts intergrowth of crichtonite-group mineral and Cl-apatite, while sample INT-324 contains polymineralic apatite- and dolomite-bearing assemblages. Crichtonite-group minerals are Al-rich (1.1-4.5 wt% Al2O3), moderately Zr-enriched (1.3-4.3 wt% ZrO2), and are Ca-, Sr-, and occasionally Ba-dominant in terms of A-site occupancy; they also contain significant amounts of Na and LREE. T-estimates and chemical composition of Cr-pyropes imply that samples represent relatively low-T peridotite assemblages with ambient T ranging from 720 to 820°С. Projected onto the 35 mW/m2 cratonic paleogeotherm for the Mirny kimberlite field (Griffin et al., 1999b. Tectonophysics 310, 1-35), temperature estimates yield a P range of 34-42 kbar ( 110-130 km), which corresponds to a mantle domain in the uppermost part of the diamond stability field. The presence of crichtonite-group minerals in Cr-pyropes has petrological and geochemical implications as evidence for metasomatic enrichment of some incompatible elements in the lithospheric mantle beneath the Mirny kimberlite field. The genesis of Cr-pyropes with inclusions of crichtonite-group minerals is attributed to the percolation of Ca-Sr-Na-LREE-Zr-bearing carbonate-silicate metasomatic agents through Mg- and Cr-rich depleted peridotite protoliths. The findings of several potentially new members of the crichtonite group as inclusions in garnet extend existing knowledge on the compositions and occurrences of exotic titanates stable in the lithospheric mantle.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Stalking the LREE-enriched component in ureilites

NASA Technical Reports Server (NTRS)

Goodrich, Cyrena Anne; Lugmair, Guenter W.

1993-01-01

Ureilites contain a LREE-enriched component whose origin and identity are unknown, but which may have been introduced into 4.55 Ga olivine + pyroxene assemblages at various times in the period 4.55 - 3.74 Ga. This component is volumetrically minor, inhomogeneously distributed, and can be removed with concentrated HNO3, which suggests that it may be contained in minor, interstitial phases not previously recognized in ureilites. There is evidence, however, that not all of this component is leachable. Whole rock samples of Kenna, Novo Urei, and ALHA77257 form a Nd-143/Nd-144-Sm-147/Nd-144 line with a slope corresponding to an age of 3.74 Ga. Although this line could be a mixing line, with one end-member being the LREE-enriched component and the other being a 4.55 Ga olivine + pyroxene assemblage, the observation that a pyroxene separate from Kenna plots on the line suggests that the LREE-enriched component at least partially equilibrated with the olivine and pyroxene and that the line is an isochron. We performed a leaching experiment on Kenna, using various acids and concentrations, in an attempt to isolate the LREE-enriched component and differentiate between possible hosts for it, and to determine whether all of it is leachable. Our results suggest that most of the LREE-enriched component is surface-sited, rather than contained in a discrete mineral. However, some of it is not readily leachable because it equilibrated with Kenna olivine + pyroxene at 3.79 plus or minus 0.05 Ga.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

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.

Integrated Extraction Chromatographic Separation of the Lithophile Elements Involved in Long-Lived Radiogenic Isotope Systems (Rb-Sr, U-Th-Pb, Sm-Nd, La-Ce, and Lu-Hf) Useful in Geochemical and Environmental Sciences.

PubMed

Pin, Christian; Gannoun, Abdelmouhcine

2017-02-21

A fast and efficient sample preparation method in view of isotope ratio measurements is described, allowing the separation of 11 elements involved, either as "parent" or as "daughter" isotopes, in six radiogenic isotope systems used as chronometers and tracers in earth, planetary, and environmental sciences. The protocol is based on small extraction chromatographic columns, used either alone or in tandem, through which a single nitric acid solution is passed, without any intervening evaporation step. The columns use commercially available extraction resins (Sr resin, TRU resin, Ln resin, RE resin, and again Ln resin for isolating Sr and Pb, LREE then La-Ce-Nd-Sm, Lu(Yb), and Hf, Th, and U, respectively) along with an additional, in-house prepared resin for separating Rb. A simplified scheme is proposed for samples requiring the separation of Sr, Pb, Nd, and Hf only. Adverse effects of troublesome major elements (Fe 3+ , Ti) are circumvented by masking with ascorbic acid and hydrofluoric acid, respectively. Typical recoveries in the 85-95% range are achieved, with procedural blanks of 10-100 pg, negligible with regard to the amounts of analytes processed. The fractions separated are suitable for high precision isotope ratio measurements by TIMS or MC-ICP-MS, as demonstrated by the repeat analyses of several international reference materials of basaltic composition for 87 Sr/ 86 Sr, 208,207,206 Pb/ 204 Pb, 143 Nd/ 144 Nd, 176 Hf/ 177 Hf, and 230 Th/ 232 Th. Concentration data could be obtained by spiking and equilibrating the sample with appropriate isotopic tracers before the onset of the separation process and, finally, measuring the isotope ratios modified by the isotope dilution process.

Sabzevar Ophiolite, NE Iran: Progress from embryonic oceanic lithosphere into magmatic arc constrained by new isotopic and geochemical data

NASA Astrophysics Data System (ADS)

Moghadam, Hadi Shafaii; Corfu, Fernando; Chiaradia, Massimo; Stern, Robert J.; Ghorbani, Ghasem

2014-12-01

The poorly known Sabzevar-Torbat-e-Heydarieh ophiolite belt (STOB) covers a large region in NE Iran, over 400 km E-W and almost 200 km N-S. The Sabzevar mantle sequence includes harzburgite, lherzolite, dunite and chromitite. Spinel Cr# (100Cr/(Cr + Al)) in harzburgites and lherzolites ranges from 44 to 47 and 24 to 26 respectively. The crustal sequence of the Sabzevar ophiolite is dominated by supra-subduction zone (SSZ)-type volcanic as well as plutonic rocks with minor Oceanic Island Basalt (OIB)-like pillowed and massive lavas. The ophiolite is covered by Late Campanian to Early Maastrichtian (~ 75-68 Ma) pelagic sediments and four plagiogranites yield zircon U-Pb ages of 99.9, 98.4, 90.2 and 77.8 Ma, indicating that the sequence evolved over a considerable period of time. Most Sabzevar ophiolitic magmatic rocks are enriched in Large Ion Lithophile Elements (LILEs) and depleted in High Field Strength Elements (HFSEs), similar to SSZ-type magmatic rocks. They (except OIB-type lavas) have higher Th/Yb and plot far away from mantle array and are similar to arc-related rocks. Subordinate OIB-type lavas show Nb-Ta enrichment with high Light Rare Earth Elements (LREE)/Heavy Rare Earth Elements (HREE) ratio, suggesting a plume or subcontinental lithosphere signature in their source. The ophiolitic rocks have positive εNd (t) values (+ 5.4 to + 8.3) and most have high 207Pb/204Pb, indicating a significant contribution of subducted sediments to their mantle source. The geochemical and Sr-Nd-Pb isotope characteristics suggest that the Sabzevar magmatic rocks originated from a Mid-Ocean Ridge Basalt (MORB)-type mantle source metasomatized by fluids or melts from subducted sediments, implying an SSZ environment. We suggest that the Sabzevar ophiolites formed in an embryonic oceanic arc basin between the Lut Block to the south and east and the Binalud mountains (Turan block) to the north, and that this small oceanic arc basin existed from at least mid-Cretaceous times. Intraoceanic subduction began before the Albian (100-113 Ma) and was responsible for generating Sabzevar SSZ-related magmas, ultimately forming a magmatic arc between the Sabzevar ophiolites to the north and the Cheshmeshir and Torbat-e-Heydarieh ophiolites to the south-southeast.

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

USGS Publications Warehouse

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

Schoneveld, Louise; Spandler, Carl; Hussey, Kelvin

2015-08-01

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

The amphiboles of the REE-rich A-type peralkaline Strange Lake pluton - fingerprints of magma evolution

NASA Astrophysics Data System (ADS)

Siegel, Karin; Williams-Jones, Anthony E.; van Hinsberg, Vincent J.

2017-09-01

Major and trace element compositions of amphibole in igneous environments commonly reflect evolving magma compositions. In this study, we use the amphibole-group minerals from the Strange Lake, REE-enriched peralkaline granitic pluton to gain insights into the evolution of the magma. This 1240 Ma old pluton consists of two main intrusive facies, an early hypersolvus granite, which occurs as separate northern and southern intrusions, and a more evolved transsolvus granite. In the hypersolvus granite the amphibole is a late interstitial phase, whereas in the transsolvus granite, it is present as phenocrysts. The amphibole compositions vary from calcic-sodic (ferro-ferri-katophorite) in the southern hypersolvus granite to sodic (arfvedsonite, ferro-ferri-leakeite) in the other, more evolved granitic units. High Na, Si, Li, and low Al and Ca concentrations in the amphibole phenocrysts of the transsolvus granite indicate formation from a more evolved magma compared to the hypersolvus granite, despite the fact that these crystals formed early. We interpret the increasing Fe3+/Fe2+ ratios in the amphibole of the hypersolvus granite to reflect crystal chemical effects (Na/Ca-ratio) and increasingly oxidizing conditions in the magma, whereas in the phenocrysts of the transsolvus granite, the increasing ratio was the product of increasing proportions of F- and OH- in the melt. The amphiboles of all the granite units have elevated Nb, Zr, Hf and REE concentrations compared to the bulk rock, suggesting that these elements are compatible in amphibole. By contrast the much lower Ti concentration was due to saturation of the magma in sodium-titanosilicates. The amphibole REE concentrations vary greatly among the granite units. Amphibole of the southern and northern hypersolvus granite contains 0.16 and 0.07 wt.% ∑ REE + Y, on average, respectively, and in the transsolvus granite, the average ∑ REE content is only 0.01 wt.%, despite the more evolved nature of its host transsolvus granite. We intrepret this compositional difference to be due to the fact that the latter represents phenocrysts, which crystallized early, whereas the hypersolvus arfvedsonite is a late interstitial phase. Chondrite-normalized REE profiles emphasise the wide range in LREE-, and the narrow range in HREE-concentrations of the amphiboles. The variations in the LREE-profiles reflect the variable crystallization of primary LREE-bearing phases, including monazite-(Ce), pyrochlore group minerals and gagarinite-(Ce), prior to or contemporaneous with the amphibole, as well as the exsolution of a LREE-rich fluoride melt. The LREE are incompatible in the amphibole structure (apparent D < 0.01) and are preferably accommodated by the octahedral C-site, whereas the HREE occupy the B-site. The chondrite-normalized HREE profiles are steep and display an increasing relative enrichment that culminates in compatible behavior for Yb and Lu (apparent D > 1). Owing to their small ionic radius and their compatibility with the amphibole structure, HREE concentrations were more controlled by partitioning (crystal chemical effects) than by the concentrations in the corresponding magma. Large proportions of the bulk HREE content (up to 70%) reside in the amphibole, and their later release through hydrothermal replacement helps to explain the extreme and unusual HREE enrichment of the Strange Lake pluton.

Actinide abundances in ordinary chondrites

NASA Technical Reports Server (NTRS)

Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

1990-01-01

Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

Distribution and origin of major and trace elements (particularly REE, U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains, France)

NASA Astrophysics Data System (ADS)

Aubert, D.; Probst, A.; Stille, P.

2003-04-01

Physical and chemical weathering of rocks and minerals lead to soil formation and allow the removal of chemical elements from these systems to ground- or surface waters. But most of the time the determination of element concentrations in soils is not sufficient to estimate whether they are being accumulated or what is their ability to be released in the environment. Thus, the distribution and chemical binding for a given element is very important because it determines its mobility and potential bioavailability throughout a soil profile. Heavy metals and REE (Rare Earth Elements) are particularly of environmental concern because of their potential toxicity. For most of them, their chemical form strongly depends on the evolution of physico-chemical parameters like pH or redox conditions that will induce adsorption-desorption, complexation or co-precipitation phenomena in the material. The purpose of this study is to determine the distribution of several major and trace elements (especially REE, Th and U) in an acidic forested podzolic soil profile from the Vosges Mountains (France). To achieve this goal we use a 7 step sequential extraction procedure that allows determining precisely the origin and the behaviour of particular elements in the environment (Leleyter et al., 1999). In addition we performed leaching experiments using very dilute acetic and hydrochloric acid in order to establish the origin of REE in this soil. The results of the sequential extraction indicate that most of the metals, Th and U are mainly bound to Fe oxides. Organic matter appears also to be a great carrier of P, Ca, Fe and REE even if its content is very low in the deep horizons of the soil. Moreover, we show that in each soil horizon, middle REE (MREE) to heavy REE (HREE) are more labile than light REE (LREE). Leaching experiments using dilute acid solution further suggest that in the shallowest horizons REE largely derive from atmospheric deposition whereas at greater depth, weathering and particularly phosphate mineral weathering (apatite) is the main contributor to labile REE in the soil.

The Darzi-Vali bauxite deposit, West-Azarbaidjan Province, Iran: Critical metals distribution and parental affinities

NASA Astrophysics Data System (ADS)

Khosravi, Maryam; Abedini, Ali; Alipour, Samad; Mongelli, Giovanni

2017-05-01

The Darzi-Vali bauxite deposit, located 20 km east of Bukan, in northwestern Iran, occurs as discontinuous layers and lenses within the Upper Permian carbonate rocks of the Ruteh Formation. These layers extend laterally for over ∼1 km and vary in thickness ranging from 2 to 17 m. We studied the chemical variations in a selected stratigraphic section throughout the deposit, focusing in particular on numbers of selected special metals that make the deposit of potential economic importance. The critical elements Co, Ga, Nb, Ta, LREEs, and HREEs, along with transition metal Ni, are variously depleted throughout the deposit with respect to Ti, which is assumed to be a less mobile element. Among the critical elements, Cr has only demonstrated conservative behavior. Factor analysis suggests that the factors controlling the distribution of LREEs and HREEs in the ore, which most likely depend on the local composition of groundwater during weathering, are different from those controlling the distribution of other critical elements. Further, the Darzi-Vali ore has ΣREE contents (773 ppm) much higher with respect to other deposits located in NW of Iran, making this deposit worthy of further investigations. As for parental affinity, the Eu anomalies show negligible fluctuations (0.82-0.94) all along the deposit confirming that bauxitization does not affect the effectiveness of this provenance proxy. The average Eu/Eu* value (0.89) of the ore is relatively far afield from that of the average carbonate bedrock (1.3) and close to that of the average mafic protolith (0.94), and similar results are also obtained using the Sm/Nd and Tb/Tb* proxies. Bivariate plots of Eu anomaly versus Sm/Nd and Tb anomalies further support the idea that mafic rocks are probably related to the volcanic activities. These volcanic activities affected the Iranian platform during the Upper Permian as proposed for other bauxite deposits in northwestern Iran. These mafic rocks were the probable precursor of the Darzi-Vali bauxite ore.

Refertilization process in the Patagonian subcontinental lithospheric mantle of Estancia Sol de Mayo (Argentina)

NASA Astrophysics Data System (ADS)

Melchiorre, Massimiliano; Coltorti, Massimo; Gregoire, Michel; Benoit, Mathieu

2015-05-01

Anhydrous mantle xenoliths equilibrated at 1003-1040 °C from Estancia Sol de Mayo (ESM, Central Patagonia, Argentina) and entrained in post-plateau alkaline lavas belonging to Meseta Lago Buenos Aires have been investigated aiming at reconstructing the depletion and enrichment processes that affected this portion of the Patagonia lithospheric mantle. Xenoliths are characterized by a coarse-grained protogranular texture and are devoid of evident modal metasomatism. They show two texturally different clinopyroxenes: protogranular (cpx1) and texturally related to spinel (cpx2). Three different types of orthopyroxenes are also recognized: large protogranular crystals with exsolution lamellae (opx1); small clean and undeformed grains without exsolution lamellae (opx2) and small grains arranged in a vein (opx3). Major element composition of clinopyroxenes and orthopyroxenes highlights two different trends characterized by i) a high Al2O3 content at almost constant mg# and ii) a slight increase in Al2O3 content with decreasing mg#. Clinopyroxenes are enriched in LREE and are characterized by prominent to slightly negative Nb, Zr and Ti anomalies. No geochemical differences are observed between cpx1 and cpx2, while a discrimination can be observed between opx1 and opx2 (LREE-depleted; prominent to slightly negative Ti and Zr anomalies) and opx3 (prominent positive Zr anomaly). Partial melting modeling using both major and trace elements indicates a melting degree between ~ 5% and ~ 13% (up to ~ 23% according to major element modeling) for lherzolites and between ~ 20% and ~ 30% for harzburgites (down to ~ 5% according to trace element modeling). La/Yb and Al2O3, as well as Sr and Al2O3 negative correlations in clinopyroxenes point to a refertilization event affecting this lithospheric mantle. The agent was most probably a transitional alkaline/subalkaline melt, as indicated by the presence of orthopyroxene in the vein and the similar geochemical features of ESM clinopyroxenes and those from Northern Patagonia pyroxenites which are derived from transitional alkaline/subalkaline lavas.

Magma Differentiation Processes That Develop an "Enriched" Signature in the Izu Bonin Rear Arc: Evidence from Drilling at IODP Site U1437

NASA Astrophysics Data System (ADS)

Heywood, L. J.; DeBari, S. M.; Schindlbeck, J. C.; Escobar-Burciaga, R. D.

2015-12-01

The Izu Bonin rear arc represents a unique laboratory to study the development of continental crust precursors at an intraoceanic subduction zone., Volcanic output in the Izu Bonin rear arc is compositionally distinct from the Izu Bonin main volcanic front, with med- to high-K and LREE-enrichment similar to the average composition of the continental crust. Drilling at IODP Expedition 350 Site U1437 in the Izu Bonin rear arc obtained volcaniclastic material that was deposited from at least 13.5 Ma to present. IODP Expedition 350 represents the first drilling mission in the Izu Bonin rear arc region. This study presents fresh glass and mineral compositions (obtained via EMP and LA-ICP-MS) from unaltered tephra layers in mud/mudstone (Lithostratigraphic Unit I) and lapillistone (Lithostratigraphic Unit II) <4.5 Ma to examine the geochemical signature of Izu Bonin rear arc magmas. Unit II samples are coarse-grained tephras that are mainly rhyolitic in composition (72.1-77.5 wt. % SiO2, 3.2-3.9 wt. % K2O and average Mg# 24) and LREE-enriched. These rear-arc rhyolites have an average La/Sm of 2.6 with flat HREEs, average Th/La of 0.15, and Zr/Y of 4.86. Rear-arc rhyolite trace element signature is distinct from felsic eruptive products from the Izu Bonin main volcanic front, which have lower La/Sm and Th/La as well as significantly lower incompatible element concentrations. Rear arc rhyolites have similar trace element ratios to rhyolites from the adjacent but younger backarc knolls and actively-extending rift regions, but the latter is typified by lower K2O, as well as a smaller degree of enrichment in incompatible elements. Given these unique characteristics, we explore models for felsic magma formation and intracrustal differentiation in the Izu Bonin rear arc.

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.

REY-Th-U Solute Dynamics in the Critical Zone: Combined Influence of Chemical Weathering, Atmospheric Deposit Leaching, and Vegetation Cycling (Mule Hole Watershed, South India)

NASA Astrophysics Data System (ADS)

Braun, Jean-Jacques; Riotte, Jean; Battacharya, Shrema; Violette, Aurélie; Prunier, Jonathan; Bouvier, Vincent; Candaudap, Frédéric; Maréchal, Jean-Christophe; Ruiz, Laurent; Panda, Smruthi Rekha; Subramanian, S.

2017-12-01

The source and proportion of REY, Th, and U exported by groundwater and by the ephemeral stream along with the elemental proportions passing through vegetation have been assessed in the subhumid tropical forested CZO of Mule Hole, Southern India. The study relies on a pluriannual hydrogeochemical monitoring combined with a hydrological model. The significant difference between the soil input (SI) and output (SO) solute fluxes (mmol/km2/yr) of LREE (SI-SO = 13,250-1,500), HREE (1,930-235), Th (64-12), and U (63-25) indicates a strong uptake by roots carried by canopy and forest floor processes. The contribution of atmospheric dust leaching can reach about 60% of LREE and 80% of HREE. At the watershed scale, the U solute flux exported by groundwater (180 mmol/km2/yr) mainly originates from the breakdown of primary U-bearing accessory minerals and dominates by a factor of 25 the stream flux. The precipitation of authigenic U-bearing phases and adsorption onto Fe-oxides and oxyhydroxides play a significant role for limiting the U mobility. In the groundwater, the plagioclase chemical weathering is efficiently traced by the positive Eu-anomaly. The very low (REY) to nil (Th) contents are explained by the precipitation of authigenic phases. In the stream flow, dominated by the overland flow (87% of the yearly stream flow), the solute exports (in mmol/km2/yr) of REY (1,080 for LREE and 160 for HREE) and of Th (14) dominate those by groundwater. Their mobility is enhanced by chelation with organic ligands produced by forest floor and canopy processes.

Hyperacid volcano-hydrothermal fluids from Copahue volcano, Argentina: Analogs for "subduction zone fluids"?

NASA Astrophysics Data System (ADS)

Varekamp, J. C.

2007-12-01

Hyperacid concentrated Chlorine-Sulfate brines occur in many young arc volcanoes, with pH values <1, high concentrations of volcanogenic elements (S, Cl, F, As, B) and the main rock forming elements (Ca, Al, Mg, K, Na, P). Sulfur isotope data and Silica thermometry from such fluids sampled over a ten year period from the Copahue volcanic system (Argentina) suggest reservoir temperatures of 175-300 oC, whereas the surface fluids do not exceed local boiling temperatures. These fluids are generated at much lower P-T conditions than fluids associated with a dehydrating subducted sediment complex below arc volcanoes, but their fundamental chemical compositions may have similarities. Incompatible trace element, major element concentrations and Pb isotope compositions of the fluids were used to determine the most likely rock protoliths for these fluids. Mean rock- normalized trace element diagrams then indicate which elements are quantitatively extracted from the rocks and which are left behind or precipitated in secondary phases. Most LILE show flat rock-normalized patterns, indicating close to congruent dissolution, whereas Ta-Nb-Ti show strong depletions in the rock-normalized diagrams. These HFSE are either left behind in the altered rock protolith or were precipitated along the way up. The behavior of U and Th is almost identical, suggesting that in these low pH fluids with abundant ligands Th is just as easily transported as U, which is not the case in more dilute, neutral fluids. Most analyzed fluids have steeper LREE patterns than the rocks and have negative Eu anomalies similar to the rocks. Fluids that interacted with newly intruded magma e.g., during the 2000 eruption, have much less pronounced Eu anomalies, which was most likely caused by the preferential dissolution of plagioclase when newly intruded magma interacted with the acid fluids. The fluids show a strong positive correlation between Y and Cd (similar to MORB basalts, Yi et al., JGR, 2000), suggesting that Cd is mainly a rock-derived element that may not show chalcophilic behavior. The fluids are strongly enriched (relative to rock) in As, Zn and Pb, suggesting that these elements were carried with the volcanic gas phase into the system. In summary, if these fluids are broadly similar to fluids from dehydrating subducted sediments, they tend to transport preferently the LILE, LREE, U as well as Th, while the HFSE are left behind.

Hf-Nd Isotopic Correlation in the Deccan Flood Basalt Province

NASA Astrophysics Data System (ADS)

Saha, A.; Basu, A. R.; Barling, J.; Anbar, A. D.; Hooper, P. R.

2001-12-01

Hafnium isotopes along with other isotopic and geochemical characteristics, including incompatible trace elements, of several of the lower formations of the Deccan Flood Basalt Province were analyzed to characterize petrogenesis of different tholeiitic lava suites, especially with respect to potential mantle and crustal sources. The rare earth elements of the different formations (from top to bottom- Mahabaleshwar, Ambenali, Bushe, Khandala and Neral) all show an LREE-enriched signature, concentrations varying between 30 to 60 times chondrite for La. (La/Lu)n values range from 4.1 to above 8 with the exception of Ambenali, which has a less LREE-enriched signature with (La/Lu)n values ranging between 3.6 to 5.3. Hafnium isotopic data of the lower formations of the Deccan show initial \\epsilonHf(T) values covering a range from -3 to -28. 176Lu/177Hf varies between 0.20 to 0.70. f(Lu/Hf) varies within a narrow range, between -0.90 to -0.97 while f(Sm/Nd) ranges from -0.84 to -0.86. Bushe gives the lowest range of \\epsilonHf(T) from -21 to -28 with the corresponding \\epsilonNd(T) varying between -4.0 and -16.9, while Khandala for almost the same range of neodymium isotopic values has \\epsilonHf(T) between -11 and -15. The \\epsilonHf(T) values of Neral is in between those of Khandala and Bushe, around -19. Ambenali, has the narrowest range with \\epsilonHf(T) of -3 and \\epsilonNd(T) between 3 and 5. The Ambenali suite reflects the least contaminated of the Deccan suite of lavas as analyzed here and previously confirmed by other isotopic studies. In Hf-Nd isotope correlation plot, the lower Deccan formations of Neral, Khandala and Bushe define individual subparallel arrays that are shallower than the oceanic basalt array and the overall terrestrial array, including the crustal array, although the bulk of the lower formation data fall within the crustal array of Vervoort et al (1999). From these subparallel Hf-Nd arrays, it is evident that the other end-members contributing to the Ambenali-type source magmas are distinctly different for each of these lava suites, and can be characterized by their \\epsilonHf(T) values as mentioned above. Although these end-members are discernible in \\epsilonNd vs \\epsilonSr plot (e.g., Peng et al, 1994) of previous studies, our new Hf-isotopic data provide clear evidence of major contributions from the ancient Indian continental crustal reservoirs in the petrogenesis of the lower lava formations of the Deccan Flood Basalt Province.

Re-Os systematics of early proterozoic ferropicrites, Pechenga Complex, northwestern Russia: Evidence for ancient 187Os-enriched plumes

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Morgan, John W.; Hanski, Eero J.; Smolkin, Valery F.

1997-08-01

The Re-Os isotopic systematics of various ferropicritic flows and sills of the Pechenga Complex, Russia, have been examined. During crystallization about 1.98 Ga ago, many of these bodies became highly differentiated. In addition, some of the larger igneous units are associated with major NiCu ore deposits. The melts that produced these rocks have been termed ferropicritic because of their high FeO and MgO contents. They are also enriched in light rare earth elements (LREEs), TiO 2, Zr, and many other incompatible trace elements. Previous studies have concluded that the ferropicrites were most likely derived from an Fe-rich mantle plume that had a complex history of long-term LREE depletion (initial ɛNd = + 1.4), but that also experienced a LREE enrichment event within 200 Ma of the generation of the rocks. Whole rock samples believed to be most representative of primary melt compositions indicate that initial melt concentrations of rhenium and osmium were approximately 1.1 ppb and 0.5 ppb, respectively. The high primary melt concentrations presumably made the osmium contained in the melts relatively immune to the effects of crustal contamination. Nonetheless, all ore-bearing intrusions examined show osmium isotopic evidence for crustal contamination. For example, the initial γOs for some primary magmatic sulfides from the Pilgujärvi intrusion average +46. Other ore-bearing intrusions, such as the Kammikivi sill, appear to have been similarly contaminated by crustal osmium during the injection of magma, with initial yo, values as high as +251. The seemingly high levels of crustal osmium may be attributed to the rapidly diminishing concentrations of osmium in the melts as the larger bodies differentiated, combined with localized in situ assimilation of the metasedimentary rocks that comprise the country rocks. The Re-Os systematics of some whole rock samples of both mineralized and sulfide-poor intrusions were affected by post-magmatic events, especially the greenschist grade metamorphism that impacted the rocks between about 1.7 and 1.8 Ga ago. The metamorphic effects are reflected in the recrystallization of many of the primary sulfides. As a consequence of this open-system behavior in many whole rock samples, the primary igneous Re-Os systematics of these rocks are best examined via analysis of magmatic phases such as chromite, olivine, clinopyroxene, and primary sulfides. Chromite and ilmenite+sulfide separates from two sulfide-poor lava flows, the Lammas and Keskitunturi, have characteristically low 187Re/ 188Os ( < l), and because of the limited age correction, precisely define the initial γOs of these systems to be +6.0±0.7. Because of the identical initial compositions of the two, spatially distinct lava flows, and the fact that these flows were extruded onto only slightly older volcanic rocks, we conclude that the +6.0 value reflects the composition of the mantle source and not minor crustal contamination. Although 187Os-enriched, plume-derived systems are common during the Phanerozoic, this is the earliest known evidence for the existence of long-term, Re-enriched mantle reservoirs. The most commonly invoked model to explain 187Os enrichments in Phanerozoic systems, oceanic crustal recycling, in this instance requires that very large proportions of oceanic crust were recycled into the mantle source and that the event was likely very ancient. Other options, such as core-mantle interaction and a stratified mantle, are also discussed.

Petrologic evolution of divergent peralkaline magmas from the Silent Canyon caldera complex, southwestern Nevada volcanic field

USGS Publications Warehouse

Sawyer, D.A.; Sargent, K.A.

1989-01-01

The Silent Canyon volcanic center consists of a buried Miocene peralkaline caldera complex and outlying peralkaline lava domes. Two widespread ash flow sheets, the Tub Spring and overlying Grouse Canyon members of the Miocene Belted Range Tuff, were erupted from the caldera complex and have volumes of 60-100 km3 and 200 km3, respectively. Eruption of the ash flows was preceded by widespread extrusion of precaldera comendite domes and was followed by extrusion of postcollapse peralkaline lavas and tuffs within and outside the caldera complex. Lava flows and tuffs were also deposited between the two major ash flow sheets. Rocks of the Silent Canyon center vary significantly in silica content and peralkalinity. Weakly peralkaline silicic comendites (PI 1.0-1.1) are the most abundant precaldera lavas. Postcollapse lavas range from trachyte to silicic comendite; some have anomalous light rare earth element (LREE) enrichments. Silent Canyon rocks follow a common petrologic evolution from trachyte to low-silica comendite; above 73% SiO2, compositions of the moderately peralkaline comendites diverge from those of the weakly peralkaline silicic comendites. The development of divergent peralkaline magmas, toward both pantelleritic and weakly peralkaline compositions, is unusual in a single volcanic center. -from Authors

Geochronology and geochemistry of the Early Jurassic Yeba Formation volcanic rocks in southern Tibet: Initiation of back-arc rifting and crustal accretion in the southern Lhasa Terrane

NASA Astrophysics Data System (ADS)

Wei, Youqing; Zhao, Zhidan; Niu, Yaoling; Zhu, Di-Cheng; Liu, Dong; Wang, Qing; Hou, Zengqian; Mo, Xuanxue; Wei, Jiuchuan

2017-05-01

Understanding the geological history of the Lhasa Terrane prior to the India-Asia collision ( 55 ± 10 Ma) is essential for improved models of syn-collisional and post-collisional processes in the southern Lhasa Terrane. The Miocene ( 18-10 Ma) adakitic magmatism with economically significant porphyry-type mineralization has been interpreted as resulting from partial melting of the Jurassic juvenile crust, but how this juvenile crust was accreted remains poorly known. For this reason, we carried out a detailed study on the volcanic rocks of the Yeba Formation (YF) with the results offering insights into the ways in which the juvenile crust may be accreted in the southern Lhasa Terrane in the Jurassic. The YF volcanic rocks are compositionally bimodal, comprising basalt/basaltic andesite and dacite/rhyolite dated at 183-174 Ma. All these rocks have an arc-like signature with enriched large ion lithophile elements (LILEs; e.g., Rb, Ba and U) and light rare earth elements (LREEs) and depleted high field strength elements (HFSEs; e.g., Nb, Ta, Ti). They also have depleted whole-rock Sr-Nd and zircon Hf isotopic compositions, pointing to significant mantle isotopic contributions. Modeling results of trace elements and isotopes are most consistent with the basalts being derived from a mantle source metasomatized by varying enrichment of subduction components. The silicic volcanic rocks show the characteristics of transitional I-S type granites, and are best interpreted as resulting from re-melting of a mixed source of juvenile amphibole-rich lower crust with reworked crustal materials resembling metagraywackes. Importantly, our results indicate northward Neo-Tethyan seafloor subduction beneath the Lhasa Terrane with the YF volcanism being caused by the initiation of back-arc rifting. The back-arc setting is a likely site for juvenile crustal accretion in the southern Lhasa Terrane.

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.

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

Resolving the potential mantle reservoirs that influence volcanism in the West Antarctic Rift System

NASA Astrophysics Data System (ADS)

Maletic, E. L.; Darrah, T.

2017-12-01

Lithospheric extension and magmatism are key characteristics of active continental rift zones and are often associated with long-lasting alkaline magmatic provinces. In these settings, a relationship between lithospheric extension and mantle plumes is often assumed for the forces leading to rift evolution and the existence of a plume is commonly inferred, but typically only extension is supported by geological evidence. A prime example of long-lasting magmatism associated with an extensive area of continental rifting is the West Antarctic Rift System (WARS), a 2000 km long zone of ongoing extension within the Antarctic plate. The WARS consists of high alkaline silica-undersaturated igneous rocks with enrichments in light rare earth elements (LREEs). The majority of previous geochemical work on WARS volcanism has focused on bulk classification, modal mineralogy, major element composition, trace element chemistry, and radiogenic isotopes (e.g., Sr, Nd, and Pb isotopes), but very few studies have evaluated volatile composition of volcanics from this region. Previous explanations for WARS volcanism have hypothesized a plume beneath Marie Byrd Land, decompression melting of a fossilized plume head, decompression melting of a stratified mantle source, and mixing of recycled oceanic crust with one or more enriched mantle sources from the deep mantle, though researchers are yet to reach a consensus. Unlike trace elements and radiogenic isotopes which can be recycled between the crust and mantle and which are commonly controlled by degrees of partial melting and prior melt differentiation, noble gases are present in low concentrations and chemically inert, allowing them to serve as reliable tracers of volatile sources and subsurface processes. Here, we present preliminary noble gas isotope (e.g., 3He/4He, CO2/3He, CH4/3He, 40Ar/36Ar, 40Ar*/4He) data for a suite of lava samples from across the WARS. By coupling major and trace element chemistry with noble gas elemental and isotopic composition and other volatiles from a suite of volcanic rocks in the WARS, we can better constrain a magmatic source and provide geological evidence that could support or oppose the existence of a mantle plume, HIMU plume, or deconvolve mantle-lithosphere interactions.

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.

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.

Chemistry of amphiboles and clinopyroxenes from Euganean (NE Italy) cumulitic enclaves: implications for the genesis of melts in an extensional setting

NASA Astrophysics Data System (ADS)

Bartoli, O.; Meli, S.; Sassi, R.; Magaraci, D.

2009-04-01

The magmatism of the Euganean Volcanic District (Veneto Volcanic Province, VVP) developed in the last phases of the Alpine orogenesis; the geochemical and geophysical data are consistent with an extensional geodynamic context (Milani et al., 1999). Cumulitic gabbroic enclaves occur within the Euganean trachytes, and Bartoli et al. (2008) pointed to their cogenetic origin with the Euganean host lavas. Sr isotopic data suggest that these cumulates derived from uncontaminated mantle-derived liquids. We analysed both cumulus and intercumulus amphiboles and clinopyroxenes by electron microprobe and LA-ICP-MS. The cumulus-intercumulus Cpx are diopsides and augites. The Mg#Cpx varies in a wide range (Mg#cumulus-Cpx= 0.74-0.84 and Mg#intercumulus-Cpx= 0.67-0.68). They show a MREE enrichment relative to LREE and HREE (LaN/SmN= 0.46-0.68 and TbN/YbN= 2.18-4.77). No significant Eu anomaly (Eu/Eu* = 0.78-1.23) was observed. On a chondrite-normalized spiderdiagram Cpx exhibits significant Pb and Co negative anomalies, and less evident negative anomalies for Sr and Zr. La, Sm and HREE increase, whereas Ba, Ti, Li and V decrease from core to rim. These Cpx exhibit high Cr contents (701-2958 ppm). Moreover, they display trace element differences when compared to Cpx from MORB gabbros. We analyzed also amphiboles: pargasites, edenites and kaersutites. In the cumulus Amph Mg# varies in the range 0.60-0.69, whereas in the intercumulus assemblage from 0.57 to 0.63. The high K2O and TiO2 contents are distinct from that of amphiboles in MORB gabbros. LREE are enriched relative to HREE (LaN/YbN = 5.07-7.56). Moreover, TbN/YbN = 2.50-4.02 indicates a HREE depletion relative to MREE. REE patterns lack a significant Eu anomaly (Eu/Eu* = 1.06-1.19). From core to rim Th and U decrease in cumulus crystals, but they increase in the intercumulus Amph. Ba (258-282 ppm) is enriched relative to other LILE and Nb-Ta are enriched relative to LREE. Cr varies in the range 423-594 ppm. The similar REE and HFSE content of intercumulus and cumulus Amph may suggest the existence of some post-cumulus processes. We calculated the chemistry of the liquids which should have been in equilibrium with cumulus phases, employing a set of Ds•l. In the liquid in equilibrium with Cpx LREE and MREE are enriched up to 40 and 11 times respectively relative to HREE, which are at about N-MORB concentrations (LaN/YbN = 42.5 and SmN/YbN = 11). Some LILE (i.e., Rb and Ba), Th and U are enriched relative to HFSE and REE. The theoretical composition of the liquid in equilibrium with Amph differs from Cpx-liquid in the marked enrichment of U and Th over LILE and HFSE. A LREE and MREE enrichment is observed (LaN/YbN = 35.4 and SmN/YbN = 3.6). The discrepancies of calculated liquid compositions cannot be ascribed only to the uncertainty in the choice of Ds•l. This may indicate trace element modifications in response to post-cumulus processes involving the amphiboles. The concentrations of HFSE in the calculated liquids (Zr/Hf = 60.2-72.7, Zr/Nb = 1.7-6.5 and Th/Hf = 3.8-6.9) and the incompatible element ratios, (e.g., La/Nb = 0.5-0.7, Pb/Ce = 0.01-0.05, La/Y = 2.3-2.8 and Ce/Nd = 1.9-2.8), are not comparable to those of N-MORB but to those of HIMU-OIB suggesting that typical MORB-type mantle couldn't be the source of these liquids. Nb and Ta are variable, possibly due to an heterogeneity in the lithospheric mantle. The existence of some peculiar trace element signatures of the recalculated liquids (LILE enrichment, high LREE/HREE ratio and abrupt enrichment in U and Th) has been attributed to slab-derived melts/fluids with an abundant sedimentary component. Our estimates are in agreement with the geodynamic scenario proposed by Macera et al. (2007), who explained the occurrence of both HIMU-OIB-type magmatism and subduction-related metasomatism in the VVP mantle lithosphere. According to their model, a mantle plume with HIMU-OIB geochemical signature rose from the deep mantle twice with subsequent partial melting episodes of the plume material: the first time during Paleocene, before the subducted European lithospheric slab (from which the LILE-, U- and Th-enriched fluids/melts derived) intercepted the mantle plume, and the second time during middle Eocene, after slab detachment and opening of a plate window. The liquids we have modeled can derive from partial melting of a subcontinental mantle source percolated by HIMU-OIB- and subduction-related fluids/melts with an abundant sedimentary component. Similarly, our recalculated liquids display some trace element signatures close to those shown by the liquids computed by Tiepolo & Tribuzio (2005) for cumulates of the Adamello batholith during alpine orogeny.

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.

Trace element and Sm Nd systematics of volcanic and intrusive rocks from the 3 Ga Lumby Lake Greenstone belt, Superior Province: evidence for Archean plume arc interaction

NASA Astrophysics Data System (ADS)

Hollings, Pete; Wyman, Derek

1999-02-01

The metavolcanic Lumby Lake belt comprises mafic tholeiites intercalated with thin felsic pyroclastic units. Al-undepleted komatiites are present towards the top of the stratigraphy. Identification of Al-depleted pyroclastic komatiites associated with chemical and siliciclastic sedimentary rocks indicates the upper portion of the 3 Ga Lumby Lake stratigraphy is directly comparable to a stratigraphic sequence developed on a paleoregolith in the nearby Steep Rock greenstone belt. The lower portion of the Lumby Lake sequence therefore represents a rarely preserved association of komatiite-tholeiite and calc alkaline volcanism developed prior to rifting episodes identified in ˜3 Ga terranes of the northern Superior Province. Al-undepleted komatiites are characterised by elevated MgO (18-24 wt.%) and Ni (600-1500 ppm) contents, in conjunction with variable LREE depletion (La/Sm n=0.5-0.8). Intercalated spinifex textured komatiitic basalts possess lower MgO (10-11 wt.%) and Ni (150-180 ppm) and flat to weakly enriched LREE (La/Sm n=0.9-1.1). Pyroclastic Al-depleted komatiites (Al 2O 3/TiO 2=4-5) are strongly LREE enriched (La/Yb n=6.7-10.5) with variable HFSE anomalies. Compositionally uniform tholeiites with variably depleted to enriched LREE (La/Sm n=0.8-1.2) and minor HFSE anomalies dominate the stratigraphy of the belt. A distinct subset of tholeiites, occurring towards the centre of the belt, is characterised by low Al 2O 3/TiO 2 ratios, LREE enrichment and the absence of HFSE anomalies. Minor intermediate (SiO 2=53-64 wt.%) volcanic rocks with pronounced REE fractionation (La/Yb n=0.8-1.1), high Al 2O 3/TiO 2 and Zr/Y ratios also occur throughout the belt. Two distinct subtypes of felsic pyroclastic rocks are recognised intercalated sporadically throughout the stratigraphy. Both types display pronounced LREE enrichment (La/Sm n=3.9-6.1) but Type 1 has strongly fractionated HREE patterns (Gd/Yb n=1.5-4.6) whereas, Type 2 HREE patterns are generally flat (Gd/Yb n=1.7-1.9). Intrusive counterparts to both subtypes have been identified within the Marmion Lake batholith to the south of the greenstone belt. The felsic subtypes may be derived from similar parental magmas by variable degrees of hornblende involvement during fractionation processes. Sm/Nd isotope systematics from a range of rock compositions have yielded ɛNd values of +2 to +5, typical of the range for Archean volcanic and intrusive rocks. Komatiite-tholeiite associations within Archean terranes are interpreted as the result of plume related magmatism likely in a geodynamic setting comparable to Phanerozoic oceanic plateaux. In contrast intermediate and felsic rocks are typical of calc alkaline suites generally attributed to Archean subduction related environments. The coeval eruption of the two magma suites in the Lumby Lake belt is best interpreted as the result of the sporadic subduction of plume-modified oceanic spreading centres over 10s of m.y. and the eventual impingement of a mantle plume upon an active subduction zone. This process can also account for the young age of basement material relative to overlying rift sequences in 3 Ga terranes of the Superior Province.

Integrated elemental and Sr-Nd-Pb-Hf isotopic studies of Mesozoic mafic dykes from the eastern North China Craton: implications for the dramatic transformation of lithospheric mantle

NASA Astrophysics Data System (ADS)

Liu, Shen; Feng, Caixia; Santosh, M.; Feng, Guangying; Coulson, Ian M.; Xu, Mengjing; Guo, Zhuang; Guo, Xiaolei; Peng, Hao; Feng, Qiang

2018-02-01

Evolution of the lithospheric mantle beneath the North China Craton (NCC) from its Precambrian cratonic architecture until Paleozoic, and the transformation to an oceanic realm during Mesozoic, with implications on the destruction of cratonic root have attracted global attention. Here we present geochemical and isotopic data on a suite of newly identified Mesozoic mafic dyke swarms from the Longwangmiao, Weijiazhuang, Mengjiazhuang, Jiayou, Huangmi, and Xiahonghe areas (Qianhuai Block) along the eastern NCC with an attempt to gain further insights on the lithospheric evolution of the region. The Longwangmiao dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 4.3) and EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.706; ε Nd (t) < -6.3, (206Pb/204Pb) i > 16.6, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.8, ε Hf (t) < -22.4). The Weijiazhuang dykes are sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7), and display similar EM1-like isotopic features ((87Sr/86Sr) i > 0.706; ε Nd (t) < -7.0, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -23.3). The Mengjiazhuang dykes are also sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 2.4) and EM1-like isotopic features((87Sr/86Sr) i > 0.706; ε Nd (t) < -18.4, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). The Jiayou dykes also display sub-alkaline affinity with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7) and EM1-like Sr-Nd-Pb-Hf isotopic features ((87Sr/86Sr) i > 0.706; ε Nd(t) < -15.3, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -18.4). The Huangmi dykes are alkaline (with Na2O + K2O ranging to more than 5.9 wt.%)) with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 9.3) and EM1-like isotopic composition ((87Sr/86Sr) i > 0.705; ε Nd (t) < -15.1, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -12.2). The Xiahonghe dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N = 2.12-2.84) and similar EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.705; ε Nd (t)<-18.0, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). Our data from the various mafic dyke suites suggest that the magmas were derived from EM1-like lithospheric mantle, corresponding to lithospheric mantle modified by the previously foundered lower crust beneath the eastern NCC. Our results suggest contrasting lithospheric evolution from Triassic (212 Ma) to Cretaceous (123 Ma) beneath the NCC. These mafic dykes mark an important phase of lithospheric thinning in the eastern North China Craton.

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

Petrogenesis and magmatic evolution of ∼130 Ma A-type granites in Southeast China

NASA Astrophysics Data System (ADS)

Sun, Fajun; Xu, Xisheng; Zou, Haibo; Xia, Yan

2015-02-01

A number of Late Mesozoic (∼130 Ma) A-type granitic plutons have been identified in Southeast China. Here we investigate the petrogenesis of one of these granitic plutons in Southeast China, the Sanqingshan-Damaoshan (SD) granites in northeastern Jiangxi Province, using zircon U-Pb geochronology, Hf isotopic analyses, and major and trace element analyses. The SD granites are metaluminous to weakly peraluminous and show typical A-type affinity, which is characterized by high SiO2, Na2O + K2O, rare earth element (REE), high field strength element (HFSE) contents, Ga/Al and Fe# [FeOt/(FeOt + MgO)] values. Zircon grains from the SD granites and some other ∼130 Ma A-type granites commonly contain oscillatory zoning ;cores; surrounded by unzoned to weakly zoned ;rims;. Detailed studies of zircons from the SD granites show that ;rims; are enriched in LREE, Th and U compared with ;cores;. Chondrite-normalized REE patterns of the ;cores; increase steeply from La to Lu and show pronounced Ce and Eu anomalies, while REE patterns of the ;rims; display higher REE abundances with flatter LREE patterns and moderate Ce anomalies. Nevertheless, Lu-Hf isotopic analyses and Ti-in zircon thermometer show similar characteristics between ;rims; and ;cores;, indicating that the ;rims; may crystallize under the effect of internal magmatic hydrothermal fluids. U-rich ;rims; are more susceptible to Pb loss caused by self-irradiation, which may lead to significant younger U-Pb ages. As a result, U-Pb ages of zircon ;cores; (∼130 Ma) represent crystallization ages of the SD granites. εHf(t) values of zircon grains from the SD granites are between -6.4 and -0.4 with Mesoproterozoic model ages (T2DM) ranging from 1.22 to 1.59 Ga, suggesting that the granites may be formed by partial melting of Proterozoic basement. Compared with other adjacent ∼130 Ma A-type granitic plutons in SE China, the SD granites have similar geochemical characteristics and Hf isotopic compositions to those of Xiangshan, Daqiaowu, Yangmeiwan, and Tongshan granites, but different from the Baijuhuajian granite. εHf(t) values of the Baijuhuajian granites are higher than other granites, indicating significant participation of juvenile materials. These ∼130 Ma A-type granites indicate a back-arc extension setting due to the roll-back of paleo-Pacific plate, where the crust and lithospheric mantle became progressively thinned. The upwelling of asthenosphere triggered the partial melting of crustal rocks and generated the Sanqingshan-Damaoshan, Tongshan, Daqiaowu and Yangmeiwan granitic plutons. With ongoing back-arc extension and increased subduction angle during the roll-back of subducted paleo-Pacific slab, the back-arc extension gradually intensified, resulting in significant additions of mantle juvenile materials to the crustal magma and the formation of the Baijuhuajian granite.

Eclogitic inclusions in diamonds: Evidence of complex mantle processes over time

NASA Astrophysics Data System (ADS)

Taylor, Lawrence A.; Snyder, Gregory A.; Crozaz, Ghislaine; Sobolev, Vladimir N.; Yefimova, Emiliya S.; Sobolev, Nikolai V.

1996-08-01

The first ion-probe trace element analyses of clinopyroxene-garnet pairs both included within diamonds and from the eclogite host xenoliths are reported; these diamondiferous eclogites are from the Udachnaya and Mir kimberlite pipes, Yakutia, Russia. The major and trace element analyses of these diamond-inclusion and host-rock pairs are compared in order to determine the relative ages of the diamonds, confirm or deny genetic relationships between the diamonds and the eclogites, evaluate models of eclogite petrogenesis, and model igneous processes in the mantle before, during, and after diamond formation. The most striking aspect of the chemical compositions of the diamond inclusions is the diversity of relationships with their eclogite hosts. No single distinct pattern of variation from diamond inclusion minerals to host minerals is found for all four samples. Garnet and clinopyroxene inclusions in the diamonds from two samples (U-65/3 and U-66/3) have lower Mg#s, lower Mg, and higher Fe contents, and lower LREE than those in the host eclogite. We interpret such variations as due to metasomatism of the host eclogite after diamond formation. One sample, U-41/3 shows enrichment in diamond-inclusion MREE enrichment relative to the eclogite host and may indicate a metasomatic event prior to, or during, diamond formation. Bulanova [2] found striking differences between inclusions taken from within different portions of the very same diamond. Clinopyroxene inclusions taken from the central (early) portions of Yakutian diamonds were lower in Mg# and Mg contents (by up to 25%) than those later inclusions at the rims of diamonds. These trends are parallel to those between diamond inclusions and host eclogites determined for four of the five samples from the present study and may merely represent changing magmatic and/or P-T conditions in the mantle. Garnet trace element compositions are similar in relative proportions, but variable in abundances, between diamond inclusions and host eclogites. This is probably due to the rapid diffusion of trace elements in garnet under mantle temperatures and consequent alteration of the garnet, and not due to juvenile diamonds 'locking in' source heterogeneities (c.f., [3]). Trace element compositions of clinopyroxenes included in diamonds are generally similar to those in the host eclogite. However, one host clinopyroxene does show enrichment in the LREE compared to that in the inclusion and may be attributed to mantle metasomatism, not related to kimberlite transport. In another eclogite, M-46, the host clinopyroxene is depleted in the LREE and Fe, and enriched in the HREE and Mg, relative to the inclusion and is consistent with partial melting of the eclogite subsequent to diamond formation. Sm/Nd ratios in clinopyroxenes appear to be little affected by these processes for most samples, allowing SmNd isotopic studies to yield important information about ancient protoliths. Eclogitic mineral inclusions in Yakutian diamonds appear consanguineous with the diamonds, a contention supported by the observations of Bulanova [2]. Therefore, ReOs whole-rock and Sm/Nd clinopyroxene age determinations of the Udachnaya eclogites also yield the time of diamond formation, approximately 2.9 Ga [32,33].

Geochemistry of komatiites and basalts from the Rio das Velhas and Pitangui greenstone belts, São Francisco Craton, Brazil: Implications for the origin, evolution, and tectonic setting

NASA Astrophysics Data System (ADS)

Verma, Sanjeet K.; Oliveira, Elson P.; Silva, Paola M.; Moreno, Juan A.; Amaral, Wagner S.

2017-07-01

The Neoarchean Rio das Velhas and Pitangui greenstone belts are situated in the southern São Francisco Craton, Minas Gerais, Brazil. These greenstone belts were formed between ca. 2.79-2.73 Ga, and consist mostly of mafic to ultramafic volcanics and clastic sediments, with minor chemical sediments and felsic volcanics that were metamorphosed under greenschist facies. Komatiites are found only in the Rio das Velhas greenstone belt, which is composed of high-MgO volcanic rocks that have been identified as komatiites and high-Mg basalts, based on their distinctive geochemical characteristics. The Rio das Velhas komatiites are composed of tremolite + actinolite + serpentine + albite with a relict spinifex-texture. The Rio das Velhas komatiites have a high magnesium content ((MgO)adj ≥ 28 wt.%), an Al-undepleted Munro-type [(Al2O3/TiO2)adj and (CaO/Al2O3)adj] ratio ranging from 27 to 47 and 0.48 to 0.89, relatively low abundances of incompatible elements, a depletion of light rare earth elements (LREE), a pattern of non-fractionated heavy rare- earth elements (HREE), and a low (Gd/Yb)PM ratio (≤ 1.0). Negative Ce anomalies suggest that alteration occurred during greenschist facies metamorphism for the komatiites and high-Mg basalts. The low [(Gd/Yb)PM < 1.0] and [(CaO/Al2O3)adj < 0.9)], high [(Al2O3/TiO2)adj > 18] and high HREE, Y, and Zr content suggest that the Rio das Velhas komatiites were derived from the shallow upper mantle without garnet involvement in the residue. The chemical compositions [(Al2O3/TiO2)adj, (FeO)adj, (MgO)adj, (CaO/Al2O3)adj, Na, Th, Ta, Ni, Cr, Zr, Y, Hf, and REE] indicate that the formation of the komatiites, high-Mg basalts and basalts occurred at different depths and temperatures in a heterogeneous mantle. The komatiites and high-Mg basalts melted at liquidus temperatures of 1450-1550 °C. The Pitangui basalts are enriched in the highly incompatible LILE (large-ion lithophile elements) relative to the moderately incompatible HFS (high field strength) elements. The Zr/Th ratio ranging from 76 to 213 and the relationship between the Nb/Th and Th/Yb ratios indicate that there is no crustal contamination in the Pitangui greenstone basalts. New multi-dimensional discrimination diagrams and conventional normalized multi-element diagrams indicate an island arc (IA) setting for the komatiites and high-Mg basalts from the Rio das Velhas and a mid ocean-ridge (MOR) to IA setting for the basalts from the Pitangui greenstone belts.

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.

Stratigraphy, geochemistry and tectonic significance of the Oligocene magmatic rocks of western Oaxaca, southern Mexico

USGS Publications Warehouse

Martiny, B.; Martinez-Serrano, R. G.; Moran-Zenteno, D. J.; MacIas-Romo, C.; Ayuso, R.A.

2000-01-01

In Western Oaxaca, Tertiary magmatic activity is represented by extensive plutons along the continental margin and volcanic sequences in the inland region. K-Ar age determinations reported previously and in the present work indicate that these rocks correspond to a relatively broad arc in this region that was active mainly during the Oligocene (~ 35 to ~ 25 Ma). In the northern sector of western Oaxaca (Huajuapan-Monte Verde-Yanhuitlan), the volcanic suite comprises principally basaltic andesite to andesitic lavas, overlying minor silicic to intermediate volcaniclastic rocks (epiclastic deposits, ash fall tuffs, ignimbrites) that were deposited in the lacustrine-fluvial environment. The southern sector of the volcanic zone includes the Tlaxiaco-Laguna de Guadalupe region and consists of intermediate to silicic pyroclastic and epiclastic deposits, with silicic ash fall tuffs and ignimbrites. In both sectors, numerous andesitic to dacitic hypabyssal intrusions (stocks and dikes) were emplaced at different levels of the sequence. The granitoids of the coastal plutonic belt are generally more differentiated than the volcanic rocks that predominate in the northern sector and vary in composition from granite to granodiorite. The studied rocks show large-ion lithophile element (LILE) enrichment (K, Rb, Ba, Th) relative to high-field-strength (HFS) elements (Nb, Ti, Zr) that is characteristic of subduction-related magmatic rocks. On chondrite-normalized rare earth element diagrams, these samples display light rare earth element enrichment (LREE) and a flat pattern for the heavy rare earth elements (HREE). In spite of the contrasting degree of differentiation between the coastal plutons and inland volcanic rocks, there is a relatively small variation in the isotopic composition of these two suites. Initial 87Sr/86Sr ratios obtained and reported previously for Tertiary plutonic rocks of western Oaxaca range from 0.7042 to 0.7054 and ??Nd values, from -3.0 to +2.4, and for the volcanic rocks, from 0.7042 to 0.7046 and 0 +2.6. The range of these isotope ratios and those reported for the basement rocks in this region suggest a relatively low degree of old crustal involvement for most of the studied rocks. The Pb isotopic compositions of the Tertiary magmatic rocks also show a narrow range [(206Pb/204Pb) = 18.67-18.75; (207Pb/204Pb) = 15.59-15.62; (208Pb/204Pb) = 38.44-38.59], suggesting a similar source region for the volcanic and plutonic rocks. Trace elements and isotopic compositions suggest a mantle source in the subcontinental lithosphere that has been enriched by a subduction component. General tectonic features in this region indicate a more active rate of transtensional deformation for the inland volcanic region than along the coastal margin during the main events of Oligocene magmatism. The lower degree of differentiation of the inland volcanic sequences, particularly the upper unit of the northern sector, compared to the plutons of the coastal margin, suggests that the differentiation of the Tertiary magmas in southern Mexico was controlled to a great extent by the characteristics of the different strain domains. (C) 2000 Elsevier Science B.V. All rights reserved.

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.

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

NASA Astrophysics Data System (ADS)

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

2005-09-01

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

The Parent Magmas of the Cumulate Eucrites: A Mass Balance Approach

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1996-01-01

The cumulate eucrite meteorites are gabbros that are related to the eucrite basalt meteorites. The eucrite basalts are relatively primitive (nearly flat REE patterns with La approx. 8-30 x CI), but the parent magmas of the cumulate eucrites have been inferred as extremely evolved (La to greater than 100 x CI). This inference has been based on mineral/magma partitioning, and on mass balance considering the cumulate eucrites as adcumulates of plagioclase + pigeonite only; both approaches have been criticized as inappropriate. Here, mass balance including magma + equilibrium pigeonite + equilibrium plagiociase is used to test a simple model for the cumulate eucrites: that they formed from known eucritic magma types, that they consisted only of magma + crystals in chemical equilibrium with the magma, and that they were closed to chemical exchange after the accumulation of crystals. This model is tested for major and Rare Earth Elements (REE). The cumulate eucrites Serra de Mage and Moore County are consistent, in both REE and major elements, with formation by this simple model from a eucrite magma with a composition similar to the Nuevo Laredo meteorite: Serra de Mage as 14% magma, 47.5% pigeonite, and 38.5% plagioclase; Moore County as 35% magma, 37.5% pigeonite, and 27.5% plagioclase. These results are insensitive to the choice of mineral/magma partition coefficients. Results for the Moama cumulate eucrite are strongly dependent on choice of partition coefficients; for one reasonable choice, Moama's composition can be modeled as 4% Nuevo Laredo magma, 60% pigeonite, and 36% plagioclase. Selection of parent magma composition relies heavily on major elements; the REE cannot uniquely indicate a parent magma among the eucrite basalts. The major element composition of Y-791195 can be fit adequately as a simple cumulate from any basaltic eucrite composition. However, Y-791195 has LREE abundances and La/Lu too low to be accommodated within the model using any basaltic eucrite composition and any reasonable partition coefficients. Postcumulus loss of incompatible elements seems possible. It is intriguing that Serra de Mage, Moore County, and Moama are consistent with the same parental magma; could they be from the same igneous body on the eucrite parent asteroid (4 Vesta)?

Persistence of fertile and hydrous lithospheric mantle beneath the northwestern Ethiopian plateau: Evidence from modal, trace element and Sr-Nd-Hf isotopic compositions of amphibole-bearing mantle xenoliths

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Aulbach, Sonja

2017-07-01

We present new trace element compositions of amphiboles, Sr-Nd-Hf isotope compositions of clinopyroxenes and mineral modes for spinel peridotite xenoliths that were entrained in a Miocene alkali basalt (Gundeweyn, northwestern Ethiopian plateau), in order to understand the geochemical evolution and variation occurring within the continental lithospheric mantle (CLM) in close proximity to the East African Rift system, and its dynamic implications. With the exception of a single amphibole-bearing sample that is depleted in LREE (La/YbN = 0.45 × Cl), amphiboles in lherzolites and in one harzburgite show variable degrees of LREE enrichment (La/YbN = 2.5-12.1 × Cl) with flat HREE (Dy/YbN = 1.5-2.1 × Cl). Lherzolitic clinoyroxenes have 87Sr/86Sr (0.70227 to 0.70357), 143Nd/144Nd (0.51285 to 0.51346), and 176Hf/177Hf (0.28297 to 0.28360) ranging between depleted lithosphere and enriched mantle. LREE-enriched clinopyroxenes generally have more enriched isotope compositions than depleted ones. While lherzolites with isotope compositions similar to those of the Afar plume result from the most recent metasomatic overprint, isotope compositions more depleted than present-day MORB can be explained by an older melt extraction and/or isotopic rehomogenisation event, possibly related to the Pan-African orogeny. Several generations of amphibole are recognized in accord with this multi-stage evolution. Texturally unequilibrated amphibole occurring within the peridotite matrix and in melt pockets attest to continued hydration and refertilization of the lithospheric mantle subsequent to Oligocene flood basalt magmatism, during which an earlier-emplaced inventory of amphibole was likely largely consumed. However, a single harzburgite contains amphibole with the highest Mg# and lowest TiO2 content, which is interpreted as sampling a volumetrically subordinate mantle region beneath the Ethiopian plateau that was not tapped during flood basalt magmatism. Strikingly, both trace-element enriched and depleted lherzolites have high clinopyroxene and orthopyroxene and low olivine contents (median 15, 24 and 56 vol.%), combined with primitive olivine Mg# (median 89.5), indicating the presence of refertilized mantle beneath Gundeweyn. Despite its fertility and FeO-rich character (hence high inferred density), and impingement by the Afar plume, the CLM beneath the Ethiopian plateau, though apparently thinned through thermochemical erosion, has so far resisted whole-sale delamination or dripping. This is tentatively ascribed to insufficient stress and density contrasts at the periphery of the Afar plume, which reached its greatest thermochemical buoyancy in the Afar region, northeast of Gundeweyn.

Extreme isotopic variations in the upper mantle: evidence from Ronda

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Zindler, Alan

1986-12-01

The Ronda Ultramafic Complex in southern Spain represents a piece of the Earth's mantle which has been tectonically emplaced into the crust. Nd and Sr isotopic analyses are presented for leached, hand-picked Cr-diopside separates prepared from 15 rock and 18 river sediment samples from Ronda. These results demonstrate that within this small, contiguous body there exists the entire range of Nd isotopic compositions, and much of the range of Sr compositions, found in rocks derived from the sub-oceanic mantle. The sediment cpx samples show that the average isotopic composition of the massif becomes progressively less "depleted" moving from SW to NE along the long axis of the massif. The rock cpx samples document 143Nd/ 144Nd variations from 0.5129 to 0.5126 and 87Sr/ 86Sr variations from 0.7031 to 0.7039 within a uniform outcrop less than 10 m in extent. Thus, extreme isotopic fluctuations exist over a wide range of wavelengths. Sr and Nd isotopes are generally inversely correlated, forming a trend on a Nd-Sr diagram that sharply crosscuts that of the "mantle array". Many of the 143Nd/ 144Nd values, and all of the Sm/Nd values, from one section of the massif are lower than that SCV015SCV0 of the bulk earth, implying that this region existed, or was influenced by a component which existed, in a LREE-enriched environment for a significant period of time. Among the sediment cpxs there is a positive correlation between 143Nd/ 144Nd and 147Sm/ 144Nd. The rock cpx separates display considerably more scatter. A simple, single-stage differentiation event starting with a uniform mantle source cannot explain these results. At least one episode of mixing with a LREE-enriched component is required. If these results from Ronda are typical of the upper mantle, basalts with different isotopic compositions need not derive from spatially separated mantle sources.

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.

Heavy rare earth elements affect early life stages in Paracentrotus lividus and Arbacia lixula sea urchins

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

Oral, Rahime

Background: Heavy rare earth elements (HREEs) have been scarcely studied for their toxicity, in spite of their applications in several technologies. Thus HREEs require timely investigations for their adverse health effects. Methods: Paracentrotus lividus and Arbacia lixula embryos and sperm were exposed to trichloride salts of five HREEs (Dy, Ho, Er, Yb and Lu) and to Ce(III) as a light REE (LREE) reference to evaluate: 1) developmental defects (% DD) in HREE-exposed larvae or in the offspring of HREE-exposed sperm; 2) mitotic anomalies; 3) fertilization success; and 4) reactive oxygen species (ROS) formation, and nitric oxide (NO) and malondialdehyde (MDA)more » levels. Nominal HREE concentrations were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Results: HREEs induced concentration-related DD increases in P. lividus and A. lixula larvae, ranging from no significant DD increase at 10{sup −7} M HREEs up to ≅100% DD at 10{sup −5} M HREE. Larvae exposed to 10{sup −5} M Ce(III) resulted in less severe DD rates compared to HREEs. Decreased mitotic activity and increased aberration rates were found in HREE-exposed P. lividus embryos. Significant increases in ROS formation and NO levels were found both in HREE-exposed and in Ce(III) embryos, whereas only Ce(III), but not HREEs resulted in significant increase in MDA levels. Sperm exposure to HREEs (10{sup −5}–10{sup −4} M) resulted in a concentration-related decrease in fertilization success along with increase in offspring damage. These effects were significantly enhanced for Dy(III), Ho(III), Er(III) and Yb(III), compared to Lu(III) and to Ce(III). Conclusion: HREE-associated toxicity affected embryogenesis, fertilization, cytogenetic and redox endpoints showing different toxicities of tested HREEs. - Highlights: • Different toxicities were exerted by five tested HREEs on sea urchin early life stages. • Sea urchin embryos and sperm were sensitive to HREE levels ranging from 1 to 100 μM, according to different exposures. • The findings support investigations on comparative toxicity studies of HREEs in other test systems.« less

Zircon and cassiterite U-Pb ages, petrogeochemistry and metallogenesis of Sn deposits in the Sibao area, northern Guangxi: constraints on the neoproterozoic granitic magmatism and related Sn mineralization in the western Jiangnan Orogen, South China

NASA Astrophysics Data System (ADS)

Chen, Lei; Wang, Zongqi; Yan, Zhen; Gong, Jianghua; Ma, Shouxian

2018-01-01

A number of Sn deposits associated with Neoproterozoic granites are located in the western Jiangnan Orogen of northern Guangxi. The distribution of Sn mineralization is controlled by faults occurring within and around the Neoproterozoic granites. The hydrothermal alteration and mineralization of these Sn deposits exhibit zoning from the granite to the wall rock. The laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of the cassiterite and zircon from ore-bearing granite in the Menggongshan Sn deposit are 829 ± 19 Ma and 822 ± 4 Ma, respectively, indicating that the Sn mineralization and granites formed in the Neoproterozoic and can considered to be products of coeval magmatic and hydrothermal activities. The ore-bearing granite and Neoproterozoic granites in northern Guangxi are high-K, calc-alkaline, peraluminous, S-type granites that are depleted in Nb, Ti, Sr and Ba and highly enriched in Rb, U and Pb. All the granites show steep fractionated light rare earth element (LREE) and flat heavy rare earth element (HREE) patterns, with strongly negative Eu anomalies. The ɛHf(t) values of the ore-bearing granite vary from - 9.0 to - 1.7, with an average value of - 4.1. Additionally, the ore-bearing granite exhibits low oxygen fugacity values. The magmatic source experienced partial melting during their evolution, and the source was dominated by recycled heterogeneous continental crustal materials. Our evidence confirms that the Neoproterozoic granites in northern Guangxi formed in a collisional tectonic setting. The collision between the Cathaysia and Yangtze blocks or between the Sibao arc (Jiangnan arc) and the Yangtze Block caused asthenospheric upwelling, leading to partial melting and recycling of the crust, forming the peraluminous S-type granites in the Neoproterozoic. The Sn mineralization has a close genetic relationship with the Neoproterozoic granite. The highly differentiated, peraluminous, B-enriched, crustally derived Neoproterozoic granites provided the heat source and ore-forming material for the Sn mineralization. Furthermore, the low oxygen fugacity of these Neoproterozoic granites also favoured the Sn mineralization.

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.

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.

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.

First insights on the molybdenum-copper Bled M'Dena complex (Eglab massif, Algeria)

NASA Astrophysics Data System (ADS)

Lagraa, Karima; Salvi, Stefano; Béziat, Didier; Debat, Pierre; Kolli, Omar

2017-03-01

Molybdenum-Copper showings in the Eglab massif (eastern part of the Reguibat rise of Algeria), are found in quartz-monzodiorite and granodiorite of the Bled M'Dena complex, a Paleoproterozoic circular structure of ∼5 km in diameter, comprising volcanic and intrusive suites. The latter consist of quartz-diorite, quartz-monzodiorite and granodiorite with a metaluminous normative composition. They display an "adakitic character" with moderate light rare-earth element (LREE) enrichment, minor Eu anomalies, high Sr/Y ratio and low Yb concentration, suggestive of a hydrous, arc magma of volcanic-arc affinity. The mineralization occurs mostly in quartz + molybdenite + chalcopyrite stockwork veins marked by widespread propylitic alteration along the selvages. Molybdenite and chalcopyrite are commonly associated with calcite, which precipitated at relatively late stages of the hydrothermal alteration. Fluid inclusions related to the mineralization stage, range from aqueous to aqueous-carbonic to solid bearing. The latter inclusions have the highest homogenization temperature (up to ∼400 °C), are salt saturated, and commonly contain molybdenite and/or chalcopyrite crystals. The petrology and geochemistry of the host rocks, the style of the hydrothermal alteration, the ore mineral associations, and the characteristics of the fluid inclusions, are all coherent in indicating that the Bled M'Dena represents a Paleoproterozoic porphyry style Mo mineralization, which is far unreported in the African continent.

Discrimination of side-window glass of Korean autos by laser ablation inductively coupled plasma mass spectrometry.

PubMed

Lee, Sin-Woo; Ryu, Jong-Sik; Min, Ji-Sook; Choi, Man-Yong; Lee, Kwang-Sik; Shin, Woo-Jin

2016-07-15

Fragments of glass from cars are often found at crime scenes and can be crucial evidence for solving the crime. The glass fragments are important as trace evidence at crime scenes related to car accidents and burgled homes. By identifying the origin of glass fragments, it is possible to infer the identity of a suspect. Our results represent a promising approach to a thorough forensic investigation of car glass. Thirty-five samples from the side windows of cars produced and used in South Korea were collected from the official agencies of five car manufacturers and from two glassmakers. In addition, 120 samples from side mirrors were collected from the same suppliers as well as from small businesses. Their chemical compositions (including Pb isotopes) were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and linear discriminant analysis (LDA) was performed. The percentages of major elements (Si, Ca, and Fe) in side-window glass varied within narrow ranges (30.0 ± 2.36%, 5.93 ± 0.52%, and 0.33 ± 0.05%, respectively), while the differences among Pb isotope ratios were not significant. In contrast, light rare earth elements (LREEs) were different from each glassmaker. From the LDA, the types of side-window glass were successfully discriminated according to car manufacturer, glassmaker, and even glass thickness. However, glass from side mirrors cannot be used for good forensic identifiers. Discrimination techniques for side-window glass, although not for side mirrors, using chemical compositions combined with multivariate statistical analyses provide evidence for forensic investigations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Mineralogy and Geochemistry of Granitic rocks within Lichen Hills, Outback Nunatak, Northern Victoria Land, Antarctica

NASA Astrophysics Data System (ADS)

KIM, T.; KIM, Y.; Lee, I.; Lee, J.; Woo, J.

2015-12-01

The study areas, Lichen Hills and Outback Nunatak are located in the Northern Victoria Land which is close to Pacific Ocean side of Transantarctic Mountain (TAM), Antarctica. According to the study of Zeller and Dreschoff (1990), the radioactivity values of Lichen hills and Frontier Mt. area in the Victoria Land were very high. To identify the geochemical characteristics of granitic rocks in these areas, 13 samples of Lichen Hills rocks and 4 samples of Outback Nunatak rocks are analyzed. For mineralogical study, samples were observed in macroscale as well as microscale including microscope electron probe analysis. Rock samples of Lichen Hills, Outback Nunatak are mainly leucogranite and granitic pegmatite. These rock samples are composed of quartz, k-feldspar, plagioclase, muscovite, garnet, tourmaline like granite. In SEM-EDS analysis, the observed light colored minerals show relatively high Th, U, Dy, Ce, Nb concentration. This suggests that rock samples may contain minerals such as fergusonite, monazite, thorite, allanite, karnasurtite which are considered to be REE-bearing minerals. Samples of related rocks have been analyzed in terms of major, trace and rare earth element (REE) concentrations using X-ray fluorescence (XRF) spectrometer and Inductively Coupled Plasma Mass Spectrometer (ICP-MS). As concentration of SiO2 increase, Al2O3, TiO2, Fe2O3, MgO, P2O5 concentration decrease and Na2O, K2O, MnO concentration increase. Analyzed trace elements and REE are normalized using CI Chondrite, Primitive mantle. The normalized data show that LREE are enriched compared to HREE. The distinct negative anomalies of Eu, Sr are observed, indicating that rock-forming melts are fairly processed state of fractional crystallization. It means that Th, U, Nb, Ta are much enriched in the melts.

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

NASA Astrophysics Data System (ADS)

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

2011-09-01

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

Mineralized aplite—pegmatite at Jabal Sa'id, Hijaz region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Hackett, Damien

The Jabal Sa'id aplite—pegmatite, located at 23°49'03″N, 40°56'30″E, is part of the Jabal Hadb ash Sharar granite complex and resulted from emplacement of a residual volatile-rich fraction of alkali granite magma dominantly above a chilled carapace. Mineralization is layered, with four peak grades in layers 20-25 m wide, one of which may represent a mineral resource with greater potential than the aplite—pegmatite as a whole. The grades of all elements, except Zr, increase towards the upper part of the body. Chemical composition is extremely variable. Major-oxide data confirm previously determined geochemical characteristics and genetic relationships that suggested this body is an apogranite. However, the abundant new data also show that differences between the aplite—pegmatite and cognate alkali microgranite are not as great as previously reported, except for Na 2O which is extremely depleted in the apogranite. REE data support suggested genetic relationships and indicate that feldspar fractionation was important during crystallization. They also show that the content of HREE is comparatively constant throughout the aplite—pegmatite, and that variations in total REE content are caused by variations in the content of LREE. Bastnaesite and synchysite-(Y) are the principal rare-earth-element minerals, and are accompanied by monazite and synchesite; pyrochlore and thorite are also important ore minerals. Other elements concentrated in the aplite—pegmatite, such as Ta, Sn and U, occur only in solid solution in these minerals. The grain size of the ore minerals is commonly in the range 0.02-0.2 mm, and the grain size of gangue minerals, quartz, microcline and lesser amounts of aegirine and arfvedsonite, is typically in the range 1.0-4.0 mm. The ore minerals occur typically along gangue mineral boundaries. Zoning within the body permits calculation of high- and low-grade reserves which correspond to the upper and lower part of the apogranite.

Chemical stratification of cratonic lithosphere: constraints from the Northern Slave craton, Canada

NASA Astrophysics Data System (ADS)

Kopylova, Maya G.; Russell, James K.

2000-08-01

We describe the mineralogical and chemical composition of the Northern Slave mantle as deduced from xenoliths of peridotite within the Jericho kimberlite, Northwest Territories. Our data set includes modal, major, trace and rare earth element compositions of bulk samples of spinel peridotite, low-T and high-T garnet peridotite and minor pyroxenite. Compared to primitive upper mantle, Jericho peridotite shows depletion in the major elements and enrichment in incompatible elements (except for HREE). The Slave mantle is also uniquely stratified. Older, depleted spinel peridotite extends to a depth of 80-100 km and is underlain by garnet peridotite which shows a gradual decrease in Mg# with depth to 200 km. The youngest layer of fertile garnet peridotite, enriched in clinopyroxene and garnet, is underlain by a pyroxenite-rich horizon at the base of the petrological lithosphere. The Northern Slave is further distinguished from the Kaapvaal and Siberian upper mantle by a marked vertical stratification in Mg#, lower abundances of orthopyroxene and higher abundances of clinopyroxene. In addition, a deeper layer of garnet peridotite below Jericho shows less depletion than low-T peridotite from other cratons. The Northern Slave peridotite results from a series of chemical events that include: (i) high-degree melting of pyrolite at P>3 Gpa for low-T peridotite and lower pressure melting for high-T peridotite, (ii) enrichment of low-T spinel peridotite in orthopyroxene, and (iii) pervasive metasomatic enrichment in alkali and LREE's by kimberlite-related fluids. The chemical stratification described for two of the three lithospheric domains of the Slave craton makes this craton an exception among cratons with commonly unstratified lithospheres. The gradual increase in fertility with depth below the Slave craton is related to age stratification and may have formed by incremental downward growth of mantle lithosphere with time, and/or later re-fertilization of deeper mantle horizons.

Mid-to-Lower-level Plutonic Rocks From Crust of the Southern Mariana Forearc: Implications for Growth of Continental Crust

NASA Astrophysics Data System (ADS)

Fryer, P.; Reagan, M.

2006-12-01

Tonalitic plutonic rocks dredged from the southern Mariana forearc are similar in terms of major element composition to tonalitic plutonic rocks of the Tanzawa Mountains on the Izu Peninsula of Japan. The tonalites of the Tanzawa Mountains have been interpreted to represent mid-lower crustal plutonic rocks that make up the 6.0 to 6.3 km/s layer identified in seismic velocity profiles of the Izu arc at 32°N. The tonalities of the southern Mariana forearc may be analogous to the Tanzawa tonalities in terms of lithology and presumably seismic velocities, but have distinctive trace element and isotopic compositions. The exposure of these rocks on the southern Mariana forearc in a location where it is narrower by up to 80 km than elsewhere along its strike indicates a truncation of the arc lithosphere by tectonic erosion in the southern Mariana forearc. If tectonic processes in the forearc have exposed silicic plutonic rock of the arc lithosphere within 150 km of the volcanic front, then the structure of the Mariana arc and forearc is likely similar to that of the Izu arc, where seismic velocity structure suggests 25% of the arc/forearc lithosphere is comprised of a mid-crustal level tonalitic plutonic complex. The trace element and Sr isotopic compositions of the tonalities dredged from the Mariana forearc links them to a suprasubduction-zone environment. The Pb isotopic compositions, however, are consistent with crystallization ages that may be as old as Cretaceous. The compositions of these tonalites differ markedly from those of silicic volcanic rocks that have erupted throughout the history of the IBM arc and suggest that they represent a minor component of the arc. Nevertheless, the presence of Cretaceous tonalites in the Mariana forearc suggests that a portion of its crust may predate subduction initiation. The presence of silicic mid-to-lower crustal level plutonics beneath the Mariana arc as well as Eocene rhyolites on Saipan indicate that average major element composition of the arc crust may be comparable with average continental crust. This is consistent with estimates of the average composition of the Izu arc crust from seismic velocity studies and petrologic studies of exposures of the Izu arc crust in southern Japan's Izu peninsula. These data imply that the island arc that developed along the entire margin of the Philippine Sea plate may have had a generally similar structure and composition. Most components of the IBM arc crust, however, have relatively flat rare-earth patterns and low rare-earth concentrations compared with average continental crust. The averaged composition of the IBM crust, as a whole, differs markedly from that suggested by studies of the velocity structure of the central Aleutian arc. If the continental crust was generated in oceanic island arc settings throughout the history of the Earth, then its sources were significantly more enriched in LREE than the sources for the Cenozoic IBM arcs.

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.

Trace element and Pb isotope composition of plagioclase from dome samples from the 2004-2005 eruption of Mount St. Helens, Washington: Chapter 35 in A volcano rekindled: the renewed eruption of Mount St. Helens, 2004-2006

USGS Publications Warehouse

Kent, Adam J.R.; Rowe, Michael C.; Thornber, Carl R.; Pallister, John S.; Sherrod, David R.; Scott, William E.; Stauffer, Peter H.

2008-01-01

Plagioclase crystals from gabbronorite inclusions in three dacite samples have markedly different trace-element and Pbisotope compositions from those of plagioclase phenocrysts, despite having a similar range of anorthite contents. Inclusions show some systematic differences from each other but typically have higher Ti, Ba, LREE, and Pb and lower Sr and have lower 208Pb/206Pb and 207Pb/206Pb ratios than coexisting plagioclase phenocrysts. The compositions of plagioclase from inclusions cannot be related to phenocryst compositions by any reasonable petrologic model. From this we suggest that they are unlikely to represent magmatic cumulates or restite inclusions but instead are samples of mafic Tertiary basement from beneath the volcano.

Carboniferous-Permian tectonic transition envisaged in two magmatic episodes at the Kuruer Cu-Au deposit, Western Tianshan (NW China)

NASA Astrophysics Data System (ADS)

Yu, Jie; Li, Nuo; Qi, Nan; Guo, Jian-Ping; Chen, Yan-Jing

2018-03-01

The Western Tianshan in NW China is one of the most important gold provinces in the Central Asian Orogenic Belt (CAOB). The recently discovered Kuruer Cu-Au deposit has been interpreted to represent a transition from high-sulfidation epithermal to porphyry mineralization system. In this study, we present new LA-ICP-MS zircon U-Pb ages for the many magmatic rock types at Kuruer, including the Dahalajunshan Formation andesitic tuff (333.2 ± 1.6 Ma), diorite porphyry (269.7 ± 2.0 Ma), slightly-altered (264.4 ± 2.6 Ma) and intensively-altered (270.5 ± 2.5 Ma) albite porphyry. These ages reveal two distinct magmatic episodes: The Early Carboniferous Dahalajunshan Formation (wall rocks) andesitic tuff samples contain narrow ranges of SiO2 (60.29-61.28 wt.%), TiO2 (0.96-0.98 wt.%), Al2O3 (16.55-16.57 wt.%) and Fe2O3T (5.36-5.57 wt.%). The tuff is characterized by LREE enrichment and HFSE depletion, as well as LREE/HREE enrichment ((La/Yb)N = 8.31-8.76) and negative Eu anomalies (δEu = 0.64-0.76). Zircon εHf (t) values are 5.4-8.2, and two-stage Hf model ages (TDM2) are 821-1016 Ma, indicating partial melting of a moderately depleted mantle wedge with Precambrian continental crustal input. The ore-forming Middle Permian diorite porphyry and (quartz) albite porphyry have variable major oxide compositions (e.g., SiO2 = 53.09-53.12 wt.% for the diorite porphyry, 70.84-78.03 wt.% for the albite porphyry, and 74.07-75.03 wt.% for the quartz albite porphyry) but similar chondrite-normalized REE and primitive mantle-normalized multi-element patterns. These porphyries display LREE enrichment and HFSE depletion, as well as elevated LREE/HREE enrichment and negative Eu anomalies. The positive zircon εHf(t) values (11.7-15.9 for the diorite porphyry, 8.9-14.9 for the albite porphyry) and young two-stage Hf model ages (TDM2) (282-542 Ma for the diorite porphyry, 337-717 Ma for the albite porphyry) indicate a major juvenile continental crustal involvement. We propose that the Carboniferous and Middle Permian magmatism was formed in a continental arc and post-collisional settings, respectively, with the latter episode responsible for the Cu-Au mineralization.

Petrology and deformation style of lithospheric mantle beneath the Heldburg Dike swarm (Central Germany) subset of Central European Volcanic Province

NASA Astrophysics Data System (ADS)

Kukuła, Anna; Puziewicz, Jacek; Hidas, Károly; Ntaflos, Theodoros; Matusiak-Małek, Magdalena; Milke, Ralf

2017-04-01

The Heldburg Dike swarm is a set of Cenozoic alkali basalt dikes occurring in the central part of Germany at the border between Thuringia and Bavaria. We studied xenoliths from Strauf, Feldstein, Bramberg and from the active quarry in Zeilberg. The peridotites from Strauf, Feldstein and Bramberg have the composition of spinel lherzolite (15), spinel harzburgite (9) and dunite (3). They vary in size from 1.5 cm (Strauf) up to 20 cm (Zeilberg). We distinguish groups (A, A- and B) of peridotites based on different forsterite content in olivine. Group A consists of olivine (89.6 - 91.8 Fo), orthopyroxene (Mg# 0.90-0.93, Al 0.05-0.18 a pfu), clinopyroxene (Mg# 0.87-0.95, Al 0.06-0.26 a pfu) and spinel (Cr# 0.13-0.65, Mg# 0.54-0.78). Clinopyroxene rare earth elements (REE) patterns are S-shaped (Feldstein, Bramberg) or U-shaped (Strauf); spoon-shaped patterns occur occasionally. Trace element (TE) patterns show negative Nb, Ta, Zr, Hf, Ti and positive Th, U anomalies. The most magnesian clinopyroxene (xenolith 3140, Feldstein) is strongly aluminous and LREE depletedwith weak anomalies in TE patterns. Group A- is contains olivine (88.9-89.5 Fo), orthopyroxene (Mg# 0.89-0.90, Al 0.10-0.13 a pfu) and clinopyroxene (Mg# 0.90-0.92, Al 0.10-0.17 a pfu). Clinopyroxene is increasingly enriched in REEs from Lu to La. TE patterns are similar to those of group A but with less pronounced anomalies. Group B (3 xenoliths only) consists of olivine Fo 86.7-88.9, orthopyroxene (Mg# 0.88-0.89, Al 0.07-0.19 a pfu), clinopyroxene (Mg# 0.88-0.90, Al 0.10-0.26 a pfu). Clinopyroxene is enriched in LREE, concave upward in Pr. TE patterns are similar to those in group A. One of group B harzburgites contains grains (up to 0.5 mm) of Ca-Mg carbonate located in interstices. The clinopyroxene chemical composition plots away from the melting trend in the MgO-Al2O3 diagram of Upton et al. (2011), suggesting a later addition of the clinopyroxene. The composition of orthopyroxene corresponds to ca. 15-30 % of melting of primitive mantle, which was overprinted by silicate and/or carbonatite metasomatism. The xenolith 3140 seems not to be affected by metasomatic overprint. Based on the EBSD analyses of 15 xenoliths, olivine grains are characterized by relatively strong CPO (crystal preferred orientation) with J indices 4.4 - 13.3, and they have orthorhombic (8 xenoliths) or [100]-fiber CPO (6 xenoliths) symmetries except for one [010]-fiber symmetry observed in group B (Tommasi et al., 1999). Pyroxenes have weaker CPO and the distribution of their crystallographic axes is inconsistent with their coeval deformation with olivine. We propose that their CPO postdates that of olivine, hence strongly support a later origin for pyroxenes. Funding. This study was possible thanks to the project NCN UMO-2014/15/B/ST10/00095 of Polish National Centre for Science to JP Tommasi, A., B. Tikoff, and A. Vauchez (1999). Upper mantle tectonics: three-dimensional deformation, olivine crystallographic fabrics and seismic properties, Earth Planet Sc Lett,168, 173-186. Upton, B.G.J., Downes, H., Kirstein, L.A., Bonadiman, C., Hill, P.G., Ntaflos, T. (2011). The lithospheric mantle and lower crust-mantle relationships under Scotland: a xenolithic perspective. J Geol Soc, 168, 873-886.

Petrogenesis of Pliocene Alkaline Volcanic Rocks from Southeastern Styrian Basin, Austria

NASA Astrophysics Data System (ADS)

Ali, Sh.; Ntaflos, Th.

2009-04-01

Petrogenesis of Pliocene Alkaline Volcanic Rocks from Southeastern Styrian Basin, Austria Sh. Ali and Th. Ntaflos Dept. of Lithospheric Research, University of Vienna, Austria Neogene volcanism in the Alpine Pannonian Transition Zone occurred in a complex geodynamic setting. It can be subdivided into a syn-extentional phase that comprises Middle Miocene dominantly potassic, intermediate to acidic volcanism and a post-extensional phase, which is characterized by eruption of alkaline basaltic magmas during the Pliocene to Quartenary in the Styrian Basin. These alkaline basaltic magmas occur as small eruptive centers dominating the geomorphology of the southeastern part of the Styrian Basin. The eruptive centers along the SE Styrian Basin from North to South are: Oberpullendorf, Pauliberg, Steinberg, Strandenerkogel, Waltrafelsen and Klöch. The suite collected volcanic rocks comprise alkali basalts, basanites and nephelinites. Pauliberg: consists of alkali basalts that exhibit a narrow range of SiO2 (44.66-47.70 wt %) and wide range of MgO (8.52-13.19-wt %), are enriched in TiO2 (3.74-4.18 wt %). They are enriched in incompatible trace elements such as Zr (317-483 ppm), Nb (72.4-138 ppm) and Y (30.7-42 ppm). They have Nb/La ratio of 1.89 (average) and Cen/Ybn=15.22-23.11. Oberpullendorf: it also consists of alkali basalts with higher SiO2 (50.39 wt %) and lower TiO2 (2.80 wt %) if compared with the Pauliberg suite. Incompatible trace elements are lower than in Pauliberg; Zr =217 ppm, Nb=49.8 ppm, Y=23.6 ppm and Nb/La=1.93. The Oberpullendorf alkalibasalts are relative to Pauliberg lavas more depleted in LREE (Cen/Ybn=12.78). Steinberg: it consists of basanites with SiO2=44.49-46.85 wt %, MgO=6.30-9.13-wt %, and TiO2 =2.09-2.26 wt %. They are enriched in incompatible trace elements such as Zr (250-333 ppm), Nb (94-130 ppm), Y (24.7-31.9 ppm) and Nb/La=1.59 (average). The Cen/Ybn ratio varies between 18.17 and 22.83 indicating relative steep REE chondrite normalized patterns. Strandenerkogel: it consists of nephelinites with narrow compositional ranges; SiO2 =40.99-42.44 wt %, MgO=6.63-6.92 wt % and TiO2=2.03-2.07 wt %. They are enriched in incompatible trace elements such as Zr (362-382 ppm), Nb (139-153 ppm) and Y (39.5-40.7 ppm). They have Nb/La ratio of 1.20 and are strongly enriched in LREE (Cen/Ybn=25.04-28.11). Waltrafelsen: there are like in Strandenerkogel and have SiO2=42.42 wt %, MgO=6.55 wt %, and TiO2=2.01 wt %. The incompatible trace elements such as Zr (362 ppm), Nb (145 ppm) and Y (38.3 ppm) are similar to that of Stranerkogel. They have Nb/La ratio of 1.27 and are strongly enriched in LREE (Cen/Ybn=24.92). Klöch: it consists of basanites with similar to Steinberg composition (SiO2=45.34-46.60 wt %, MgO=8.98-10.11 wt %, and TiO2= 2.28-2.37 wt %. Incompatible trace elements such as Zr (252-273 ppm), Nb (94.2-101 ppm) and Y (24.4-27.2 ppm) are high. They have Nb/La ratio of 1.71 (average). Their REE abundances compared to Steinberg are slightly lower (Cen/Ybn=18.19-20.17). The Nb/La ratio of all the studied rock varieties is greater than one indicates an OIB-like asthenospheric mantle source for the basaltic magma. All the studied rock varieties except alkali basalts of Pauliberg have Tbn/Ybn ratios which are comparable to those of the alkali basalts of Hawaii ((Tbn/Ybn range from 1.89 to 2.45); the Hawaiian basalts are considered to have been derived from a garnet-lherzolite mantle source (Frey et al. 1991; McKenzie & O'Nions, 1991). The chondrite normalized HREE abundances indicate the presence of garnet as a residual phase in the melt source region as can be inferred from the Dy/Yb ratio (average 2.93) which is greater than that of chondritic Dy/Yb ratio (1.57) All the studied rock varieties display alkaline affinity and negative K-anomaly. The negative K-anomaly suggests either a source character, (e.g. frozen HIMU-like veins or pockets in the depleted lherzolite)? or it is consistent with the presence of a K-bearing hydrous phase in the residual mantle. References FREY, F. A., GARCIA, M. O., WISE, W. S., KENNEDY, A., GURRIET, P. & ALBAREDE, F. 1991. The evolution of Mauna Kea volcano, Hawaii: Petrogenesis of tholeiitic and alkali basalts. Journal of Geophysical Research 96, 14347-75. MCKENZIE, D. P. & O'NIONS, R. K. 1991. Partial melting distributions from inversion of rare earth element concentrations. Journal of Petrology 32, 1021-91.

Geochemistry of serpentinites in subduction zones: A review

NASA Astrophysics Data System (ADS)

Deschamps, Fabien; Godard, Marguerite; Guillot, Stéphane; Hattori, Kéiko

2013-04-01

Over the last decades, numerous studies have emphasized the role of serpentinites in the subduction zones geodynamics. Their presence and effective role in this environment is acknowledged notably by geophysical, geochemical and field observations of (paleo-) subduction zones. In this context, with the increasing amount of studies concerning serpentinites in subduction environments, a huge geochemical database was created. Here, we present a review of the geochemistry of serpentinites, based on the compilation of ~ 900 geochemical analyses of abyssal, mantle wedge and subducted serpentinites. The aim was to better understand the geochemical evolution of these rocks during their subduction history as well as their impact in the global geochemical cycle. When studying serpentinites, it is often a challenge to determine the nature of the protolith and their geological history before serpentinisation. The present-day (increasing) geochemical database for serpentinites indicates little to no mobility of incompatible elements at the scale of the hand-sample in most serpentinized peridotites. Thus, Rare Earth Elements (REE) distribution can be used to identify the initial protolith for abyssal and mantle wedge serpentinites, as well as magmatic processes such as melt/rock interactions taking place before serpentinisation. In the case of subducted serpentinites, the interpretation of trace element data is more difficult due to secondary enrichments independent of the nature of the protolith, notably in (L)REE. We propose that these enrichments reflect complex interactions probably not related to serpentinisation itself, but mostly to fluid/rock or sediment/rock interactions within the subduction channel, as well as intrinsic feature of the mantle protolith which could derive from the continental lithosphere exhumed at the ocean-continent transition. Additionally, during the last ten years, numerous studies have been carried out, notably using in situ approaches, to better constrain the geochemical budget of fluid-mobile elements (FME; e.g. B, Li, Cl, As, Sb, U, Th, Sr) stored in serpentinites and serpentine phases. These elements are good markers of the fluid/rock interactions taking place during serpentinisation. Today, the control of serpentinites on the behaviour of these elements, from their incorporation to their gradually release during subduction, is better understood. Serpentinites must be considered as a component of the FME budget in subduction zones and their role, notably on arc magmas composition, is undoubtedly underestimated presently in the global geochemical cycle.

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

Major and trace element, and Sr isotope compositions of clinopyroxene phenocrysts in mafic dykes on Jiaodong Peninsula, southeastern North China Craton: Insights into magma mixing and source metasomatism

NASA Astrophysics Data System (ADS)

Liang, Yayun; Deng, Jun; Liu, Xuefei; Wang, Qingfei; Qin, Cheng; Li, Yan; Yang, Yi; Zhou, Mian; Jiang, Jieyan

2018-03-01

Early Cretaceous mafic dyke swarms are widely developed on Jiaodong Peninsula in the southeastern part of the North China Craton (NCC), but their petrogenesis remains enigmatic. We have examined the in-situ major element, trace element and Sr isotope compositions of the clinopyroxene phenocrysts in these dykes in order to evaluate the extent of magma mixing and source metasomatism. Depending on the type of mineral zoning, the clinopyroxene phenocrysts in our samples can be classified into two groups: Group I (reverse zoning) and Group II (no zoning). Based on core compositions, the Group I phenocrysts with obvious reverse zoning can be divided into two subgroups: Groups IA and IB. The cores of Group IA clinopyroxenes have low values of Mg#, low Al2O3 contents, high Na2O contents, and high 87Sr/86Sr ratios, and they were probably derived from newly accreted lower crust that formed through the underplating of basaltic magma. In contrast, the cores of Group IB clinopyroxenes have lower Mg# values and lower contents of Al2O3, ΣREE (total rare earth elements), and incompatible elements, but they have similar 87Sr/86Sr ratios; these cores crystallised from crust-derived andesitic-dacitic magma. Group IA and IB clinopyroxene phenocryst rims (Group I rims) all have similar compositions with higher values of Mg# and higher Al2O3, Cr and Ni contents than the cores. The rims have high 87Sr/86Sr ratios, are enriched in LREEs (light rare earth elements) and LILEs (large ion lithophile elements), and are depleted in HFSEs (high field strength elements); these characteristics indicate that all the high-Mg rims were derived from a similar magma, possibly a relatively primitive magma derived from lithospheric mantle. We suggest, therefore, that the reversely-zoned clinopyroxene phenocrysts (Group I) in the Jiaodong mafic dykes provide evidence of magma mixing between a magma derived from lithospheric mantle and crust-derived andesitic-dacitic melt alongside with the newly accreted lower crust. The Group II clinopyroxene phenocrysts, which lack zoning, display major and trace element compositions and 87Sr/86Sr ratios that are similar to those of the Group I rims, which indicates that all the high-Mg clinopyroxenes were derived from a common source in the lithospheric mantle. These high-Mg clinopyroxenes exhibit high 87Sr/86Sr ratios, high Sr contents and remarkable depletions in HFSEs, reflecting metasomatism of the mantle source by aqueous fluids derived by dehydration of the subducting slab and its marine sediments. The metasomatism of the source reveals that the lithospheric mantle beneath Jiaodong Peninsula was metasomatised by fluids from the subducting Paleo-Pacific slab. Progressive thinning of the lithosphere mantle under the NCC was induced by continuous thermo-mechanical erosion, promoting the partial melting of lithospheric mantle and generating the mafic dykes at Jiaodong. Table A2 Analytical results for the trace element standards used during LA-ICP-MS analyses of clinopyroxene phenocrysts. Table A3 Analytical results for the Sr isotope standards used during MC-ICP-MS analyses of clinopyroxene phenocrysts. Table A4 Major element contents (wt%) of clinopyroxene phenocrysts from the mafic dykes on Jiaodong Peninsula. Table A5 Representative Sr isotopic compositions of clinopyroxene phenocrysts from the mafic dykes on Jiaodong Peninsula. Table A6 Geochemistry of the mafic dykes on Jiaodong Peninsula. Table A7 Partition coefficients (KD) and end-member components used for REE modeling.

Magnetic Nanofluid Rare Earth Element Extraction Process Report, Techno Economic Analysis, and Results for Geothermal Fluids

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

Pete McGrail

This GDR submission is an interim technical report and raw data files from the first year of testing on functionalized nanoparticles for rare earth element extraction from geothermal fluids. The report contains Rare Earth Element uptake results (percent removal, mg Rare Earth Element/gram of sorbent, distribution coefficient) for the elements of Neodymium, Europium, Yttrium, Dysprosium, and Cesium. A detailed techno economic analysis is also presented in the report for a scaled up geothermal rare earth element extraction process. All rare earth element uptake testing was done on simulated geothermal brines with one rare earth element in each brine. The raremore » earth element uptake testing was conducted at room temperature.« less

Slab-derived components in the subcontinental lithospheric mantle beneath Chilean Patagonia: Geochemistry and Sr-Nd-Pb isotopes of mantle xenoliths and host basalt

NASA Astrophysics Data System (ADS)

Jalowitzki, Tiago; Gervasoni, Fernanda; Conceição, Rommulo V.; Orihashi, Yuji; Bertotto, Gustavo W.; Sumino, Hirochika; Schilling, Manuel E.; Nagao, Keisuke; Morata, Diego; Sylvester, Paul

2017-11-01

In subduction zones, ultramafic xenoliths hosted in alkaline basalts can yield significant information about the role of potential slab-derived components in the subcontinental lithospheric mantle (SCLM). Chemical and isotopic heterogeneities in such xenoliths are usually interpreted to reflect melt extraction followed by metasomatic re-enrichment. Here we report new whole-rock major, trace element and isotopic (Sr-Nd-Pb) data for a Proterozoic suite of 17 anhydrous spinel-lherzolites and Eocene (new K-Ar data) host alkaline basalt found near Coyhaique ( 46°S), Aysén Region, Chile. These Patagonian nodules are located in a current back-arc position, 100 km east of the present day volcanic arc and 320 km from the Chile Trench. The mantle xenoliths consist of coarse- to medium-grained spinel-lherzolites with trace element compositions characteristic of a subduction zone setting, such as pronounced negative Nb, Ta and Ti anomalies coupled with significant enrichment of LILEs (e.g., U) and chalcophile elements (W, Pb and Sn). Most of them are characterized by flat to depleted light-rare earth element (LREE) patterns (Ce/YbN = 0.6-1.1) coupled with less radiogenic Sr-Pb (87Sr/86Sr = 0.702422-0.703479; 206Pb/204Pb = 18.212-18.539) and more radiogenic Nd isotopic compositions (143Nd/144Nd = 0.512994-0.513242), similar to the depleted mantle component (DMM or PREMA). In contrast, samples with slight LREE enrichment (Ce/YbN = 1.3-1.8) show more radiogenic Sr-Pb (87Sr/86Sr = 0.703791-0.704239; 206Pb/204Pb = 18.572-18.703) and less radiogenic Nd isotopic compositions (143Nd/144Nd = 0.512859-0.512934), similar to the EM-2 reservoir. These new geochemical and isotope data suggest that the Coyhaique spinel-lherzolites are derived from a heterogeneous SCLM resulting from mixing between a depleted mantle component and up to 10% of slab-derived components. The enriched component added to the SCLM represents variable extents of melts of both subducted Chile Trench sediments and modified oceanic crust throughout the initial stages of the Farallón-Aluk ridge collision during Paleocene to Eocene time. However, based on the tectonic evolution of southern South America, we cannot exclude the influence of long-lived subduction events beneath south Patagonia. Although we believe that the studied samples were brought to the surface in this geodynamic context, there is no evidence that ocean island basalt (OIB)-like melts related to the Farallón-Aluk asthenospheric slab window affected the peridotite composition. The host alkaline basalt is a single unit with a HIMU-like OIB signature characterized by marked positive Nb-Ta anomalies coupled with negative anomalies in highly incompatible and fluid-mobile elements (Rb, K, Pb, and Sr). The compositional similarity between the HIMU-like OIB mantle source and the host basalt is also evident from trace element ratios [(Ba-Th-K-La-Zr)/Nb] as well as by the low 87Sr/86Sri (0.703039-0.703058) and relatively high 143Nd/144Ndi (0.512880-0.512874) and 206Pb/204Pb (19.333-19.389) isotopic ratios. The low 206Pb/204Pb ratios compared to end-member HIMU lavas (e.g., Sta. Helena and the Cook-Austral Islands) suggest that this region was modified by processes associated with a prolonged period of subduction related to the Andean orogenesis and the recycling of several oceanic plates beneath the continent, following the Mesozoic breakup of Gondwana or an even older subduction-related event with young recycling ages (< 2 Ga).

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.

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).

Rare earth elements: end use and recyclability

USGS Publications Warehouse

Goonan, Thomas G.

2011-01-01

Rare earth elements are used in mature markets (such as catalysts, glassmaking, lighting, and metallurgy), which account for 59 percent of the total worldwide consumption of rare earth elements, and in newer, high-growth markets (such as battery alloys, ceramics, and permanent magnets), which account for 41 percent of the total worldwide consumption of rare earth elements. In mature market segments, lanthanum and cerium constitute about 80 percent of rare earth elements used, and in new market segments, dysprosium, neodymium, and praseodymium account for about 85 percent of rare earth elements used. Regardless of the end use, rare earth elements are not recycled in large quantities, but could be if recycling became mandated or very high prices of rare earth elements made recycling feasible.

Rare Earth Elements | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

- Mineral Resources main content Rare Earth Elements Rare earth elements and the supply and demand of these deposits containing rare earth elements to meet the perceived future demand. High prices for rare earth earth element occurrences in the DGGS publications catalog. Department of Natural Resources, Division of

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Pyroxenite and peridotite xenoliths from Hexigten, Inner Mongolia: Insights into the Paleo-Asian Ocean subduction-related melt/fluid-peridotite interaction

NASA Astrophysics Data System (ADS)

Zou, Dongya; Liu, Yongsheng; Hu, Zhaochu; Gao, Shan; Zong, Keqing; Xu, Rong; Deng, Lixu; He, Detao; Gao, Changgui

2014-09-01

The in situ major, trace-element and Sr-isotopic compositions of the peridotite and pyroxenite xenoliths from the Hexigten region in the Xing-Meng orogenic belt (XMOB) were examined to evaluate the influences and contributions of the Paleo-Asian Oceanic slab subduction on the lithospheric mantle transformation. Pyroxenes in the Type 1 pyroxenite exhibit low and variable Mg# (67-85) and relatively high 87Sr/86Sr ratios (0.7036-0.7053), indicating that they were formed by assimilation and fractional crystallization processes during a basaltic underplating event. The peridotite and Type 2 pyroxenite xenoliths sampled the lithospheric mantle and recorded subduction-related metasomatism. The mineral chemistries of the Type 1 peridotite suggest that the lithospheric mantle beneath this area suffered 1-15% melt extraction. Clinopyroxene (Cpx) in some Type 1 peridotites are characterized by high (La/Yb)N coupled with marked depletions in high field strength elements (HFSE) (Nb, Ta, Zr, Hf and Ti) and negative correlations between the low Ti/Eu (Nb/La) and 87Sr/86Sr ratios (0.7037-0.7055), suggesting metasomatism by subduction-related CO2-rich fluids. Olivine (Ol) and orthopyroxene (Opx) in the Type 2 peridotite are characterized by a relatively low Mg# but high Ni contents. In addition to the normal incompatible element-depleted Opx, Opx with enrichments in Rb, Ba, Th, U, Nb, Ta and LREE were observed, as well. The Mg# of incompatible element-depleted Opx exhibits weak zonations (i.e., decreasing from the cores to the rims). Cpx and Opx of the Type 2 pyroxenite exhibit similarly high Mg# and Ni contents. Rb, Ba, Th, U, Nb, Ta and LREE contents and 87Sr/86Sr ratios of the Cpx increase from the cores to the rims. Moreover, Opx in the Type 2 peridotite and Cpx in the Type 2 pyroxenite exhibit increased Nb/Ta ratios and Ni contents relative to those in the Type 1 peridotites. These observations collectively suggest a rutile-bearing eclogite-derived silicic melt-peridotite reaction as the origin for the Type 2 peridotite and pyroxenite. Considering the geological setting, it is suggested that the melt/fluid-peridotite interactions were caused by the Paleo-Asian Ocean subduction, which could have contributed significantly to the transformation of the lithospheric mantle beneath the northern margin of the NCC, as well.

Early Cretaceous bimodal volcanic rocks in the southern Lhasa terrane, south Tibet: Age, petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Wang, Chao; Ding, Lin; Liu, Zhi-Chao; Zhang, Li-Yun; Yue, Ya-Hui

2017-01-01

Limited geochronological and geochemical data from Early Cretaceous igneous rocks of the Gangdese Belt have resulted in a dispute regarding the subduction history of Neo-Tethyan Ocean. To approach this issue, we performed detailed in-situ zircon U-Pb and Hf isotopic, whole-rock elemental and Sr-Nd isotopic analyses on Late Mesozoic volcanic rocks exposed in the Liqiongda area, southern Lhasa terrane. These volcanic rocks are calc-alkaline series, dominated by basalts, basaltic andesites, and subordinate rhyolites, with a bimodal suite. The LA-ICPMS zircon U-Pb dating results of the basaltic andesites and rhyolites indicate that these volcanic rocks erupted during the Early Cretaceous (137-130 Ma). The basaltic rocks are high-alumina (average > 17 wt.%), enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs), showing subduction-related characteristics. They display highly positive zircon εHf(t) values (+ 10.0 to + 16.3) and whole-rock εNd(t) values (+ 5.38 to + 7.47). The silicic suite is characterized by low Al2O3 (< 15.4 wt.%), Mg# (< 40), and TiO2 (< 0.3 wt.%) abundances; enriched and variable concentrations of LILEs and REEs; and strongly negative Eu anomalies (Eu/Eu* = 0.08-0.19), as well as depleted Hf isotopic compositions (εHf(t) = + 4.9 to + 16.4) and Nd isotopic compositions (εNd(t) = + 5.26 to + 6.71). Consequently, we envision a process of basaltic magmas similar to that of MORB extracted from a source metasomatized by slab-derived components for the petrogenesis of mafic rocks, whereas the subsequent mafic magma underplating triggered partial melting of the juvenile crust to generate acidic magma. Our results confirm the presence of Early Cretaceous volcanism in the southern Lhasa terrane. Combined with the distribution of the contemporary magmatism, deformation style, and sedimentary characteristics in the Lhasa terrane, we favor the suggestion that the Neo-Tethyan oceanic lithosphere was flat-lying beneath the Lhasa terrane during the Early Cretaceous. Appendix Table A2. LA-MC-ICPMS zircon Hf isotopes of volcanic rocks from Liqiongda area. Appendix Table A3. Whole-rock major, trace element and Sr-Nd isotope data of the volcanic rocks from the Liqiongda area.

Sm-Nd isotopic compositions of LREE minerals for use as reference materials for in situ analysis by LA-MC-ICPMS

NASA Astrophysics Data System (ADS)

Fisher, C. M.; McFarlane, C. R.; Sylvester, P.; Hanchar, J. M.; Lam, R.; Schmitz, M. D.

2009-12-01

Recent work has demonstrated the possibility of obtaining both accurate and precise in situ Sm-Nd isotopic data in light rare earth enriched (LREE) accessory minerals including apatite, titanite, and monazite, using laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS). A distinct advantage of using LA-MC-ICPMS is that Sm-Nd isotopic data from these minerals can be determined in sub-grain domains potentially avoiding problems of isotopic mixing from inherited or xenocrystic components and allowing both valuable tracer isotope and geochronologic data to be obtained. However, a number of analytical obstacles complicate accurate Sm-Nd determination by LA-MC-ICPMS including mass bias corrections, the 144Sm isobaric interference on 144Nd, and potential offset (ca. 20-40 ppm) from thermal ionization mass spectrometry (TIMS) determination of similar materials. Thus, in order to verify Sm-Nd isotopic determination from unknowns, matrix-matched quality control standards (i.e., reference materials) must be developed to test the data handling protocol. This talk will present new Sm-Nd isotopic data determined by both TIMS as well as LA-MC-ICPMS of a number of natural potential reference minerals including Durango apatite, Fish Canyon titanite, Daibosatsu allanite, Trebilcock monazite, as well as a monazite from the Doi Inthanon core complex in northern Thailand. Our preliminary LA-MC-ICPMS results demonstrate that Durango apatite, Fish Canyon titanite, and Thailand monazite show both inter- and intra-grain homogeneity at current levels of precision (ca. 0.3-0.5 ɛNd) and close agreement with our TIMS data.

Petrological constraints on evolution of continental lithospheric mantle beneath the northwestern Ethiopian plateau: Insight from mantle xenoliths from the Gundeweyn area, East Gojam, Ethiopia

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Zhu, Bin; Fentie, Birhanu; Abraham, Samuel; Haji, Muhammed

2016-01-01

Detailed petrographical observations and in-situ major- and trace-element data for minerals from ten spinel peridotite xenoliths from a new locality in Gundeweyn area, East Gojam, have been examined in order to understand the composition, equilibrium temperature and pressure conditions as well as depletion and enrichment processes of continental lithospheric mantle beneath the Ethiopian plateau. The peridotite samples are very fresh and, with the exception of one spinel harzburgite, are all spinel lherzolites. Texturally, the xenoliths can be divided into two groups as primary and secondary textures. Primary textures are protogranular and porphyroclastic while secondary ones include reaction, spongy and lamellae textures. The Fo content of olivine and Cr# of spinel ranges from 86.5 to 90.5 and 7.7 to 14.1 in the lherzolites, respectively and are 89.8 and 49.8, respectively, in the harzburgite. All of the lherzolites fall into the lower Cr# and Fo region in the olivine-spinel mantle array than the harzburgite, which indicates that they are fertile peridotites that experienced low degrees of partial melting and melt extraction. Orthopyroxene and clinopyroxene show variable Cr2O3 and Al2O3 contents regardless of their lithology. The Mg# of orthopyroxene and clinopyroxene are 87.3 to 90.1 and 85.8 to 90.5 for lherzolite and 90.4 and 91.2 for harzburgite, respectively. The peridotites have been equilibrated at a temperature and pressure ranging from 850 to 1100 °C and 10.2 to 30 kbar, respectively, with the highest pressure record from the harzburgite. They record high mantle heat flow between 60 and 150 mW/m2, which is not typical for continental environments (40 mW/m2). Such a high geotherm in continental area shows the presence of active mantle upwelling beneath the Ethiopian plateau, which is consistent with the tectonic setting of nearby area of the Afar plume. Clinopyroxene of five lherzolites and one harzburgite samples have a LREE enriched pattern and the rest exhibit LREE depletion relative to HREE. These suggest that the lithospheric mantle of the Ethiopian plateau has experienced at least two major processes, specifically, partial melting and metasomatism that produce LREE-depleted and -enriched signature of continental lithospheric mantle, respectively. There is also no clear relationship between degree of LREE enrichment and petrography of the studied peridotite. Based on our data, we conclude that the lithospheric mantle beneath Gundeweyn has experienced melt extraction during and/or before pan-African orogeny and then interacted with various degrees of asthenospheric melt. The interaction is probably related to mantle upwelling, which is mainly focused beneath East Africa rift system (EARS).

Role of tectonomagmatic processes for surface environmental changes and evolution of biosphere on terrestrial planets: Evidence for evolution of the life on the Earth

NASA Astrophysics Data System (ADS)

Sharkov, Evgenii; Bogina, Maria

It is known that ecological systems on the Earth in the Middle Paleoproterozoic was experienced fundamental change, which finally led to the appearance of multicellular organisms. Though life has been already existed in the Paleoarchean (Harris et al., 2009 and references herein), the multicellular organisms appeared only in the middle Paleoproterozoic about 1.6 Ga ago. It was preceded by fundamental change of tectononagmatic processes at period from 2.35 to 2.0 Ga, when early Precambrian high-Mg magmas, derived from depleted mantle, were gradually changed by geochemical-enriched Fe-Ti picrites and basalts, similar to Phanerozoic within-plate magmas. A drastic change of the tectonic pattern occurred at ca. 2 Ga when plate-tectonics changed plume-tectonics of the early Precambrian. Since that time tectonomagmatic processes irretrievably changed over the whole Earth and gradually change of ancient continental crust for secondary oceanic (basaltic) crust has occurred. New type of magmatic melts, appeared in the Middle Paleoproterozoic, was characterized by elevated and high contents of Fe, Ti, Cu, P, Mn, alkalis, LREE, and other incompatible elements (Zr, Ba, Sr, U, Th, F, etc.). A large-scale influx of alkalis in the World Ocean presumably neutralized its water, making it more suitable for the life, while input of Fe-group metals, P, and other trace elements, which are required for metabolism and fermentation, rapidly expanded the possibility for the development of bio-sphere. This caused a rapid evolution of organic life, especially photosynthesizing cyanobacteria and, subsequently, the emergence of oxidizing atmosphere, marked by formation of cupriferous red beds at all Precambrian shields and generation of first hydrocarbon deposits (Melezhik et al., 2005). A drop in atmospheric CO2 presumably suppressed the greenhouse effect, while significant intensification of relief ruggedness caused by wide development of plate tectonics after 2 Ga resulted in the change of atmospheric circulation. All these processes finally led to the global glaciations. The latters commenced earlier, in the Paleoproterozoic, simultaneously with first manifestations of Fe-Ti basaltic magmatism, which came into force only in the middle Paleoproterozoic. Thus, a fundamental change in tectonomagmatic activity acted as the trigger for environmental changes and biospheric evolution, supplying a qualitatively new material on the Earth's surface. Data available on Venus and Mars suggest that their tectonomagmatic evolution also occurred at the close scenario. Two major types of morphostructures, which are vast plains, composed by young basaltic flows, and older lightweight uplifted segments with a complicated topography (tesseras on the Venus and earths (terras) on the Mars), can evidence about two-stage evolution of these planets. Presence of drainage systems on Mars and valles on Venus assumes existence of liquid water on early stages of their development. Like on the Earth, red beds and global glacials appeared on the Mars at the middle stage of it's evolu-tion, and may be at this period ancient microorganisms existed on Mars (McKay et al., 1996). Powerful eruptions of gigantic volcanoes of Tharsis and Elysium, probably, led to fall of tem-perature and disappearance of liquid water on Mars. In contrast to Mars, on Venus appeared speeded up greenhouse effect, which also led to dry and very hot surface. So, development of tectonomagmatic processes was favourable for the biosphere evolution only on the Earth.

Is the Mantle-Crust Transition in the Finero Complex (southern Alps) a Fossil Continental Moho?

NASA Astrophysics Data System (ADS)

Zanetti, A.; Langone, A.; Tommasi, A.; Vauchez, A.; Padron-Navarta, J. A.; Giovanardi, T.; Mazzucchelli, M.

2017-12-01

The geophysical studies indicate that the mantle-continental crust discontinuity is usually the site of complex intercalations of rocks having different physical and chemical properties. The possibility to directly characterize such rocks is extremely limited, because very few fossil continental Moho discontinuities crop out: in addition, most of them are considered to be representative of island arc environments. To address this issue, a comprehensive investigation has been carried out in the Finero Complex (Ivrea-Verbano Zone; Southern Alps), where the Phlogopite Peridotite (PP) mantle unit is surrounded by mafic-ultramafic rocks interpreted as intrusive crustal bodies. The crustal unit placed in contact with the PP is the Layered Internal Zone (LIZ), which is overlaid by the Amphibole Peridotite unit. At the contact with LIZ, the typical phlogopite-amphibole-harzburgite forming the PP unit is replaced by a weakly-deformed amphibole-biotite-bearing orthopyroxenite layer. Orthopyroxenite amphibole shows the typical LILE and LREE enrichments and the HFSE and HREE depletion observed in the rest of the mantle unit. This suggests that orthopyroxenite was segregated during the pervasive metasomatic event characterising the PP unit. The LIZ is formed by hornblendites, amphibole-garnet gabbros, pyroxenites and garnet hornblendites. The Amphibole Peridotite unit consists of peridotites, hornblendites and pyroxenites. In the LIZ, the melt intrusion locally involved the assimilation of early gabbroic cumulates, and the segregation of garnet hornblendites by substitution of pyroxenites. In the Amphibole Peridotite, late porous-flow melt migration produced secondary recrystallisation fronts, associated to the development of trace element gradients due to ion-exchange processes. Our observations suggest that the transition between PP and LIZ is primary. The LIZ and Amphibole Peridotite units record multiple events of migration of melt, whose composition varied from LREE-depleted to extremely LREE-enriched. The large variety of rocks, geochemical signatures and petrologic processes recorded by the studied mantle-crust transition evidences as it worked for a very long time as a primary lithospheric discontinuity, representing a preferential level of channelling for the uprising melts.

Actinide abundances in ordinary chondrites

USGS Publications Warehouse

Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

1990-01-01

Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

Suprasubduction volcanic rocks of the Char ophiolite belt, East Kazakhstan: new geochemical and first geochronological data

NASA Astrophysics Data System (ADS)

Safonova, Inna; Simonov, Vladimir; Seltmann, Reimar; Yamamoto, Shinji; Xiao, Wenjiao

2016-04-01

The Char ophiolite belt is located in the western Central Asian Orogenic Belt, a world largest accretionary orogen, which has evolved during more than 800 Ma. The Char belt formed during Kazakhstan - Siberia collision. It has been known for hosting fragments of Late Devonian-Early Carboniferous oceanic crust, MORB, OPB and OIB, of the Paleo-Asian Ocean (Safonova et al., 2012). The Char is surrounded by two Paleozoic island-arc terranes: Zharma-Saur in the west and Rudny Altai in the east, however, until recent times, no island-arc units have been found within it. We were the first to find island-arc units as tectonic sheets occurring adjacent to those consisting of oceanic rocks. In places, island-arc andesites cut oceanic basalts. The Char volcanic and subvolcanic rocks of a probable suprasubduction origin are basalt, microgabbro, dolerite, andesite, tonalite and dacite. The mafic to andesitic volcanics possessing low TiO2 (0.85 wt.%av.) and show MgO vs. major elements crystallization trends suggesting two magma series: tholeiitic and calc-alkaline. The tholeiitic varieties are less enriched in incompatible elements then the calc-alkaline ones. Two samples are high-Mg and low-Ti andesibasalts similar to boninites. The rocks possess moderately LREE enriched rare-earth element patterns and are characterized by negative Nb anomalies present on the multi-element spectra (Nb/Lapm = 0.14-0.47; Nb/Thpm = 0.7-1.6).The distribution of rare-earth elements (La/Smn = 0.8-2.3, Gd/Ybn = 0.7-1.9) and the results of geochemical modeling in the Nb-Yb system suggest high degrees of melting of a depleted harzburgite-bearing mantle source at spinel facies depths. Fractional crystallization of clinopyroxene, plagioclase and opaque minerals also affected the final composition of the volcanic rocks. Clinopyroxene monomineral thermometry indicates crystallization of melts at 1020-1180°C. Melt inclusion composition based numerical calculations show that primary melts were derived at 1350-1530°C and 14-26 kbar and crystallized at 1150-1190°C (Simonov et al., 2010). All these features are indicative of a supra-subduction origin of rocks. The age of gabbro, dolerite, andesite and tonalite was determined by LA ICP MS U-Pb zircon dating performed in the University of Kyoto, Japan. The andesites and tonalites yielded Carboniferous ages of ca. 322-336 Ma and the gabbro and dolerite appeared Devonian (387-395 Ma). Thus, the Char volcanic rocks possess geochemical signatures of supra-subduction magmas and could be derived at high degree melting of relatively shallow mantle sources. The volcanic units probably formed at one or two island-arcs or at an intra-oceanic arc and continental margin arc during the Middle Devonian - Mississippian. Later, the island-arc units were probably accreted to the active margin of the Kazakhstan continent. The work was supported by RFBR Project no. 16-05-00313. Contribution to IGCP#592 of UNESCO-IUGS. Safonova, I.Yu., Simonov V.A., Kurganskaya E.V., Obut O.T., Romer R.L., Seltmann R., 2012. Late Paleozoic oceanic basalts hosted by the Char suture-shear zone, East Kazakhstan: geological position, geochemistry, petrogenesis and tectonic setting. Journal of Asian Earth Sciences 49, 20-39. Simonov V.A., Safonova I.Yu., Kovyazin S.V., 2010. Petrogenesis of island-arc complexes of the Char zone, East Kazakhstan. Petrology 18, 59-72.

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

NASA Astrophysics Data System (ADS)

Tang, Jianwu; Johannesson, Karen H.

2010-12-01

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

Terrestrial Chemical Alteration of Hot Desert Meteorites

NASA Astrophysics Data System (ADS)

Crozaz, G.; Floss, C.

2001-12-01

Large numbers of meteorites have recently been recovered from terrestrial hot deserts. They include objects whose study holds the promise of significantly increasing our knowledge of the origin and petrogenesis of rare groups of meteorites (e.g., martian and lunar rocks, ureilites, etc). However, these meteorites have typically been exposed to harsh desert conditions for more than 10,000 yr since their fall on earth. A number of alterations have been described, including mineralogical and chemical changes (e.g., Crozaz and Wadhwa, 2001, and references therein). Through weathering, Fe-bearing minerals are progressively altered into clays and iron oxides and hydroxides, which often fill cracks and mineral fractures, together with terrestrial quartz and carbonates. In addition, for whole rock samples, elevated Ba, Sr, and U seem to be the telltale signs of terrestrial contamination (e.g., Barrat et al., 1999). In our work, we use the rare earth elements (REE) as monitors of terrestrial alteration. These elements are important because they are commonly used to decipher the petrogenesis and chronology of meteorites. We have made in-situ concentration measurements, by secondary ion mass spectrometry (SIMS), of individual grains in shergottites (assumed to have formed on Mars), lunar, and angritic meteorites. Terrestrial contamination, in the form of LREE enrichment and Ce anomalies, is encountered in the olivine and pyroxene, the two minerals with the lowest REE concentrations, of all objects analyzed. However, the contamination is highly heterogeneous, affecting some grains and not others of a given phase. Therefore, provided one uses a measurement technique such as SIMS to obtain data on individual grains and to identify the unaltered ones, it is still possible to obtain geochemical information about the origins of hot desert meteorites. On the other hand, great caution must be exercised if one uses data for whole rocks or mineral separates. The U-Pb, Rb-Sr and Sm-Nd systematics are likely to be affected by terrestrial contamination even in samples with a fresh appearance. Leachates are particularly suspicious (Crozaz and Wadhwa, 2001; Dreibus et al., 2001). In the case of shergottites which have proven difficult to date (Nyquist et al., 2001), this is a complicating and especially unfortunate factor. References: Barrat et al. (1999) MAPS 34, 91-97. Crozaz G. and Wadhwa M. (2001) GCA 65, 971-978. Dreibus et al. (2001) MAPS, in press. Nyquist et al. (2001) Space Sci. Rev., in press.

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.

Lower-crustal xenoliths from Jurassic kimberlite diatremes, upper Michigan (USA): Evidence for Proterozoic orogenesis and plume magmatism in the lower crust of the southern Superior Province

USGS Publications Warehouse

Zartman, Robert E.; Kempton, Pamela D.; Paces, James B.; Downes, Hilary; Williams, Ian S.; Dobosi, Gábor; Futa, Kiyoto

2013-01-01

Jurassic kimberlites in the southern Superior Province in northern Michigan contain a variety of possible lower-crustal xenoliths, including mafic garnet granulites, rare garnet-free granulites, amphibolites and eclogites. Whole-rock major-element data for the granulites suggest affinities with tholeiitic basalts. P–T estimates for granulites indicate peak temperatures of 690–730°C and pressures of 9–12 kbar, consistent with seismic estimates of crustal thickness in the region. The granulites can be divided into two groups based on trace-element characteristics. Group 1 granulites have trace-element signatures similar to average Archean lower crust; they are light rare earth element (LREE)-enriched, with high La/Nb ratios and positive Pb anomalies. Most plot to the left of the geochron on a 206Pb/€204Pb vs 207Pb/€204Pb diagram, and there was probably widespread incorporation of Proterozoic to Archean components into the magmatic protoliths of these rocks. Although the age of the Group 1 granulites is not well constrained, their protoliths appear to be have been emplaced during the Mesoproterozoic and to be older than those for Group 2 granulites. Group 2 granulites are also LREE-enriched, but have strong positive Nb and Ta anomalies and low La/Nb ratios, suggesting intraplate magmatic affinities. They have trace-element characteristics similar to those of some Mid-Continent Rift (Keweenawan) basalts. They yield a Sm–Nd whole-rock errorchron age of 1046 ± 140 Ma, similar to that of Mid-Continent Rift plume magmatism. These granulites have unusually radiogenic Pb isotope compositions that plot above the 207Pb/€204Pb vs 206Pb/€204Pb growth curve and to the right of the 4·55 Ga geochron, and closely resemble the Pb isotope array defined by Mid-Continent Rift basalts. These Pb isotope data indicate that ancient continental lower crust is not uniformly depleted in U (and Th) relative to Pb. One granulite xenolith, S69-5, contains quartz, and has a unique peraluminous composition. It has the lowest εNd and εHf values of the suite. Its isotopic compositions indicate that it is significantly older than the other granulites. Broken zircon cores encased by younger overgrowths suggest that this granulite includes a large component of pre-existing sedimentary rocks. Two distinct populations of zircons from S69-5 were dated by sensitive high-resolution ion microprobe. Abundant rounded zircons yield ages of 1104 ± 42 (2σ) Ma, which coincide with the Mid-Continent Rift flood basalt eruptions. Their morphology is similar to those found in lower-crustal rocks that have undergone granulite-facies metamorphism and thus they are considered to represent the age of Group 2 granulites. Also present are less abundant elongate zircon grains that yield a mean age of 1387 ± 32 (2σ) Ma. Their elongate shapes indicate growth from a melt or fluid, possibly associated with 1·3–1·5 Ga anorogenic granite magmatism exposed in the shallow crust to the south in Wisconsin, or related to an initial encroachment of the Keweenawan plume upon the lower crust. Older ages recognized in zircon cores are less well constrained but may be related to tectono-magmatic events in the southern Superior craton. Within the studied suite only S69-5 was recognized as a remnant of the Late Archean lower crust into which the Group 1 and 2 mafic granulite precursor basalts were intruded. Collectively, the data show that the lower crust beneath northern Michigan formed in Archean times and underwent a variety of tectono-magmatic processes throughout the Proterozoic, including orogenesis, partial melting and mafic magmatic underplating in response to upwelling mantle plumes.

Health risk assessment of rare earth elements in cereals from mining area in Shandong, China.

PubMed

Zhuang, Maoqiang; Wang, Liansen; Wu, Guangjian; Wang, Kebo; Jiang, Xiaofeng; Liu, Taibin; Xiao, Peirui; Yu, Lianlong; Jiang, Ying; Song, Jian; Zhang, Junli; Zhou, Jingyang; Zhao, Jinshan; Chu, Zunhua

2017-08-29

To investigate the concentrations of rare earth elements in cereals and assess human health risk through cereal consumption, a total of 327 cereal samples were collected from rare earth mining area and control area in Shandong, China. The contents of 14 rare earth elements were determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The medians of total rare earth elements in cereals from mining and control areas were 74.22 μg/kg and 47.83 μg/kg, respectively, and the difference was statistically significant (P < 0.05). The wheat had the highest rare earth elements concentrations (109.39 μg/kg and 77.96 μg/kg for mining and control areas, respectively) and maize had the lowest rare earth elements concentrations (42.88 μg/kg and 30.25 μg/kg for mining and control areas, respectively). The rare earth elements distribution patterns for both areas were characterized by enrichment of light rare earth elements. The health risk assessment demonstrated that the estimated daily intakes of rare earth elements through cereal consumption were considerably lower than the acceptable daily intake (70 μg/kg bw). The damage to adults can be neglected, but more attention should be paid to the effects of continuous exposure to rare earth elements on children.

Constraining the Protolith of Large, Macroscopically Layered Kyanite-bearing Eclogite Xenoliths from the Kaapvaal Craton, South Africa

NASA Astrophysics Data System (ADS)

Rebelo, C. C.; Gurney, J. J.; Richardson, S. H.; Shaw-Kahle, B.

2015-12-01

We describe the geochemistry of a suite of ten layered, kyanite-bearing eclogites from the Roberts Victor kimberlite, Kaapvaal Craton, South Africa. All samples are characterized by clear zonation corresponding to the presence or absence of kyanite and the state of preservation of clinopyroxene. The sampled zones are defined as KF (free of kyanite, with well-preserved garnet and clinopyroxene), KZ (preserved clinopyroxene is absent; garnet occurs with kyanite); and TZ (partially preserved clinopyroxene and more altered garnet; kyanite may or may not be present). We report on results of petrographic observations, mineral chemistry, and trace element and oxygen isotope analyses for the different zones. Results from adjacent zones are presented as geochemical transects perpendicular to the layering for each xenolith. We use the results to infer the geochemical evolution of likely protoliths for the various samples. Mineral chemistry of garnets across the different zones shows decreasing FeO*, Cr2O3, MgO and MnO and increasing in CaO from KF into KZ. Clinopyroxene shows increasing in Al2O3 and Na2O from KF into KZ. Clinopyroxenes approach a more jadeitic composition towards the KZ and are more diopsidic in KF. Trace element analyses were conducted with laser ablation ICP-MS on hand-picked mineral separates. Garnets show subchondritic LREE depletion and superchondritic HREE enrichment in both KF and KZ. Positive europium anomalies in garnet are present in all zones, with relatively larger anomalies in garnet grains from KZ. Preserved clinopyroxenes show complementary REE patterns to garnet grains, with superchondritic LREEs and subchondritic HREEs. For the suite of xenoliths, results from mass spectrometry on oxygen extracted by laser fluorination on mineral separates show that δ18O values are above the accepted mantle value and fall within the range of hydrothermally altered oceanic crustal material. At this stage of the research, the bulk protolith is interpreted to be of crustal origin.

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.

Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Danielson, L.; Nickodem, K.

2014-01-01

Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.

Melt/mantle interaction and melt evolution in the Sartohay high-Al chromite deposits of the Dalabute ophiolite (NW China)

NASA Astrophysics Data System (ADS)

Zhou, M.-F.; Robinson, P. T.; Malpas, J.; Aitchison, J.; Sun, M.; Bai, W.-J.; Hu, X.-F.; Yang, J.-S.

2001-06-01

The Sartohay block of the Dalabute ophiolite consists chiefly of mantle harzburgite and lherzolite with minor dunite. These rocks host voluminous chromite deposits with lenticular or vein-like shapes. The podiform chromitites are associated with, and cross-cut by, numerous troctolite dykes. Chromite in the chromitites has Al 2O 3 (23-31 wt%), TiO 2 (0.29-0.44 wt%), and Cr 2O 3 contents (<45 wt%) with Cr#s [100Cr/(Cr+Al)] (<60), typical of high-Al chromite deposits. The host peridotites in Sartohay have been texturally and geochemically modified by magmas from which the high-Al chromitites and mafic dykes formed. Dunites commonly envelop the podiform chromite bodies and show transitional contacts with the peridotites. Some of the peridotites and chromitites contain plagioclase that crystallized from impregnated melts. The dunite locally grades into troctolite with increasing plagioclase contents. As a result of melt impregnation, peridotites and dunites show variable Ca and Al contents and LREE enrichment. The parental magma of the chromitites was likely tholeiitic in composition, derived from partial melting of the asthenospheric mantle in a rising diapir. The interaction between this magma and pre-existing lithospheric mantle, composed of depleted lherzolite, would have formed a more silicic, tholeiitic magma from which high-Al chromitites crystallized. During this interaction, harzburgite and dunite were depleted in modal pyroxene and enriched in some incompatible elements (such as Al, Ca and LREE) due to melt impregnation.

Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model

USGS Publications Warehouse

Verplanck, Philip L.; Van Gosen, Bradley S.

2011-01-01

The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

Petrogenesis of the Yaochong granite and Mo deposit, Western Dabie orogen, eastern-central China: Constraints from zircon U-Pb and molybdenite Re-Os ages, whole-rock geochemistry and Sr-Nd-Pb-Hf isotopes

NASA Astrophysics Data System (ADS)

Chen, Wei; Xu, Zhaowen; Qiu, Wenhong; Li, Chao; Yu, Yang; Wang, Hao; Su, Yang

2015-05-01

The Dabie orogen is among the most famous continent-continent collisional orogenic belts in the world, and is characterized by intensive post-collisional extension, magmatism and Mo mineralization. However, the genetic links between the mineralization and the geodynamic evolution of the orogen remain unresolved. In this paper, the Yaochong Mo deposit and its associated granitic stocks were investigated to elucidate this issue. Our new zircon U-Pb ages yielded an Early Cretaceous age (133.3 ± 1.3 Ma) for the Yaochong granite, and our molybdenite Re-Os dating gave a similar age (135 ± 1 Ma) for the Mo deposit. The Yaochong stock is characterized by high silica and alkali but low Mg, Fe and Ca. It is enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs: Rb, K, Th and U), but strongly depleted in heavy REEs, and high field strength elements (HFSEs: Nb, Ta, Ti and Y). The Yaochong granite has initial 87Sr/86Sr ratios of 0.7087-0.7096, and Pb isotopic ratios of (206Pb/204Pb)i = 16.599-16.704, (207Pb/204Pb)i = 15.170-15.618 and (208Pb/204Pb)i = 36.376-38.248. The granite has εNd(t) of -18.0 to -16.3 and εHf(t) values of -26.5 to -20.0. All these data indicate that the Yaochong granite is a high-K calc-alkaline fractionated I-type granite, and may have originated from partial melting of the thickened Yangtze continental crust. The Mo ores also show low radiogenic Pb isotopes similar to the Yaochong stock. Medium Re content in molybdenite (21.8-74.8 ppm) also suggests that the ore-forming materials were derived from the thickened lower crust with possibly minor mixing with the mantle. Similar to the Eastern Dabie orogen, the thickened crust beneath the Western Dabie orogen may also have experienced tectonic collapse, which may have exerted fundamental geodynamic controls on the two-stage Mo mineralization in the region.

Petrography, mineralogy, and geochemistry of lunar meteorite Sayh al Uhaymir 300

NASA Astrophysics Data System (ADS)

Hsu, Weibiao; Zhang, Aicheng; Bartoschewitz, Rainer; Guan, Yunbin; Ushikubo, Takayuki; KrńHenbÜHl, Urs; Niedergesaess, Rainer; Pepelnik, Rudolf; Reus, Ulrich; Kurtz, Thomas; Kurtz, Paul

2008-08-01

We report here the petrography, mineralogy, and geochemistry of lunar meteorite Sayh al Uhaymir 300 (SaU 300). SaU 300 is dominated by a fine-grained crystalline matrix surrounding mineral fragments (plagioclase, pyroxene, olivine, and ilmenite) and lithic clasts (mainly feldspathic to noritic). Mare basalt and KREEPy rocks are absent. Glass melt veins and impact melts are present, indicating that the rock has been subjected to a second impact event. FeNi metal and troilite grains were observed in the matrix. Major element concentrations of SaU 300 (Al2O3 21.6 wt% and FeO 8.16 wt%) are very similar to those of two basalt-bearing feldspathic regolith breccias: Calcalong Creek and Yamato (Y-) 983885. However, the rare earth element (REE) abundances and pattern of SaU 300 resemble the patterns of feldspathic highlands meteorites (e.g., Queen Alexandra Range (QUE) 93069 and Dar al Gani (DaG) 400), and the average lunar highlands crust. It has a relatively LREE-enriched (7 to 10 x CI) pattern with a positive Eu anomaly (˜11 x CI). Values of Fe/Mn ratios of olivine, pyroxene, and the bulk sample are essentially consistent with a lunar origin. SaU 300 also contains high siderophile abundances with a chondritic Ni/Ir ratio. SaU 300 has experienced moderate terrestrial weathering as its bulk Sr concentration is elevated compared to other lunar meteorites and Apollo and Luna samples. Mineral chemistry and trace element abundances of SaU 300 fall within the ranges of lunar feldspathic meteorites and FAN rocks. SaU 300 is a feldspathic impact-melt breccia predominantly composed of feldspathic highlands rocks with a small amount of mafic component. With a bulk Mg# of 0.67, it is the most mafic of the feldspathic meteorites and represents a lunar surface composition distinct from any other known lunar meteorites. On the basis of its low Th concentration (0.46 ppm) and its lack of KREEPy and mare basaltic components, the source region of SaU 300 could have been within a highland terrain, a great distance from the Imbrium impact basin, probably on the far side of the Moon.

Timing, mantle source and origin of mafic dykes within the gravity anomaly belt of the Taihang-Da Hinggan gravity lineament, central North China Craton

NASA Astrophysics Data System (ADS)

Liu, Shen; Feng, Caixia; Feng, Guangying; Xu, Mengjing; Coulson, Ian M.; Guo, Xiaolei; Guo, Zhuang; Peng, Hao; Feng, Qiang

2017-09-01

Six mafic dyke swarms crop out in Hebei Province within the Taihang-Da Hinggan gravity lineament magmatic belt, China, and were sampled. Here, we present new zircon laser ablation-inductively coupled plasma-mass spectrometry U-Pb age, whole rock geochemical, and Sr-Nd-Pb-Hf isotopic data for the six areas where these mafic dykes occur. The mafic (dolerite) dykes formed between 131.6 ± 1.6 and 121.6 ± 1.1 Ma, and are enriched in the light rare earth elements (LREE), some of the large ion lithophile elements (LILE; e.g., Rb, Ba, and Sr) and Pb, and are depleted in Th, U, Nb and Ta; some samples are also depleted in Eu. The dykes have high initial 87Sr/86Sr ratios (0.7055-0.7057), negative εNd (t) values (-12.5 to -11.9), relatively constant Pb isotopic ratios ((206Pb/204Pb)i = 16.45-16.51, (207Pb/204Pb)i = 15.44-15.51, (208Pb/204Pb)i = 36.49-36.53), negative εHf (t) values (-18.2 to -15.1), and old Nd (TNdDM2; 2.17-2.47 Ga) and Hf (THfDM2; 2.28-2.33 Ga) model ages. These geochronological, geochemical, and isotopic data indicate that the dykes were derived from magmas generated by low to moderate degree partial melting (1.0%-10%) of an EM1-like garnet lherzolite mantle source; these magmas fractionated olivine, clinopyroxene, and hornblende prior to emplacement, and assimilated minimal amounts of crustal material. Several possible models have previously been proposed to explain the origin of Mesozoic magmatism in this region. However, here we propose a foundering model for these studied mafic dykes, involving the foundering of eclogite from thickened lower crust due to the collision between the Siberian Craton and the North China Craon.

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

NASA Astrophysics Data System (ADS)

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

2010-03-01

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

Charnockites and granites of the western Adirondacks, New York, USA: a differentiated A-type suite

USGS Publications Warehouse

Whitney, P.R.

1992-01-01

Granitic rocks in the west-central Adirondack Highlands of New York State include both relatively homogeneous charnockitic and hornblende granitic gneisses (CG), that occur in thick stratiform bodies and elliptical domes, and heterogeneous leucogneisses (LG), that commonly are interlayered with metasedimentary rocks. Major- and trace-element geochemical analyses were obtained for 115 samples, including both types of granitoids. Data for CG fail to show the presence of more than one distinct group based on composition. Most of the variance within the CG sample population is consistent with magmatic differentiation combined with incomplete separation of early crystals of alkali feldspar, plagioclase, and pyroxenes or amphibole from the residual liquid. Ti, Fe, Mg, Ca, P, Sr, Ba, and Zr decrease with increasing silica, while Rb and K increase. Within CG, the distinction between charnockitic (orthopyroxene-bearing) and granitic gneisses is correlated with bulk chemistry. The charnockites are consistently more mafic than the hornblende granitic gneisses, although forming a continuum with them. The leucogneisses, while generally more felsic than the charnockites and granitic gneisses, are otherwise geochemically similar to them. The data are consistent with the LG suite being an evolved extrusive equivalent of the intrusive CG suite. Both CG and LG suites are metaluminous to mildly peraluminous and display an A-type geochemical signature, enriched in Fe, K, Ce, Y, Nb, Zr, and Ga and depleted in Ca, Mg, and Sr relative to I- and S-type granites. Rare earth element patterns show moderate LREE enrichment and a negative Eu anomaly throughout the suite. The geochemical data suggest an origin by partial melting of biotite- and plagioclase-rich crustal rocks. Emplacement occurred in an anorogenic or post-collisional tectonic setting, probably at relatively shallow depths. Deformation and granulite-facies metamorphism with some partial melting followed during the Ottawan phase of the Grenville Orogeny, yielding the present migmatitic granitic and charnockitic gneisses. ?? 1992.

Low-K granophyres of the Stillwater Complex, Montana

USGS Publications Warehouse

Czamanske, G.K.; Zientek, M.L.; Manning, C.E.

1991-01-01

Small bodies of granophyre occur as a volumetrically insignificant but ubiquitous component of the Banded series of the Stillwater Complex. White to pink granophyre typically occurs as veins, 1-12cm thick and as much as 100m long. A geochemically similar body of coalescing alaskite dikes, associated with an occurrence of Pt-group elements in the Banded series of the complex, crops out approximately 2km south-southeast of Picket Pin Mountain over an area 130 by 210m. Considering host rocks and chemistry, these rocks are comparable to the most siliceous examples of oceanic plagiogranite. The Stillwater granophyres, however, are enriched in Si, Th, U, and LREEs, and depleted in K, Fe, and Eu, relative to oceanic granophyres. -from Authors

Calcium isotopic fractionation in mantle peridotites by melting and metasomatism and Ca isotope composition of the Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Kang, Jin-Ting; Ionov, Dmitri A.; Liu, Fang; Zhang, Chen-Lei; Golovin, Alexander V.; Qin, Li-Ping; Zhang, Zhao-Feng; Huang, Fang

2017-09-01

To better constrain the Ca isotopic composition of the Bulk Silicate Earth (BSE) and explore the Ca isotope fractionation in the mantle, we determined the Ca isotopic composition of 28 peridotite xenoliths from Mongolia, southern Siberia and the Siberian craton. The samples are divided in three chemical groups: (1) fertile, unmetasomatized lherzolites (3.7-4.7 wt.% Al2O3); (2) moderately melt-depleted peridotites (1.3-3.0 wt.% Al2O3) with no or very limited metasomatism (LREE-depleted cpx); (3) strongly metasomatized peridotites (LREE-enriched cpx and bulk rock) further divided in subgroups 3a (harzburgites, 0.1-1.0% Al2O3) and 3b (fertile lherzolites, 3.9-4.3% Al2O3). In Group 1, δ44/40Ca of fertile spinel and garnet peridotites, which experienced little or no melting and metasomatism, show a limited variation from 0.90 to 0.99‰ (relative to SRM 915a) and an average of 0.94 ± 0.05‰ (2SD, n = 14), which defines the Ca isotopic composition of the BSE. In Group 2, the δ44/40Ca is the highest for three rocks with the lowest Al2O3, i.e. the greatest melt extraction degrees (average 1.06 ± 0.04 ‰, i.e. ∼0.1‰ heavier than the BSE estimate). Simple modeling of modal melting shows that partial melting of the BSE with 103 ln ⁡αperidotite-melt ranging from 0.10 to 0.25 can explain the Group 2 data. By contrast, δ44/40Ca in eight out of nine metasomatized Group 3 peridotites are lower than the BSE estimate. The Group 3a harzburgites show the greatest δ44/40Ca variation range (0.25-0.96‰), with δ44/40Ca positively correlated with CaO and negatively correlated with Ce/Eu. Chemical evidence suggests that the residual, melt-depleted, low-Ca protoliths of the Group 3a harzburgites were metasomatized, likely by carbonate-rich melts/fluids. We argue that such fluids may have low (≤0.25‰) δ44/40Ca either because they contain recycled crustal components or because Ca isotopes, similar to trace elements and their ratios, may be fractionated by kinetic and/or chromatographic effects of melt percolation in the mantle. The δ44/40Ca in Group 3b lherzolites (0.83-0.89‰) are lower than in the BSE as well, but the effects of metasomatism on δ44/40Ca are smaller, possibly because of the high Ca contents in their protoliths and/or smaller δ44/40Ca differences between the protoliths and metasomatic agents. The BSE estimates based on fertile peridotites in this study fall in the δ44/40Ca ranges for oceanic and continental basalts, various meteorites (achondrites; carbonaceous, ordinary and enstatite chondrites), Mars, and the Moon. These results provide benchmarks for the application of Ca isotopes to planet formation, mantle evolution, and crustal recycling.

Geochronology and geochemistry of early Paleozoic igneous rocks of the Lesser Xing'an Range, NE China: Implications for the tectonic evolution of the eastern Central Asian Orogenic Belt

NASA Astrophysics Data System (ADS)

Wang, Zhi-wei; Xu, Wen-liang; Pei, Fu-ping; Wang, Feng; Guo, Peng

2016-09-01

This paper presents new zircon U-Pb, Hf isotope, and whole-rock major and trace element data for early Paleozoic igneous rocks of the Lesser Xing'an Range, NE China, in order to constrain the early Paleozoic tectonic evolution of the eastern Central Asian Orogenic Belt (CAOB). Zircon U-Pb dating indicates that early Paleozoic magmatic events within the northern Songnen-Zhangguangcai Range Massif (SZM) can be subdivided into four stages: Middle Cambrian ( 505 Ma), Late Cambrian ( 490 Ma), Early-Middle Ordovician ( 470 Ma), and Late Ordovician (460-450 Ma). The Middle Cambrian monzogranites are K-rich, weakly to strongly peraluminous, and characterized by pronounced heavy rare earth element (HREE) depletions, high Sr/Y ratios, low Y concentrations, low primary zircon εHf(t) values (- 6.79 to - 1.09), and ancient two-stage model (TDM2) ages (1901-1534 Ma). These results indicate derivation from partial melting of thickened ancient crustal materials that formed during the amalgamation of the northern SZM and the northern Jiamusi Massif (JM). The Late Cambrian monzonite, quartz monzonite, and monzogranite units are chemically similar to A-type granites, and contain zircons with εHf(t) values of - 2.59 to + 1.78 and TDM2 ages of 1625-1348 Ma. We infer that these rocks formed from primary magmas generated by partial melting of Mesoproterozoic accreted lower crustal materials in a post-collisional extensional environment. The Early-Middle Ordovician quartz monzodiorite, quartz monzonite, monzogranite, and rhyolite units are calc-alkaline, relatively enriched in light REEs (LREEs) and large ion lithophile elements (LILEs; e.g., Rb, Th, and U), depleted in HREEs and high field strength elements (HFSEs; e.g., Nb, Ta, and Ti), and contain zircons with εHf(t) values of - 7.33 to + 4.98, indicative of formation in an active continental margin setting. The Late Ordovician alkali-feldspar granite and rhyolite units have A-type granite affinities that suggest they formed in an extensional environment. A comparison of early Paleozoic magmatic events and Hf isotopic model ages between the northern SZM and the JM indicates that these two massifs have similar histories of Mesoproterozoic and early Paleozoic crustal accretion and reworking, although the SZM contains much older crustal materials than the JM.

Generation of alkaline magmas in subduction zones by melting of mélange diapirs

NASA Astrophysics Data System (ADS)

Cruz-Uribe, A. M.; Marschall, H.; Gaetani, G. A.; Le Roux, V.

2016-12-01

Alkaline lavas occur globally in subduction-related volcanic arcs. Existing explanations for the occurrence of alkaline lavas in volcanic arcs invoke at least one - and in some cases multiple - `metasomatic' events in addition to the traditional three-component mixing of altered oceanic crust (AOC), sediment melt, and depleted mantle, in order to explain the range of rock types found in a given region. These multi-stage models posit the existence of metasomatized mantle wedge peridotite containing phlogopite or amphibole-enriched veins, which partially melt when fluxed by the addition of materials from the subducted slab. The mélange diapir model is informed by observations and modeling of the subduction side of the arc system, and predicts the generation of alkaline arc magmas by advection of buoyant material from the slab-wedge interface into the mantle wedge below arcs. Here we report results from experiments in which natural mélange materials partially melted at upper mantle conditions were found to produce alkaline magmas compositionally similar to those found in arcs worldwide. The starting material for our experiments is a chlorite-omphacite fels (SY400) from the island of Syros, Greece, that is representative of a hybrid rock containing AOC, sediment, and mantle components. Melting experiments were performed using a piston cylinder apparatus at conditions relevant to the heating-decompression path of mélange diapirs (1000-1300 °C, 1.5-2.5 GPa). The compositions of experimentally produced melts range from 51-61 wt% SiO2, and fall within the trachyte and tephrite-phonolite series (7.5-12.9 wt% Na2O+K2O). Restitic phases in equilibrium with melt include clinopyroxene, garnet (at high P), phlogopite (at high P), amphibole, olivine, rutile, and ilmenite. Partial melts produced in our experiments have trace-element abundance patterns that are typical of alkaline arc lavas, such as enrichment in large ion lithophile elements (Cs, Rb, Ba, Pb, Sr) and alkalis (K and Na), and depletion in Nb and Ta. The presence of a light rare earth element (LREE)-bearing accessory phase results in trace element fractionation by a factor of 4.2 for Nd/Hf and 2.6 for Sr/Nd. Melting of mélange diapirs provides a simple, single-stage model for the origin of alkaline magmatism in the arc and backarc regions of subduction zones.

Constraints on the origin of adakites and porphyry Cu-Mo mineralization in Chongjiang, Southern Gangdese, the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Hu, Yong-bin; Liu, Ji-qiang; Ling, Ming-xing; Liu, Yan; Ding, Xing; Liu, Dun-yi; Sun, Wei-dong

2017-11-01

Chongjiang is a low-grade porphyry Cu deposit, located in the Gangdese belt, south Tibet. The petrogenesis and geodynamic settings of the Miocene intrusions associated with the deposit remain controversial. This study presents new results on in situ zircon Hf-O isotopic compositions and U-Pb ages, whole rock major and trace elements, and Sr-Nd isotopes for the adakitic intrusions from Chongjiang deposit. The ore-bearing biotite monzogranite porphyry has adakitic characteristics, with enriched large-ion-lithophile elements (LILE) and light rare earth elements (LREE), and depleted in high-field-strength elements (HFSE), P and Ti. LA-ICP-MS zircon U-Pb dating indicates that the ore-bearing and barren adakites were emplaced at 14.9 ± 0.3 Ma and 12.9 ± 0.3 Ma, respectively. The porphyry is characterized by relatively high initial 87Sr/86Sr ratios (0.7059 to 0.7066), and negative whole-rock εNd(t) values (- 3.8 to - 2.6). Zircon δ18O is slightly higher than mantle values (5.0 to 7.2‰), with varied εHf(t) (- 1.0 to 7.6). Most of the in situ zircon Hf-O isotopic data plot in a binary mixing trend between MORB and lower continental crust-derived melts. These results indicate contributions from mixing of a mantle-like source (e.g., slab melts) with continental crust. Interestingly, most of the samples plot in the field defined by Dabie adakites (representing partial melting of the lower continental crust), with several samples near/in the circum-Pacific adakite field (representing partial melting of subducted oceanic slabs), which seemingly indicates that Chongjiang adakites mostly formed through partial melting of lower continental crust, with a small amount derived from oceanic slab melts. These may be plausibly explained by plagioclase retention in the thickened Tibetan continental crust, which lowers Sr contents in the magmas during crustal assimilation. Such a model is supported by other adakite discrimination diagrams, which all point towards slab melting. Crustal contamination can compellingly explain the low grade of the Chongjiang deposit. Considering the temporal-spatial distribution of porphyry Cu deposits, geochemical characteristics and high oxygen fugacity, we propose that the subducting Ninetyeast Ridge probably played a critical role in controlling the formation of Miocene adakites and porphyry copper deposits in the eastern Gangdese belt.

In Situ Trace Element Measurements on Roda and the Origin of Diogenites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Herrin, J. S.

2011-01-01

The origin of diogenites remains poorly understood. A recent model interprets many diogenites to have been formed from melts that were derived by remelting initial magma ocean cumulates, and these penultimate parent melts were then contaminated by melts derived from remelting of the basaltic (eucritic) crust to form the ultimate diogenite parent melts [1] (hereafter the remelting model). This is a very complicated petrogenesis that has profound implications for the geological evolution of 4 Vesta if correct. This model was developed based on trace element analyses of bulk rock samples that had been leached in acids to remove phosphates; the compositions of the residues were interpreted to be close to those of cumulus orthopyroxenes plagioclase, chromite and olivine [1]. In situ measurements of phases in diogenites can be used to test this model. We have begun a campaign of laser ablation ICP-MS of orthopyroxene grains in diogenites for this purpose. Here we report our first results on one diogenite, Roda. We have determined a suite of trace lithophile elements on nine, mm-sized pyroxene grains separated from Roda that have previously been studied [2, 3]. A key observation supporting the remelting model is the very low Eu/Eu* of leached residues; values too low to represent orthopyroxene that crystallized from melts with chondritic Sm/Eu and Gd/Eu [1]. (Eu* = Eu interpolated from REE diagrams.) Crustal remelts have low Sm/Eu and Gd/Eu, and orthopyroxenes that crystallized from parent melts contaminated by them would have very low Eu/Eu* [1]. Roda grains have Eu/Eu* of 0.243 to 0.026; the latter a value lower than any measured on bulk diogenite leached residues (0.041) [1]. There is a general negative correlation between Eu/Eu* and some incompatible elements (Zr, Nb, Hf), but not others (LREE). This appears inconsistent with the remelting model as it would suggest an evolving parent melt with La de-creasing as Zr increased and Eu/Eu* decreased. Grain R-15 includes trace-element-rich trapped melt phases [2, 3]. This grain has the highest Eu/Eu* and LREE contents, indicating that the trapped melt had a high Eu/Eu*. Thus, our first data on one diogenite do not provide support for the remelting model [1]. Roda is unusual in that its orthopyroxene grains show wide ranges in trace element contents [4]. Previous in situ REE analyses of grain R-15 did not reveal evidence for subsolidus equilibration with trace-element-rich trapped melt phases, and led to the suggestion that Roda may be polymict, with different grains representing different lithologies of diverse compositions [3]. Thus, based on our results on Roda, it is perhaps premature to abandon the remelting model. In situ measurements on a suite of diogenites is planned to further address this issue.

Accumulation of rare earth elements by siderophore-forming Arthrobacter luteolus isolated from rare earth environment of Chavara, India.

PubMed

Emmanuel, E S Challaraj; Ananthi, T; Anandkumar, B; Maruthamuthu, S

2012-03-01

In this study, Arthrobacter luteolus, isolated from rare earth environment of Chavara (Quilon district, Kerala, India), were found to produce catechol-type siderophores. The bacterial strain accumulated rare earth elements such as samarium and scandium. The siderophores may play a role in the accumulation of rare earth elements. Catecholate siderophore and low-molecular-weight organic acids were found to be present in experiments with Arthrobacter luteolus. The influence of siderophore on the accumulation of rare earth elements by bacteria has been extensively discussed.

Google Earth locations of USA and seafloor hydrothermal vents with associated rare earth element data

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

Andrew Fowler

Google Earth .kmz files that contain the locations of geothermal wells and thermal springs in the USA, and seafloor hydrothermal vents that have associated rare earth element data. The file does not contain the actual data, the actual data is available through the GDR website in two tier 3 data sets entitled "Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge (MOR) Hydrothermal Vents" and "Rare earth element content of thermal fluids from Surprise Valley, California"

Supra-subduction zone extensional magmatism in Vermont and adjacent Quebec: Implications for early Paleozoic Appalachian tectonics

USGS Publications Warehouse

Kim, J.; Coish, R.; Evans, M.; Dick, G.

2003-01-01

Metadiabasic intrusions of the Mount Norris Intrusive Suite occur in fault-bounded lithotectonic packages containing Stowe, Moretown, and Cram Hill Formation lithologies in the northern Vermont Rowe-Hawley belt, a proposed Ordovician arc-trench gap above an east-dipping subduction zone. Rocks of the Mount Norris Intrusive Suite are characteristically massive and weakly foliated, have chilled margins, contain xenoliths, and have sharp contacts that both crosscut and are parallel to early structural fabrics in the host metasedimentary rocks. Although the mineral assemblage of the Mount Norris Intrusive Suite is albite + actinolite + epidote + chlorite + calcite + quartz, intergrowths of albite + actinolite are probably pseudomorphs after plagioclase + clinopyroxene. The metadiabases are subalkaline, tholeiitic, hypabyssal basalts with preserved ophitic texture. A backarc-basin tectonic setting for the intrusive suite is suggested by its LREE (light rare earth element) enrichment, negative Nb-Ta anomalies, and Ta/Yb vs. Th/Yb trends. Although no direct isotopic age data are available, the intrusions are broadly Ordovician because their contacts are clearly folded by the earliest Acadian (Silurian-Devonian) folds. Field evidence and geochemical data suggest compelling along-strike correlations with the Coburn Hill Volcanics of northern Vermont and the Bolton Igneous Group of southern Quebec. Isotopic and stratigraphic age constraints for the Bolton Igneous Group bracket these backarc magmas to the 477-458 Ma interval. A tectonic model that begins with east-dipping subduction and progresses to outboard west-dipping subduction after a syncollisional polarity reversal best explains the intrusion of deformed metamorphosed metasedimentary rocks by backarc magmas.

Distribution behavior of uranium, neptunium, rare-earth elements ( Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiClKCI eutectic salt and liquid cadmium or bismuth

NASA Astrophysics Data System (ADS)

Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

1995-12-01

Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCI eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system.

Alkali element constraints on Earth-Moon relations

NASA Technical Reports Server (NTRS)

Norman, M. D.; Drake, M. J.; Jones, J. H.

1994-01-01

Given their range of volatilities, alkali elements are potential tracers of temperature-dependent processes during planetary accretion and formation of the Earth-Moon system. Under the giant impact hypothesis, no direct connection between the composition of the Moon and the Earth is required, and proto-lunar material does not necessarily experience high temperatures. Models calling for multiple collisions with smaller planetesimals derive proto-lunar materials mainly from the Earth's mantle and explicitly invoke vaporization, shock melting and volatility-related fractionation. Na/K, K/Rb, and Rb/Cs should all increase in response to thermal volatization, so theories which derive the Moon substantially from Earth's mantle predict these ratios will be higher in the Moon than in the primitive mantle of the Earth. Despite the overall depletion of volatile elements in the Moon, its Na/K and K/Rb are equal to or less than those of Earth. A new model presented here for the composition of Earth's continental crust, a major repository of the alkali elements, suggests the Rb/Cs of the Moon is also less than that of Earth. Fractionation of the alkali elements between Earth and Moon are in the opposite sense to predictions based on the relative volatilities of these elements, if the Moon formed by high-T processing of Earth's mantle. Earth, rather than the Moon, appears to carry a signature of volatility-related fractionation in the alkali elements. This may reflect an early episode of intense heating on Earth with the Moon's alkali budget accreting from cooler material.

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.

[Rare earth elements content in farmland soils and crops of the surrounding copper mining and smelting plant in Jiangxi province and evaluation of its ecological risk].

PubMed

Jin, Shu-Lan; Huang, Yi-Zong; Wang, Fei; Xu, Feng; Wang, Xiao-Ling; Gao, Zhu; Hu, Ying; Qiao Min; Li, Jin; Xiang, Meng

2015-03-01

Rare earth elements content in farmland soils and crops of the surrounding copper mining and smelting plant in Jiangxi province was studied. The results showed that copper mining and smelting could increase the content of rare earth elements in soils and crops. Rare earth elements content in farmland soils of the surrounding Yinshan Lead Zinc Copper Mine and Guixi Smelting Plant varied from 112.42 to 397.02 mg x kg(-1) and 48.81 to 250.06 mg x kg(-1), and the average content was 254.84 mg x kg(-1) and 144.21 mg x kg(-1), respectively. The average contents of rare earth elements in soils in these two areas were 1.21 times and 0.68 times of the background value in Jiangxi province, 1.36 times and 0.77 times of the domestic background value, 3.59 times and 2.03 times of the control samples, respectively. Rare earth elements content in 10 crops of the surrounding Guixi Smelting Plant varied from 0.35 to 2.87 mg x kg(-1). The contents of rare earth elements in the leaves of crops were higher than those in stem and root. The contents of rare earth elements in Tomato, lettuce leaves and radish leaves were respectively 2.87 mg x kg(-1), 1.58 mg x kg(-1) and 0.80 mg x kg(-1), which were well above the hygienic standard limit of rare earth elements in vegetables and fruits (0.70 mg x kg(-1)). According to the health risk assessment method recommended by America Environmental Protection Bureau (USEPA), we found that the residents' lifelong average daily intake of rare earth elements was 17.72 mg x (kg x d)(-1), lower than the critical value of rare earth elements damage to human health. The results suggested that people must pay attention to the impact of rare earth elements on the surrounding environment when they mine and smelt copper ore in Jiangxi.

Concentrations and health risk assessment of rare earth elements in vegetables from mining area in Shandong, China.

PubMed

Zhuang, Maoqiang; Zhao, Jinshan; Li, Suyun; Liu, Danru; Wang, Kebo; Xiao, Peirui; Yu, Lianlong; Jiang, Ying; Song, Jian; Zhou, Jingyang; Wang, Liansen; Chu, Zunhua

2017-02-01

To investigate the concentrations of rare earth elements in vegetables and assess human health risk through vegetable consumption, a total of 301 vegetable samples were collected from mining area and control area in Shandong, China. The contents of 14 rare earth elements were determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The total rare earth elements in vegetables from mining and control areas were 94.08 μg kg -1 and 38.67 μg kg -1 , respectively, and the difference was statistically significant (p < 0.05). The leaf vegetable had the highest rare earth elements concentration (984.24 μg kg -1 and 81.24 μg kg -1 for mining and control areas, respectively) and gourd vegetable had the lowest rare earth elements concentration (37.34 μg kg -1 and 24.63 μg kg -1 for mining and control areas, respectively). For both areas, the rare earth elements concentration in vegetables declined in the order of leaf vegetable > taproot vegetable > alliaceous vegetable > gourd vegetable. The rare earth elements distribution patterns for both areas were characterized by enrichment of light rare earth elements. The health risk assessment demonstrated that the estimated daily intakes (0.69 μg kg -1 d -1 and 0.28 μg kg -1 d -1 for mining and control areas, respectively) of rare earth elements through vegetable consumption were significantly lower than the acceptable daily intake (70 μg kg -1 d -1 ). The damage to adults can be neglected, but more attention should be paid to the effects of continuous exposure to low levels of rare earth elements on children. Copyright © 2016 Elsevier Ltd. All rights reserved.

An Overview of the Southern Mariana Subduction Factory: Arc, Cross-Chains, and Back-Arc Basin

NASA Astrophysics Data System (ADS)

Stern, R. J.; Hargrove, U. S.; Leybourne, M. I.; Pearce, J. A.; Bloomer, S. H.

2002-12-01

The Mariana arc system south of 18°N provides 3 opportunities to study the magmatic outputs of the IBM Subduction Factory: 1) Along the Magmatic arc; 2) Across arc cross-chains; and 3) Along the back-arc basin spreading axis. In spite of being located near population centers of Guam and Saipan, this is a relatively poorly known part of the arc system. There is a clear break in the trend and morphology of the magmatic arc west of the144°E fault and slab tear, and we surveyed and sampled the region north and east of this during the Cook 7 expedition in March-April 2001. Systematic morphologic covariations are observed along the arc and backarc basin magmatic systems, with the shallower ridge depths adjacent to more magmatically-robust arc segments. Our preliminary results reveal a compositional discontinuity in back-arc basin basalts (BABB) south of a bathymetric break near 15°30'N, with BABB in shallower segments to the north having a strong subduction component (higher Ba/Nb, Rb, Zr, etc.) and deeper regions to the south being more MORB-like. This is close to the morphological break along the magmatic front, with larger (>10E11 m3) edifices of the Central Island Province north of 16°N and smaller, entirely submarine volcanoes to the south, implying a more robust magmatic budget in the north; a similar variations are observed for cross-chain volcanoes, with smaller ones associated with the smaller, southern arc volcanoes and larger ones associated with the larger arc volcanoes of the Central Island Province. In contrast to the back-arc basin spreading axis, no systematic compositional variations are observed along or across the arc. Arc and cross-chains comprise a coherent, low- to medium-K, dominantly tholeiitic suite. REE patterns show moderate LREE-enrichment, with chondrite-normalized La/Yb = 1.5-2. Rear-arc volcanoes sometimes are slightly less fractionated, slightly more potassic, and slightly more LREE-enriched, but these are second order differences. The strong increase in K and LREE enrichment and decrease in fluid-mobile elements observed for the Kasuga cross-chain to the north is not observed in the southern cross-chains.

What governs the enrichment of Pb in the continental crust? An answer from the Mexican Volcanic Belt

NASA Astrophysics Data System (ADS)

Goldstein, S. L.; Lagatta, A.; Langmuir, C. H.; Straub, S. M.; Martin-Del-Pozzo, A.

2009-12-01

One of Al Hofmann’s many important contributions to our understanding of geochemical cycling in the Earth is the observation that Pb behaves like the light rare earth elements Ce and Nd during melting to form oceanic basalts, but is enriched in the continental crust compared to the LREE by nearly an order of magnitude (Hofmann et al. 1986). This is unusual behavior, and has been called one of the Pb paradoxes, since in most cases, the ratios of elements are effectively the same in the continental crust and oceanic basalts if they show similar mantle melting behavior. One of several mechanisms suggested to mediate this special enrichment is hydrothermal circulation at ocean ridges, which preferentially transports Pb compared to the REE from the interior of the ocean crust to the surface. We confirm the importance of hydrothermal processes at the East Pacific to mediate Pb enrichment at the Trans-Mexican Volcanic Belt (TMVB, through comparison of Pb isotope and Ce/Pb ratios of TMVB lavas with sediments from DSDP Site 487 near the Middle America trench. The lavas of the Trans-Mexican Volcanic Belt include “high Nb” alkali basalts (HNAB), whose trace element patterns lack subduction signatures. The HNAB basalts and hydrothermally affected sediments from DSDP 487, form end-members that bound calcalkaline lavas from volcanoes Colima, Toluca, Popocatépetl, and Malinche in Ce/Pb versus Pb isotope space. The HNAB represent the high Ce/Pb and high Pb-isotope end-member. The hydrothermal sediments have Pb isotopes like Pacific MORB but Ce/Pb ratios typical of the arcs and the continental crust, and an order of magnitude lower than MORB. No analyzed calcalkaline lavas are have compositions outside of the bounds formed by the HNAB and the hydrothermal sediments. The Ce/Pb and Pb isotope ratios show that the calcalkaline lava compositions are inconsistent with contributions from HNAB and EPR MORB, rather the contributions are from HNAB upper mantle and subducted hydrothermal sediments. The Trans-Mexican Volcanic Belt data confirm the two-step process of Pb enrichment in the arc lavas (and more generally in the continental crust). In the first step, hydrothermal processes at the East Pacific Rise preferentially transport Pb from the basaltic oceanic crust to surface sediments. In the second step, during subduction, these sediments are the main source of asthenospheric mantle-derived Pb to the lavas. Our data also confirm the importance of subduction contributions to the Quaternary Mexican arc, despite the >40 km thick continental crust. Ref: Hofmann et al. (1986) EPSL 79 p. 33-45.

Biogeochemistry of the rare-earth elements with particular reference to hickory trees

USGS Publications Warehouse

Robinson, W.O.; Bastron, H.; Murata, K.J.

1958-01-01

Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H2SO3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water. ?? 1958.

The Not-So-Rare Earths.

ERIC Educational Resources Information Center

Muecke, Gunter K.; Moller, Peter

1988-01-01

Describes the characteristics of rare earth elements. Details the physical chemistry of rare earths. Reviews the history of rare earth chemistry and mineralogy. Discusses the mineralogy and crystallography of the formation of rare earth laden minerals found in the earth's crust. Characterizes the geologic history of rare earth elements. (CW)

The elements of the Earth's magnetism and their secular changes between 1550 and 1915

NASA Technical Reports Server (NTRS)

Fritsche, H.

1983-01-01

The results of an investigation about the magnetic agents outside the Earth's surface as well as the Earth's magnetic elements for the epochs 1550, 1900, 1915 are presented. The secular changes of the Earth's magnetic elements during the time interval 1550 - 1900 are also included.

Real World of Industrial Chemistry: Technology of the Rare Earths.

ERIC Educational Resources Information Center

Kremers, Howard E.

1985-01-01

The 17 rare earth elements account for one-fifth of the 83 naturally occurring elements and collectively rank as the 22nd most abundant "element." Properties of these elements (including their chemical similarity), their extraction from the earth, and their uses are discussed. (JN)

High-K calc-alkaline magmatism at the Archaean-Proterozoic boundary: implications for mantle metasomatism and continental crust petrogenesis. Example of the Bulai pluton (Central Limpopo Belt, South Africa)

NASA Astrophysics Data System (ADS)

Laurent, Oscar; Martin, Hervé; Doucelance, Régis; Moyen, Jean-François; Paquette, Jean-Louis

2010-05-01

The Neoarchaean Bulai pluton, intrusive within the supracrustal granulites of the Central Limpopo Belt (Limpopo Province, South Africa) is made up of large volumes of porphyritic granodiorites with subordinate enclaves and dykes which have monzodioritic and charno-enderbitic compositions. New U-Pb LA-ICP-MS dating on separated zircons yielded pluton emplacement ages ranging between 2.60 and 2.63 Ga, which are slightly older than previous proposed ages (~ 2.57-2.61 Ga). The whole-rock major- and trace-element composition of the Bulai pluton evidences unequivocal affinities with "high-Ti" late-Archaean sanukitoids. It belongs to a high-K calc-alkaline differentiation suite, with metaluminous affinities (0.7 < A/CNK < 1) and relatively high Mg# (0.4-0.6). These rocks have "juvenile" affinities, such as eNd ranging between -0.5 and 0.5, and in addition, are very rich in all incompatible trace elements, which is particularly obvious in monzodioritic enclaves and enderbites where primitive mantle-normalized LILE and LREE contents are up to 300. These characteristics point to an enriched mantle source for the Bulai batholith. Chondrite normalized, REE patterns are strongly fractionated ([La/Yb]N ~ 25-80), mainly due to high LREE contents (LaN ~ 250-630), and chiefly high HFSE contents (Nb ~ 15-45 ppm ; up to 770 ppm Zr) indicate that the metasomatic agent is a silicic melt rather than a hydrous fluid. Moreover, based on high Nb/Ta, Th/Rb, La/Rb and low Sr/Nd and Ba/La, we suggest that the metasomatic agent is a granitic melt generated by melting of terrigenous sediments. Interactions of this melt with mantle peridotites implies that sediments are located under a mantle slice; geometry which is easily achieved in subduction zone settings. This conclusion is supported by the fact that Bulai trace element patterns are very similar to those of sub-actual potassic magmas generated in magmatic arc environments by interactions between mantle and terrigenous sediments (e.g. Sunda arc). Geochemical modeling indicates that the mafic facies of the Bulai pluton can be achieved by a two-stage process: 1) a liquid produced by melting of subducted terrigenous sediment is entirely consumed by metasomatic reactions with mantle peridotites, producing a metasomatic amphibole- and phlogopite-bearing assemblage ; 2) Low-degree melting of this metasomatized mantle gives rise to magmas with the same trace element signature than the Bulai mafics. Such a petrogenetic model is consistent with previous geochemical and experimental study about sanukitoids, which concluded that these magmas result of interactions between slab melts and the overlying mantle wedge. Subsequently, at crustal levels, the Bulai monzodiorite not only underwent significant fractional crystallization, but also induce melting of the host rocks, and mixed with the resulting felsic crustal magmas. Such that it can be concluded that the whole Bulai suite can be derived through AFC processes. Our geochemical study failed in demonstrating any significant role played by melting of subducted metabasalts, which contrasts to Archaean times, and would point to lower thermal regimes as the wet solidus of metasediments is ~ 50 to 100°C lower than that of metabasalts at slab pressures. In addition the fact that the whole felsic melts were consumed by reaction with peridotite is indicative of lower degrees of melting of the slab compared with Archaean processes. Both conclusions imply that the geodynamic changes that took place at the Archaean-Proterozoic transition and witnessed by sanukitoid-related rocks are the result of progressive and global cooling of Earth.

[Physiological effects of rare earth elements and their application in traditional Chinese medicine].

PubMed

Zhou, Jie; Guo, Lanping; Xiao, Wenjuan; Geng, Yanling; Wang, Xiao; Shi, Xin'gang; Dan, Staerk

2012-08-01

The process in the studies on physiological effects of rare earth elements in plants and their action mechanisms were summarized in the aspects of seed germination, photosynthesis, mineral metabolism and stress resistance. And the applications of rare earth elements in traditional Chinese medicine (TCM) in recent years were also overviewed, which will provide reference for further development and application of rare earth elements in TCM.

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.

Accessory and rock forming minerals monitoring the evolution of zoned mafic ultramafic complexes in the Central Ural Mountains

NASA Astrophysics Data System (ADS)

Krause, J.; Brügmann, G. E.; Pushkarev, E. V.

2007-04-01

This study describes major and trace element compositions of accessory and rock forming minerals from three Uralian-Alaskan-type complexes in the Ural Mountains (Kytlym, Svetley Bor, Nizhnii Tagil) for the purpose of constraining the origin, evolution and composition of their parental melts. The mafic-ultramafic complexes in the Urals are aligned along a narrow, 900 km long belt. They consist of a central dunite body grading outward into clinopyroxenite and gabbro lithologies. Several of these dunite bodies have chromitites with platinum group element mineralization. High Fo contents in olivine (Fo 92-93) and high Cr/(Cr + Al) in spinel (0.67-0.84) suggest a MgO-rich (> 15 wt.%) and Al 2O 3-poor ultramafic parental magma. During its early stages the magma crystallized dominantly olivine, spinel and clinopyroxene forming cumulates of dunite, wehrlite and clinopyroxenite. This stage is monitored by a common decrease in the MgO content in olivine (Fo 93-86) and the Cr/(Cr + Al) value of coexisting accessory chromite (0.81-0.70). Subsequently, at subsolidus conditions, the chromite equilibrated with the surrounding silicates producing Fe-rich spinel while Al-rich spinel exsolved chromian picotite and chromian titanomagnetite. This generated the wide compositional ranges typical for spinel from Uralian-Alaskan-type complexes world wide. Laser ablation analyses (LA-ICPMS) reveal that clinopyroxene from dunites and clinopyroxenite from all three complexes have similar REE patterns with an enrichment of LREE (0.5-5.2 prim. mantle) and other highly incompatible elements (U, Th, Ba, Rb) relative to the HREE (0.25-2.0 prim. mantle). This large concentration range implies the extensive crystallization of olivine and clinopyroxene together with spinel from a continuously replenished, tapped and crystallizing magma chamber. Final crystallization of the melt in the pore spaces of the cooling cumulate pile explains the large variation in REE concentrations on the scale of a thin section, the REE-rich rims on zoned clinopyroxene phenocrysts (e.g. La Rim/La Core ˜ 2), and the formation of interstitial clinopyroxene with similar REE enrichment. Trace element patterns of the parental melt inferred from clinopyroxene analyses show negative anomalies for Ti, Zr, Hf, and a positive anomaly for Sr. These imply a subduction related geotectonic setting for the Uralian zoned mafic-ultramafic complexes. Ankaramites share many petrological and geochemical features with these complexes and could represent the parental melts of this class of mafic-ultramafic intrusions. Diopside from chromitites and cross cutting diopside veins in dunite has similar trace element patterns with LREE/HREE ratios (e.g. La/Lu = 5-60) much higher than those in diopside from all other lithologies. We suggest that the chromitites formed at high temperatures (800-900 °C) during the waning stages of solidification as a result of the interaction of an incompatible element-rich melt or fluid with the dunite cumulates.

Rare Earth Element Concentration of Wyoming Thermal Waters Update

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

Quillinan, Scott; Nye, Charles; Neupane, Hari

Updated version of data generated from rare earth element investigation of produced waters. These data represent major, minor, trace, isotopes, and rare earth element concentrations in geologic formations and water associated with oil and gas production.

2nd International Symposium on Fundamental Aspects of Rare-earth Elements Mining and Separation and Modern Materials Engineering (REES-2015)

NASA Astrophysics Data System (ADS)

Tavadyan, Levon, Prof; Sachkov, Viktor, Prof; Godymchuk, Anna, Dr.; Bogdan, Anna

2016-01-01

The 2nd International Symposium «Fundamental Aspects of Rare-earth Elements Mining and Separation and Modern Materials Engineering» (REES2015) was jointly organized by Tomsk State University (Russia), National Academy of Science (Armenia), Shenyang Polytechnic University (China), Moscow Institute of Physics and Engineering (Russia), Siberian Physical-technical Institute (Russia), and Tomsk Polytechnic University (Russia) in September, 7-15, 2015, Belokuriha, Russia. The Symposium provided a high quality of presentations and gathered engineers, scientists, academicians, and young researchers working in the field of rare and rare earth elements mining, modification, separation, elaboration and application, in order to facilitate aggregation and sharing interests and results for a better collaboration and activity visibility. The goal of the REES2015 was to bring researchers and practitioners together to share the latest knowledge on rare and rare earth elements technologies. The Symposium was aimed at presenting new trends in rare and rare earth elements mining, research and separation and recent achievements in advanced materials elaboration and developments for different purposes, as well as strengthening the already existing contacts between manufactures, highly-qualified specialists and young scientists. The topics of the REES2015 were: (1) Problems of extraction and separation of rare and rare earth elements; (2) Methods and approaches to the separation and isolation of rare and rare earth elements with ultra-high purity; (3) Industrial technologies of production and separation of rare and rare earth elements; (4) Economic aspects in technology of rare and rare earth elements; and (5) Rare and rare earth based materials (application in metallurgy, catalysis, medicine, optoelectronics, etc.). We want to thank the Organizing Committee, the Universities and Sponsors supporting the Symposium, and everyone who contributed to the organization of the event and to publication of this proceeding.

Two main and a new type rare earth elements in Mg alloys: A review

NASA Astrophysics Data System (ADS)

Kong, Linghang

2017-09-01

Magnesium (Mg) alloys stand for the lightest structure engineering materials. Moreover, the strengthening of Mg alloys in ductility, toughness and corrosion predominates their wide applications. With adding rare earth elements in Mg, the mechanical properties will be improved remarkably, especially their plasticity and strength. A brief overview of the addition of rare earth elements for Mg alloys is shown. The basic mechanisms of strengthening Mg alloys with rare earth elements are reviewed, including the solid solution strengthening, grain refinement and long period stacking ordered (LPSO) phase. Furthermore, the available rare earth elements are summarized by type, chemical or physical effects and other unique properties. Finally, some challenge problems that the research is facing and future expectations of ra-re-earth Mg alloys are stated and discussed.

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.

Leaching behavior of rare earth elements in Fort Union lignite coals of North America

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

Laudal, Daniel A.; Benson, Steven A.; Addleman, Raymond Shane

Rare earth elements are crucial materials in an incredible array of consumer goods, energy system components and military defense applications. However, the global production and entire value chain for rare earth elements is dominated by China, with the U.S. currently 100% import reliant for these critical materials. Traditional mineral ores including those previously mined in the U.S., however, have several challenges. Chief among these is that the content of the most critical and valuable of the rare earths are deficient, making mining uneconomical. Further, the supply of these most critical rare earths is nearly 100% produced in China from amore » single resource that is only projected to last another 10 to 20 years. The U.S. currently considers the rare earths market an issue of national security. It is imperative that alternative domestic sources of rare earths be identified and methods developed to produce them. Recently, coal and coal byproducts have been identified as one of these promising alternative resources. This paper details the results of a study on characterization of North Dakota lignite and lignite-related feedstocks as an assessment of their feasibility for rare earth element recovery. The abundance, distribution and modes of occurrence of the rare earth elements in the samples collected were determined in this initial study to inform the selection of appropriate extraction and concentration methods to recover the rare earth elements. Materials investigated include the lignite coals, clay-rich sediments associated with the coal seams, and materials associated with a lignite beneficiation system and power plant. The results show that high rare earth element levels exist both in lignite coals and associated sediments. The form of the rare earth elements in the clay materials is primarily as ultra-fine mineral grains. In the lignite coals, approximately 80-95% of the rare earths content is organically associated, primarily as coordination complexes.« less

The role of hydrothermal fluids in the production of subduction zone magmas: Evidence from siderophile and chalcophile trace elements and boron

NASA Astrophysics Data System (ADS)

Noll, P. D.; Newsom, H. E.; Leeman, W. P.; Ryan, J. G.

1996-02-01

In order to evaluate the processes responsible for the enrichments of certain siderophile/ chalcophile trace elements during the production of subduction-related magmas, representative lavas from seven subduction zones have been analyzed for Pb, As, Sb, Sn, W, Mo, Tl, Cu, and Zn by inductively coupled plasma-mass spectrometry (ICP-MS), radiochemical epithermal neutron activation analysis (RENA), and atomic absorption (AA). The siderophile/chalcophile elements are compared to the highly fluid-mobile element B, the light rare earth elements (LREEs), U, and Th in order to place constraints on their behavior in subduction zones. Boron, As, Sb, and Pb are all enriched in arc lavas and continental crustal rocks more so than expected assuming normal magmatic processes (melting and crystallization). Tin, W, and Mo show little evidence of enrichment. Correlations of Pb/Ce, As/Ce, and Sb/Ce with B/La are statistically significant and have high correlation coefficients (and, more importantly, slopes approaching one) suggesting that Pb, As, and Sb behave similarly to B (i.e., that they are fluid-mobile). In addition, across-arc traverses show that B/La, As/Ce, Pb/Ce, and Sb/Ce ratios decrease dramatically with distance towards the back-arc basin. W/Th, Tl/La, Sn/Sm, and Mo/Ce ratios and Cu and Zn concentrations have much less systematic across-arc variations and correlations with B/La are not as strong (and in some cases, not statistically significant) and the regression lines have much lower slopes. Mixing models between upper mantle, slab-derived fluid, and sediment are consistent with a fluid-derived component in the arcs displaying extra enrichments of B, Pb, As, and Sb. These observations imply efficient mobilization of B, Pb, As, Sb, and possibly Tl into arc magma source regions by hydrothermal fluids derived from metamorphic dehydration reactions within the slab. Tin, W, and Mo show little, if any, evidence of hydrothermal mobilization. Copper appears to be slightly enriched in arc lavas relative to mid-ocean ridge basalts (MORBs) whereas Zn contents of arc lavas, MORB, ocean island basalts (OIBs), and continental crustal samples are similar suggesting that the bulk partition coefficient for Zn is approximately equal to one. However, Zn contents of the upper mantle are lower than these reservoirs implying an enrichment of the source region in Zn prior to melting. These nonigneous enrichments have implications not only for arc magma genesis but also for continental crust formation and crust-mantle evolution. The mobility of Pb, As, Sb, and B in hot, reducing, acidic hydrothermal fluids may be greatly enhanced relative to the large-ion lithophile elements (LILEs; including U) as a result of HS -, H 2S, OH -, or other types of complexing. In the case of Pb, continued transport of Pb from subducted slabs into arc magma source regions throughout Earth history coupled with a U fluxing of the mantle a the end of the Archean may account for the depletion of Pb in the upper mantle, the low U/Pb of most arc volcanics and continental crustal rocks, and provide an explanation for the Pb- Paradox (Hofmann et al., 1986;McCulloch, 1993;Miller et al., 1994). Recycled slabs will then retain high U/Pb ratios upon entering the deep mantle and may eventually become incorporated into the source regions of many OIBs; some with HIMU (high 238U/ 204Pb) signatures.

Lanthanum-rich fluorbritholite-(Ce) from young alkaline volcanic rock of Eifel (Germany) and its crystal structure. Cation ordering in britholites

NASA Astrophysics Data System (ADS)

Zubkova, N. V.; Chukanov, N. V.; Pekov, I. V.; Schäfer, C.; Yapaskurt, V. O.; Pushcharovsky, D. Yu.

2015-09-01

Structure (R=0.0213) of lanthanum-rich fluorbritholite (Ce) [(Ce2.47La2.31Nd0.22Pr0.13Y0.07)5.20Ca4.20Th0.27Mn0.19Sr0.09]9.95(Si5.37P0.63)6O24.16F1.95 from sanidinite in Laacher See, Eifel, Germany was studied on a monocrystal. The structure [space group P63/m, a = 9.58949 (13), c = 7.0289 (11) Å, V = 559.770 (14)Å3] is identical to structures of members of apatite supergroup. Relationships of major cations in polyhedra M(1)O9 = (Ca0.6 REE 0.4), and in polyhedral M(2)O6F = ( REE 0.7Ca0.3). Substantial structural order M(1) and M(2) is defined, simplified structural formula: (Ca, LREE)2( LREE,Ca)3(SiO4)3F. Analysis of data on crystal chemistry of britholite was carried out. It was demonstrated that distribution of cations on M(1)and M(2)-positions is always characteristic of partial structural order. Clear tendency of LREE concentration in M(2) position was noted.

Allochthonous 2.78 Ga oceanic plateau slivers in a 2.72 Ga continental arc sequence: Vizien greenstone belt, northeastern Superior Province, Canada

NASA Astrophysics Data System (ADS)

Skulski, T.; Percival, J. A.

1996-04-01

Embedded within the vast granitoid terrane of the Minto block of northeastern Superior Province are Late Archean greenstone belts of the Goudalie domain that preserve a long-lived record of continent-ocean interaction. The Vizien greenstone belt is one such belt and it contains four fault-bounded structural panels. The 2786 Ma mafic-ultramafic sequence is an allochthonous package of pillowed basaltic andesite, komatiite and volcaniclastic rocks cut by peridotite and gabbro sills. The mafic rocks are LREE-depleted tholeiites which have primitive mantle (PRIM)-normalized abundances of Th < Nb < La, and ɛNd values of +1.5 to + 3.2 reflecting extraction from a depleted mantle source. The 2724 Ma lac Lintelle continental calc-alkaline volcanic sequence consists of massive basalt, plagioclase-porphyritic andesite, dacite, rhyolite, capped by quartz-rich sandstones/conglomerates with 2.97 Ga Nd model ages. Lac Lintelle volcanic rocks are LREE enriched, with low TiO 2 (< 1%) and Zr (< 200 ppm), PRIM-normalized enrichment in Th > La > Nb, and a range of ɛNd values from -0.1 to +1.7. The ~ 2722 Ma lac Serindac bimodal, subaerial tholeiitic volcanic sequence contains andesite (locally with tonalite xenoliths), basalt, gabbro sills, lenses of quartz-rich sedimentary rocks and a thick, upper rhyolite sequence. The lac Serindac tholeiites are LREE-enriched, have PRIM-normalized Th > La > Nb, high Zr (to 300 ppm) and Ti contents, and low ɛNd values from +0.8 in basalt to -1.4 in rhyolite. The < 2718 Ma basement-cover sequence comprises 2.94 Ga tonalitic gneiss unconformably overlain by clastic sediments and a thin upper sequence of 2700 Ma gabbro, siliceous high-Mg basalt (SHMB) and andesite. The SHMB are characterised by LREE depletion and ɛNd values of +2.6, whereas the andesite is LREE-enriched and has ɛNd values of -0.3. The 2786 Ma mafic-ultramafic sequence is interpreted as a sliver of plume-related oceanic plateau crust. The 2724 lac Lintelle sequence represents a continental arc formed on the eastern protocraton. The ~ 2722 Ma lac Serindac volcanic sequence represents late continental rift deposits. The various 2.8-2.7 Ga supracrustal sequences were accreted, deformed and metamorphosed to mid-amphibolite facies during late-stage assembly of the Minto block between 2.718 and 2.693 Ga.

[Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

PubMed

Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

2015-11-01

In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha.

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

USGS Publications Warehouse

Birdwell, Justin E.

2012-01-01

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Trace element mobility at the slab-mantle interface: constraints from "hybrid

NASA Astrophysics Data System (ADS)

Marocchi, M.; Tropper, P.; Mair, V.; Bargossi, G. M.; Hermann, J.

2009-04-01

Subduction mélanges and hybrid rocks are considered, together with mafic rocks, metasediments and serpentinite as an important volatile-bearing portion of subducting slabs (cf. Spandler et al., 2008 and references therein; Miller et al., 2009). In particular, metasomatic rocks occurring in exhumed HP mélanges have recently attracted growing interest for two main reasons: i) metasomatic rocks forming at the interface between ultramafic and crustal rocks of subducting slabs constitute new bulk compositions which can affect the redistribution of major and trace elements and modify the composition of slab fluids moving to the mantle wedge and ii) these mineral assemblages, consisting mainly of hydrous phases can potentially store and transport water at great depth in subduction zones. Ultramafic rocks belonging to the Hochwart peridotite (Ulten Zone, central-eastern Italian Alps) preserve a series of metasomatic mineral zones generated by infiltration of hydrous fluids/melts, which occurred at the gneiss-peridotite interface (Tumiati et al., 2007; Marocchi et al., 2009). The peridotite body of Mt. Hochwart represents an almost unique occurrence where subduction-related mantle metasomatism can be studied on an outcrop scale. The ultramafic body consists of metaperidotites exposed as a hectometre-size lens along a steep gully, associated to monomineralic zones that developed at the contact between the peridotite body and the garnet-bearing gneiss country rocks. The formation of the metasomatic zones composed exclusively of hydrous phases involved extensive H2O-metasomatism as already documented for the Ulten peridotites (Scambelluri et al., 2006; Marocchi et al., 2007). Whole-rock geochemistry and trace element composition of hydrous phases (phlogopite and amphibole) in different metasomatic zones indicate mobility of many elements, including elements such as Ta, which are considered to have scarce mobility in fluids. Trace element composition of accessory minerals in the phlogopite-rich zone suggests that the trace element signature of subduction zone fluids may be fractionated in this zone. The progressive depletion in some trace elements (LREE and LILE) and enrichment in Li from the gneiss towards the peridotite suggests a strong influence of bulk composition on the trace element budget of hydrous minerals. Since these metasomatic zones can be representative of the processes occurring at the slab-mantle interface, we can infer that metasomatic reactions between slab-derived fluids and ultramafic mantle wedge will follow a specific series of reactions and create mineral zones similar to those observed in this study. Despite the mobility of many elements, in the trace element profiles for amphibole and phlogopite across the different zones, we observe a rapid decrease even of the "fluid mobile" element contents within the reaction zone. With the exception of Li, we assist to an abrupt decrease of most of trace element concentrations going towards the peridotite side contact. Thus, according to the present study, it is not likely that the "crustal trace element signature" (i.e. LILE and LREE-enriched) could be able to travel far into the mantle. Our results further favour the evidence that the primary composition of subduction zone fluids reaching the source region of arc magmas is substantially modified by metasomatic reactions occurring in the mantle wedge. Furthermore, we underline that metasomatic rocks such as those observed at Mt. Hochwart are potentially able to transport H2O and other trace elements to greater depths in subduction zones. References: Marocchi M, Hermann J, Morten L (2007)-Lithos 99: 85-104. Marocchi M, Mair V, Tropper P, Bargossi GM (2009)-Mineral Petrol, in press Miller DP, Marschall RH, Schumacher JC (2009)- Lithos 107: 53-67. Scambelluri M, Hermann J, Morten L, Rampone E (2006)- Contrib Mineral Petrol 151:372-394. Spandler CJ, Hermann J, Faure K, Mavrogenes JA, Arculus RJ (2008)- Contrib Mineral Petrol 155: 181-198. Tumiati S, Godard G, Martin S, Klőtzli U, Monticelli D (2007)- Lithos 94: 148-167.

Deep-sea mud in the Pacific Ocean as a potential resource for rare-earth elements

NASA Astrophysics Data System (ADS)

Kato, Yasuhiro; Fujinaga, Koichiro; Nakamura, Kentaro; Takaya, Yutaro; Kitamura, Kenichi; Ohta, Junichiro; Toda, Ryuichi; Nakashima, Takuya; Iwamori, Hikaru

2011-08-01

World demand for rare-earth elements and the metal yttrium--which are crucial for novel electronic equipment and green-energy technologies--is increasing rapidly. Several types of seafloor sediment harbour high concentrations of these elements. However, seafloor sediments have not been regarded as a rare-earth element and yttrium resource, because data on the spatial distribution of these deposits are insufficient. Here, we report measurements of the elemental composition of over 2,000 seafloor sediments, sampled at depth intervals of around one metre, at 78 sites that cover a large part of the Pacific Ocean. We show that deep-sea mud contains high concentrations of rare-earth elements and yttrium at numerous sites throughout the eastern South and central North Pacific. We estimate that an area of just one square kilometre, surrounding one of the sampling sites, could provide one-fifth of the current annual world consumption of these elements. Uptake of rare-earth elements and yttrium by mineral phases such as hydrothermal iron-oxyhydroxides and phillipsite seems to be responsible for their high concentration. We show that rare-earth elements and yttrium are readily recovered from the mud by simple acid leaching, and suggest that deep-sea mud constitutes a highly promising huge resource for these elements.

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.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

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 Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

NASA Technical Reports Server (NTRS)

Schwandt, Craig S.; McKay, Gordon A.

1997-01-01

Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

Effect of the addition of low rare earth elements (lanthanum, neodymium, cerium) on the biodegradation and biocompatibility of magnesium.

PubMed

Willbold, Elmar; Gu, Xuenan; Albert, Devon; Kalla, Katharina; Bobe, Katharina; Brauneis, Maria; Janning, Carla; Nellesen, Jens; Czayka, Wolfgang; Tillmann, Wolfgang; Zheng, Yufeng; Witte, Frank

2015-01-01

Rare earth elements are promising alloying element candidates for magnesium alloys used as biodegradable devices in biomedical applications. Rare earth elements have significant effects on the high temperature strength as well as the creep resistance of alloys and they improve magnesium corrosion resistance. We focused on lanthanum, neodymium and cerium to produce magnesium alloys with commonly used rare earth element concentrations. We showed that low concentrations of rare earth elements do not promote bone growth inside a 750 μm broad area around the implant. However, increased bone growth was observed at a greater distance from the degrading alloys. Clinically and histologically, the alloys and their corrosion products caused no systematic or local cytotoxicological effects. Using microtomography and in vitro experiments, we could show that the magnesium-rare earth element alloys showed low corrosion rates, both in in vitro and in vivo. The lanthanum- and cerium-containing alloys degraded at comparable rates, whereas the neodymium-containing alloy showed the lowest corrosion rates. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Compositional Trends in Acid Fluids of Copahue Volcano, Argentina: Evidence for a failed eruption in 2004?

NASA Astrophysics Data System (ADS)

Kading, T. J.; Brophy, M.; Varekamp, J. C.

2008-12-01

The concentrations and fluxes of major, minor, and trace elements in the crater lake, volcanic spring, and acidified watershed of Copahue Volcano, Neuquen province, Argentina, have been monitored over the last decade. The 2000 Copahue eruption resulted in enhanced S/Cl, increased concentrations and fluxes of rock forming elements (especially Mg and Na) with strongly raised Mg/Cl and Mg/K values. The degree of LREE enrichment decreased and a pronounced Eu anomaly developed in the fluids (Eu/Eu*> rock values). These patterns are explained as the result of hot acid fluid attack on newly intruded magma, with early dissolution of olivine (Mg spike) and plagioclase (Na spike, Eu anomaly). Similar compositional changes were observed in water samples taken in November, 2004, but no eruption occurred. These may be the signals of a small magmatic intrusion into the hydrothermal system, which failed to continue into an eruption. The compositional changes of Copahue volcanic fluids over the last decade will be discussed in the context of chemical signals of an actual and a suspected 'failed eruption'.

Sulfur in Earth's Mantle and Its Behavior During Core Formation

NASA Technical Reports Server (NTRS)

Chabot, Nancy L.; Righter,Kevin

2006-01-01

The density of Earth's outer core requires that about 5-10% of the outer core be composed of elements lighter than Fe-Ni; proposed choices for the "light element" component of Earth's core include H, C, O, Si, S, and combinations of these elements [e.g. 1]. Though samples of Earth's core are not available, mantle samples contain elemental signatures left behind from the formation of Earth's core. The abundances of siderophile (metal-loving) elements in Earth's mantle have been used to gain insight into the early accretion and differentiation history of Earth, the process by which the core and mantle formed, and the composition of the core [e.g. 2-4]. Similarly, the abundance of potential light elements in Earth's mantle could also provide constraints on Earth's evolution and core composition. The S abundance in Earth's mantle is 250 ( 50) ppm [5]. It has been suggested that 250 ppm S is too high to be due to equilibrium core formation in a high pressure, high temperature magma ocean on early Earth and that the addition of S to the mantle from the subsequent accretion of a late veneer is consequently required [6]. However, this earlier work of Li and Agee [6] did not parameterize the metalsilicate partitioning behavior of S as a function of thermodynamic variables, limiting the different pressure and temperature conditions during core formation that could be explored. Here, the question of explaining the mantle abundance of S is revisited, through parameterizing existing metal-silicate partitioning data for S and applying the parameterization to core formation in Earth.

How PNNL Extracts Rare Earth Elements from Geothermal Brine

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

None

2016-07-12

By looking at a problem at a nanoscale level, PNNL researchers are developing an economic way to extract valuable rare earth elements from geothermal fluids. This novel approach may help meet the high demand for rare earth elements that are used in many clean energy technologies.

Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

NASA Technical Reports Server (NTRS)

Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2012-01-01

There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

Isotopic and trace element geochemistry of the Seligdar magnesiocarbonatites (South Yakutia, Russia): Insights regarding the mantle evolution beneath the Aldan-Stanovoy shield

NASA Astrophysics Data System (ADS)

Doroshkevich, Anna G.; Prokopyev, Ilya R.; Izokh, Andrey E.; Klemd, Reiner; Ponomarchuk, Anton V.; Nikolaeva, Irina V.; Vladykin, Nikolay V.

2018-04-01

The Paleoproterozoic Seligdar magnesiocarbonatite intrusion of the Aldan-Stanovoy shield in Russia underwent extensive postmagmatic hydrothermal alteration and metamorphic events. This study comprises new isotopic (Sr, Nd, C and O) data, whole-rock major and trace element compositions and trace element characteristics of the major minerals to gain a better understanding of the source and the formation process of the carbonatites. The Seligdar carbonatites have high concentrations of P2O5 (up to 18 wt%) and low concentrations of Na, K, Sr and Ba. The chondrite-normalized REE patterns of these carbonatites display significant enrichments of LREE relative to HREE with an average La/Ybcn ratio of 95. Hydrothermal and metamorphic overprints changed the trace element characteristics of the carbonatites and their minerals. These alteration processes were responsible for Sr loss and the shifting of the Sr isotopic compositions towards more radiogenic values. The altered carbonatites are further characterized by distinct 18O- and 13C-enrichments compared to the primary igneous carbonatites. The alteration most likely resulted from both the percolation of crustal-derived hydrothermal fluids and subsequent metamorphic processes accompanied by interaction with limestone-derived CO2. The narrow range of negative εNd(T) values indicates that the Seligdar carbonatites are dominated by a homogenous enriched mantle source component that was separated from the depleted mantle during the Archean.

Innovative Approaches to Remote Sensing in NASA's Earth System Science Pathfinder (ESSP) Program

NASA Technical Reports Server (NTRS)

Peri, Frank; Volz, Stephen

2013-01-01

NASA's Earth Venture class (EV) of mission are competitively selected, Principal Investigator (PI) led, relatively low cost and narrowly focused in scientific scope. Investigations address a full spectrum of earth science objectives, including studies of the atmosphere, oceans, land surface, polar ice regions, and solid Earth. EV has three program elements: EV-Suborbital (EVS) are suborbital/airborne investigations; EV-Mission (EVM) element comprises small complete spaceborne missions; and EV-Instrument (EVI) element develops spaceborne instruments for flight as missions-of-opportunity (MoO). To ensure the success of EV, the management approach of each element is tailored according to the specific needs of the element.

Authenticating the recovery location of meteorites: The case of Castenaso

NASA Astrophysics Data System (ADS)

Folco, Luigi; D'Orazio, Massimo; Perchiazzi, Natale

2007-03-01

This forensic work aims to authenticate the recovery location of Castenaso, a 120 g ordinary chondritic (L5) meteorite reportedly found in 2003 along the sandy bank of the Idice Stream, near the village of Castenaso (Bologna, Emilia-Romagna, Italy). Using the hypothesis that Castenaso was instead a hot-desert meteorite, we conducted a comparative mineralogical and geochemical study of major weathering effects on European and Saharan ordinary chondrites as potential markers of the environment where Castenaso resided during its terrestrial lifetime.Inductively coupled plasma-mass spectrometry (ICP-MS) data reveals that Castenaso is significantly enriched in Sr, Ba, Tl, and U, and suggests geochemical alteration in a hot-desert environment. The alteration is minor: Castenaso is not coated by desert varnish and does not show significant light rare earth element (LREE) enrichment or loss of Ni and Co.The apparent contrast in size, morphology, and composition between the soil particles filling the external fractures of Castenaso and those from the bank of the Idice Stream observed under the scanning electron microscope (SEM) suggests that Castenaso did not reside at the reported find location. Abraded quartz grains (up to 1 mm in size) in Castenaso are undoubtedly from a hot-desert eolian environment: they are well-rounded and show external surfaces characterized by the presence of dish-shaped concavities and upturned silica plates that have been subject to solution-precipitation and subsequent smoothing.We therefore conclude that Castenaso is one of the many hot-desert ordinary chondrite finds, probably from the Sahara, that is currently available on the market. This forensic work provides the scientific grounds for changing the name of this meteorite.

Modification of REE distribution of ordinary chondrites from Atacama (Chile) and Lut (Iran) hot deserts: Insights into the chemical weathering of meteorites

NASA Astrophysics Data System (ADS)

Pourkhorsandi, Hamed; D'Orazio, Massimo; Rochette, Pierre; Valenzuela, Millarca; Gattacceca, Jérôme; Mirnejad, Hassan; Sutter, Brad; Hutzler, Aurore; Aboulahris, Maria

2017-09-01

The behavior of rare earth elements (REEs) during hot desert weathering of meteorites is investigated. Ordinary chondrites (OCs) from Atacama (Chile) and Lut (Iran) deserts show different variations in REE composition during this process. Inductively coupled plasma-mass spectrometry (ICP-MS) data reveal that hot desert OCs tend to show elevated light REE concentrations, relative to OC falls. Chondrites from Atacama are by far the most enriched in REEs and this enrichment is not necessarily related to their degree of weathering. Positive Ce anomaly of fresh chondrites from Atacama and the successive formation of a negative Ce anomaly with the addition of trivalent REEs are similar to the process reported from Antarctic eucrites. In addition to REEs, Sr and Ba also show different concentrations when comparing OCs from different hot deserts. The stability of Atacama surfaces and the associated old terrestrial ages of meteorites from this region give the samples the necessary time to interact with the terrestrial environment and to be chemically modified. Higher REE contents and LREE-enriched composition are evidence of contamination by terrestrial soil. Despite their low degrees of weathering, special care must be taken into account while working on the REE composition of Atacama meteorites for cosmochemistry applications. In contrast, chondrites from the Lut desert show lower degrees of REE modification, despite significant weathering signed by Sr content. This is explained by the relatively rapid weathering rate of the meteorites occurring in the Lut desert, which hampers the penetration of terrestrial material by forming voluminous Fe oxide/oxyhydroxides shortly after the meteorite fall.

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

NASA Astrophysics Data System (ADS)

Lan, C.; Zhao, T.

2016-12-01

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

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

Trofanenko, J.; Williams-Jones, A. E.; Simandl, G. J.

The Wicheeda carbonatite is a deformed plug or sill that hosts relatively high grade light rare earth elements (LREE) mineralization in the British Columbia alkaline province. It was emplaced within metasedimentary rocks belonging to the Kechika Group, which have been altered to potassic fenite near the intrusion and sodic fenite at greater distances from it. The intrusion comprises a ferroan dolomite carbonatite core, which passes gradationally outward into calcite carbonatite. The potentially economic REE mineralization is hosted by the dolomite carbonatite. We recognized three types of dolomite. Dolomite constitutes the bulk of the dolomite carbonatite, dolomite replaced dolomite near veinsmore » and vugs, and dolomite occurs in veins and vugs together with the REE mineralization. Carbon and oxygen isotope ratios indicate that the calcite carbonatite crystallized from a magma of mantle origin, that dolomite is of primary igneous origin, that dolomite has a largely igneous signature with a small hydrothermal component, and that dolomite is of hydrothermal origin. Furthermore, the REE minerals comprise REE fluorocarbonates, ancylite-(Ce), and monazite-(Ce). In addition to dolomite, they occur with barite, molybdenite, pyrite, and thorite. Minor concentrations of niobium are present as magmatic pyrochlore in the calcite carbonatite. model is proposed in which crystallization of calcite carbonatite preceded that of dolomite carbonatite. During crystallization of the latter, an aqueous-carbonic fluid was exsolved, which mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite, where they precipitated mainly in response to the increase in pH that accompanied fluid-rock interaction and, in the case of the REE fluorocarbonates, decreasing temperature. These fluids altered the host metasedimentary rock to potassic fenite adjacent to the carbonatite and, distal to it, they mixed with formational waters to produce sodic fenite.« less

The Nature and Origin of the REE Mineralization in the Wicheeda Carbonatite, British Columbia, Canada

DOE PAGES

Trofanenko, J.; Williams-Jones, A. E.; Simandl, G. J.; ...

2016-01-01

The Wicheeda carbonatite is a deformed plug or sill that hosts relatively high grade light rare earth elements (LREE) mineralization in the British Columbia alkaline province. It was emplaced within metasedimentary rocks belonging to the Kechika Group, which have been altered to potassic fenite near the intrusion and sodic fenite at greater distances from it. The intrusion comprises a ferroan dolomite carbonatite core, which passes gradationally outward into calcite carbonatite. The potentially economic REE mineralization is hosted by the dolomite carbonatite. We recognized three types of dolomite. Dolomite constitutes the bulk of the dolomite carbonatite, dolomite replaced dolomite near veinsmore » and vugs, and dolomite occurs in veins and vugs together with the REE mineralization. Carbon and oxygen isotope ratios indicate that the calcite carbonatite crystallized from a magma of mantle origin, that dolomite is of primary igneous origin, that dolomite has a largely igneous signature with a small hydrothermal component, and that dolomite is of hydrothermal origin. Furthermore, the REE minerals comprise REE fluorocarbonates, ancylite-(Ce), and monazite-(Ce). In addition to dolomite, they occur with barite, molybdenite, pyrite, and thorite. Minor concentrations of niobium are present as magmatic pyrochlore in the calcite carbonatite. model is proposed in which crystallization of calcite carbonatite preceded that of dolomite carbonatite. During crystallization of the latter, an aqueous-carbonic fluid was exsolved, which mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite, where they precipitated mainly in response to the increase in pH that accompanied fluid-rock interaction and, in the case of the REE fluorocarbonates, decreasing temperature. These fluids altered the host metasedimentary rock to potassic fenite adjacent to the carbonatite and, distal to it, they mixed with formational waters to produce sodic fenite.« less

Opportunities for Small Satellites in NASA's Earth System Science Pathfinder (ESSP) Program

NASA Technical Reports Server (NTRS)

Peri, Frank; Law, Richard C.; Wells, James E.

2014-01-01

NASA's Earth Venture class (EV) of missions are competitively selected, Principal Investigator (PI) led, relatively low cost and narrowly focused in scientific scope. Investigations address a full spectrum of earth science objectives, including studies of the atmosphere, oceans, land surface, polar ice regions, and solid Earth. EV has three program elements: EV-Suborbital (EVS) are suborbital/airborne investigations; EV-Mission (EVM) element comprises small complete spaceborne missions; and EV-Instrument (EVI) element develops spaceborne instruments for flight as Missions-of-Opportunity (MoO). To ensure the success of EV, frequent opportunities for selecting missions has been established in NASA's Earth Science budget. This paper will describe those opportunities and how the management approach of each element is tailored according to the specific needs of the element.

Determination of thorium and of rare earth elements in cerium earth minerals and ores

USGS Publications Warehouse

Carron, M.K.; Skinner, D.L.; Stevens, R.E.

1955-01-01

The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

Geochemistry of Archean Mafic Amphibolites from the Amsaga Area, West African Craton, Mauritania: What Is the Message?

NASA Astrophysics Data System (ADS)

El Atrassi, F.; Debaille, V.; Mattielli, N. D. C.; Berger, J.

2014-12-01

While Archean terrains are mainly composed of a TTG (Tonalite-trondhjemite-granodiorite) suite, more mafic lithologies such as amphibolites are also a typical component of those ancient terrains. Although mafic rocks represent only ~10% of the Archean cratons, they may provide key evidence of the role and nature of basaltic magmatism in the formation of the Archean crust as well as the evolution of the Archean mantle. This study focuses on the Archean crust from the West African Craton in Mauritania (Amsaga area). The Amsaga Archean Crust mainly consists of TTG and thrust-imbricated slices of mafic volcanic rocks, which have been affected by polymetamorphic events from the amphibolite to granulite facies. Our main objectives aim to the identification of the mafic lithology origin and a better understanding of their role in the continental crust emplacement. Our petrological observations show that these amphibolites have fine to medium granoblastic and nematoblastic textures. The amphibolites are dominated by amphibolite-facies mineral assemblages (mainly amphibole and plagioclase), but garnet and clinopyroxene occur in a few samples. Two groups are distinct in their geochemical characteristics (major and trace elements), although both have tholeiitic basalt composition. The first group show LREE-enriched patterns and negative Nb-Ta anomalies. The second group is characterized by near-flat LREE patterns and flat HREE patterns. This second group clearly shows no Nb-Ta anomalies. The first group could be related to arc-like basalts, as it is many similarities with some Archean amphibolites probably formed in a supra-subduction zone, for instance the volcanic rocks from the southern edge of the Isua Supracrustal Belt. On the contrary, the second group has a MORB-like signature which is more unusual during the Archean. Different scenarios will be discussed regards to the Archean geodynamics.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Geodynamic evolution of the Sabzevar zone, northern central Iranian micro-continent

NASA Astrophysics Data System (ADS)

Omrani, Hadi; Moazzen, Mohssen; Oberhänsli, Roland

2018-02-01

The Northern Central Iranian Micro-continent (CIM) represents Neotethys-related oceanic crust remnants, emplaced due to convergence between CIM and Eurasia plates during Eocene. Mafic and ultramafic units are exposed along the northern part of the CIM in the Sabzevar area. The geology and field relation of Sabzevar ophiolite indicate northward subduction of the Sabzevar basin. The average whole rock chemistry of mafic (gabbros) and ultramafic samples (lherzolite, harzburgite and dunite) is characterized by a range of MgO of 11.16-31.88, CaO 5.22-11.53 and Al2O3 2.77-14.57, respectively. Low LREE/HREE ratio of ultramafic samples is accompanied by enrichment of large ion lithophile elements (LILE) such as Sr, Pb and K. Mafic samples show two distinct groups with low and high LREE/HREE ratios. The spider diagram of mafic samples indicates enrichment in Sr, Pb and K and depletion in REE. Petrological and geochemical evidence and field relations show that the mafic rocks formed in a supra-subduction zone setting. Petrological studies reveal the role of fractional crystallization and assimilation effect by released fluids during subduction related generation of the Sabzevar mafic rocks. We suggest that the studied mafic rocks likely represent the basement of an initial island arc, which was generated in a supra-subduction zone setting within the Neotethys branch of the Sabzevar Ocean at the north of CIM. Copper, gold and chromite mineralizations are studied in relation to island arc setting and supra-subduction environment. Similarities in lithology, ophiolite age and mineralization between Sabzevar ophiolite and Bardaskan-Torbat Heydariyeh ophiolites testify for their separation due to rotation (or faulting) of the Central Iranian Micro-continent.

Early Paleozoic subduction initiation volcanism of the Iwatsubodani Formation, Hida Gaien belt, Southwest Japan

NASA Astrophysics Data System (ADS)

Tsukada, Kazuhiro; Yamamoto, Koshi; Gantumur, Onon; Nuramkhaan, Manchuk

2017-06-01

In placing Japanese tectonics in an Asian context, variation in the Paleozoic geological environment is a significant issue. This paper investigates the geochemistry of the lower Paleozoic basalt formation (Iwatsubodani Formation) in the Hida Gaien belt, Japan, to consider its tectonic setting. This formation includes the following two types of rock in ascending order: basalt A with sub-ophitic texture and basalt B with porphyritic texture. Basalt A has a high and uniform FeO*/MgO ratio, moderate TiO2, high V, and low Ti/V. The HFSE and REE are nearly the same as those in MORB, and all the data points to basalt A being the "MORB-like fore-arc tholeiitic basalt (FAB)" reported, for example, from the Izu-Bonin-Mariana arc. By contrast, basalt B has a low FeO*/MgO ratio, low TiO2, and low V and Ti/V. It has an LREE-enriched trend and a distinct negative Nb anomaly in the MORB-normalized multi-element pattern and a moderately high LREE/HREE. All these factors suggest that basalt B is calc-alkaline basalt. It is known that FAB is erupted at the earliest stage of arc formation—namely, subduction initiation—and that boninitic/tholeiitic/calc-alkaline volcanism follows at the supra-subduction zone (SSZ). Thus, the occurrence of basalts A (FAB) and B (calc-alkaline rock) is strong evidence of early Paleozoic arc-formation initiation at an SSZ. Evidence for an early Paleozoic SSZ arc is also recognized from the Oeyama, Hayachine-Miyamori, and Sergeevka ophiolites. Hence, both these ophiolites and the Iwatsubodani Formation probably coexisted in a primitive SSZ system in the early Paleozoic.

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

NASA Astrophysics Data System (ADS)

Zahra Afshooni, Seyedeh; Esmaeily, Dariush

2010-05-01

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

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.'

Os, Nd and Sr isotope and trace element geochemistry of the Muli picrites: Insights into the mantle source of the Emeishan Large Igneous Province

NASA Astrophysics Data System (ADS)

Li, Jie; Xu, Ji-Feng; Suzuki, Katsuhiko; He, Bin; Xu, Yi-Gang; Ren, Zhong-Yuan

2010-09-01

A suite of picrites and basalts from the Muli area, in the northwestern part of the Emeishan continental flood basalt province, provides new and valuable information on the geochemistry of the Emeishan Large Igneous Province (LIP) and its source. The Muli picrites can be classified as type-1 or type-2. The former shows ocean-island basalt-like trace element characteristics, with γ Os (260 Ma) values and ɛ Nd (260 Ma) values ranging from + 7.5 to + 11.5 and from + 6.0 to + 7.8, respectively. This is the first time that picrites with highly radiogenic Os and high Os contents (up to 3.3 ppb) have been recognized in the Emeishan LIP. These characteristics probably reflect a relatively enriched component in the Emeishan LIP source. The type-2 picrites are characterized by non-radiogenic γ Os (260 Ma) values ranging from - 4.2 to - 0.3, and they may be further subdivided into type-2A and type-2B picrites. Type-2A picrites contain moderate amounts of the light rare earth elements (LREEs), have low Ce N/Yb N values (1.1-2.0), and a relatively high initial ɛ Nd (+ 5.0 to + 6.6). In terms of Os and Nd isotopes, the Muli type-2A picrites are similar to the Song Da komatiites of Vietnam and the Gorgona Island picrites, revealing the existence of a depleted mantle component in the Emeishan LIP source. In contrast with the type-2A picrites, type-2B lavas exhibit a negative Nb anomaly and relatively lower initial ɛ Nd and γ Os values (Nb/La > 1.8; ɛ Nd (260 Ma) = - 5.5 to + 6.4; γ Os (260 Ma) = - 4.2 to - 1.9), suggesting that the type-2B lavas have a depleted mantle source, similar to type-2A, but that the type-2B lavas are also influenced by various degrees of mixing of depleted plume-derived melt, sub-continental lithospheric mantle, and/or continental crust. Given that the basalts in the Muli area show similar geochemical features to those of the type-2B picrites, their origins are inferred to be similar.

Chemical interactions in the subduction factory: New insights from an in situ trace element and hydrogen study of the Ichinomegata and Oki-Dogo mantle xenoliths (Japan)

NASA Astrophysics Data System (ADS)

Satsukawa, Takako; Godard, Marguerite; Demouchy, Sylvie; Michibayashi, Katsuyoshi; Ildefonse, Benoit

2017-07-01

The uppermost mantle in back arc regions is the site of complex interactions between partial melting, melt percolation, and fluid migration. To constrain these interactions and evaluate their consequences on geochemical cycles, we carried out an in situ trace element and water study of a suite of spinel peridotite xenoliths from two regions of the Japan back arc system, Ichinomegata (NE Japan) and Oki-Dogo (SW Japan), using LA-ICPMS and FTIR spectrometry, respectively. This study provides the first full dataset of trace element and hydrogen compositions in peridotites including analyses of all their main constitutive silicate minerals: olivine, orthopyroxene and clinopyroxene. The Ichinomegata peridotites sample a LREE-depleted refractory mantle (Mg# olivine = 0.90; Cr# spinel = 0.07-0.23; Yb clinopyroxene = 7.8-13.3 × C1-chondrite, and La/Yb clinopyroxene = 0.003-0.086 × C1-chondrite), characterized by Th-U positive anomalies and constant values of Nb/Ta. The composition of the studied Ichinomegata samples is consistent with that of an oceanic mantle lithosphere affected by cryptic metasomatic interactions with hydrous/aqueous fluids (crypto-hydrous metasomatism). In contrast, the Oki-Dogo peridotites have low Mg# olivine (0.86-0.93) and a broad range of compositions with clinopyroxene showing "spoon-shaped" to flat, and LREE-enriched patterns. They are also characterized by their homogeneous compositions in the most incompatible LILE (e.g., Rb clinopyroxene = 0.01-0.05 × primitive mantle) and HFSE (e.g., Nb clinopyroxene = 0.01-2.16 × primitive mantle). This characteristic is interpreted as resulting from various degrees of melting and extensive melt-rock interactions. FTIR spectroscopy shows that olivine in both Ichinomegata and Oki-Dogo samples has low water contents ranging from 2 to 7 ppm wt. H2O. In contrast, the water contents of pyroxenes from Ichinomegata peridotites (113-271 ppm wt. H2O for orthopyroxene, and 292-347 ppm wt. H2O for clinopyroxene) are significantly higher than in Oki-Dogo peridotites (9-35 ppm wt. H2O for orthopyroxene, and 15-98 ppm wt. H2O for clinopyroxene). This indicates a relationship between melt-rock interaction and water concentrations in pyroxenes. Our study suggests that the water content of the Japan mantle wedge is controlled by the late melt/fluid/rock interactions evidenced by trace element geochemistry: a mechanism triggered by magma-rock interactions may have acted as an efficient dehydrating process in the Oki-Dogo region while the Ichinomegata mantle water content is controlled by slab-derived crypto-hydrous metasomatism.

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.

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.

Early post-collisional Brasiliano magmatism in Botuverá region, Santa Catarina, southern Brazil: Evidence from petrology, geochemistry, isotope geology and geochronology of the diabase and lamprophyre dikes

NASA Astrophysics Data System (ADS)

Sacks de Campos, Roberto; Philipp, Ruy Paulo; Massonne, Hans-Joachim; Chemale, Farid

2012-08-01

The post-collisional magmatism related to Brasiliano orogeny represented the final stage of the Dom Feliciano Belt in Rio Grande do Sul and Santa Catarina states, southern Brazil, presenting high-K calc-alkaline to shoshonitic and alkaline chemical signatures. Magmatic episodes related to this early period were found in Botuverá region, Santa Catarina state, represented by diabase and lamprophyre (spessartite-type) dikes intrusive in metavolcano-sedimentary rocks of the Brusque Metamorphic Complex (CMB). These dikes have massive structure and igneous textures ranging from very fine equigranular to porphyritic, and the latter is characterized by the presence of phenocrysts of plagioclase and hornblende. The dikes have northeast direction and sharp contacts with the metamorphic rocks, indicating that its position was after the main orogenic regional metamorphism that affected the CMB, interpreted as of collisional nature. The diabase has a basic composition, whereas spessartite lamprophyres are intermediate, with geochemical affinities to the tholeiitic series, with a significant enrichment in light rare-earth elements (LREE) and large ion lithophile elements (LILE) such as Cs, Rb, Ba, K and Sr, and negative anomalies for high-field-strength elements (HFS) such as Nb, Ta, U and T. The concentration of standard trace elements and the Th/Yb and Ta/Yb ratios indicate that these magmas were derived from an enriched mantle source and were strongly contaminated by crust. Except for higher values of K, these features are similar to those found in basaltic volcanic rocks associated with the post-collisional period in south Brazil. The widely dispersed values of ɛND (618), ranging between -13.74 and +5.52, highlights the heterogeneity of the source and reinforces the importance of a crustal component in the generation of these rocks. The extremely low value of ɛNd (618), of -21.67 obtained for spessartite lamprophyres supports the importance of the involvement of crust in the genesis of this rock. Using the U-Pb and LA-ICP-MS method, a concordant age of 618 ± 8.7 Ma was obtained in zircon crystals of a diabase dike of the region of Barra do Areia, in Botuverá, SC. The existence of inherited zircon grains older than 1800 Ma in this sample supports the involvement of Paleoproterozoic continental crust. The data analysis characterizes the first magmatic age related to the post-collisional period of the Brasiliano orogeny in this region of the Santa Catarina Shield.

A volatile rich Earth's core?

NASA Astrophysics Data System (ADS)

Morard, G.; Antonangeli, D.; Andrault, D.; Nakajima, Y.

2017-12-01

The composition of the Earth's core is still an open question. Although mostly composed of iron, it contains impurities that lower its density and melting point with respect to pure Fe. Knowledge of the nature and abundance of light elements (O, S, Si, C or H) in the core has major implications for establishing the bulk composition of the Earth and for building the model of Earth's differentiation. Geochemical models of the Earth's formation point out that its building blocks were depleted in volatile elements compared to the chondritic abundance, therefore light elements such as S, H or C cannot be the major elements alloyed with iron in the Earth's core. However, such models should be compatible with the comparison of seismic properties of the Earth's core and physical properties of iron alloys under extreme conditions, such as sound velocity or density of solid and liquid. The present work will discuss the recent progress for compositional model issued from studies of phase diagrams and elastic properties of iron alloys under core conditions and highlight the compatibility of volatile elements with observed properties of the Earth's core, in potential contradiction with models derived from metal-silicate partitioning experiments.

Early Precambrian crustal evolution of south India

NASA Technical Reports Server (NTRS)

Srinivasan, R.

1986-01-01

The Early Precambrian sequence in Karnataka, South India provides evidences for a distinct trend of evolution which differs from trends exhibited in many other Early Precambrian regions of the world. The supracrustal rock associations preserved in greenstone belts and as inclusions in gneisses and granulites suggest the evolution of the terrain from a stable to a mobile regime. The stable regime is represented by (1) layered ultramafic-mafic complexes, (2) orthoquartzite-basalt-rhyodacite-iron formation, and (30 ortho-quartzite-carbonate-Mn-Fe formation. The mobile regime, which can be shown on sedimentological grounds to have succeeded the stable regime, witnessed the accumulation of a greywacke-pillow basalt-dacite-rhyolite-iron formation association. Detrital sediments of the stable zone accumulated dominantly in fluvial environment and the associated volcanics are ubaerial. The volcanics of the stable regime are tholeiites derived from a zirconium and LREE-enriched sources. The greywackes of the mobile regime are turbidities, and the volcanic rocks possess continental margin (island-arc or back-arc) affinity; they show a LREE depleted to slightly LREE-enriched pattern. The evolution from a stable to a mobile regime is in contrast to the trend seen in most other regions of the world, where an early dominantly volcanic association of a mobile regime gives way upward in the sequence to sediments characteristic of a stable regime.

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

PubMed

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

2017-09-15

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

Origin of dioritic magma and its contribution to porphyry Cu-Au mineralization at Pulang in the Yidun arc, eastern Tibet

NASA Astrophysics Data System (ADS)

Cao, Kang; Yang, Zhi-Ming; Xu, Ji-Feng; Fu, Bin; Li, Wei-Kai; Sun, Mao-Yu

2018-04-01

The giant Pulang porphyry Cu-Au deposit in the Yidun arc, eastern Tibet, formed due to westward subduction of the Garze-Litang oceanic plate in the Late Triassic. The deposit is hosted in an intrusive complex comprising primarily coarse-grained quartz diorite and cored quartz monzonite. Here, we investigate a suite of simultaneous (216.6 ± 1.9 Ma) diorite porphyries within the complex. The diorite porphyries are geochemically similar to mafic magmatic enclaves (MME) hosted in coarse-grained quartz diorite, and both are characterized by low SiO2 (59.4-63.0 wt%) and high total alkali (Na2O + K2O = 7.0-9.2 wt%), K2O (3.5-6.4 wt%), MgO (3.2-5.5 wt%), and compatible trace element (e.g., Cr = 72-149 ppm) concentrations. They are enriched in large-ion lithophile and light rare earth elements (LILE and LREE, respectively), but depleted in high field-strength and heavy rare earth elements (HFSE and HREE, respectively), and yield variably high (La/Yb)N ratios (17-126, average 65) with weak to negligible Eu anomalies. Furthermore, they yield low (87Sr/86Sr)i ratios (0.7054-0.7067), weakly negative εNd(t) (-2.8 to -0.8) values, and variable zircon εHf(t) (-5.4 to +0.8) and δ18O (6.0‰-6.7‰) values. These geochemical features indicate that the diorite porphyry and MME formed through crustal assimilation of a magma produced during low-degree partial melting of metasomatized phlogopite-rich subcontinental lithospheric mantle. In contrast, the coarse-grained quartz diorite and quartz monzonite have relatively high concentrations of SiO2 (61.1-65.3 wt%), K2O (4.1-5.4 wt%), and total alkali (Na2O + K2O = 7.1-8.1 wt%), and low concentrations of MgO (generally <3.0 wt%) and compatible trace elements (e.g., Cr = 38-61 ppm). They yield high Sr/Y ratios (50-63) that indicate an adakitic affinity, and are enriched in LILE, depleted in HFSE, and yield lower (La/Yb)N values (13-20, average 17) than the diorite porphyry and MME. They yield low (87Sr/86Sr)i ratios (0.7046-0.7066), negative εNd(t) (-3.3 to -1.7) values, and zircon εHf(t) and δ18O values of -2.9 to -0.1 and 5.7‰-6.5‰, respectively, suggesting that they represent high-K calc-alkaline to shoshonitic adakitic magmas that were sourced from subduction-modified juvenile lower crust. Observations of the newly identified diorite porphyry and previously reported MME suggest that input of such dioritic magma into the upper crustal porphyry magma chamber would have contributed not only the necessary metals (e.g., Cu and Au), sulfur, but also H2O to the system, thus aiding in the generation of the giant Pulang porphyry Cu-Au deposit.

Two-types of Early Cretaceous adakitic porphyries from the Luxi terrane, eastern North China Block: Melting of subducted Paleo-Pacific slab and delaminated newly underplated lower crust

NASA Astrophysics Data System (ADS)

Wang, Hao; Xu, Zhaowen; Lu, Xiancai; Fu, Bin; Lu, Jianjun; Yang, Xiaonan; Zhao, Zengxia

2016-01-01

The origin and tectonic setting of Early Cretaceous adakitic rocks from the Luxi terrane in the eastern North China Block (NCB) remain debated. To resolve this issue, we determined whole-rock geochemistry, zircon U-Pb ages, and in situ Hf-O isotopes of the Mengyin and Liujing adakitic porphyries from the Luxi terrane. Zircon U-Pb dating results reveal that both the Mengyin and Liujing plutons were emplaced during the Early Cretaceous, with weighted mean 206Pb/238U ages of 130 ± 1 Ma (2σ) and 131 ± 2 Ma (2σ), respectively. In addition, abundant Neoarchean-Paleoproterozoic inherited zircon cores are identified in the Mengyin adakitic porphyry with 207Pb/206Pb ages ranging from 2.53 to 2.42 Ga. Rocks of both plutons are silicic (SiO2 = 65.4-70.2 wt.%), metaluminous, and alkaline in composition, comprising mainly quartz syenite porphyries. Samples from both plutons are enriched in large ion lithophile elements (LILEs) (e.g., Rb, Sr, and Ba), and light rare earth elements (LREEs), depleted in high field strength elements (HFSEs) (e.g., Nb, Ta, and Ti), and heavy rare earth elements (HREEs), and have either positive or no Eu anomalies. In addition, both adakitic porphyries have high Mg# values (51-64), high Sr and La contents, low Y and Yb contents, and high Sr/Y (Mengyin = 149-264; Liujing = 58-110) and (La/Yb)N (Mengyin = 32.4-45.3; Liujing = 43.8-53.1) ratios, similar to adakitic rocks worldwide. The Mengyin adakitic porphyry has higher whole-rock εNd(t) values (-5.8 to - 4.1), more radiogenic Pb [(206Pb/204Pb)i = 18.35-18.39, (207Pb/204Pb)i = 15.55-15.56, (208Pb/204Pb)i = 38.20-38.23], higher zircon rim εHf(t) values (+ 3.3 to + 8.8) and δ18O values (+ 6.5‰ to + 7.9‰), and lower (87Sr/86Sr)i ratios (0.7049-0.7050) than the Liujing adakitic porphyry [εNd(t) = - 12.4 to - 12.2, (206Pb/204Pb)i = 17.63-17.72, (207Pb/204Pb)i = 15.56-15.58, (208Pb/204Pb)i = 37.76-37.94, εHf(t) = - 14.8 to - 11.2, δ18O = + 5.9‰ to + 7.1‰, (87Sr/86Sr)i = 0.7090-0.7091]. The Mengyin adakitic porphyry was most likely derived from partial melting of subducted oceanic slab with some input of NCB Neoarchean-Paleoproterozoic lower crust components. The Liujing adakitic porphyry was probably derived from partial melting of delaminated newly underplated thick lower crust, which then interacted with above asthenospheric mantle peridotite. Slab rollback together with the ridge subduction of the Paleo-Pacific slab was the most likely geodynamic mechanism for formation of the Early Cretaceous Mengyin and Liujing adakitic porphyries.

Trace element analyses of fluid-bearing diamonds from Jwaneng, Botswana

NASA Astrophysics Data System (ADS)

Schrauder, Marcus; Koeberl, Christian; Navon, Oded

1996-12-01

Fibrous diamonds from Botswana contain abundant micro-inclusions, which represent syngenetic mantle fluids under high pressure. The major element composition of the fluids within individual diamonds was found to be uniform, but a significant compositional variation exists between different diamond specimens. The composition of the fluids varies between a carbonatitic and a hydrous endmember. To constrain the composition of fluids in the mantle, the trace element contents of thirteen micro-inclusion-bearing fibrous diamonds from Botswana was studied using neutron activation analysis. The concentrations of incompatible elements (including K, Na, Br, Rb, Sr, Zr, Cs, Ba, Hf, Ta, Th, U, and the LREEs) in the fluids are higher than those of mantle-derived rocks and melt inclusions. The compatible elements (e.g., Cr, Co, Ni) have abundances that are similar to those of the primitive mantle. The concentrations of most trace elements decrease by a factor of two from the carbonate-rich fluids to the hydrous fluids. Several models may explain the observed elemental variations. Minerals in equilibrium with the fluid were most likely enriched in incompatible elements, which does not agree with derivation of the fluids by partial melting of common peridotites or eclogites. Fractional crystallization of a kimberlite-like magma at depth may yield carbonatitic fluids with low mg numbers (atomic ratio [Mg/(Mg+Fe)]) and high trace element contents. Fractionation of carbonates and additional phases (e.g., rutile, apatite, zircon) may, in general, explain the concentrations of incompatible elements in the fluids, which preferably partition into these phases. Alternatively, mixing of fluids with compositions similar to those of the two endmembers may explain the observed variation of the elemental contents. The fluids in fibrous diamonds might have equilibrated with mineral inclusions in eclogitic diamonds, while peridotitic diamonds do not show evidence of interaction with these fluids. The chemical composition of the fluids in fibrous diamonds indicates that, at p, T conditions that are characteristic for diamond formation, carbonatitic and hydrous fluids are efficient carriers of incompatible elements.

The New Element Americium (Atomic Number 95)

DOE R&D Accomplishments Database

Seaborg, G.T.; James, R.A.; Morgan, L.O.

1948-01-01

Several isotopes of the new element 95 have been produced and their radiations characterized. The chemical properties of this tripositive element are similar to those of the typical tripositive lanthanide rare-earth elements. Element 95 is different from the latter in the degree and rate of formation of certain compounds of the complex ion type, which makes possible the separation of element 95 from the lanthanide rare-earths. The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series.

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

Elemental weathering fluxes and saprolite production rate in a Central African lateritic terrain (Nsimi, South Cameroon)

NASA Astrophysics Data System (ADS)

Braun, Jean-Jacques; Marechal, Jean-Christophe; Riotte, Jean; Boeglin, Jean-Loup; Bedimo Bedimo, Jean-Pierre; Ndam Ngoupayou, Jules Remy; Nyeck, Brunot; Robain, Henri; Sekhar, M.; Audry, Stéphane; Viers, Jérôme

2012-12-01

The comparison between contemporary and long-term weathering has been carried out in the Small Experimental Watershed (SEW) of Nsimi, South Cameroon in order to quantify the export fluxes of major and trace elements and the residence time of the lateritic weathering cover. We focus on the hillside system composed of a thick lateritic weathering cover topped by a soil layer. This study is built on the recent improvements of the hillside hydrological functioning and on the analyses of major and trace elements. The mass balance calculation at the weathering horizon scale performed with the parent rock as reference indicates (i) strong depletion profiles for alkalis (Na, K, Rb) and alkaline earths (Mg, Ca, Sr, Ba), (ii) moderate depletion profiles for Si, P, Cd, Cu, Zn, Ni and Co, (iii) depletion/enrichment profiles for Al, Ga, Ge, Sn, Pb, LREE, HREE, Y, U, Fe, V, Cr, Mn. It is noteworthy that (i) Mn and Ce are not significantly redistributed according to oxidative processes as it is the case for Fe, V and Cr, and (ii) Ge is fractionated compared to silica with enrichment in Fe-rich horizons. The calculations performed for the topsoil with iron crust as parent material reference reveal that the degradation of the iron crust is accompanied by the loss of most of the constituting elements, among which are those specifically accumulated as the redox sensitive elements (Fe, V, Cr) and iron oxide related elements like Th. The overall current elemental fluxes from the hillside system at the springs and the seepage zones are extremely low due to the inert lateritic mineralogy. Ninety-four percent of the whole Na flux generated from the hillside corrected from atmospheric deposits (77 mol/ha/yr) represents the current weathering rates of plagioclase (oligoclase) in the system, the other remaining 6% may be attributed to the dissolution of hornblende. The silica hillside flux is 300 mol/ha/yr and can be mostly attributed to the plagioclase and kaolinite dissolution. Al and Ga are exported from the lateritic regolith and maybe due to the dissolution of kaolinite crystals. Compared to the other immobile elements (Zr, Hf, Nb and Th), Ti is significantly exported. Among redox-sensitive elements (Fe, V, Cr, Mn, Ce), only Ce and Mn are exported out of the hillside system. The other elements (Fe, V, Cr) are likely able to be mobilized but over a short distance only. Rb, Sr, Ba, Ni, Cu, Zn are affected by export processes. LREE and Y are exported but in very low amounts (in the range from μmol/ha/yr to mmol/ha/yr) while HREE and U are exported in negligible quantities. A first attempt is carried out to compare the mature ridge top profile from Nsimi SEW with the immature ridge top weathering profile from the Mule Hole SEW (South India), developed on similar granodioritic basement, in order to get deeper insight into (i) the contemporary saprolite production rates and (ii) the combined effect of precipitation (in terms of Mean Annual Rainfall, MAR) and evapotranspiration on the aggressiveness of the draining solutions. Considering (i) the contemporary Na flux as representative of the dissolution of plagioclase crystals and conservative during saprolitization processes and (ii) steady state of the inter-annual recharge (R) over a 10 years period, the current saprolite production rates (σr) are of 22 mm/kyr for Mule Hole SEW and 2 mm/kyr for Nsimi SEW, respectively. Even with a very low R/MAR ratio (0.04) compared to Nsimi, the chemical weathering at Mule Hole is active and related to the groundwater exports. At Mule Hole, plagioclase crystals are still present in the saprolite and the soil cover leading to a diffuse weathering front. The high Nsimi R/MAR ratio (0.2) allows the solution to be still aggressive with respect to the plagioclase and other weatherable minerals at the bedrock interface resulting in their complete breakdown in a few centimetres (sharp weathering front) leading to a mature saprolite. For the Nsimi SEW, if we consider (i) the low contemporary saprolite production rate (2 mm/kyr), (ii) the Miocene age (average 15 Myr) of the South Cameron Plateau landscape and (ii) the limited movement of Africa continent since Eocene, the long term saprolite production rate should have remained in its lower range, from 2 to 10 m/Myr. This suggests that, for thick weathering profiles the migration of the weathering front into the bedrock occurs at a relatively uniform rate regardless of present-day climatic conditions. Climate variation leading to the alternation of setup of savanna or humid forest will have an effect on physical erosion rather than chemical erosion for such deep weathering profiles.

Diversity and Petrogenesis of <4.4 Ma Rhyolites from the Izu Bonin Rear-Arc

NASA Astrophysics Data System (ADS)

Heywood, L. J.; DeBari, S. M.; Schindlbeck, J. C.; Escobar-Burciaga, R. D.; Gill, J.

2016-12-01

The Izu Bonin subduction zone has a history of abundant rhyolite production that is relevant to the development of intermediate to silicic middle crust. This study presents major and trace elemental compositions (via electron microprobe and LA-ICP-MS) of unaltered volcanic glass and phenocrysts from select medium- to high-K tephra intervals from IODP Site 1437 (Expedition 350, Izu Bonin Rear Arc). These data provide a time-resolved record of regional explosive magmatism ( 4.4Ma to present). Tephra from Site 1437 is basaltic to rhyolitic glass with accompanying phenocrysts, including hornblende. Glass compositions form a medium-K magmatic series with LREE enrichment (LaN/YbN = 2.5-6) whose trace element ratios and isotopic compositions are distinct from magmas with similar SiO2 contents in the main Izu Bonin volcanic front. Other workers have shown progressive enrichment in K and other trace element ratios moving from volcanic front westwards through the extensional region to the western seamounts in the rear arc. The <4.4 Ma rear-arc rhyolites from Site 1437 show pronounced negative Eu anomalies, high LaN/SmN (2-3.5), Ba/La <25 and Th of 1.5-4 ppm. These rhyolites show the highest variability for a given SiO2 content among all rear-arc magmas (rhyolites have 1.5-3.5 wt% K2O, Zr/Y of 1-8, LaN of 5-9 ppm) consistent with variability in literature reports of other rhyolite samples dredged from surrounding seamounts. Rhyolites have been dredged from several nearby seamounts with other high-K rhyolites dredged as close as nearby Meireki Seamount ( 3.8 Ma) and further afield in the Genroku seamount chain ( 1.88 Ma), which we compare to Site 1437 rhyolites. An extremely low-K rhyolite sill (13.6 Ma) was drilled lower in the section at Site U1437, suggesting that the mechanism for producing rhyolites in the Western Seamounts region changed over time. Rhyolites are either produced by differentiation of mafic magmas, by melting of pre-existing arc crust (as hypothesized in the Izu Bonin volcanic front), or through a combination of various processes. Because the oldest rear-arc rhyolites are low-K with limited LREE enrichment, any scenario that requires melting of pre-existing crust to produce the 4.4 Ma high-K rhyolites would require a crustal source that is younger than 13.6 Ma.

Temporal Geochemical Variations in Glass and Minerals from Early Oligocene to Miocene Volcanic Sediments, DSDP Site 296, Kyushu Palau Ridge: Is There a Geochemical Signal for Arc Rifting?

NASA Astrophysics Data System (ADS)

Hickey-Vargas, R.; Samajpati, E.

2015-12-01

Volcaniclastic sediments and sedimentary rocks from DSDP Site 296, located within a basin at the crest of the northern Kyushu Palau ridge (KPR), record the latter part of the first stage of Izu Bonin Mariana (IBM) arc evolution, up to the cessation of volcanism caused by arc rifting and opening of the Shikoku basin. The lower section consists of early to late Oligocene coarse volcaniclastic sedimentary rocks, and is overlain by late Oligocene to Pleistocene nannofossil chalks and oozes with volcanic sand and ash-rich layers. We have studied the chemical composition of pyroxene, feldspar and glass grains separated from the coarse volcaniclastic rocks at depths from 435 to 1082 meters below sea floor, and of glass shards in layers in the overlying sediments of late Oligocene to early Miocene age. Overall, pyroxene and feldspar compositions show little systematic variation with depth in the core, although for pyroxene, highest En and highest Al2O3 contents are found in the interval from 600-900 meters bsf. An contents in feldspars show a bimodal distribution throughout the core, with most values > 90 or in the range 60-70, with more abundant intermediate compositions in the 600-900 meter interval. Compositions of glass shards vary widely, from basalt to rhyolite, and from low K, light rare earth (LREE)-depleted to high K, strongly LREE-enriched character, without systematic variation with depth in the core. However, all cores sampled from early Oligocene to early Miocene contain relatively low K basalt and basaltic andesite glass. Like the pyroxenes, a wider range of compositions is found in glass from the 600 to 900 mbsf interval. The Site 296 sequence overlaps in age with the uppermost sedimentary section of recently drilled IODP Site 1438, located 230 km to the southwest in the Amami Sankaku basin, thus the two sites may contain volcanic debris shed from contemporaneous sections of the KPR.

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.

The role of liquid-liquid immiscibility and crystal fractionation in the genesis of carbonatite magmas: insights from Kerimasi melt inclusions

NASA Astrophysics Data System (ADS)

Guzmics, Tibor; Zajacz, Zoltán; Mitchell, Roger H.; Szabó, Csaba; Wälle, Markus

2015-02-01

We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate melt, whereas Mg, Mn, Fe, Co, Cu, Zn, Al, Sc, Ti, Hf and Zr are partitioned into the silicate melt. Potassium and Rb show no preferential partitioning. Kerimasi melt inclusions show that the immiscible calcic carbonate melt is strongly enriched in Sr, Ba, Pb, LREE, P, W, Mo and S relative to other trace elements. Comparison of our data with experimental results indicates that preferential partitioning of oxidized sulfur (as SO4 2-), Ca and P (as PO4 3-) into the carbonate melt may promote the partitioning of Nb, Ta, Pb and all REE, excluding Sc, into this phase. Therefore, it is suggested that P and S enrichment in calcic carbonate magmas promotes the genesis of REE-rich carbonatites by liquid immiscibility. Our study shows that changes in the partition coefficients of elements between minerals and the coexisting melts along the liquid line of descent are rather significant at Kerimasi. This is why, in addition to the REE, Nb, Ta and Zr are also enriched in Kerimasi calciocarbonatites. We consider significant amounts of apatite and perovskite precipitated from melilite-nephelinite-derived carbonate melt as igneous minerals can have high LREE, Nb and Zr contents relative to other carbonatite minerals.

Calcium Isotopic Systematics of Peridotite Xenoliths from eastern North China Craton: Implications for Melt-rock Interaction

NASA Astrophysics Data System (ADS)

Zhang, Z.; Zhao, X.; Huang, S.; Xiao, Y.; Li, X.

2017-12-01

In order to better constrain and understand the Ca isotopic variations in the mantle, we report high-precision Ca isotopic data of orthopyroxene (Opx) and clinopyroxene (Cpx) for a set of peridotitic xenoliths from ChangLe, eastern North China craton (NCC). These xenoliths range from lherzolites, Cpx-rich lherzolites to wehrlites, and are variably metasomatised. Lherzolites (Fo≈91) are fertile in mineral composition, and have spoon-shaped to slightly LREE-enriched rare earth element (REE) patterns. They may represent fragments of newly accreted lithospheric mantle that makes up parts of the Late Mesozoic-Cenozoic lithosphere beneath the eastern NCC. Cpx-rich lherzolites and wehrlites formed by reaction of refractory residual peridotites with evolved, Fe-rich silicate melts at high melt/rock ratios, as evidenced by partial to complete replacement of Opx with Cpx, relatively lower Fo contents of Ol (<88) than that from the lherzolites and convex-upward trace element patterns. Our results show that there are large δ44/40Ca variations (1‰) in these peridotitic xenoliths. Lherzolites have δ44/40Ca similar to typical upper mantle value(1.05 ± 0.04). Specifically, lherzolites orthopyroxenes have δ44/40Ca ranging from 1.04 to 1.79, and lherzolites clinopyroxenes have δ44/40Ca from 0.80 to 1.04. In contrast, δ44/40Ca in Cpx-rich lherzolites and wehrlites tend to have lower values reltaive to those of lherzolites. Their clinopyroxenes have δ44/40Ca ranging from 0.42 to 0.92, and their orthopyroxenes have δ44/40Ca ranging from 0.80 to 1.04. Collectively, we identify a positive correlation between clinopyroxene δ44/40Ca and Mg#. Model calculations show that kinetic isotopic fractionation caused by diffusion, probably during mantle melt-rock interaction, is responsible for the positive correlation between clinopyroxene δ44/40Ca and Mg# in these NCC peridotites. Our study shows that melt-rock interaction plays an important role in producing Ca isotopic heterogeneity of the subcontinental mantle.

Provenance and tectonic setting of siliciclastic rocks associated with the Neoproterozoic Dahongliutan BIF: Implications for the Precambrian crustal evolution of the Western Kunlun orogenic belt, NW China

NASA Astrophysics Data System (ADS)

Hu, Jun; Wang, He; Wang, Min

2017-10-01

The Late Neoproterozoic Dahongliutan BIF is associated with siliciclastic rocks in the Tianshuihai terrane of the Western Kunlun orogenic belt (WKO), NW China. The sedimentary rocks have various weathering indices (e.g., CIA = 57-87, PIA = 61-96 and Th/U = 4.85-12.45), indicative of varying degrees of weathering in the source area. The rocks have trace element ratios, such as Th/Sc = 0.60-1.21 and Co/Th = 0.29-1.67, and light rare earth element (LREE) enriched chondrite-normalized REE patterns, suggesting that they were mainly sourced from intermediate and felsic rocks. Available U-Pb ages of detrital zircon from these rocks reveal that the detrital sources may have been igneous and metamorphic rocks from the WKO and the Tarim Block. Our study suggests that the Dahongliutan BIF and hosting siliciclastic rocks may have deposited in a setting transitional from a passive to active continental margin, probably related to the Late Neoproterozoic-Early Cambrian seafloor spreading and subduction of the Proto-Tethys Ocean. U-Pb dating of 163 detrital zircons defines five major age populations at 2561-2329 Ma, 2076-1644 Ma, 1164-899 Ma, 869-722 Ma and 696-593 Ma. These age groups broadly correspond to the major stages of supercontinent assembly and breakup events widely accepted for Columbia, Rodinia and Gondwana. Some zircons have TDM2 model ages of 3.9-1.8 Ga and negative εHf(t) values, suggesting that the Archean to Paleoproterozoic (as old as Eoarchean) crustal materials were episodically reworked and incorporated into the late magmatic process in the WKO. Some Neoproterozoic zircons have TDM2 model ages of 1.47-1.07 Ga and 1.81-1.53 Ga and positive εHf(t) values, indicating juvenile crustal growth during the Mesoproterozoic. Our new results, combined with published data, imply that both the Tianshuihai terrane in the WKO and the Tarim Block share the same Precambrian tectonic evolution history.

The Late Jurassic Panjeh submarine volcano in the northern Sanandaj-Sirjan Zone, northwest Iran: Mantle plume or active margin?

NASA Astrophysics Data System (ADS)

Azizi, Hossein; Lucci, Federico; Stern, Robert J.; Hasannejad, Shima; Asahara, Yoshihiro

2018-05-01

The tectonic setting in which Jurassic igneous rocks of the Sanandaj-Sirjan Zone (SaSZ) of Iran formed is controversial. SaSZ igneous rocks are mainly intrusive granodiorite to gabbroic bodies, which intrude Early to Middle Jurassic metamorphic basement; Jurassic volcanic rocks are rare. Here, we report the age and petrology of volcanic rocks from the Panjeh basaltic-andesitic rocks complex in the northern SaSZ, southwest of Ghorveh city. The Panjeh magmatic complex consists of pillowed and massive basalts, andesites and microdioritic dykes and is associated with intrusive gabbros; the overall sequence and relations with surrounding sediments indicate that this is an unusually well preserved submarine volcanic complex. Igneous rocks belong to a metaluminous sub-alkaline, medium-K to high-K calc-alkaline mafic suite characterized by moderate Al2O3 (13.7-17.6 wt%) and variable Fe2O3 (6.0-12.6 wt%) and MgO (0.9-11.1 wt%) contents. Zircon U-Pb ages (145-149 Ma) define a Late Jurassic (Tithonian) age for magma crystallization and emplacement. Whole rock compositions are enriched in Th, U and light rare earth elements (LREEs) and are slightly depleted in Nb, Ta and Ti. The initial ratios of 87Sr/86Sr (0.7039-0.7076) and εNd(t) values (-1.8 to +4.3) lie along the mantle array in the field of ocean island basalts and subcontinental metasomatized mantle. Immobile trace element (Ti, V, Zr, Y, Nb, Yb, Th and Co) behavior suggests that the mantle source was enriched by fluids released from a subducting slab (i.e. deep-crustal recycling) with some contribution from continental crust for andesitic rocks. Based the chemical composition of Panjeh mafic and intermediate rocks in combination with data for other gabbroic to dioritic bodies in the Ghorveh area we offer two interpretations for these (and other Jurassic igneous rocks of the SaSZ) as reflecting melts from a) subduction-modified OIB-type source above a Neo-Tethys subduction zone or b) plume or rift tectonics involving upwelling metasomatized mantle (mostly reflecting the 550 Ma Cadomian crust-forming event).

Hydrothermal mobilization of pegmatite-hosted REE and Zr at Strange Lake, Canada: A reaction path model

NASA Astrophysics Data System (ADS)

Gysi, Alexander P.; Williams-Jones, Anthony E.

2013-12-01

Petrological and geochemical observations of pegmatites in the Strange Lake pluton, Canada, have been combined with numerical simulations to improve our understanding of fluid-rock interaction in peralkaline granitic systems. In particular, they have made it possible to evaluate reaction paths responsible for hydrothermal mobilization and mineralization of rare earth elements (REE) and Zr. The focus of the study was the B-Zone in the northwest of the pluton, which contains a pegmatite swarm and is the target of exploration for an economically exploitable REE deposit. Many of the pegmatites are mineralogically zoned into a border consisting of variably altered primary K-feldspar, arfvedsonite, quartz, and zirconosilicates, and a core rich in quartz, fluorite and exotic REE minerals. Textural relationships indicate that the primary silicate minerals in the pegmatites were leached and/or replaced during acidic alteration by K-, Fe- and Al-phyllosilicates, aegirine, hematite, fluorite and/or quartz, and that primary zirconosilicates (e.g., elpidite) were replaced by gittinsite and/or zircon. Reaction textures recording coupled dissolution of silicate minerals and crystallization of secondary REE-silicates indicate hydrothermal mobilization of the REE. The mobility of the light (L)REE was limited by the stability of REE-F-(CO2)-minerals (basnäsite-(Ce) and fluocerite-(Ce)), whereas zirconosilicates and secondary gadolinite-group minerals controlled the mobility of Zr and the heavy (H)REE. Hydrothermal fluorite and fluorite-fluocerite-(Ce) solid solutions are interpreted to indicate the former presence of F-bearing saline fluids in the pegmatites. Numerical simulations show that the mobilization of REE and Zr in saline HCl-HF-bearing fluids is controlled by pH, ligand activity and temperature. Mobilization of Zr is significant in both saline HF- and HCl-HF-bearing fluids at low temperature (250 °C). In contrast, the REE are mobilized by saline HCl-bearing fluids, particularly at high temperature (400 °C). The LREE are more mobile than the HREE in saline HCl-bearing fluids due to the greater stability of LREE-chloride complexes. The simulated mineralogy is consistent with the zonation observed in the pegmatites and with fluid-rock interaction at conditions that were rock-buffered in the pegmatite borders (low fluid/rock ratio; and pH > 4) and fluid-buffered in the cores (high fluid/rock ratio; pH ⩽ 2). We propose a model in which saline HCl-HF-bearing fluids created pathways during acidic alteration from the pegmatite cores outward. This led to the mobilization of REE and Zr due to progressive alteration of primary silicate minerals and increased acidity upon cooling. The key requirement for REE and Zr mobilization in peralkaline igneous intrusions is the formation of an acidic subsystem with high fluid/rock ratios that increases the overall permeability of the rocks. In these zones, the extent of late stage hydrothermal redistribution and concentration of REE and Zr depends on the buffering capacity of the rocks and the availability of fluids that may produce autometasomatic rock alteration, interact with external rock units and/or mix with fluids from other sources. b The detection limits of Yb were 1043 ppm for zircon, 380 ppm for gadolinite-group minerals and 380 ppm for REE-F-(CO2)-minerals. bAja et al. (1995). cMigdisov et al. (2011). dTagirov et al. (1997). eTagirov and Schott (2001). fMigdisov et al. (2009) with REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). b Calculated using the methods of the Chermak and Rimstidt (1989), Berman and Brown (1985) and Holland (1989) with molar volume of arfvedsonite from Hawthorne (1976). cZotov et al. (1998). d GEM-Selektor v.3 database (http://gems.web.psi.ch). eMigdisov et al. (2009).

The elemental abundances (with uncertainties) of the most Earth-like planet

NASA Astrophysics Data System (ADS)

Wang, Haiyang S.; Lineweaver, Charles H.; Ireland, Trevor R.

2018-01-01

To first order, the Earth as well as other rocky planets in the Solar System and rocky exoplanets orbiting other stars, are refractory pieces of the stellar nebula out of which they formed. To estimate the chemical composition of rocky exoplanets based on their stellar hosts' elemental abundances, we need a better understanding of the devolatilization that produced the Earth. To quantify the chemical relationships between the Earth, the Sun and other bodies in the Solar System, the elemental abundances of the bulk Earth are required. The key to comparing Earth's composition with those of other objects is to have a determination of the bulk composition with an appropriate estimate of uncertainties. Here we present concordance estimates (with uncertainties) of the elemental abundances of the bulk Earth, which can be used in such studies. First we compile, combine and renormalize a large set of heterogeneous literature values of the primitive mantle (PM) and of the core. We then integrate standard radial density profiles of the Earth and renormalize them to the current best estimate for the mass of the Earth. Using estimates of the uncertainties in i) the density profiles, ii) the core-mantle boundary and iii) the inner core boundary, we employ standard error propagation to obtain a core mass fraction of 32.5 ± 0.3 wt%. Our bulk Earth abundances are the weighted sum of our concordance core abundances and concordance PM abundances. Unlike previous efforts, the uncertainty on the core mass fraction is propagated to the uncertainties on the bulk Earth elemental abundances. Our concordance estimates for the abundances of Mg, Sn, Br, B, Cd and Be are significantly lower than previous estimates of the bulk Earth. Our concordance estimates for the abundances of Na, K, Cl, Zn, Sr, F, Ga, Rb, Nb, Gd, Ta, He, Ar, and Kr are significantly higher. The uncertainties on our elemental abundances usefully calibrate the unresolved discrepancies between standard Earth models under various geochemical and geophysical assumptions.

[Analysis of X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry of Pangxidong Composite Granitoid Pluton and Its Implications for Magmatic Differentiation].

PubMed

Zeng, Chang-yu; Ding, Ru-xin; Li, Hong-zhong; Zhou, Yong-zhang; Niu, Jia; Zhang, Jie-tang

2015-11-01

Pangxidong composite granitoid pluton located in the southwestern margin of Yunkai massif. The metamorphic grade of this pluton increases from outside to inside, that is, banded-augen granitic gneisses, gneissoid granites and granites distribute in order from edge to core. X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry are conducted to study the geochemical characteristics of the three types of rocks. The result shows that all the three types of rocks are peraluminous rocks and their contents of main elements and rare earth elements change gradually. From granitic gneisses to granites, the contents of Al₂O₃, CaO, MgO, TiO₂, total rare earth elements and light rare earth elements increase, but the contents of SiO₂ and heavy rare earth elements decrease. It is suggested that the phylogenetic relationship exists between granitic gneisses, gneissoid granites and granites during the multi-stage tectonic evolution process. Furthermore, the remelting of metamorphosed supracrustal rocks in Yunkai massif is probably an important cause of granitoid rocks forming. The evolutionary mechanism is probably that SiO₂ and heavy rare earth elements were melt out from the protolith and gradually enriched upward, but Al₂O₃, CaO, MgO, TiO₂ and light rare earth elements enriched downward.

Semiconductor sensor for optically measuring polarization rotation of optical wavefronts using rare earth iron garnets

DOEpatents

Duncan, Paul G.

2002-01-01

Described are the design of a rare earth iron garnet sensor element, optical methods of interrogating the sensor element, methods of coupling the optical sensor element to a waveguide, and an optical and electrical processing system for monitoring the polarization rotation of a linearly polarized wavefront undergoing external modulation due to magnetic field or electrical current fluctuation. The sensor element uses the Faraday effect, an intrinsic property of certain rare-earth iron garnet materials, to rotate the polarization state of light in the presence of a magnetic field. The sensor element may be coated with a thin-film mirror to effectively double the optical path length, providing twice the sensitivity for a given field strength or temperature change. A semiconductor sensor system using a rare earth iron garnet sensor element is described.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Condensation and fractionation of rare earths in the solar nebula

NASA Technical Reports Server (NTRS)

Davis, A. M.; Grossman, L.

1979-01-01

The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

Membrane assisted solvent extraction for rare earth element recovery

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

Bhave, Ramesh R.; Kim, Daejin; Peterson, Eric S.

Systems and methods for the recovery of rare earth elements are provided. The systems and methods generally include membrane assisted solvent extraction using permeable hollow fibers having an immobilized organic phase within the pores of the hollow fibers. The permeable hollow fibers are generally in contact with an acidic aqueous feed on one side thereof and a strip solution on another side thereof. The systems and methods generally include the simultaneous extraction and stripping of rare earth elements as a continuous recovery process that is well suited for post-consumer products, end-of-life products, and other recovery sources of rare earth elements.

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.

Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

NASA Technical Reports Server (NTRS)

Righter, Kevin; Pando, K.; Danielson, L.; Nickodem, K.

2014-01-01

Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

MaRGEE: Move and Rotate Google Earth Elements

NASA Astrophysics Data System (ADS)

Dordevic, Mladen M.; Whitmeyer, Steven J.

2015-12-01

Google Earth is recognized as a highly effective visualization tool for geospatial information. However, there remain serious limitations that have hindered its acceptance as a tool for research and education in the geosciences. One significant limitation is the inability to translate or rotate geometrical elements on the Google Earth virtual globe. Here we present a new JavaScript web application to "Move and Rotate Google Earth Elements" (MaRGEE). MaRGEE includes tools to simplify, translate, and rotate elements, add intermediate steps to a transposition, and batch process multiple transpositions. The transposition algorithm uses spherical geometry calculations, such as the haversine formula, to accurately reposition groups of points, paths, and polygons on the Google Earth globe without distortion. Due to the imminent deprecation of the Google Earth API and browser plugin, MaRGEE uses a Google Maps interface to facilitate and illustrate the transpositions. However, the inherent spatial distortions that result from the Google Maps Web Mercator projection are not apparent once the transposed elements are saved as a KML file and opened in Google Earth. Potential applications of the MaRGEE toolkit include tectonic reconstructions, the movements of glaciers or thrust sheets, and time-based animations of other large- and small-scale geologic processes.

Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as a novel eluent.

PubMed

Kifle, Dejene; Wibetoe, Grethe

2013-09-13

One of the major difficulties in the rare earth elements separation is purification of yttrium from heavy rare earth elements. Thus, an HPLC method using acetic acid as novel eluent was explored for selective separation of yttrium form the heavy rare earth elements. When acetic acid is used as a mobile phase yttrium eluted with the lighter lanthanides. This is contrary to its relative position amongst heavier lanthanides when eluents commonly used for separation of rare earth elements were employed. The shift in elution position of yttrium with acetic acid as eluent may reflect a relatively lower stability constant of the yttrium-AcOH complex (in the same order as for the lighter lanthanides) compared to the corresponding AcOH complexes with heavy lanthanides, enabling selective separation of yttrium from the latter. The method was successfully used for selective separation of yttrium in mixed rare earth sample containing about 80% of yttrium and about 20% of heavy rare earth oxides. Thus, the use of AcOH as eluent is an effective approach for separating and determining the trace amounts of heavy rare earth elements in large amounts of yttrium matrix. Separation was performed on C18 column by running appropriate elution programs. The effluent from the column was monitored with diode array detector at absorbance wavelength of 658nm after post column derivatization with Arsenazo III. Copyright © 2013 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Isotopic Composition of the Neolithic Alpine Iceman's Tooth Enamel and Clues to his Origin

NASA Astrophysics Data System (ADS)

Muller, W.; Muller, W.; Halliday, A. N.

2001-12-01

Five small enamel fragments from three teeth of the upper right jaw from the mummy of the Neolithic Alpine Iceman have been investigated for their isotopic composition in order to shed light on his geographic origins. Soils from approximately contemporaneous sites were sampled for comparison. Tooth enamel forms ontogenetically very early and is not re-mineralized during later lifetime (unlike with bone material). Therefore, unique insights into the Iceman's childhood can be acquired. Enamel also is the densest tissue of a human body and is thus less susceptible to post-mortem alteration. Both radiogenic (Sr, Pb, Nd) and stable isotopes (O, C) are investigated. Radiogenic isotopes allow reconstruction of the local geological background, because humans incorporate Sr, Pb and Nd from their local environment by eating local food. Stable isotopes provide information about altitude and/or position relative to the main Alpine watershed. High spatial-resolution laser-ablation ICPMS profiles reveal that most elements are distributed in a manner that is essentially similar to modern human teeth except of that La, Ce, Nd (LREE) show up to a 100-fold enrichment towards the outer enamel surface. These uptake-profiles may reflect interaction with melt water, consistent with data for the composition of samples of the Iceman's skin. Biogenic apatites (enamel, bone) have very low in-vivo LREE concentrations, but take up LREEs post-mortem from the burial environment. Ice core samples from the finding site show concentrations up to 400 ppt Ce. Such high uptake of the LREEs precludes the derivation of an in-vivo Nd isotopic signal, but both other radiogenic tracers, Sr and Pb, show pristine (in-vivo) concentrations of 87 ppm and 0.1 ppm, respectively. Strontium isotopic compositions were determined on fragments from the canine, the first and second premolar (1 - 9 mg) and two hip bone samples, utilizing three sequential leaching steps for each sample to detect possible alteration-related disturbance. Enamel fragments from three teeth are characterized by virtually similar and high 87Sr/^{86}Sr ratios of 0.7203-0.7206, consistent with the compositions of crystalline gneisses and schists close to the finding site. Sites overlying bedrock built up by limestone from further south or north can clearly be excluded as the Iceman's childhood area. Among the three teeth, enamel mineralized approximately during a 2-3 year interval starting with the canine at the age of ~2 years. Hence, during this period, the food source for the Iceman must have remained essentially constant. Two compact bone samples from the damaged hip region have 87Sr/^{86}Sr ratios of 0.7175 and 0.7181, significantly lower than that of the enamel. The internal variation in the Iceman's bone Sr isotopic composition argues for somewhat different Sr turnover times within the skeleton, but it is evident that during the last 1-3 decades of his life, food from a different region was utilized. The 87Sr/^{86}Sr ratios of the initial bone leachates point towards post-mortem alteration with water having 87Sr/^{86}Sr ratios higher than ~0.718, consistent with that measured for contemporaneous ice samples (0.720-0.723). These Sr isotopic variations among ice samples may have implications for the post depositional (climate) history of the Iceman's finding site, since it appears unlikely that substantial compositional differences among adjacent ice samples would be preserved if the site had thawed near completely during e.g. the Roman warm period.

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

NASA Astrophysics Data System (ADS)

Echeverría, Lina M.

1980-08-01

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

Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

DOEpatents

Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

2015-02-10

Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

EPA Science Inventory

Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Northwest Africa 773: Lunar Mare Breccia with a Shallow-formed Olivine-Cumulate Component, Very-Low-Ti Heritage, and a KREEP Connection

NASA Technical Reports Server (NTRS)

Jolliff, B. L.; Korotev, R. L.; Zeigler, R. A.; Floss, C.; Haskin, L. A.

2003-01-01

Northwest Africa 773 is one of the more unusual lunar meteorites found in recent years because it contains a prominent clast lithology, which appears to be an olivine-rich cumulate and because it is a very-low-Ti (VLT) mare breccia with relatively high incompatible-trace-element concentrations and LREE/HREE enrichment. A lunar origin was verified by Fagan and coworkers on the basis of noble-gas contents, oxygen isotopes, and mineral compositions. Fagan et al. described two lithologies: (1) heterolithic impact breccia with a regolith component and (2) cumulus olivine gabbronorite. Here, we refer to these as the breccia (Bx) lithology and the olivine-cumulate (OC) lithology. The impact breccia components are predominantly volcanic (basaltic), and, in this context, the occurrence of the cumulus lithology is especially significant: is it related to the volcanic components or does it represent a deep-seated rock entrained by the basaltic magma as it rose to the surface? Elevated incompatible-element concentrations with more or less KREEP-like inter-element ratios and very-low-Ti concentrations distinguish both lithologies of this meteorite from Apollo mare basalts. Here, we summarize key compositional information (bulk and mineral), especially related to the OC lithology, to show that it formed at shallow depth and comes from a VLT ultramafic precursor that mixed with a KREEP-like trace-element component deep in the crust or upper mantle.

Rare Earth Element Mines, Deposits, and Occurrences

USGS Publications Warehouse

Orris, Greta J.; Grauch, Richard I.

2002-01-01

Data on rare earth (including yttrium) mines, deposits, and occurrences were compiled as part of an effort by the USGS and the University of Arizona Center for Mineral Resources to summarize current knowledge on the supply and demand outlook and related topics for this group of elements. Economic competition and environmental concerns are increasingly constraining the mining and processing of rare earths from the Mountain Pass mine in California. For many years, the deposit at Mountain Pass was the world's dominant source of rare earth elements and the United States was essentially self-sufficient. Starting approximately 10 years ago, the U.S. has become increasingly dependent (> 90 percent of separated rare earths) upon imports from China, now the dominant source of rare earths. A knowledge of the known economic and noneconomic sources of rare earths is basic to evaluating the outlook for rare earth supply and associated issues.

NETL’s Rare Earth Elements Research

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

None

The National Energy Technology Laboratory has established a Rare Earth Elements (REE) program. REEs are a series of 17 chemical elements found in the Earth’s crust. They are an essential component to technology, health care, transportation and national defense.

A comprehensive analysis of the content of heavy rare-earth elements and platinum in snow samples to assess the ecological hazard of air pollution in urban areas

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.; Tarasova, N. P.; Trunova, A. N.; Sychkova, V. A.

2017-07-01

Snow samples from the territory of the Setun River Valley Wildlife Sanctuary are analyzed for the content of rare-earth elements, heavy metals, and other hazardous elements by the inductively coupled plasma mass-spectrometry method. The changes in the concentrations of rare-earth elements, Pt, Pd, and indicator ratios of elements in the solid fractions of snow are revealed. A trend toward a decrease in the content of several elements northeastward of the Moscow Ring Road (MRR) is established. The level of seasonal atmospheric contamination of the area under study is assessed, and a possible source is identified.

The effect of melt composition on the partitioning of trace elements between titanite and silicate melt

NASA Astrophysics Data System (ADS)

Prowatke, S.; Klemme, S.

2003-04-01

The aim of this study is to systematically investigate the influence of melt composition on the partitioning of trace elements between titanite and different silicate melts. Titanite was chosen because of its important role as an accessory mineral, particularly with regard to intermediate to silicic alkaline and calc-alkaline magmas [e.g. 1] and of its relative constant mineral composition over a wide range of bulk compositions. Experiments at atmospheric pressure were performed at temperatures between 1150°C and 1050°C. Bulk compositions were chosen to represent a basaltic andesite (SH3 - 53% SiO2), a dacite (SH2 - 65 SiO2) and a rhyolite (SH1 - 71% SiO2). Furthermore, two additional experimental series were conducted to investigate the effect of Al-Na and the Na-K ratio of melts on partitioning. Starting materials consisted of glasses that were doped with 23 trace elements including some selected rare earth elements (La, Ce, Pr, Sm, Gd, Lu), high field strength elements (Zr, Hf, Nb, Ta) and large ion lithophile elements (Cs, Rb, Ba) and Th and U. The experimental run products were analysed for trace elements using secondary ion mass spectrometry at Heidelberg University. Preliminary results indicate a strong effect of melt composition on trace element partition coefficients. Partition coefficients for rare-earth elements uniformly show a convex-upward shape [2, 3], since titanite accommodates the middle rare-earth elements more readily than the light rare-earth elements or the heavy rare-earth elements. Partition coefficients for the rare-earth elements follow a parabolic trend when plotted against ionic radius. The shape of the parabola is very similar for all studied bulk compositions, the position of the parabola, however, is strongly dependent on bulk composition. For example, isothermal rare-earth element partition coefficients (such as La) are incompatible (D<1) in alkali-rich silicate melts and strongly compatible (D>>1) in alkali-poor melt compositions. From our experimental data we present an model that combines the influence of the crystal lattice on partitioning with the effect of melt composition on trace element partition coefficients. [1] Nakada, S. (1991) Am. Mineral. 76: 548-560 [2] Green, T.H. and Pearson, N.J. (1986) Chem. Geol. 55: 105-119 [3] Tiepolo, M.; Oberti, R. and Vannucci, R. (2002) Chem. Geol. 191: 105-119

Equilibrium distribution of rare earth elements between molten KCl-LiCl eutectic salt and liquid cadmium

NASA Astrophysics Data System (ADS)

Sakata, Masahiro; Kurata, Masaki; Hijikata, Takatoshi; Inoue, Tadashi

1991-11-01

Distribution experiments for several rare earth elements (La, Ce, Pr, Nd and Y) between molten KCl-LiCl eutectic salt and liquid Cd were carried out at 450, 500 and 600°C. The material balance of rare earth elements after reaching the equilibrium and their distribution and chemical states in a Cd sample frozen after the experiment were examined. The results suggested the formation of solid intermetallic compounds at the lower concentrations of rare earth metals dissolved in liquid Cd than those solubilities measured in the binary alloy system. The distribution coefficients of rare earth elements between two phases (mole fraction in the Cd phase divided by mole fraction in the salt phase) were determined at each temperature. These distribution coefficients were explained satisfactorily by using the activity coefficients of chlorides and metals in salt and Cd. Both the activity coefficients of metal and chloride caused a much smaller distribution coefficient of Y relative to those of other elements.

Catalytic Graphitization of Coal-Based Carbon Materials with Light Rare Earth Elements.

PubMed

Wang, Rongyan; Lu, Guimin; Qiao, Wenming; Yu, Jianguo

2016-08-30

The catalytic graphitization mechanism of coal-based carbon materials with light rare earth elements was investigated using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, selected-area electron diffraction, and high-resolution transmission electron microscopy. The interface between light rare earth elements and carbon materials was carefully observed, and two routes of rare earth elements catalyzing the carbon materials were found: dissolution-precipitation and carbide formation-decomposition. These two simultaneous processes certainly accelerate the catalytic graphitization of carbon materials, and light rare earth elements exert significant influence on the microstructure and thermal conductivity of graphite. Moreover, by virtue of praseodymium (Pr), it was found that a highly crystallographic orientation of graphite was induced and formed, which was reasonably attributed to the similar arrangements of the planes perpendicular to (001) in both graphite and Pr crystals. The interface between Pr and carbon was found to be an important factor for the orientation of graphite structure.

[Contents of macromineral and trace elements in spirulina (Arthrospira platensis) from France, Chad, Togo, Niger, Mali, Burkina-Faso and Central African Republic].

PubMed

Vicat, Jean-Paul; Doumnang Mbaigane, Jean-Claude; Bellion, Yves

2014-01-01

Data on mineral elements in spirulinas being limited, we analyzed macrominerals and trace elements of samples from France and Africa. Spirulinas cultivated in France have a composition in macromineral elements similar to those of the literature. The entire contents of trace elements are low. Unlike marine cyanobacteria, they do not concentrate rare-earth elements. Spirulina harvested in Chad has high levels in macrominerals and trace elements, due to traditional drying and harvesting methods. Rare-earth element levels are attributed to this pollution and not to their concentration in spirulinas, because rare-earth element normalized profiles of spirulina are strictly parallel to those of ouadis mud and very different from those of ouadis water. Despite the sometimes high content of total As, normal water consumption in Chad presents no health problems. Spirulinas grown in Togo, Niger, Mali, Burkina-Faso and Central African Republic have chemical compositions similar to those of Chad spirulinas, but with a lower content of macromineral and trace elements, reflecting a lower mineral pollution. Rare-earth element normalized patterns dismiss an aeolian pollution and the pollution is rather of pedological origin. They show no toxicity problem except spirulinas from Burkina-Faso, whose Pb content is too high. The variability of composition of spirulinas can be largely attributed to the mineral pollution of the samples. Significant levels of rare-earth elements sometimes found in the literature reflect this pollution. Copyright © 2013 Académie des sciences. Published by Elsevier SAS. All rights reserved.

Rare Earth Extraction from NdFeB Magnet Using a Closed-Loop Acid Process.

PubMed

Kitagawa, Jiro; Uemura, Ryohei

2017-08-14

There is considerable interest in extraction of rare earth elements from NdFeB magnets to enable recycling of these elements. In practical extraction methods using wet processes, the acid waste solution discharge is a problem that must be resolved to reduce the environmental impact of the process. Here, we present an encouraging demonstration of rare earth element extraction from a NdFeB magnet using a closed-loop hydrochloric acid (HCl)-based process. The extraction method is based on corrosion of the magnet in a pretreatment stage and a subsequent ionic liquid technique for Fe extraction from the HCl solution. The rare earth elements are then precipitated using oxalic acid. Triple extraction has been conducted and the recovery ratio of the rare earth elements from the solution is approximately 50% for each extraction process, as compared to almost 100% recovery when using a one-shot extraction process without the ionic liquid but with sufficient oxalic acid. Despite its reduced extraction efficiency, the proposed method with its small number of procedures at almost room temperature is still highly advantageous in terms of both cost and environmental friendliness. This study represents an initial step towards realization of a closed-loop acid process for recycling of rare earth elements.

Trace element distributions in primitive achondrites

NASA Technical Reports Server (NTRS)

Davis, Andrew M.; Prinz, Martin; Weisberg, Michael K.

1993-01-01

The primitive achondrites have approximately chondritic bulk chemical composition but achondritic textures. Clayton et al. show that nine of these meteorites, the acapulcoites and the lodranites, have similar oxygen isotopic compositions. The acapulcoites appear to be highly metamorphosed, but undifferentiated meteorites of chondritic composition; whereas, the lodranites appear to have lost a feldspathic partial melt. In order to learn more about metamorphic processes and partial melt removal, we have measured the trace element compositions of constituent phases of a number of primitive achondrites by ion microprobe. We have analyzed two acapulcoites, Acapulco and ALH81261 (paired with ALH77081), and three londranites, Lodran, LEW88280, and MAC88177. In addition, we analyzed LEW88663, which has the bulk composition, mineral chemistry, and oxygen isotopic composition of L-chondrites, but is metal-free and has an achondrite texture; and Divnoe, a plagioclase-poor, olivine-rich primitive achondrite with an oxygen isotopic composition similar to that of the group IAB iron meteorites. These meteorites show a variety of REE patterns in their constituent phases, and there are consistent differences between acapulcoites and lodranites that are consistent with removal of a LREE- and Eu-enriched melt that is apparently responsible for the low plagioclase content of lodranites.

A global geochemical model for the evolution of the mantle

NASA Technical Reports Server (NTRS)

Anderson, D. L.

1979-01-01

It is proposed that the upper mantle transition region, 220 to 670 km, is composed of eclogite which has been derived from primitive mantle by about 20 percent partial melting and that this is the source and sink of oceanic crust. The remainder of the upper mantle is garnet peridotite which is the source of continental basalts and hotspot magmas. This region is enriched in incompatible elements by hydrous and CO2 rich metasomatic fluids which have depleted the underlying layers in the L.I.L. elements and L.R.E.E. The volatiles make this a low-velocity, high attenuation, low viscosity region. The eclogite layer is internally heated and its controls the convection pattern in the upper mantle. Plate tectonics is intermittent. The continental thermal anomaly at a depth of 150-220 km triggers kimberlite and carbonatite activity, alkali and flood basalt volcanism, vertical tectonics and continental breakup. Hot spots remain active after the continents leave and build the oceanic islands. Mantle plumes rise from a depth of about 220 km. Midocean ridge basalts rise from the depleted layer below this depth. Material from this layer can also be displaced upwards by subducted oceanic lithosphere to form back-arc basins.

Composition of monazites from pegmatites in eastern Minas Gerais, Brazil

USGS Publications Warehouse

Murata, K.J.; Dutra, C.V.; da Costa, M.T.; Branco, J.J.R.

1959-01-01

Two zoned pegmatites in south-eastern Minas Gerais were sampled in detail for their content of monazite and xenotime and the monazite was analysed for certain of the rare-earth elements and thorium. The ratio of xenotime to monazite increases in both pegmatites from the wall toward the quartz core. The content of the less basic rare-earth elements and of thorium in monazite rises in the same direction. These variation trends suggest that during the crystallization of these pegmatites there was a fractionation of the elements leading to a more or less steady enrichment of the less basic rare-earth elements and of thorium in the residual fluids. One mode of explaining these observed effects postulates that the rare-earth elements and thorium were present in pegmatitic fluids as co-ordination complexes rather than as simple cations. ?? 1959.

Quantitative Analysis of Trace Element Impurity Levels in Some Gem-Quality Diamonds

NASA Astrophysics Data System (ADS)

McNeill, J. C.; Klein-Bendavid, O.; Pearson, D. G.; Nowell, G. M.; Ottley, C. J.; Chinn, I.; Malarkey, J.

2009-05-01

Perhaps the most important information required to understand the origin of diamonds is the nature of the fluid that they crystallise from. Constraining the identity of the diamond-forming fluid for high purity gem diamonds is hampered by analytical challenges because of the very low analyte levels involved. Here we use a new ultra- low blank 'off-line' laser ablation method coupled to sector-field ICPMS for the quantitative analysis of fluid-poor gem diamonds. Ten diamonds comprised of both E- and P-type parageneses, from the Premier Mine, South Africa, were analysed for trace element abundances. We assume that the elemental signatures arise from low densities of sub-microscopic fluid inclusions that are analogous to the much higher densities of fluid inclusions commonly found within fluid-rich diamonds exhibiting fibrous growth. Repeatability of multiple (>20) blanks yielded consistently low values so that using the current procedure our limits of quantitation (10-ã blank) are <1pg for most trace elements, except for Sr, Zr, Ba, from 2-9pg and Pb ~30pg. Trace element patterns of the Premier diamond suite show enrichment of LREE over HREE. Abundances broadly decrease with increasing elemental compatibility. As a suite the chondrite normalised diamond patterns show negative Sr, Zr, Ti and Y anomalies and positive U, and Pb anomalies. All sample abundances are very depleted relative to chondrites (0.1 to 0.001X ch). HREE range from 0.1 to 1ppb as do Y, Nb, Cs. Other lighter elements vary from 2-30ppb. Pb reaches several ppb and Ti ranges from ppb values up to 2ppm. No significant difference were observed between the trace element systematics of the eclogitic and peridotitic diamonds. Overall, these initial data have inter-element fractionation patterns similar to those evident from fluid-rich fibrous diamonds and can be sued to infer that both types of diamond-forming fluids share a common origin.

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

NASA Astrophysics Data System (ADS)

Brandmeier, Melanie; Wörner, Gerhard

2017-04-01

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

Experimental Parameters Affecting Stripping of Rare Earth Elements from Loaded Sorptive Media in Simulated Geothermal Brines

DOE Data Explorer

Dean Stull

2016-05-24

Experimental results from several studies exploring the impact of pH and acid volume on the stripping of rare earth elements (REEs) loaded onto ligand-based media via an active column. The REEs in this experiment were loaded onto the media through exposure to a simulated geothermal brine with known mineral concentrations. The data include the experiment results, rare earth element concentrations, and the experimental parameters varied.

[Distribution characteristic and current situation of soil rare earth contamination in the Bayan Obo mining area and Baotou tailing reservoir in Inner Mongolia].

PubMed

Guo, Wei; Fu, Rui-ying; Zhao, Ren-xin; Zhao, Wen-jing; Guo, Jiang-yuan; Zhang, Jun

2013-05-01

The pollution status and distribution characteristic of rare earth elements in soil were analyzed around Bayan Obo mining area and Baotou tailing reservoir located in Inner Mongolia grassland ecosystem, aiming at grasping the overall situation of grassland ecosystem pollution caused by rare earth elements and providing basic information as well as theoretical basis. The results indicated that seven rare earth elements in soils from different directions of Baotou tailing reservoir accumulated to a certain extent compared to the soil background value of Inner Mongolia. The pollution degree was Ce > La > Nd > Pr > Sm > Y > Eu. Within 50 m from the edge of tailing reservoir, soil rare earth contamination was the most serious, with the concentrations of La, Ce, Pr, Nd, Sm, Eu and Y reaching 11,45.0 mg x kg(-1), 23,636.0 mg x kg(-1), 4568.16 mg x kg(-1) , 6855.51 mg x kg(-1), 582.18 mg x kg(-1), 94.21 mg x kg(-1)), and 136.25 mg x kg(-1), respectively. Owing to the dominant wind direction of northwest, soils from the southeast were contaminated most seriously. For Bayan Obo mining area, the concentrations of seven rare earth elements in soil from the mining area were significantly higher than those of other areas investigated, with the concentrations of La, Ce, Pr, Nd, Sm, Eu and Y reaching 3112.56 mg x kg(-1), 7142.12 mg x kg(-1), 1467.12 mg x kg(-1), 2552.80 mg x kg(-1), 210.80 mg x kg(-1), 36.20 mg x kg(-1) and 63.22 mg x kg(-1), respectively. The soils of six areas of Bayan Obo mining area were all contaminated by rare earth elements, and the contamination degree was in the order of mining area > outside the dump > east side of the railway > the dump > outside the urban area > west side of the railway. Besides, the transportation of rare earth ore led to the soil rare earth contamination along the railway, and the distribution characteristic of rare earth elements in soils along the railway was affected by the dominant wind direction of northwest. Baotou tailing reservoir and Bayan Obo mining area had the same contamination characteristic, and the concentrations of rare earth elements were in accordance with those in the tailings. The health and stabilization of local grassland ecosystem are being threatened by excessive soil rare earth elements.

REE chemistry and Sm-Nd systematics of late Archean weathering profiles in the Fortescue Group, Western Australia

NASA Technical Reports Server (NTRS)

MacFarlane, A. W.; Danielson, A.; Holland, H. D.; Jacobsen, S. B.

1994-01-01

Two weathering profiles, each consisting of an upper, sericite-rich zone and a lower, chlorite-rich zone, are preserved between flows of the Mt. Roe Basalt in the Fortescue Group, Hamersley Basin, Western Australia. REE concentrations in samples from these two profiles, which originally developed ca 2,760 Ma, show large variations depending on stratigraphic position. LREE abundances and (La/Yb)N are greatest at depths of 3-6 m below the paleosurface of the Mt. Roe #1 profile and are somewhat lower in samples above this level. The LREEs reach concentrations 6-9 times greater than in the underlying basalt, and thus appear to have been mobilized downward in the paleosol and concentrated in its middle part. LREE concentrations in the #2 profile show a similar distribution but with a sharp increase in all REE concentrations within 50 cm of the paleosurface. The distinction between the REE profiles in the two paleosols may be related to the difference in the overlying material. The #1 paleosol is overlain by a few meters of sediments and then by basalt, whereas the #2 paleosol is directly overlain by basalt. The LREEs appear to have been mobilized both during chemical weathering of the parental basalt and during later lower-greenschist-facies metamorphism and metasomatism of the paleosols. Remobilization of the REEs during the regional metamorphism of the Fortescue Group is confirmed by a whole-rock Sm-Nd reference isochron of Mt. Roe #1 samples with an age of 2,151 +/- 360 Ma. Variable initial 143Nd/144Nd values of unweathered basalt samples which may represent the paleosol protolith prevents a confident determination of the magnitude of LREE mobility. Both the initial mobilization of the REEs during weathering and the metasomatic remobilization appear to have taken place under redox conditions where Ce was present dominantly as Ce3+, because Ce anomalies are not developed within the sericite zone samples regardless of concentration. Europium anomalies in the paleoweathering profile are somewhat variable and were probably modified by mobilization of Eu2+ at metamorphic conditions. In all samples, the HREEs appear to have been relatively immobile and correlate with Al, Ti, Cr, V, Zr, and Nb. Sm-Nd systematics and REE patterns of four unweathered basalt samples indicate derivation of the Mt. Roe Basalts from a heterogeneous and enriched source having epsilon Nd between -4.0 and -7.4. Initial 143Nd/144Nd values of these basalts are even lower than those reported by NELSON et al. (1992) for Fortescue Group basalts and indicate a substantial crustal component in the generation of Mt. Roe Basalts.

Earth, Air, Fire and Water in Our Elements

ERIC Educational Resources Information Center

Lievesley, Tara

2007-01-01

The idea that everything is made of the four "elements", earth, air, fire and water, goes back to the ancient Greeks. In this article, the author talks about the origins of ideas about the elements. The author provides an account that attempts to summarise thousands of years of theoretical development of the elements in a thousand words or so.

REE geochemistry of 3.2 Ga BIF from the Mapepe Formation, Barberton Greenstone Belt, South Africa

NASA Astrophysics Data System (ADS)

Yahagi, T. R.; Yamaguchi, K. E.; Haraguchi, S.; Sano, R.; Teraji, S.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Banded iron formations (BIFs) are chemical sediments interbedded with Fe- and Si-rich layers, characteristically present in the early history of the Earth. A popular hypothesis for the formation of BIFs postulates that dissolved oxygen produced by photosynthesizers such as cyanobacteria oxidized dissolved ferrous Fe supplied by submarine hydrothermal activities. During precipitation of Fe-oxide minerals, phosphorus and rare earth elements (REEs) were most likely adsorbed on their surface. Therefore, chemical compositions of REEs that adsorbed onto Fe-oxide have useful information on the seawater chemistry at the time of deposition. Especially, information on the redox state of seawater and the extent of the contribution of hydrothermal activity during BIF deposition are expected to have been recorded. Occurrence of BIF has been traditionally tied to the chemical evolution of the atmosphere. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 Ga ago. Contrary, however, some studies have suggested that such oxygenation could have occurred much earlier (e.g., Hoashi et al., 2009). In this study, we used 3.2 Ga old BIF from the Mapepe Formation at the bottom of the Fig Tree Group of the Swaziland Supergroup in the northeastern part of the Barberton Greenstone Belt, South Africa. We aimed to constrain the marine environment, and by inference atmospheric environment, at the time of BIF deposition from REE geochemistry. Major elements and REE compositions of 37 samples were measured using XRF and ICP-MS, respectively. Samples with less than 1.0 wt% Al2O3 are considered to be "pure" BIFs with minimal amount of continental contamination, and are expected to have inherited marine REE signatures. Abundance of REE normalized by C1 chondrite for the analyzed samples commonly exhibits positive Eu anomaly and LREE

Water Contents of the Mantle Beneath the Rio Grande Rift: FTIR Analysis of Kilbourne Hole Peridotite Xenoliths

NASA Technical Reports Server (NTRS)

Schaffer, Lillian A.; Peslier, Anne; Brandon, Alan

2013-01-01

Although nominally anhydrous mantle minerals contain only trace amounts of water, they are the main reservoir of water in the mantle. Added up at the scale of the Earth's mantle, these trace amounts of water represent oceans worth in mass]. Mantle xenoliths from Kilbourne Hole in southern New Mexico are ideal to study mantle water distribution in a rift tectonic setting as they come from a recently-erupted maar in the middle of the Rio Grande Rift. Eleven lherzolites, one harzburgite, and one dunite are being analyzed for water contents by FTIR. The xenoliths will also be analyzed for major and trace element composition, Fe3+/Summation (Fe) ratios, and characterized petrologically. Olivines exhibit variable water contents with less water at the rims compared to the cores. This is probably due to H loss during decompression and xenolith transport by the host magma. Mantle water contents appear to have been primarily preserved in the core of the olivines, based on diffusion modeling of the typically plateau-shaped water content profiles across these grains. Water concentrations are in equilibrium between clino- and orthopyroxene, but olivine concentrations are typically not in equilibrium with those of either pyroxene. Lherzolites analyzed so far have water contents of 2-12 ppm H2O in olivines, 125-165 ppm H2O in orthopyroxenes, and 328-447 ppm H2O in clinopyroxenes. These water contents are similar to, but with a narrower range, than those for the respective minerals in other continental peridotite xenoliths. The lherzolites have bulk-rock (BR) Al2O3 contents that range between 3.17 and 3.78 wt%, indicating similar degrees of partial melting, which could explain the narrow range of their pyroxene water contents. Primitive mantle normalized rare earth element (REE) profiles of the bulk lherzolites vary from light REE depleted to flat, with no significant differences between, nor relation to, their mineral water contents. Consequently, the metasomatic agents that enriched LREEs in these lherzolites were most likely water-poor. The harzburgite and the dunite have lower weight percent Al2O3 compared to the lherzolites (2.11% and 0.34% respectively) indicating higher degrees of melting. Their olivine water contents, however, are similar to those of the lherzolites. Moreover, no correlations are observed between pyroxene water contents and indices of melting or metasomatism between the lherzolite group, the harzburgite, and the dunite, although the latter has the lowest pyroxene water contents. More samples will be analyzed to determine if the water contents are controlled by melting, metasomatism, or a combination of the two in the Kilbourne Hole mantle.

Rare earths and other trace elements in Luna 16 soil.

NASA Technical Reports Server (NTRS)

Helmke, P. A.; Haskin, L. A.

1972-01-01

An analysis has been made of four small samples of material brought to earth by the Luna 16 mission, with the aim to determine rare earths and other trace elements in these samples. The analytical results are tabulated, and the rare earth abundances are compared with the average for chondrites. A comparison is also made with the results of similar analyses of Apollo samples.

Geochemistry and Pb Isotopes from the Jan Mayen Fracture Zone and the Extinct Aegir Ridge

NASA Astrophysics Data System (ADS)

Sayit, K.; Hanan, B. B.; Ito, G.; Howell, S. M.; Vogt, P. R.; Breivik, A. J.; Mjelde, R.; Pedersen, R. B.; Arrgh Scientific Team

2011-12-01

The Aegir Ridge appears as a major gap or "hole" in the N-Atlantic LIP, created by the Iceland hotspot. The Aegir Ridge created anomalously thick crust (8-11 km) during the first 2-4 Myr spreading, followed by a decrease in magma production and crustal thickness of 3.5-6 km (51.4-25 Ma). Possible explanations are, the lithospheric structure of the newly rifting Kolbeinsey Ridge and Jan Mayen micro-continent diverted mantle flow from the hotspot away from Aegir Ridge, and/or plume flux was low at that time. We report trace element and Pb isotope results for basalts dredged from the Jan Mayen FZ and Aegir Ridge flanks ~69-64 °N. Dredges returned Mn crust, erratic cobbles, hyaloclastite, and basalt diabase. Trace elements reveal distinct chemical groups, including very-depleted melts with very high Zr/Nb ratios (60.7) at one end, and melts of highly enriched characteristics on the other (2.7). The very-depleted compositions show significant LREE depletion relative to HREE [Ce/Yb]N=0.3), while the highly enriched compositions show LREE enrichment [Ce/Yb]N=2.2. Th/Nb ratios vary between 0.07-0.49, indicating variable Th enrichment. Trace element systematics indicate that between group elemental variations can't be solely explained by fractional crystallization and/or partial melting, the observed variations are largely source-related. Trace element systematics are consistent with a mixed MORB/OIB/SCLM mantle source, where relatively enriched samples resemble Faeroe Island lavas, and depleted ones are akin to Kolbeinsey Ridge lavas. Jan Mayen FZ rocks have initial (40Ma) 206Pb/204Pb: 207Pb/204Pb: 208Pb/204Pb =18.2-18.57:15.47-15.54:37.83-38.46 and AR, 16.59-18.75:15.16-15.53:37:36.62-38.51. Jan Mayen FZ, and Aegir Ridge samples with 206Pb/204Pb > 18.2 have higher 207Pb/204Pb and 208Pb/204Pb than the Iceland Neovolcanic lavas and are similar to the Iceland Tertiary and anomalous Öræfajökull basalts. Aegir Ridge basalts with 206Pb/204Pb <17.5 plot below the NHRL in the 206Pb/204Pb vs 207Pb/204Pb and above it in the 206Pb/204Pb vs 208Pb/204Pb diagrams, a characteristic of the British Tertiary Province basalts formed during the early stages of opening of the North Atlantic. We can't be certain that the dredged samples represent primary Aegir Ridge material, or if they were derived from elsewhere along the Iceland-Faeroe Ridge (eg, Faeroes), and transported to the dredge locations. If these rocks were erupted at the Aegir Ridge, the data show that at this time the ambient N-Atlantic upper mantle was relatively uncontaminated by the Iceland Plume, but significantly polluted by continental material, presumably during the early opening of the N-Atlantic Ocean Basin. ARRGH Cruise Scientific Team: Rolf Mjelde, Rolf Birger Pedersen, Helene Kraft, Marcus Fink, Ernst Flüh

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

Preliminary Geochemical Data for the Diabase Dykes from the Izmir-Ankara-Erzincan Suture Belt, Central Anatolia

NASA Astrophysics Data System (ADS)

Balcı, Uǧur; Sayıt, Kaan

2017-04-01

The Izmir-Ankara-Erzincan Suture Belt preserves oceanic and continental fragments originated from the closure of the northern branch of Neotethys. In the Bogazkale area (Central Anatolia), the pieces of the Neotethyan oceanic lithosphere exist in a chaotic manner, forming an ophiolitic mélange. Within the mélange, diabase dykes occur, which are found to cut various types of oceanic lithospheric rocks, including pillow basalts, gabbros and serpentinized ultramafics. We here present the preliminary geochemical results obtained from the diabase dykes and put some constraints on their petrogenesis. The investigated diabase dykes are chiefly composed of plagioclase and a mafic phase, which is clinopyroxene and/or hornblende. A detailed examination reveals two petrographic types on the basis of predominating mafic mineral phase, namely clinopyroxene-dominated Type 1, and hornblende-dominated Type 2. Ophitic to sub-ophitic textures, where lath-shaped plagioclase crystals are enclosed by clinopyroxene, can be observed in almost all Type 1 dykes. In Type 2 samples, altered mafic phases can be seen enclosed within plagioclase crystals, forming poikilitic texture. Polysynthetic twinning is common in plagioclase. Hornblende occasionally displays simple twinning. Both types appear to have been variably affected by low-grade hydrothermal alteration as reflected by the presence of secondary mineral phases, such as chlorite, epidote, prehnite, and actinolite. The whole-rock geochemistry appear to be consistent with the petrographical grouping, revealing distinct immobile trace element systematics for the two types. Both types have basaltic composition with sub-alkaline characteristics (Nb/Y=0.2-0.3 for Type 1; Nb/Y=0.02-0.08 for Type 2). The relatively low MgO contents of the dykes suggest that they do not represent primary magmas, but evolved through fractionation of mafic phases. In the N-MORB normalized diagrams, Type 2 diabases exhibit marked negative Nb anomalies, with HFSE abundances around or slightly more enriched than N-MORB. Type 1 diabases, on the other hand, do not possess any negative Nb anomalies and display enrichment in highly incompatible elements. In the chondrite-normalized diagrams, Type 1 diabases display slight LREE enrichment relative to HREE, whereas Type 2 diabases show flat to slightly LREE-depleted patterns. The N-MORB-like Nb contents of Type 2 dykes suggest that they have been derived from depleted asthenopheric mantle source. The marked enrichment of Th and La over Nb indicates that their source has been metasomatized by slab-derived fluids/melts. However, the enrichment in highly incompatible elements in Type 1 dykes implies their derivation from a relatively enriched source region and/or small degrees of partial melting. Trace element systematics suggest that Type 2 diabases may have formed in an oceanic back-arc basin environment, whereas Type 1 diabases have been generated in a mid-ocean ridge or alternatively in an oceanic back-arc basin.

Extraction of rare earth elements from low-grade Bauxite via precipitation reaction

NASA Astrophysics Data System (ADS)

Kusrini, E.; Nurani, Y.; Bahari, ZJ

2018-03-01

The aim of this research was to determine the optimum hydrometallurgical parameters to extract the rare earth elements (REE) from low-grade bauxite through acid leaching and precipitation reaction. REE or lanthanide recovery by a precipitation method with sodium sulphate and sodium phosphate as precipitation agents is reported where the effect of pH and recovery of REE are described. The metal composition of REE in low-grade bauxite after treatment were analyzed by ICP-OES. The total recovery values of REE elements at the first precipitation reaction using sodium sulphate as the precipitation agent at pH 3.5 showed ~68.2% of lanthanum, ~18.9% cerium, and ~7.8% yttrium. Lanthanum was the rare-earth element present at the highest concentration in the low-grade bauxite after the series treatments. An optimum pH of 3.5 for precipitation of rare-earth elements using sodium sulphate was demonstrated where this method is recommended for the extraction of REE elements from low-grade bauxite.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Sasselov, Dimitar; Jacobsen, Stein

2015-08-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet’s rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called “late veneer”. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet’s surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars’ elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, L.; Jacobsen, S. B.; Sasselov, D. D.

2015-12-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called "late veneer". The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars' elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Electro-kinetic Separation of Rare Earth Elements Using a Redox-Active Ligand.

PubMed

Fang, Huayi; Cole, Bren E; Qiao, Yusen; Bogart, Justin A; Cheisson, Thibault; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

2017-10-16

Purification of rare earth elements is challenging due to their chemical similarities. All of the deployed separation methods rely on thermodynamic properties, such as distribution equilibria in solvent extraction. Rare-earth-metal separations based on kinetic differences have not been examined. Herein, we demonstrate a new approach for rare-earth-element separations by exploiting differences in the oxidation rates within a series of rare earth compounds containing the redox-active ligand [{2-(tBuN(O))C 6 H 4 CH 2 } 3 N] 3- . Using this method, a single-step separation factor up to 261 was obtained for the separation of a 50:50 yttrium-lutetium mixture. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection

NASA Astrophysics Data System (ADS)

Yan, Ping; He, Man; Chen, Beibei; Hu, Bin

2017-10-01

In this work, di(2-ethylhexyl)phosphoric acid (P204) grafted magnetic nanoparticles were synthesized by fabricating P204 onto Fe3O4@TiO2 nanoparticles based on Lewis acid-base interaction between Ti and phosphate group under weakly acidic condition. The prepared Fe3O4@TiO2@P204 nanoparticles exhibited excellent selectivity for rare earth elements, and good anti-interference ability. Based on it, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for fast preconcentration and determination of trace rare earth elements in environmental samples. Under the optimal conditions, the detection limits of rare earth elements were in the range of 0.01 (Tm)-0.12 (Nd) ng L- 1 with an enrichment factor of 100-fold, and the relative standard deviations ranged from 4.9 (Pr) to 10.7% (Er). The proposed method was successfully applied to the determination of rare earth elements in environmental samples, including river water, lake water, seawater and sediment.

Shield Through Rejuvenated Stage Volcanism On Kauai and Niihau, Hawaii

NASA Astrophysics Data System (ADS)

Cousens, B.; Clague, D. A.

2013-12-01

Kauai and Niihau are the northwesternmost large islands in the Hawaiian chain and consist of shield, rare postshield, and abundant rejuvenated stage lavas. We present new geochronological, geochemical and isotopic data for all phases of volcanic activity on the adjacent islands. K-Ar ages show Niihau shield volcanism occurred from 6.3-4.4 Ma, and K-Ar and new Ar-Ar ages for postshield volcanism range from 5.4-4.7 Ma. Kauai shield volcanism (K-Ar) overlaps with shield volcanism on Niihau. A new Ar-Ar age for a Kauai postshield dike is 4.4 Ma, older than previously-dated postshield lavas (3.95-3.58 Ma). New Ar-Ar ages show that Kauai rejuvenated stage volcanism began prior to 3.42 Ma (Izuka & Sherrod, 2011), compared to ~2.3 Ma on Niihau. Tholeiitic shield lavas from Kauai vary only slightly in trace element chemistry but have variable isotopic compositions. Subtle trends in some trace element and isotopic ratios between Napali Member shield lavas from the east and west side of Kauai support the two-shield hypothesis of Holcomb et al. (1997). Shield lavas from Niihau are chemically similar to those on Kauai, although Niihau tholeiites extend to higher 143Nd/144Nd ratios. Onland and submarine postshield rocks from Niihau are slightly more alkaline and LREE-enriched compared to shield lavas, but postshield rocks from Kauai are more chemically evolved, more LREE-enriched, and have more depleted Sr and Nd isotopic signatures than Kauai tholeiites. Postshield rocks on Kauai overlap in apparent age with lavas that are chemically like later rejuvenated stage lavas, suggesting either interfingering of the chemically distinct lavas or problems with the K-Ar ages. Rejuvenated stage lavas from the two islands differ dramatically; Kauai lavas are alkaline, LREE-enriched, and have even more depleted Sr and Nd isotopic compositions than postshield lavas, whereas Niihau lavas are only mildly alkaline, have lower REE abundances than postshield basalts, but isotopically are like Kauai rejuvenated rocks. Niihau rejuvenated lavas are shifted to slightly higher 87Sr/86Sr at a given 143Nd/144Nd than Kauai rejuvenated lavas, consistent with an enhanced carbonate component in their source (Dixon et al., 2008). Rejuvenated stage lavas have a diagnostic Sr and Nd isotopic signature on both Kauai and Niihau, but on Kauai the isotopic shift begins during the postshield stage. For Kauai, age and geochemical data suggest that volcanic activity was near-continuous from shield to postshield to rejuvenated stage, with a change in mantle source at the postshield to rejuvenated transition. On Niihau, a prominent erosional and age gap separates onland shield and postshield rocks from the rejuvenated stage lavas, with the change in mantle sources at the beginning of the rejuvenated stage. ROV dives on six vents off the NW coast of Niihau recovered a suite of highly alkaline basanites with REE patterns similar to Kauai rejuvenated lavas but with isotopic ratios spanning the range of Niihau shield and postshield lavas. These alkaline lavas are highly vesicular and more altered than rejuvenated stage Niihau rocks, are undated, but may straddle the postshield to rejuvenated stage transition. No equivalents exist at other Hawaiian volcanoes.

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

Selle, J E

Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussedmore » in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.« less

Trace element partitioning in rock forming minerals of co-genetic, subduction-related alkaline and tholeiitic mafic rocks in the Ural Mountains, Russia

NASA Astrophysics Data System (ADS)

Krause, J.; Brügmann, G. E.; Pushkarev, E. V.

2009-04-01

The partitioning of trace elements between rock forming minerals in igneous rocks is largely controlled by physical and chemical parameters e.g. temperature, pressure and chemical composition of the minerals and the coexisting melt. In the present study partition coefficients for REE between hornblende, orthopyroxene, feldspars, apatite and clinopyroxene in a suite of co-genetic alkaline and tholeiitic mafic rocks from the Ural Mountains (Russia) were calculated. The results give insights to the influence of the chemical composition of the parental melt on the partitioning behaviour of the REE. Nepheline-bearing, alkaline melanogabbros (tilaites) are assumed to represent the most fractionated products of the melt that formed the ultramafic cumulates in zoned mafic-ultramafic complexes in the Ural Mountains. Co-genetic with the latter is a suite of olivine gabbros, gabbronorites and hornblende gabbros formed from a tholeiitic parental melt. Negative anomalies for the HFSE along with low Nb and Ta contents and a positive Sr anomaly indicate a subduction related origin of all parental melts. The nepheline gabbros consist predominantly of coarse-grained clinopyroxene phenocrysts in a matrix of fine grained clinopyroxene, olivine, plagioclase, K-feldspar and nepheline with accessory apatite. The tholeiitic gabbros have equigranular to porphyric textures with phenocrysts of olivine, pyroxene and hornblende in a plagioclase rich matrix with olivine hornblende, pyroxene and accessory apatite. Element concentrations of adjacent matrix grains and rims of phenochrysts were measured with LA-ICPMS. The distribution of REE between hornblende and clinopyroxene in the tholeiitic rocks is similar for most of the elements (DHbl•Cpx(La-Tm) = 2.7-2.8, decreasing to 2.6 and 2.4 for Yb and Lu, respectively). These values are about two times higher than published data (e.g. Ionov et al. 1997). Partition coefficients for orthopyroxene/clinopyroxene systematically decrease from the HREE (DOpx•Cpx(Lu) = 0.31) towards the LREE (DOpx•Cpx(Nd) = 0.01). The partition coefficients for plagioclase/clinopyroxene and K-feldspar/clinopyroxene in the alkaline melanogabbros decrease from the LREE (DPlg•Cpx(La) = 0.91, DK-fs•Cpx(La)=0.26) to the MREE (DPlg•Cpx(Sm) = 0.02, DK-fs•Cpx(Sm) = 0.006), but both mineral pairs have similar DEu (DPlg•Cpx(Eu) = 0.25, DK-fs•Cpx(Eu) = 0.23). Plagioclase/clinopyroxene partition coefficients for all REE in the tholeiitic gabbros are 3-5 times higher, if compared to those of the alkaline gabbros (DPlg•Cpx(La) = 1.7, DPlg•Cpx(Sm) = 0.034). Apatite/clinopyroxene partition coefficients for the REE decrease from the LREE (DAp•Cpx(La) = 65 in alkaline and 120 in tholeiitic gabbro) to the HREE (DAp•Cpx(Lu) = 4.5 in alkaline and 5.3 in tholeiitic gabbro). The lower partition coefficients for apatite/clinopyroxene and plagioclase/clinopyroxene in the alkaline melanogabbros can be explained by higher clinopyroxene/melt partition coefficients in this system. The higher Al2O3-content in clinopyroxene from the alkali gabbros (Al2O3 = 3.5-7 wt.%), if compared to clinopyroxene in the tholeiitic gabbros (Al2O3 = 2.0-4.5 wt.%) can account for a stronger partitioning of the REE into clinopyroxene in the alkaline rocks (e.g. Gaetani and Grove 1995). Experimental data by Gaetani (2004) also indicate a systematic increase of the Cpx/melt partition coefficients for the REE with increasing Al2O3 and Na2O contents of the parental melt in mafic systems. This is in agreement with the assumed compositional differences between the alkaline and the tholeiitic parental melts. Gaetani, G.A., 2004. Contributions to Mineralogy and Petrology, Vol. 147, 511-527. Gaetani, G.A., Grove, T.L, 1995. Geochimica et Cosmochimica Acta, Vol. 59, 1951-1962. Ionov, D.A., Griffin, W.L., O'Reily, S.Y., 1997. Chemical Geology, Vol. 141, 153-184.

Sr-Nd isotope geology and tectonomagmatic setting of the Dehsalm intrusives (Lut Block, Eastern Iran)

NASA Astrophysics Data System (ADS)

Arjmandzadeh, Reza; Francisco Santos, Jose; Ribeiro, Sara

2013-04-01

The Dehsalm porphyritic shallow intrusives belong to the Lut Block volcanic-plutonic belt (central eastern Iran). Previous research on alteration, mineralization and hydrothermal fluids indicates that a Cu-Mo porphyry type mineralization system is related with these intrusives (Arjmandzadeh et al., 2012). The rocks studied in this work range in composition from gabbro-diorite to granite, with dominance of monzonites and quartz monzonites, and have geochemical features of high-K calc alkaline to shoshonitic volcanic arc suites. The trends of major element oxides on Harker diagrams, together with textural evidence, point to the crystal fractionation of clinopyroxene, Ca - plagioclase, hornblende, apatite and oxide minerals. Primitive mantle - normalized trace element spider diagrams display strong enrichment in LILE, such as Rb, Ba and Cs, and depletions in some high field strength elements (HFSE), such as Nb, Ti, Y and HREE. Chondrite-normalized plots show significant LREE enrichments, high LaN/YbN (21.5 to 31.0) and the lack of Eu anomaly. Sr/Y and La/Yb ratios of Dehsalm intrusives are respectively 31.6-72.2 and 21.5-33.5, which reveals that, despite their K-rich composition, these rocks also have some adakitic affinity. A Rb-Sr whole rock-feldspar-biotite age of 33.4±1 Ma was obtained in a quartz monzonite sample; this date may be interpreted as close to the intrusion age, considering that the chosen sample is almost unaltered and should have suffered fast cooling. The obtained age coincides, within error, with a previous geochronological result in a similar rock from the Chah-Shaljami area (Arjmandzadeh et al., 2011), further northwest along the eastern border of the Lut Block. 87Sr/86Sr(33Ma) and ɛNd(33Ma) values range from 0.70481 to 0.70508 and from +1.5 to +2.5, respectively, which fits into a supra-subduction mantle wedge source for the parental melts and indicates that crustal contribution for magma diversification was not relevant. Sr and Nd isotope compositions together with major and trace element geochemistry point to the origin of the parental magmas by melting of a metasomatized mantle source, with garnet behaving as a residual phase, whilst phlogopite was an important contributor to the generated melts. Both geochemical features of Dehsalm porphyries and its association with Cu-Mo mineralization agree with a mature continental arc setting related to the convergence of Afghan and Lut plates during Oligocene. The data on the Dehsalm granitoids reveal a strong affinity with the contemporary rocks from Chah-Shaljami, studied in a previous work (Arjmandzadeh et al., 2011). Moreover, the wider range of compositions (including more mafic compositions) at Dehsalm provides additional support for the suggestion that parental magmas have a mantle origin. Acknowledgements This research was financially supported by the Geobiotec Research Unit (funded by the Portuguese Foundation for Science and Technology, through project PEst-C/CTE/UI4035/2011), University of Aveiro, Portugal. Ministry of Sciences, Research and Technology of Iran granted a sabbatical scholarship of R. Arjmandzadeh in Portugal References Arjmandzadeh, R., Karimpour, M.H., Mazaheri, S.A., Santos, J.F., Medina, J., Homam, S.M., 2011. Sr-Nd isotope geochemistry and petrogenesis of the Chah-Shaljami granitoids (Lut Block, Eastern Iran). Journal of Asian Earth Sciences 41: p. 283-296. Arjmandzadeh, R., Karimpour, M.H., Mazaheri, S.A., Santos, J.F., Medina, J., Homam, S.M., 2012. Petrogenesis, tectonomagmatic setting and mineralization potential of Dehsalm granitoids, Lut block, Eastern Iran. Journal of Earth Sciences, accepted.

Properties of iron alloys under the Earth's core conditions

NASA Astrophysics Data System (ADS)

Morard, Guillaume; Andrault, Denis; Antonangeli, Daniele; Bouchet, Johann

2014-05-01

The Earth's core is constituted of iron and nickel alloyed with lighter elements. In view of their affinity with the metallic phase, their relative high abundance in the solar system and their moderate volatility, a list of potential light elements have been established, including sulfur, silicon and oxygen. We will review the effects of these elements on different aspects of Fe-X high pressure phase diagrams under Earth's core conditions, such as melting temperature depression, solid-liquid partitioning during crystallization, and crystalline structure of the solid phases. Once extrapolated to the inner-outer core boundary, these petrological properties can be used to constrain the Earth's core properties.

Grain-scale Sr isotope heterogeneity in amphibolite (retrograded UHP eclogite, Dabie terrane): Implications for the origin and flow behavior of retrograde fluids during slab exhumation

NASA Astrophysics Data System (ADS)

Guo, Shun; Yang, Yueheng; Chen, Yi; Su, Bin; Gao, Yijie; Zhang, Lingmin; Liu, Jingbo; Mao, Qian

2016-12-01

To constrain the origin and flow behavior of amphibolite-facies retrograde fluids during slab exhumation, we investigate the textures, trace element contents, and in situ strontium (Sr) isotopic compositions (using LA-MC-ICP-MS) of multiple types of epidote and apatite in the UHP eclogite and amphibolites from the Hualiangting area (Dabie terrane, China). The UHP epidote porphyroblasts in the eclogite (Ep-E), which formed at 28-30 kbar and 660-720 °C, contain high amounts of Sr, Pb, Th, Ba, and light rare earth elements (LREEs) and have a narrow range of initial 87Sr/86Sr ratios (0.70431 ± 0.00012 to 0.70454 ± 0.00010). Two types of amphibolite-facies epidote were recognized in the amphibolites. The first type of epidote (Ep-AI) developed in all the amphibolites and has slightly lower trace element contents than Ep-E. The Ep-AI has a same initial 87Sr/86Sr ratio range as the Ep-E and represents the primary amphibolite-facies retrograde product that is associated with an internally buffered fluid at 8.0-10.3 kbar and 646-674 °C. The other type of epidote (Ep-AII) occurs as irregular fragments, veins/veinlets, or reaction rims on the Ep-AI in certain amphibolites. Elemental X-ray maps reveal the presence of Ep-AI relics in the Ep-AII domains (appearing as a patchy texture), which indicates that Ep-AII most likely formed by the partial replacement of the Ep-AI in the presence of an infiltrating fluid. The distinctly lower trace element contents of Ep-AII are ascribed to element scavenging by a mechanism of dissolution-transport-precipitation during replacement. The Ep-AII in an individual amphibolite exhibits large intra- and inter-grain variations in the initial 87Sr/86Sr ratios (0.70493 ± 0.00030 to 0.70907 ± 0.00022), which are between those of the Ep-AI and granitic gneisses (wall rock of the amphibolites, 0.7097-0.7108). These results verify that the infiltrating fluid was externally derived from granitic gneisses. The matrix apatite in the amphibolites has the same initial 87Sr/86Sr ratio range as the Ep-AI, indicating that the amphibolite-facies fluid involved in the apatite crystallization was also internally derived. We propose that at least two separate stages of fluids were accounted for the amphibolite-facies retrogression of the Hualiangting eclogite. The fluid responsible for the growth of most of the amphibolite minerals was locally derived and behaved in a pervasive manner, whereas the influx of gneiss-derived fluid was transient, episodic, and highly channelized with a longer transport distance (> 60 m). The disparate origins and flow behavior of these fluids significantly influence the water budget and element transfer in exhumed HP-UHP slabs. This study also indicates that examining grain-scale Sr isotopic variations provides key information regarding the isotopic (dis)equilibrium, fluid origins, and fluid-flow regimes in metamorphic or metasomatic rocks that form in subduction-zone environments.

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

NASA Astrophysics Data System (ADS)

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

1984-11-01

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

Evaluation of Rare Earth Element Extraction from North Dakota Coal-Related Feed Stocks

NASA Astrophysics Data System (ADS)

Laudal, Daniel A.

The rare earth elements consist of the lanthanide series of elements with atomic numbers from 57-71 and also include yttrium and scandium. Due to their unique properties, rare earth elements are crucial materials in an incredible array of consumer goods, energy system components and military defense applications. However, the global production and entire value chain for rare earth elements is dominated by China, with the U.S. currently 100% import reliant for these critical materials. Traditional mineral ores including previously mined deposits in the U.S., however, have several challenges. Chief among these is that the content of the most critical and valuable of the rare earths are deficient, making mining uneconomical. Further, the supply of these most critical rare earths is nearly 100% produced in China from a single resource that is only projected to last another 10 to 20 years. The U.S. currently considers the rare earths market an issue of national security. It is imperative that alternative domestic sources of rare earths be identified and methods developed to produce them. Recently, coal and coal byproducts have been identified as one of these promising alternative resources. This dissertation details a study on evaluation of the technical and economic feasibility of rare earth element recovery from North Dakota lignite coal and lignite-related feedstocks. There were four major goals of this study: i) identify lignite or lignite-related feedstocks with total rare earth element content above 300 parts per million, a threshold dictated by the agency who funded this research as the minimum for economic viability, ii) determine the geochemistry of the feedstocks and understand the forms and modes of occurrence of the rare earth elements, information necessary to inform the development of extraction and concentration methods, iii) identify processing methods to concentrate the rare earth elements from the feedstocks to a target of two weight percent, a value that would be sufficient to leverage existing separation and refining methods developed for the traditional mineral ore industry, and iv) develop a process that is economically viable and environmentally benign. To achieve these overall goals, and to prove or disprove the research hypotheses, the research scope was broken down into three main efforts: i) sampling and characterization of potential feedstocks, ii) laboratory-scale development and testing of rare earth element extraction and concentration methods, and iii) process design and technical and economic feasibility evaluation. In total, 174 unique samples were collected, and several locations were identified that exceeded the 300 ppm total rare earth elements target. The results showed that on a whole sample basis, the rare earths are most concentrated in the clay-rich sediments associated with the coal seams, but on an ash basis in certain locations within certain coal seams the content is significantly higher, an unexpected finding given prior research. At Falkirk Mine near Underwood, North Dakota three coal seams were found to have elevated levels of rare earths, ranging from about 300 to 600 ppm on an ash basis. Additionally, exceptionally high rare earths content was found in samples collected from an outcropping of the Harmon-Hansen coal zone in southwestern North Dakota that contained 2300 ppm on an ash basis. The results dictated that extraction and concentration methods be developed for these rare earth element-rich coals, instead of the mineral-rich sediments. This effort also found that at a commercial-scale, due to non-uniformity of the rare earths content stratigraphically in the coal seams, selective mining practices will be needed to target specific locations within the seams. The bulk mining and blending practices as Falkirk Mine result in a relatively low total rare earths content in the feed coal entering the Coal Creek Power Station adjacent to the mine. Characterization of the coal samples identified that the predominant modes of rare earths occurrence in the lignite coals are associations with the organic matter, primarily as coordination complexes and a lesser amount as ion-exchangeable cations on oxygen functional groups. Overall it appears that about 80-95% of rare earths content in North Dakota lignite is organically associated, and not present in mineral forms, which due to the weak organic bonding, presented a unique opportunity for extraction. The process developed for extraction of rare earths was applied to the raw lignite coals instead of fly ash or other byproducts being investigated extensively in the literature. Rather, the process uses a dilute acid leaching process to strip the organically associated rare earths from the lignite with very high efficiency of about 70-90% at equilibrium contact times. Although the extraction kinetics are quite fast given commercial leaching operations, there is some tradeoff between extraction efficiency and contact time. (Abstract shortened by ProQuest.).

The Variscan calc-alkalic plutonism of western Corsica: mineralogy and major and trace element geochemistry

NASA Astrophysics Data System (ADS)

Cocherie, A.; Rossi, Ph.; Le Bel, L.

1984-10-01

Petrographic and structural observations on the calc-alkalic plutonism of western Corsica revealed the existence of several successively emplaced units associated with large basic bodies. The present mineralogical and geochemical study deals with the genesis, evolution and relationships of these different units. Basic plutonism is represented by three genetically linked types of rock: norites and troctolites with cumulate textures characterized by low REE contents and either no Eu anomaly or a positive Eu anomaly; gabbros with enriched LREE relatively to HREE patterns, probably close to an initial basaltic liquid; and diorites ranging up to charnockites which represent liquids evolved to varying degrees, mainly by fractional crystallization. Trace element data and studies on the evolution of pyroxene pairs demonstrate the consanguinity of these calc-alkaline basic rocks which are derived from a high alumina basaltic melt. The various granitoids (granodiorites, monzogranites and leucocratic monzogranites, i.e., adamellites) have distinct evolution trends as shown by the composition of their mafic minerals and by trace element distributions. They cannot be considered as being derivatives of the basic suite and they cannot be related by a common fractionation sequence. Rather, they represent distinctive batches of crustal anatexis. In addition, hybridization phenomena with the basic melt are noticed in granodiorites. The particular problem of the low La/Yb, Eu/Eu∗ and the high U, Th, Cs leucocratic monzogranites is discussed in detail. In addition to more conventional trace element diagrams, the simultaneous statistical treatment of all the geochemical data by correspondence factor analysis is shown to be a very use tool in distinguishing between the different units and to classify the elements according to their geochemical properties.

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

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Petrogenesis of an Early Cretaceous lamprophyre dike from Kyoto Prefecture, Japan: Implications for the generation of high-Nb basalt magmas in subduction zones

NASA Astrophysics Data System (ADS)

Imaoka, Teruyoshi; Kawabata, Hiroshi; Nagashima, Mariko; Nakashima, Kazuo; Kamei, Atsushi; Yagi, Koshi; Itaya, Tetsumaru; Kiji, Michio

2017-10-01

We studied a 107 Ma vogesite (a kind of lamprophyre with alkali-feldspar > plagioclase, and hornblende ± clinopyroxene ± biotite) dike in the Kinki district of the Tamba Belt, Kyoto Prefecture, SW Japan, using petrography, mineralogy, K-Ar ages, and geochemistry to evaluate its petrogenesis and tectonic implications. The dike has the very specific geochemical characteristics of a primitive high-Mg basalt, with 48-50 wt.% SiO2 (anhydrous basis), high values of Mg# (67.3-72.4), and high Cr ( 431 ppm), Ni ( 371 ppm), and Co ( 52 ppm) contents. The vogesite is alkaline and ne-normative with high concentrations of large ion lithophile elements (LILEs: Sr = 1270-2200 ppm, Ba = 3910-26,900 ppm), light rare earth elements (LREEs) [(La/Yb)n = 58-62), and high field strength elements (HFSEs: TiO2 = 1.5-1.8 wt.%, Nb = 24-33 ppm, Zr = 171-251 ppm), and the vogesite can be classified as a high-Nb basalt (HNB). The vogesite was formed by the lowest degree of melting of metasomatized mantle in the garnet stability field, and it may also have been formed at higher melting pressures than other Kyoto lamprophyres. The low degree of melting is the primary reason for the high-Nb content of the vogesite, not mantle metasomatism, and a higher degree of melting would have changed the primary magma composition from a HNB to a Nb-enriched basalt (NEB). The vogesite magma was contaminated at an early stage of its development by melts derived from sediments drawn down a subduction zone, as indicated by some geochemical indices and the initial Nd isotope ratios. The vogesite exhibits positive correlations between εSr(107 Ma) values (5.4-50.9) and its high Ba and Sr concentrations, and it has a limited range of εNd(107 Ma) values (+ 0.97 to + 2.4). The fact that the vogesite contains centimeter-sized xenoliths of chert, which are composed of polycrystalline quartz, calcite, barite, pyrite, and magnetite, indicates that the barium contamination took place during the ascent of the lamprophyric magma through the upper crust. The episode of magmatism at c. 107 Ma extended regionally from the Kinki district, through the Chugoku district and North Kyushu in SW Japan, to Korea as a result of slab roll-back at the eastern margin of Asia.

Constraining lithospheric removal and asthenospheric input to melts in Central Asia: A geochemical study of Triassic to Cretaceous magmatic rocks in the Gobi Altai (Mongolia)

NASA Astrophysics Data System (ADS)

Sheldrick, Thomas C.; Barry, Tiffany L.; Van Hinsbergen, Douwe J. J.; Kempton, Pamela D.

2018-01-01

Throughout northeast China, eastern and southern Mongolia, and eastern Russia there is widespread Mesozoic intracontinental magmatism. Extensive studies on the Chinese magmatic rocks have suggested lithospheric mantle removal was a driver of the magmatism. The timing, distribution and potential diachroneity of such lithospheric mantle removal remains poorly constrained. Here, we examine successions of Mesozoic lavas and shallow intrusive volcanic plugs from the Gobi Altai in southern Mongolia that appear to be unrelated to regional, relatively small-scale deformation; at the time of magmatism, the area was 200 km from any active margin, or, after its Late Jurassic-Early Cretaceous closure, from the suture of the Mongol-Okhotsk Ocean. 40Ar/39Ar radiometric age data place magmatic events in the Gobi Altai between 220 to 99.2 Ma. This succession overlaps Chinese successions and therefore provides an opportunity to constrain whether Mesozoic lithosphere removal may provide an explanation for the magmatism here too, and if so, when. We show that Triassic to Lower Cretaceous lavas in the Gobi Altai (from Dulaan Bogd, Noyon Uul, Bulgantiin Uul, Jaran Bogd and Tsagaan Tsav) are all light rare-earth element (LREE) and large-ion lithophile element (LILE)-enriched, with negative Nb and Ta anomalies (Nb/La and Ta/La ≤ 1). Geochemical data suggest that these lavas formed by low degrees of partial melting of a metasomatised lithospheric mantle that may have been modified by melts derived from recycled rutile-bearing eclogite. A gradual reduction in the involvement of garnet in the source of these lavas points towards a shallowing of the depth of melting after 125 Ma. By contrast, geochemical and isotope data from the youngest magmatic rocks in the area - 107-99 Ma old volcanic plugs from Tsost Magmatic Field - have OIB-like trace element patterns and are interpreted to have formed by low degrees of partial melting of a garnet-bearing lherzolite mantle source. These rocks did not undergo significant crustal contamination, and were derived from asthenospheric mantle. The evidence of a gradual shallowing of melting in the Gobi lava provinces, culminating in an asthenospheric source signature in the youngest magmatic rocks is similar to examples from neighboring China, emphasising the wide-scale effect of a regional Mesozoic magmatic event during similar time periods. We suggest that Mongolia underwent lithospheric thinning/delamination during the Mesozoic (between 125 and 107 Ma) with patchy areas thinning sufficiently to enable the generation of relatively small-scale asthenospheric-derived magmatism to predominate in the late Cretaceous.

Petrogenesis and tectonic significance of the late Triassic mafic dikes and felsic volcanic rocks in the East Kunlun Orogenic Belt, Northern Tibet Plateau

NASA Astrophysics Data System (ADS)

Hu, Yan; Niu, Yaoling; Li, Jiyong; Ye, Lei; Kong, Juanjuan; Chen, Shuo; Zhang, Yu; Zhang, Guorui

2016-02-01

We present zircon U-Pb ages and geochemical data on the late Triassic mafic dikes (diabase) and felsic volcanic rocks (rhyolite and rhyolitic tuffs) in the East Kunlun Orogenic Belt (EKOB). These rocks give a small age window of 228-218 Ma. The mafic dikes represent evolved alkaline basaltic melts intruding ~ 8-9 Myrs older and volumetrically more abundant A-type granite batholith. Their rare earth element (REE) and multi-element patterns are similar to those of the present-day ocean island basalts (OIBs) except for a weak continental crustal signature (i.e., enrichment of Rb and Pb and weak depletion of Nb, Ta and Ti). Their trace element characteristics together with the high 87Sr/86Sr (0.7076-0.7104), low εNd(t) (- 2.18 to - 3.46), low εHf(t) (- 2.85 to - 4.59) and variable Pb isotopic ratios are consistent with melts derived from metasomatized subcontinental lithospheric mantle with crustal contamination. The felsic volcanic rocks are characterized by high LREE/HREE (e.g., [La/Yb]N of 5.71-17.00) with a negative Eu anomaly and strong depletion in Sr and P, resembling the model upper continental crust (UCC). Given the high 87Sr/86Sr (0.7213-0.7550) and less negative εNd(t) (- 3.83 to - 5.09) and εHf(t) (- 3.06 to - 3.83) than the UCC plus the overlapping isotopes with the mafic dikes and high Nb-Ta rhyolites, the felsic volcanic rocks are best interpreted as resulting from melting-induced mixing with 45-50% crustal materials and 50-55% mantle-derived mafic melts probably parental to the mafic dikes. Such mantle-derived melts underplated and intruded the deep crust as juvenile crustal materials. Partial melting of such juvenile crust produced felsic melts parental to the felsic volcanic rocks in the EKOB. We hypothesize that the late Triassic mafic dikes and felsic volcanic rocks are associated with post-collisional extension and related orogenic collapse. Such processes are probably significant in causing asthenospheric upwelling, decompression melting, induced melting of the prior metasomatized mantle lithosphere and the existing crust. This work represents our ongoing effort in understanding the origin of the juvenile crust and continental crustal accretion through magmatism in the broad context of orogenesis from seafloor subduction to continental collision and to post-collisional processes.

Age and geochemistry of Neoproterozoic granitoids in the Songnen-Zhangguangcai Range Massif, NE China: Petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Luan, Jin-Peng; Xu, Wen-Liang; Wang, Feng; Wang, Zhi-Wei; Guo, Peng

2017-10-01

This study presents new zircon U-Pb ages and geochemical data for Neoproterozoic granitoids in the Songnen-Zhangguangcai Range Massif (SZRM) of NE China. This dataset provides insights into the Neoproterozoic tectonic setting of the SZRM and the links between this magmatism and the evolution of the Rodinia supercontinent. The zircon U-Pb dating indicates that the Neoproterozoic magmatism within the SZRM can be subdivided into two stages: (1) a ∼917-911 Ma suite of syenogranites and monzogranites, and (2) an ∼841 Ma suite of granodiorites. The 917-911 Ma granitoids contain high concentrations of SiO2 (67.89-71.18 wt.%), K2O (4.24-6.91 wt.%), and Al2O3 (14.89-16.14 wt.%), and low concentrations of TFe2O3 (1.63-3.70 wt.%) and MgO (0.53-0.88 wt.%). They are enriched in the light rare earth elements (LREE) and the large ion lithophile elements (LILE), are depleted in the heavy REE (HREE) and the high field strength elements (HFSE; e.g., Nb, Ta, and Ti), and have slightly positive Eu anomalies, indicating that they are geochemically similar to high-K adakitic rocks. They have zircon εHf (t) values and TDM2 ages from -4.4 to +1.5 and 1915 Ma to 1592 Ma, respectively, suggesting that they were derived from a primary magma generated by the partial melting of ancient thickened lower crustal material. In comparison, the 841 Ma granodiorites contain relatively low concentrations of Al2O3 (14.50-14.58 wt.%) and K2O (3.27-3.29 wt.%), relatively high concentrations of TFe2O3 (3.78-3.81 wt.%) and the HREE, have negative Eu anomalies, and have zircon εHf (t) values and TDM2 ages from -4.7 to +1.0 and 1875 to 1559 Ma, respectively. These granodiorites formed from a primary magma generated by the partial melting of ancient crustal material. The ∼917-911 Ma magmatism within the SZRM is inferred to have formed in an orogenic setting, whereas the ∼841 Ma magmatism formed in an anorogenic setting related to either a post-orogenic tectonic event or the onset of Neoproterozoic continental rifting. It is proposed that the microcontinental massifs within the eastern central Asian orogenic belt of NE China formed during or following the final stage of assembly of Rodinia before rifting away from the Tarim Craton in response to the Rodinia breakup.

First results from TN273 studies of the SE Mariana Forearc rift

NASA Astrophysics Data System (ADS)

Ribeiro, J. M.; Stern, R. J.; Kelley, K. A.; Shaw, A. M.; Shimizu, N.; Martinez, F.; Ishii, T.; Ishizuka, O.; Manton, W. I.

2012-12-01

TN 273 aboard R/V Thomas Thompson (Dec. 22 2011- Jan. 22 2012) studied an unusual region of rifting affecting the southern Mariana forearc S.W. of Guam. The S.E. Mariana Forearc Rift (SEMFR) formed by diffuse tectonic and volcanic deformation (Martinez and Sleeper, this meeting) ~2.7-3.7 Ma ago to accommodate opening of the southernmost Mariana Trough backarc basin. A total of 730 km linear-track of SEMFR seafloor was surveyed with deep-towed side-scan sonar IMI-30. 14 dredges provided samples of SEMFR igneous rocks, analyzed for whole rock (WR) and glass compositions. These new results coupled with results of earlier investigations confirm that SEMFR is dominated by Miocene lavas along with minor gabbro and diabase. SEMFR lavas range in major element composition from primitive basalt to fractionated andesite (Mg# = 0.36-0.73; SiO2 = 50-57 wt%), mainly controlled by crystal fractionation. Rare Earth Element (REE) patterns range from LREE-depleted, N-MORB-like to flat patterns, reflecting different mantle processes (i.e. different sources, degree of melting …). Glassy rinds and olivine-hosted melt inclusions in these lavas contain variable volatile compositions (F = 75-358 ppm, S = 35-1126 ppm, Cl= 74-1400 ppm, CO2 = 15-520 ppm, 0.36-2.36 wt% H2O). SEMFR lavas show spider diagrams with positive anomalies in LILE and negative anomalies in HSFE. SEMFR lavas have backarc basin-like (BAB-like) chemical composition (H2O < 2.5wt%, Ba/Yb~20, Nb/Yb~1 and ɛNd~9) along with stronger enrichment in Rb and Cs than arc and BAB lavas, as demonstrated by their higher Rb/Th and Cs/Ba ratios in WR and glasses, which may reflect the role of the ultra-shallow fluids. Ultra-shallow fluids are derived from the top of the subducting slab, beneath the forearc, where most of the water and the fluid-mobile elements (Rb, Cs, Ba,) are thought to be released (Schmidt and Poli, 1998, EPSL, Savov et al., 2005, G-3). Our results suggest that i) SEMFR lavas formed by metasomatism of a BAB mantle source by ultra-shallow fluids, likely released from subducted sediments and the altered oceanic crust; and ii) the ultra-shallow fluid is aqueous and is characterized by enrichment in Cs and Rb, suggesting that Cs and Rb are decoupled from Ba in ultra-shallow subduction processes.

Antibacterial, Antifungal and Nematicidal Activities of Rare Earth Ions.

PubMed

Wakabayashi, Tokumitsu; Ymamoto, Ayumi; Kazaana, Akira; Nakano, Yuta; Nojiri, Yui; Kashiwazaki, Moeko

2016-12-01

Despite the name, rare earth elements are relatively abundant in soil. Therefore, these elements might interact with biosphere during the history of life. In this study, we have examined the effect of rare earth ions on the growth of bacteria, fungi and soil nematode. All rare earth ions, except radioactive promethium that we have not tested, showed antibacterial and antifungal activities comparable to that of copper ions, which is widely used as antibacterial metals in our daily life. Rare earth ions also have nematicidal activities as they strongly perturb the embryonic development of the nematode, Caenorhabditis elegans. Interestingly, the nematicidal activity increased with increasing atomic number of lanthanide ions. Since the rare earth ions did not show high toxicity to the human lymphoblastoid cell line or even stimulate the growth of the cultured cells at 1 mM, it raised the possibility that we can substitute rare earth elements for the antibacterial metals usually used because of their safety.

Petrogenesis of fertile mantle peridotites from the Monte del Estado massif (southwest Puerto Rico): a preserved section of Proto-Caribbean oceanic lithospheric mantle?

NASA Astrophysics Data System (ADS)

Marchesi, Claudio; Jolly, Wayne T.; Lewis, John F.; Garrido, Carlos J.; Proenza, Joaquín. A.; Lidiak, Edward G.

2010-05-01

The Monte del Estado massif is the largest and northernmost serpentinized peridotite belt in southwest Puerto Rico. It is mainly composed of spinel lherzolite and minor harzburgite with variable clinopyroxene modal abundances. Mineral and whole rock major and trace element compositions of peridotites coincide with those of fertile abyssal peridotites from mid ocean ridges. Peridotites lost 2-14 wt% of relative MgO and variable amounts of CaO by serpentinization and seafloor weathering. HREE contents in whole rock indicate that the Monte del Estado peridotites are residues after low to moderate degrees (2-15%) of fractional partial melting in the spinel stability field. However, very low LREE/HREE and MREE/HREE in clinopyroxene cannot be explained by melting models of a spinel lherzolite source and support that the Monte del Estado peridotites experienced initial low fractional melting degrees (~ 4%) in the garnet stability field. The relative enrichment of LREE in whole rock is not due to secondary processes but probably reflects the capture of percolating melt fractions along grain boundaries or as microinclusions in minerals, or the presence of exotic micro-phases in the mineral assemblage. We propose that the Monte del Estado peridotite belt represents a section of ancient Proto-Caribbean (Atlantic) lithospheric mantle originated by seafloor spreading between North and South America in the Late Jurassic-Early Cretaceous. This portion of oceanic lithospheric mantle was subsequently trapped in the forearc region of the Greater Antilles paleo-island arc generated by the northward subduction of the Caribbean plate beneath the Proto-Caribbean ocean. Finally, the Monte del Estado peridotites belt was emplaced in the Early Cretaceous probably as result of the change in subduction polarity of the Greater Antilles paleo-island arc without having been significantly modified by subduction processes.

Intraplate 'typical' and Ca-rich igneous rocks associated with carbonatites in Baluchistan, Middle East

NASA Astrophysics Data System (ADS)

Romanko, Alexander

2010-05-01

Islamic republic of Iran We present some interesting materials on a poorly studied Neogene-(Quaternary) igneous rocks of Baluchistan and Sistan province, east Iran. They were received by a group led by a regional specialists E. Romanko, A. Hushmanzadeh and M.A.A. Nogol Sadat. Some important features on the rock studied are as follows: mainly K-Na subalkaline rock affinity (also alkaline one too) with a middle K), not very High-Ti, not high, deep 87Sr/86Sr (ISr) = 0.7039 +/- 2 (trachyandesite) and 0.7049 +/- 3 (trachybasalt, both data by GIN RAS, Russia) alongside the 0.7049 on a vulcanite (Camp & Griffis, 1982), LREE-enrichment with a high LREE/HREE (La - more than 32 ppm), and a characteristical Eu/Eu* more than 1.1; up to high - 1/3 of CaO and up to a high - 0.45% of Sr in basic trachyandesites (meaning the real carbonatites ca 200 km to the east, Hanneshin, Afghanistan), complex correlation of some characteristical elements; then-High-Ti (rhutile, Ti-hornblende) and High-Ca phases (clinocoizite, also, Ca- rich ceolie - vayrakite is proposed), replacement of primary minerals due to a fairly strong rock-fluid interaction. North-East tectonic-magmatic +/- metallogenic (economic regional Cu-Au +/- Pb, Zn, poor Ag, PGE, As, Hg, Bi etc. - e.x., Anarak deposits (E.Romanko, 1984) ) zonation, related to the famous subduction of Arabian plate, exists, e.x. (calc-alkaline /1/ - intraplate /2/ ): 1: Eocene shoshonites - Paleocene-Oligocene calc-alkaline intrusives - Miocene-Recent calc-alkaline volcanic (-plutonic) rocks and 2: Paleogene? (Lut block)-Neogene subalkaline rocks - Quaternary Afghanistan carbonatites etc. Alpine compression on the moderate subductional depths up to 200 km (Trubitsin et al., 2004) in the Central Iran, at least, partly compensated, as proposed, by contemporaneous/ younger Pg?-N-Q extensional intraplate magmatism of the East Iran/ Afghanistan and nearby area.

75 FR 25850 - Materials Strategy Request for Information

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-10

... (DOE) is seeking information from stakeholders on rare earth elements and other materials used in... strategic plan for addressing the role of rare earth elements and other materials in energy technologies and...

Anthropogenic disturbance of element cycles at the Earth's surface.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard

2012-08-21

The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes.

Uncovering the end uses of the rare earth elements.

PubMed

Du, Xiaoyue; Graedel, T E

2013-09-01

The rare earth elements (REE) are a group of fifteen elements with unique properties that make them indispensable for a wide variety of emerging and conventional established technologies. However, quantitative knowledge of REE remains sparse, despite the current heightened interest in future availability of the resources. Mining is heavily concentrated in China, whose monopoly position and potential restriction of exports render primary supply vulnerable to short term disruption. We have drawn upon the published literature and unpublished materials in different languages to derive the first quantitative annual domestic production by end use of individual rare earth elements from 1995 to 2007. The information is illustrated in Sankey diagrams for the years 1995 and 2007. Other years are available in the supporting information. Comparing 1995 and 2007, the production of the rare earth elements in China, Japan, and the US changed dramatically in quantities and structure. The information can provide a solid foundation for industries, academic institutions and governments to make decisions and develop strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Bioleaching of rare earth elements from monazite sand.

PubMed

Brisson, Vanessa L; Zhuang, Wei-Qin; Alvarez-Cohen, Lisa

2016-02-01

Three fungal strains were found to be capable of bioleaching rare earth elements from monazite, a rare earth phosphate mineral, utilizing the monazite as a phosphate source and releasing rare earth cations into solution. These organisms include one known phosphate solubilizing fungus, Aspergillus niger ATCC 1015, as well as two newly isolated fungi: an Aspergillus terreus strain ML3-1 and a Paecilomyces spp. strain WE3-F. Although monazite also contains the radioactive element Thorium, bioleaching by these fungi preferentially solubilized rare earth elements over Thorium, leaving the Thorium in the solid residual. Adjustments in growth media composition improved bioleaching performance measured as rare earth release. Cell-free spent medium generated during growth of A. terreus strain ML3-1 and Paecilomyces spp. strain WE3-F in the presence of monazite leached rare earths to concentrations 1.7-3.8 times those of HCl solutions of comparable pH, indicating that compounds exogenously released by these organisms contribute substantially to leaching. Organic acids released by the organisms included acetic, citric, gluconic, itaconic, oxalic, and succinic acids. Abiotic leaching with laboratory prepared solutions of these acids was not as effective as bioleaching or leaching with cell-free spent medium at releasing rare earths from monazite, indicating that compounds other than the identified organic acids contribute to leaching performance. © 2015 Wiley Periodicals, Inc.

Effect of Solution Treatment on Microstructure and Properties of Gd - AZ91 Magnesium Alloy

NASA Astrophysics Data System (ADS)

Li, Yao; Wang, Huiling

2018-01-01

In this paper, the Gd-AZ91 alloy was manufactured by adding rare earth element Gd in AZ91 magnesium alloy. The effects of solution treatment on the microstructures of rare earth elements Gd were investigated by means of optical microscopy, scanning electron microscopy, X-ray diffraction analysis and equipment for testing mechanical properties. The experimental results show that the addition of rare earth element Gd in AZ91 magnesium alloy can refine the alloy grain, turn β-Mg17Al12 phase into a discontinuous network or point structure, and produce granular compound Al2Gd in the alloy; when solution temperature is about 380 °C, the alloy structure is the best, the tensile strength of the alloy is the largest with the value larger than 250Mpa; when the solution temperature exceeds 380 °C, the alloy structure is coarsened and the mechanical properties of the alloy are reduced. With the increase of rare earth element Gd content, the tensile strength of the alloy shows a tendency to increase gradually, which Indicates that the addition of a certain amount of rare earth elements Gd can improve the plasticity of the alloy.

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

NASA Technical Reports Server (NTRS)

Sato, M.

1985-01-01

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

NASA Astrophysics Data System (ADS)

O'Rourke, J. G.; Stevenson, D. J.

2015-12-01

Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer might inhibit the initialization of the dynamo.

Rare Earth Element Geochemistry for Produced Waters, WY

DOE Data Explorer

Quillinan, Scott; Nye, Charles; McLing, Travis; Neupane, Hari

2016-06-30

These data represent major, minor, trace, isotopes, and rare earth element concentrations in geologic formations and water associated with oil and gas production. *Note - Link below contains updated version of spreadsheet (6/14/2017)

[Leaching of Rare Earth Elements from Coal Ashes Using Acidophilic Chemolithotrophic Microbial Communities].

PubMed

Muravyov, M I; Bulaev, A G; Melamud, V S; Kondrat'eva, T F

2015-01-01

A method for leaching rare earth elements from coal ash in the presence of elemental sulfur using communities of acidophilic chemolithotrophic microorganisms was proposed. The optimal parameters determined for rare element leaching in reactors were as follows: temperature, 45 degrees C; initial pH, 2.0; pulp density, 10%; and the coal ash to elemental sulfur ratio, 10 : 1. After ten days of leaching, 52.0, 52.6, and 59.5% of scandium, yttrium, and lanthanum, respectively, were recovered.

Element Abundances in Meteorites and the Earth: Implication for the Accretion of Planetary Bodies

NASA Astrophysics Data System (ADS)

Mezger, K.; Vollstaedt, H.; Maltese, A.

2017-12-01

Essentially all known inner solar system materials show near chondritic relative abundances of refractory elements and depletion in volatile elements. To a first approximation volatile element depletion correlates with the respective condensation temperature (TC) of the elements. Possible mechanisms for this depletion are incomplete condensation and partial loss by evaporation caused by heating prior to or during the planetesimal accretion. The stable isotope compositions of almost all moderately volatile elements in different meteorite classes show only minor, or no evidence for a Rayleigh-type fractionation that could be attributed to partial condensation or evaporation. The different classes of meteorites also show that the degree of depletion in their parent bodies (i.e. mostly planetesimals) is quite variable, but nevertheless systematic. For primitive and least disturbed carbonaceous chondrites the element depletion pattern is a smooth function of TC. The accessible silicate Earth also shows this general depletion pattern, but in detail it is highly complex and requires differentiation processes that are not solely controlled by TC. If only highly lithophile elements are considered the depletion pattern of the silicate Earth reveals a step function that shows that moderately volatile lithophile elements have abundances that are ca. 0.1 times the chondritic value, irrespective of their TC. This element pattern observed for bulk silicate Earth can be modelled as a mixture of two distinct components: ca. 90% of a strongly reduced planetary body that is depleted in highly volatile elements and ca. 10% of a more volatile element rich and oxidized component. This mixture can account for the apparent Pb- paradox observed in melts derived from the silicate Earth and provides a time constraint for the mixing event, which is ca. 70 My after the beginning of the solar system. This event corresponds to the giant impact that also formed the Moon.

Recovery of rare earths from spent NdFeB magnets of wind turbine: Leaching and kinetic aspects.

PubMed

Kumari, Aarti; Sinha, Manish Kumar; Pramanik, Swati; Sahu, Sushanta Kumar

2018-05-01

Increasing demands of rare earth (RE) metals for advanced technological applications coupled with the scarcity of primary resources have led to the development of processes to treat secondary resources like scraps or end of life products that are often rich in such metals. Spent NdFeB magnet may serve as a potential source of rare earths containing around ∼30% of neodymium and other rare earths. In the present investigation, a pyro-hydrometallurgical process has been developed to recover rare earth elements (Nd, Pr and Dy) from the spent wind turbine magnet. The spent magnet is demagnetized and roasted at 1123 K to convert rare earths and iron to their respective oxides. Roasting of the magnet not only provides selectivity, but enhances the leaching efficiency also. The leaching of the roasted sample with 0.5 M hydrochloric acid at 368 K, 100 g/L pulp density and 500 rpm for 300 min selectively recovers the rare earth elements almost quantitatively leaving iron oxide in the residue. Leaching of rare earth elements with hydrochloric acid follows the mixed controlled kinetic model with activation energy (E a ) of 30.1 kJ/mol in the temperature range 348-368 K. The leaching mechanism is further established by characterizing the leach residues obtained at different time intervals by scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Individual rare earth elements from the leach solution containing 16.8 g/L of Nd, 3.8 g/L Pr, 0.28 g/L of Dy and other minor impurity elements could be separated by solvent extraction. However, mixed rare earth oxide of 99% purity was produced by oxalate precipitation followed by roasting. The leach residue comprising of pure hematite has a potential to be used as pigment or can find other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Are C1 chondrites chemically fractionated - A trace element study

NASA Technical Reports Server (NTRS)

Ebihara, M.; Wolf, R.; Anders, E.

1982-01-01

Six C1 chondrite samples and a C2 xenolith from the Plainview H5 chondrite were analyzed by radiochemical neutron activation for a large variety of elements, including rare earths. The sample processing is described, including the irradiation, chemical procedure, rare earths separation, counting techniques, radiochemical purity check, and chemical yields. The results of consistency checks on a number of elements are discussed. Abundances for siderophiles, volatiles, and rare earths are presented and discussed. Tests are presented for fractionation of rare earths and other refractories, compositional uniformity of C1's, and interelement correlations. There is no conclusive evidence for nebular fractionation affecting C1's. Three fractionation-prone rare earths have essentially the same relative abundances in C1's and all other chondrite classes, and hence are apparently not fractionated in C1's.

Magma Ocean Depth and Oxygen Fugacity in the Early Earth--Implications for Biochemistry.

PubMed

Righter, Kevin

2015-09-01

A large class of elements, referred to as the siderophile (iron-loving) elements, in the Earth's mantle can be explained by an early deep magma ocean on the early Earth in which the mantle equilibrated with metallic liquid (core liquid). This stage would have affected the distribution of some of the classic volatile elements that are also essential ingredients for life and biochemistry - H, C, S, and N. Estimates are made of the H, C, S, and N contents of Earth's early mantle after core formation, considering the effects of variable temperature, pressure, oxygen fugacity, and composition on their partitioning. Assessment is made of whether additional, exogenous, sources are required to explain the observed mantle concentrations, and areas are identified where additional data and experimentation would lead to an improved understanding of this phase of Earth's history.

COST-EFFECTIVE RARE EARTH ELEMENT RECYCLING PROCESS FROM INDUSTRIAL SCRAP AND DISCARDED ELECTRONIC PRODUCTS TO VALUABLE MAGNETIC ALLOYS AND PERMANENT MAGNETS - PHASE II

EPA Science Inventory

Rare earth element (REE) based Nd-Fe-B and Sm-Co permanent magnets have been widely used because of their excellent magnetic properties. The applications of Nd-Fe-B and Sm-Co rare earth permanent magnets include hybrid electric vehicles (HEVs), power generators for wind tur...

Substitution of Nd with other rare earth elements in melt spun Nd{sub 2}Fe{sub 14}B magnets

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

Brown, D. N.; Lau, D.; Chen, Z.

2016-05-15

This is a contemporary study of rapidly quenched Nd{sub 1.6}X{sub 0.4}Fe{sub 14}B magnetic materials (where X= Nd, Y, Ce, La, Pr, Gd and Ho). A 20% substitution of the Nd component from Nd{sub 2}Fe{sub 14}B can bring about some commercial advantage. However, there will be some compromise to the magnetic performance. Light rare earth elements are definitely more abundant (Y, Ce, La) than the heavier rare earth elements, but when they are included in RE{sub 2}Fe{sub 14}B magnets they tend to lower magnetic performance and thermal stability. Substituting heavy rare earth elements (Gd, Ho) for Nd in Nd{sub 2}Fe{sub 14}Bmore » improves the thermal stability of magnets but causes a loss in magnet remanence.« less

U.S. trade dispute with China over rare earth elements

NASA Astrophysics Data System (ADS)

Showstack, Randy

2012-03-01

The U.S. government has brought a new trade case against China over rare earth elements (REE) as well as tungsten and molybdenum, President Barack Obama announced on 13 March. Japan and the European Union also have taken similar actions against China about REEs, which are a group of 17 chemically similar metallic elements that are used in a variety of electronic, optical, magnetic, and catalytic applications. REEs are plentiful in the Earth's crust, although China currently has about 37% of the world's reserves and accounts for more than 95% of the world's production of the elements, according to the British Geological Survey. The United States has requested consultations with China at the World Trade Organization (WTO) concerning "China's unfair export restraints on rare earths, as well as tungsten and molybdenum," the Office of the United States Trade Representative announced in a 13 March statement.

(BRI) Direct and Inverse Design Optimization of Magnetic Alloys with Minimized Use of Rare Earth Elements

DTIC Science & Technology

2016-02-02

Earths ”, MS&T15-Materials Science and Technology 2015 Conference, Columbus, Ohio, October 4-8, 2015. 3. Dulikrvich, G.S., Reddy, S., Orlande, H.R.B...Schwartz, J.and Koch, C.C., “Multi-Objective Design and Optimization of Hard Magnetic Alloys Free of Rare Earths ”, MS&T15-Materials Science and Technology...AFRL-AFOSR-VA-TR-2016-0091 (BRI) Direct and Inverse Design Optimization of Magnetic Alloys with Minimized Use of Rare Earth Elements George

A miniature single element effusion cell for the vacuum deposition of transition-metal and rare-earth elements

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.

1997-08-01

A miniature single element effusion cell has been fabricated and tested that allows for the high-vacuum deposition of a variety of transition-metal and rare-earth elements. The cell is designed to operate under high-vacuum conditions, ≈10-9 Torr, with low power demands, <200 W. The virtues of this evaporator are the simplicity of design and ease of fabrication, assembly, maintenance, and operation.

Alaska's rare earth deposits and resource potential

USGS Publications Warehouse

Barker, James C.; Van Gosen, Bradley S.

2012-01-01

Alaska’s known mineral endowment includes some of the largest and highest grade deposits of various metals, including gold, copper and zinc. Recently, Alaska has also been active in the worldwide search for sources of rare earth elements (REE) to replace exports now being limitedby China. Driven by limited supply of the rare earths, combined with their increasing use in new ‘green’ energy, lighting, transportation, and many other technological applications, the rare earth metals neodymium, europium and, in particular, the heavy rare earth elements terbium, dysprosium and yttrium are forecast to soon be in critical short supply (U.S. Department of Energy, 2010).

Mineral resource of the month: rare earths

USGS Publications Warehouse

Hedrick, James B.

2004-01-01

As if classified as a top-secret project, the rare earths have been shrouded in secrecy. The principal ore mineral of the group, bastnäsite, rarely appears in the leading mineralogy texts. The long names of the rare-earth elements and some unusual arrangements of letters, many Scandinavian in origin, may have intimidated even those skilled in phonics. Somewhat obscurely labeled, the rare earths are neither rare nor earths (the historical term for oxides). They are a relatively abundant group of metallic elements that occur in nature as nonmetallic compounds and have hundreds of commercial applications.

Petrography and geochemistry of Cenozoic sedimentary sequences of the southern Samar Island, Philippines: Clues to the unroofing history of an ancient subduction zone

NASA Astrophysics Data System (ADS)

Pacle, Nichole Anthony D.; Dimalanta, Carla B.; Ramos, Noelynna T.; Payot, Betchaida D.; Faustino-Eslava, Decibel V.; Queaño, Karlo L.; Yumul, Graciano P.

2017-07-01

The Cenozoic sedimentary sequences of southern Samar Island in eastern Philippines were examined to understand the unroofing history of an ancient arc terrane. Petrographic and geochemical data revealed varying degrees of inputs from the ophiolite basement and differences in modal compositions. The sedimentary units are mostly made up of lithic fragments. The Late Oligocene to Early Miocene Daram Formation contains more chert and volcanic fragments whereas the late Middle Miocene to Early Pliocene Catbalogan Formation is dominantly composed of ultramafic components. These variances are correspondingly reflected in the geochemical signatures of these two sedimentary formations. The Catbalogan Formation clastic rocks have higher volatile-free MgO and Fe2O3 values (average: 8.4% for both oxides) compared to the Daram Formation samples (average: 5.1 and 6.3%, respectively). Geochemical variations are also reflected in the Co, Cr and Ni values: the Catbalogan Formation samples reflect higher concentrations (Co: 15-57 ppm; Cr: 231-1094 ppm; Ni: 84-484 ppm) compared to the Daram Formation samples (Co: 24-32 ppm; Cr: 234-418 ppm; Ni: 212-323 ppm). These observations suggest that the Daram Formation eroded and transported more of the crustal portions of the ophiolite, while the younger Catbalogan Formation represents a later exhumation and subsequent erosion of the ultramafic section. An oceanic island arc (OIA) setting is proposed for the two formations based on several tectonic discrimination diagrams (e.g., Th-La-Sc, La vs. Th). The OIA signature is further supported by their smooth chondrite-normalized rare earth element (REE) patterns with no obvious Eu anomaly as well as LREE enrichment which are typical of sediments deposited in OIA setting. Based on the dominantly ophiolitic provenance of the Daram and Catbalogan formations, the post-emplacement history of the nearby Samar Ophiolite is constrained during the Late Oligocene to Early Pliocene period.

Les xénolites ultramafiques du volcanisme alcalin quaternaire d'Oranie (Tell, Algérie occidentale), témoins d'une lithosphère cisaillée et enrichieUltramafic xenoliths from Quaternary alkali volcanism from Oranie (Tell, western Algeria): witnesses of a sheared and enriched lithosphere

NASA Astrophysics Data System (ADS)

Zerka, Mohamed; Cottin, Jean-Yves; Grégoire, Michel; Lorand, Jean-Pierre; Megartsi, M'Hamed; Midoun, Mohamed

Numerous ultramafic xenoliths occur within the Aı̈n-Temouchent volcanic complex (Northwestern Oranie, Algeria). Most of them are type I mantle tectonites (lherzolites and harzburgites) and composite xenoliths (harzburgite/clinopyroxenite) are rare. Only a few samples of spinel lherzolites display relatively fertile compositions when the major part of type I xenoliths have refractory major element compositions but enriched LREE contents showing that they have been affected by mantle metasomatism. The composite xenoliths are witnesses of reactions of alkaline magmas with the upper mantle. An asthenospheric rising, in relation with the large strike slip fault affecting the North African plate margin at Trias time is proposed as a possible geodynamical setting. To cite this article: M. Zerka et al., C. R. Geoscience 334 (2002) 387-394.

Cerium-based, intermetallic-strengthened aluminum casting alloy: High-volume co-product development

DOE PAGES

Sims, Zachary C.; Weiss, David; McCall, S. K.; ...

2016-05-23

Here, several rare earth elements are considered by-products to rare earth mining efforts. By using one of these by-product elements in a high-volume application such as aluminum casting alloys, the supply of more valuable rare earths can be globally stabilized. Stabilizing the global rare earth market will decrease the long-term criticality of other rare earth elements. The low demand for Ce, the most abundant rare earth, contributes to the instability of rare earth extraction. In this article, we discuss a series of intermetallic-strengthened Al alloys that exhibit the potential for new high-volume use of Ce. The castability, structure, and mechanicalmore » properties of binary, ternary, and quaternary Al-Ce based alloys are discussed. We have determined Al-Ce based alloys to be highly castable across a broad range of compositions. Nanoscale intermetallics dominate the microstructure and are the theorized source of the high ductility. In addition, room-temperature physical properties appear to be competitive with existing aluminum alloys with extended high-temperature stability of the nanostructured intermetallic.« less

Electrical and thermal conductivity of Fe-C alloy at high pressure: implications for effects of carbon on the geodynamo of the Earth's core

NASA Astrophysics Data System (ADS)

Zhang, C.; Lin, J. F.; Liu, Y.; Feng, S.; Jin, C.; Yoshino, T.

2017-12-01

Thermal conductivity of iron alloy in the Earth's core plays a crucial role in constraining the energetics of the geodynamo and the thermal evolution of the planet. Studies on the thermal conductivity of iron reveal the importance of the effects of light elements and high temperature. Carbon has been proposed to be a candidate light element in Earth's core for its meteoritic abundance and high-pressure velocity-density profiles of iron carbides (e.g., Fe7C3). In this study, we employed four-probe van der Pauw method in a diamond anvil cell to measure the electrical resistivity of pure iron, iron carbon alloy, and iron carbides at high pressures. These studies were complimented with synchrotron X-ray diffraction and focused ion beam (FIB) analyses. Our results show significant changes in the electrical conductivity of these iron-carbon alloys that are consistent previous reports with structural and electronic transitions at high pressures, indicating that these transitions should be taken into account in evaluating the electrical and thermal conductivity at high pressure. To apply our results to understand the thermal conduction in the Earth's core, we have compared our results with literature values for the electrical and thermal conductivity of iron alloyed with light elements (C, Si) at high pressures. These comparisons permit the validity of the Wiedemann-Franz law and Matthiessen's rule for the effects of light elements on the thermal conductivity of the Earth's core. We found that an addition of a light element such as carbon has an strong effect on the reducing the thermal conductivity of Earth's core, but the magnitude of the alloying effect strongly depends on the identity of the light element and the crystal and electronic structures. Based on our results and literature values, we have modelled the electrical and thermal conductivity of iron-carbon alloy at Earth's core pressure-temperature conditions to the effects on the heat flux in the Earth's core. In this presentation, we will address how carbon as a potential light element in the Earth's core can significantly affect our view of the heat flux across the core-mantle boundary and geodynamo of our planet.

Rejuvenescent Volcanism on San Cristóbal Island, Galápagos: A Late "Plumer"

NASA Astrophysics Data System (ADS)

Mahr, J.; Harpp, K. S.; Kurz, M. D.; Geist, D.; Bercovici, H.; Pimentel, R.; Cleary, Z.; Córdova Aguilar, M. D.

2016-12-01

Nestled between the two volcanoes of San Cristóbal Island in the Galápagos is a series of curiously young basaltic lava flows. These flows are not vegetated and have well-preserved flow tops, indicating that they are a rejuvenescent phase of volcanism. The young lava region covers 70 km2 of the NW coast and consists of five flow fields from 5 to 17 km2. We report new cosmogenic helium exposure ages that indicate emplacement occurred 9 to 15 ka, and that the surrounding area was active since 174 ka; a hiatus in activity may have occurred between 174 and 15 ka. These dates contrast with the fact that San Cristóbal is one of the oldest islands in the archipelago, with several K-Ar ages >2 Ma. Petrographically, the young lavas are mostly olivine-phyric (1-5 mm, average 5% abundance). Plagioclase phenocrysts are small (<1 mm) and rarely exceed 3% in abundance. Some flows range in their crystal cargo over rather short distances (<30 m). Compositional variation of this small set of young flows encompasses the compositional range exhibited by lavas from across the island. Rare earth element patterns are flat to LREE-enriched, even within the same flow field. Incompatible trace element ratios (e.g., La/Sm) indicate a wide range in extents of melting at relatively shallow depths (e.g., low Sm/Yb), comparable to conditions observed at Floreana Island. Compositions are consistent with a source that is a mixture of Galápagos plume and ancient, recycled oceanic crust (FLO source of Harpp and White, 2001). The contribution from the plume source is notable given the island's location in the eastern archipelago, where plume influence is normally lower than in the western islands. The young lavas are primitive compared to the majority of the archipelago and to other lavas on San Cristóbal, having only crystallized olivine and sparse CPX. These observations are consistent with a model in which melts pass through the crust relatively quickly, without extensive fractionation or homogenization prior to eruption. Because late stage lavas in the Galápagos have similar source compositions to the rest of the island, we propose that the mechanism for rejuvenescent volcanism in the Galápagos differs from that proposed for other ocean island systems, such as Hawai'i.

Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

NASA Astrophysics Data System (ADS)

Ma, Q.; Yang, Y.; Zhao, Z.

2017-12-01

Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites are relatively uniform and homogeneous in Sm-Nd isotopic system and thus can serve as ideal reference materials for external calibration during in situ Sm-Nd analysis.

Earth Observatory Satellite system definition study. Report no. 5: System design and specifications. Part 1: Observatory system element specifications

NASA Technical Reports Server (NTRS)

1974-01-01

The performance, design, and quality assurance requirements for the Earth Observatory Satellite (EOS) Observatory and Ground System program elements required to perform the Land Resources Management (LRM) A-type mission are presented. The requirements for the Observatory element with the exception of the instruments specifications are contained in the first part.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Jacobsen, Stein; Sasselov, Dimitar D.

2015-01-01

We propose to use evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called 'late veneer'. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. We plan to build an integrative model of Earth-like planets from the bottom up. We would like to infer their chemical compositions from their mass-radius relations and their host stars' elemental abundances, and understand the origins of volatile contents (especially water) on their surfaces, and thereby shed light on the origins of life on them.

Understanding the Role of Biology in the Global Environment: NASA'S Mission to Planet Earth

NASA Technical Reports Server (NTRS)

Townsend, William F.

1996-01-01

NASA has long used the unique perspective of space as a means of expanding our understanding of how the Earth's environment functions. In particular, the linkages between land, air, water, and life-the elements of the Earth system-are a focus for NASA's Mission to Planet Earth. This approach, called Earth system science, blends together fields like meteorology, biology, oceanography, and atmospheric science. Mission to Planet Earth uses observations from satellites, aircraft, balloons, and ground researchers as the basis for analysis of the elements of the Earth system, the interactions between those elements, and possible changes over the coming years and decades. This information is helping scientists improve our understanding of how natural processes affect us and how we might be affecting them. Such studies will yield improved weather forecasts, tools for managing agriculture and forests, information for fishermen and local planners, and, eventually, an enhanced ability to predict how the climate will change in the future. NASA has designed Mission to Planet Earth to focus on five primary themes: Land Cover and Land Use Change; Seasonal to Interannual Climate Prediction; Natural Hazards; Long-Term Climate Variability; and Atmosphere Ozone.

Method of determining lanthanidies in a transition element host

DOEpatents

De Kalb, Edward L.; Fassel, Velmer A.

1976-02-03

A phosphor composition contains a lanthanide activator element within a host matrix having a transition element as a major component. The host matrix is composed of certain rare earth phosphates or vanadates such as YPO.sub.4 with a portion of the rare earth replaced with one or more of the transition elements. On X-ray or other electromagnetic excitation, trace lanthanide impurities or additives within the phosphor are spectrometrically determined from their characteristic luminescence.

Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

NASA Astrophysics Data System (ADS)

Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

2014-11-01

Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

Initial blood storage experiment

NASA Technical Reports Server (NTRS)

Surgenor, Douglas MACN.

1988-01-01

The possibility of conducting experiments with the formed elements of the blood under conditions of microgravity opens up important opportunities to improve the understanding of basic formed element physiology, as well as, contribution to improved preservation of the formed elements for use in transfusion. The physiological, biochemical, and physical changes of the membrane of the erythrocyte, platelet, and leukocyte was studied during storage under two specific conditions: standard blood bank conditions and microgravity, utilizing three FDA approved plastic bags. Storage lesions; red cell storage on Earth; platelet storage on Earth; and leukocyte storage Earth were examined. The interaction of biomaterials and blood cells was studied during storage.

Modelling of charged satellite motion in Earth's gravitational and magnetic fields

NASA Astrophysics Data System (ADS)

Abd El-Bar, S. E.; Abd El-Salam, F. A.

2018-05-01

In this work Lagrange's planetary equations for a charged satellite subjected to the Earth's gravitational and magnetic force fields are solved. The Earth's gravity, and magnetic and electric force components are obtained and expressed in terms of orbital elements. The variational equations of orbit with the considered model in Keplerian elements are derived. The solution of the problem in a fully analytical way is obtained. The temporal rate of changes of the orbital elements of the spacecraft are integrated via Lagrange's planetary equations and integrals of the normalized Keplerian motion obtained by Ahmed (Astron. J. 107(5):1900, 1994).

Polymer monolithic capillary microextraction combined on-line with inductively coupled plasma MS for the determination of trace rare earth elements in biological samples.

PubMed

Zhang, Lin; Chen, Beibei; He, Man; Hu, Bin

2013-07-01

A rapid and sensitive method based on polymer monolithic capillary microextraction combined on-line with microconcentric nebulization inductively coupled plasma MS has been developed for the determination of trace/ultratrace rare earth elements in biological samples. For this purpose, the iminodiacetic acid modified poly(glycidyl methacrylate-trimethylolpropane trimethacrylate) monolithic capillary was prepared and characterized by SEM and FTIR spectroscopy. Factors affecting the extraction efficiency, such as sample pH, sample flow rate, sample/eluent volume, and coexisting ions were investigated in detail. Under the optimal conditions, the LODs for rare earth elements were in the range of 0.08 (Er) to 0.97 ng/L (Nd) with a sampling frequency of 8.5 h(-1), and the RSDs were between 1.5% (Sm) and 7.4% (Nd) (c = 20 ng/L, n = 7). The proposed method was successfully applied to the analysis of trace/ultratrace rare earth elements in human urine and serum samples, and the recoveries for the spiked samples were in the range of 82-105%. The developed method was simple, rapid, sensitive, and favorable for the analysis of trace/ultratrace rare earth elements in biological samples with limited sample volume. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coal fly ash as a resource for rare earth elements.

PubMed

Franus, Wojciech; Wiatros-Motyka, Małgorzata M; Wdowin, Magdalena

2015-06-01

Rare earth elements (REE) have been recognised as critical raw materials, crucial for many clean technologies. As the gap between their global demand and supply increases, the search for their alternative resources becomes more and more important, especially for the countries which depend highly on their import. Coal fly ash (CFA), which when not utilised is considered waste, has been regarded as the possible source of many elements, including REE. Due to the increase in the energy demand, CFA production is expected to grow, making research into the use of this material a necessity. As Poland is the second biggest coal consumer in the European Union, the authors have studied different coal fly ashes from ten Polish power plants for their rare earth element content. All the fly ashes have a broadly similar distribution of rear earth elements, with light REE being dominant. Most of the samples have REE content relatively high and according to Seredin and Dai (Int J Coal Geol 94: 67-93, 2012) classification can be considered promising REE raw materials.

Rare earth elements upon assessment of reasons of the geophagy in Sikhote-Alin region (Russian Federation), Africa and other world regions.

PubMed

Panichev, Alexander M; Popov, Vladimir K; Chekryzhov, Igor Yu; Seryodkin, Ivan V; Stolyarova, Tatiana A; Zakusin, Sergey V; Sergievich, Alexandr A; Khoroshikh, Pavel P

2016-12-01

Rocks eaten by wild animals on the Bolshoy Shanduyskiy kudur in the Sikhote-Alin region (Russian Federation) are zeolite-clay mineral complexes-products of weathering of zeolitized vitric tuffs of rhyolite composition, deposited in aqueous medium within the volcanic caldera of about 55 million years ago. By composition of rock-forming oxides, the tuffs refer to high-potassium calc-alkaline series. In trace elements of most favorite kudurites of the Bolshoy Shanduyskiy kudur, there are significantly increased contents of most of rare earth elements (2-5 times in comparison with surrounding rocks). The results of our analysis of geological and geochemical data on kudurs and kudurites in another part of the Sikhote-Alin, as well as on other regions of the world (particularly, in Africa and Indonesia), taking into account new data on the prevalence of rare earth elements in living matter and their medical and biological properties, enable us to consider the version of causal connection of the geophagy with rare earth elements.

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

2016-11-01

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

[Spectroscopic Research on Slag Nanocrystal Glass Ceramics Containing Rare Earth Elements].

PubMed

Ouyang, Shun-li; Li, Bao-wei; Zhang, Xue-feng; Jia, Xiao-lin; Zhao, Ming; Deng, Lei-bo

2015-08-01

The research group prepared the high-performance slag nanocrystal glass ceramics by utilizing the valuable elements of the wastes in the Chinese Bayan Obo which are characterized by their symbiotic or associated existence. In this paper, inductively coupled plasma emission spectroscopy (ICP), X-ray diffraction (XRD), Raman spectroscopy (Raman) and scanning electron microscopy (SEM) are all used in the depth analysis for the composition and structure of the samples. The experiment results of ICP, XRD and SEM showed that the principal crystalline phase of the slag nanocrystal glass ceramics containing rare earth elements is diopside, its grain size ranges from 45 to 100 nm, the elements showed in the SEM scan are basically in consistent with the component analysis of ICP. Raman analysis indicated that its amorphous phase is a three-dimensional network structure composed by the structural unit of silicon-oxy tetrahedron with different non-bridging oxygen bonds. According to the further analysis, we found that the rare earth microelement has significant effect on the network structure. Compared the nanocrystal slag glass ceramic with the glass ceramics of similar ingredients, we found that generally, the Raman band wavenumber for the former is lower than the later. The composition difference between the glass ceramics and the slag nanocrystal with the similar ingredients mainly lies on the rare earth elements and other trace elements. Therefore, we think that the rare earth elements and other trace elements remains in the slag nanocrystal glass ceramics have a significant effect on the network structure of amorphous phase. The research method of this study provides an approach for the relationship among the composition, structure and performance of the glass ceramics.

Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

NASA Technical Reports Server (NTRS)

Righter, K.; Danielson, L.; Pando, K. M.; Marin, N.; Nickodem, K.

2015-01-01

Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation.

Superconducting structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2003-04-01

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Superconducting Structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2005-09-13

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Evidence against a chondritic Earth.

PubMed

Campbell, Ian H; O'Neill, Hugh St C

2012-03-28

The (142)Nd/(144)Nd ratio of the Earth is greater than the solar ratio as inferred from chondritic meteorites, which challenges a fundamental assumption of modern geochemistry--that the composition of the silicate Earth is 'chondritic', meaning that it has refractory element ratios identical to those found in chondrites. The popular explanation for this and other paradoxes of mantle geochemistry, a hidden layer deep in the mantle enriched in incompatible elements, is inconsistent with the heat flux carried by mantle plumes. Either the matter from which the Earth formed was not chondritic, or the Earth has lost matter by collisional erosion in the later stages of planet formation.

A LOW-COST RARE EARTH ELEMENTS RECOVERY TECHNOLOGY - PHASE I

EPA Science Inventory

Rare Earth Element Concentrations in Submarine Hydrothermal Fluids

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

Fowler, Andrew; Zierenberg, Robert

Rare earth element concentrations in submarine hydrothermal fluids from Alarcon Rise, East Pacific Rise, REE concentrations in submarine hydrothermal fluids from Pescadero Basin, Gulf of California, and the Cleft vent field, southern Juan de Fuca Ridge. Data are not corrected to zero Mg.

Influence of phase composition on microstructure and properties of Mg-5Al-0.4Mn-xRE (x = 0, 3 and 5 wt.%) alloys

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

Braszczyńska-Malik, K.N., E-mail: kacha@wip.pcz.pl; Grzybowska, A.

2016-05-15

The microstructure and mechanical properties investigations of two AME503 and AME505 experimental alloys in as-cast conditions were presented. The investigated materials were fabricated on the basis of the AM50 commercial magnesium alloy with 3 and 5 wt.% cerium rich mischmetal. In the as-cast condition, both experimental alloys were mainly composed of α-Mg, Al{sub 11}RE{sub 3} and Al{sub 10}RE{sub 2}Mn{sub 7} intermetallic phases. Additionally, due to non-equilibrium solidification conditions, a small amount of α + γ divorced eutectic and Al{sub 2}RE intermetallic phase were revealed. The obtained results also show a significant influence of rare earth elements on Brinell hardness, tensilemore » and compression properties at ambient temperature and especially on creep properties at 473 K. Improved alloy properties with a rise in rare earth elements mass fraction results from an increase in Al{sub 11}RE{sub 3} phase volume fraction and suppression of α + γ eutectic volume fraction in the alloy microstructure. Additionally, the influence of rare earth elements on the dendrite arm space value was discussed. The presented results also proved the thermal stability of the intermetallic phases during creep testing. - Highlights: • Two different Mg-5Al-0.4Mn alloys containing 3 and 5 wt.% of rare earth elements were fabricated. • Addition of rare earth elements leads to a reduction of dendrite arm spaces. • Mechanical properties depend on the phase composition of the alloys. • The increase of the rare earth elements content causes rise of the creep resistance.« less

Formation of A-type granites in the Lower Yangtze River Belt: A perspective from apatite geochemistry

NASA Astrophysics Data System (ADS)

Jiang, Xiao-Yan; Li, He; Ding, Xing; Wu, Kai; Guo, Jia; Liu, Ji-Qiang; Sun, Wei-Dong

2018-04-01

Apatite is ubiquitous in A-type granites, and can be used to elucidate the volatile contents of the silicate melt, which reflect its source characteristics. A-type granites have been recognized as a distinct group of granites. A1- and A2-type subgroups are produced under different extensional settings. However, the details of the mechanisms behind the distinctive geochemical characteristics of A1- and A2-type granites remain obscure. Belts of Cretaceous A1- and A2-type granites occur along the Lower Yangtze River Belt in eastern China. Here we investigated the major and trace element compositions of apatites from contemporary A1- and A2-type granites at different localities along the Lower Yangtze River Belt, in order to decipher their discrepant source processes. Apatites from A1- and A2-type granites show similar major and trace elements, but differ in their F and Cl concentrations. Apatites from A1-type granites in the eastern part of the Lower Yangtze River Belt have much lower F and higher Cl concentrations compared to A2-type granites in the western part. Moreover, from the east to the west, the F concentrations of apatites from A1-type granites increase, while the Cl concentrations decline. In a subducted plate, F is retained by amphibole, chlorite, serpentine and mica minerals through the amphibolite stage, and finally by phengite and lawsonite during the eclogite stage, whereas, Cl is controlled by amphibole, chlorite and serpentine. The high and varied Cl concentrations in A1 subgroup apatites, therefore, may be attributed to the breakdown of amphibole, chlorite and/or serpentine decomposition during partial melting of subducted oceanic crust releasing a large amount of Cl at shallower depth. In contrast, F is transported to deeper depths in the subducted oceanic crust, and released through breakdown of phengite and lawsonite, making an important contribution to the formation of A2-type granites. Apatites from A1- and A2-type granite samples show regular changes in LREE/HREE, LREE/MREE and MREE/HREE ratios with increasing distance from the location of the subduction zone, probably as the result of nonsynchronous dehydration of the serpentine and phengite at different stages during subduction. We propose that A1- and A2-type granites on the Lower Yangtze River Belt were derived from sources metasomatised by fluids originating from the breakdown of amphibole, chlorite and/or serpentine with higher Cl, lower F, and from phengite and/or lawsonite with relatively higher F but lower Cl, respectively.

A Geochemical Study of Postshield Volcanism and the Generation of Trachyte on West Maui, HI

NASA Astrophysics Data System (ADS)

Trenkler, M. L.; Cousens, B.

2016-12-01

The West Maui Volcano provides a complete evolutionary history of a fully developed Hawaiian volcano described by three main phases: (1) the tholeiitic shield-building stage of the Wailuku Basalts; (2) the postshield alkalic stage Honolua Volcanics; and (3) the rejuvenated stage Lahaina Volcanics of silica-undersaturated rocks. On West Maui, the postshield Honolua Volcanics erupted highly differentiated rocks (benmoreite to trachyte), with little to no intermediate alkalic rocks, upon cessation of tholeiitic shield building. Utilizing K-Ar dated samples, we present 35 new major and trace element analyses of shield, postshield, and rejuvenated stage lavas on West Maui in an attempt to identify the mechanisms present during evolution from basalt to trachyte over a defined temporal and spatial range. Wailuku basalts are dominated by olivine fractionation, whereas decreasing Sc and CaO/Al2O3 with increasing degree of differentiation indicate Honolua benmoreites and trachytes heavily fractionated clinopyroxene. Major element trends are consistent with crystallization of titano-magnetite, potassium feldspar, and minor apatite. Trace element patterns of the Honolua Volcanics are uniform with strong enrichments in LILE and the LREEs indicating fractionation and lower degrees of partial melting compared to Wailuku basalts. The HREEs are enriched relative to shield basalts with Gd/Yb values of 2.0-2.8 as a result of high degrees of fractionation and the presence of crystalizing apatite. Major and trace element trends follow the evolution of the postshield Hawi Volcanics of Kohala, where alkalic basalts differentiate up to trachyte. Compared to shield lavas, the Honolua Volcanics represent a drastic decrease in magma supply rates, infrequent eruptions, and magma residence times long enough to produce highly differentiated magmas with no significant mafic magma input.

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

NASA Astrophysics Data System (ADS)

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

1997-05-01

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

Method of treating waste water

DOEpatents

Deininger, J. Paul; Chatfield, Linda K.

1991-01-01

A process of treating water to remove transuranic elements contained therein by adjusting the pH of a transuranic element-containing water source to within the range of about 6.5 to about 14.0, admixing the water source with an alkali or alkaline earth ferrate in an amount sufficient to form a precipitate within the water source, the amount of ferrate effective to reduce the transuranic element concentration in the water source, permitting the precipitate in the admixture to separate and thereby yield a supernatant liquid having a reduced transuranic element concentration, and separating the supernatant liquid having the reduced transuranic element concentration from the admixture is provided. Additionally, a water soluble salt, e.g., a zirconium salt, can be added with the alkali or alkaline earth ferrate in the process to provide greater removal efficiencies. A composition of matter including an alkali or alkaline earth ferrate and a water soluble salt, e.g., a zirconium salt, is also provided.

Demandite, lunar materials and space industrialization

NASA Technical Reports Server (NTRS)

Criswell, D. R.

1977-01-01

Terrestrial industry consumes a wide range of elements in producing the outputs which support and make industrial societies possible. 'Demandite' is a conceptual or synthetic molecule which is composed of the weight fractions of the major elements consumed by industry. Demandite needed for mature industrial activities in space will differ from the terrestrial composition because solar energy must replace hydrocarbon-energy, lunar and asteroidal bulk compositions are different from mineral deposits on the earth, and the major bulk processing in space will be the creation of radiation shielding for human habitats to provide real estate in space complete with water, atmosphere and life-stock elements. Demandite cost may be dominated by earth to deep space transport cost of minor elemental constituents depleted in the lunar soils unless careful attention is given to substitution of materials, searches of the moon (polar regions) and asteroids for the depleted elements, and continuing lowering of earth to deep space transport costs.

HISTORY OF THE ORIGIN OF THE CHEMICAL ELEMENTS AND THEIR DISCOVERIES.

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

HOLDEN,N.E.

The origin of the chemical elements show a wide diversity with some of these elements having their origin in antiquity. Still other elements have been synthesized within the past fifty years via nuclear reactions on heavy elements, because these other elements are unstable and radioactive and do not exist in nature. The names of the elements come from many sources including mythological concepts or characters; places, areas or countries; properties of the element or its compounds, such as color, smell or its inability to combine; and the names of scientists. There are also some miscellaneous names as well as somemore » obscure names for particular elements. The claim of discovery of an element has varied over the centuries. Many claims, e.g., the discovery of certain rare earth elements of the lanthanide series, involved the discovery of a mineral ore from which an element was later extracted. The honor of discovery has often been accorded not to the person who first isolated the element but to the person who discovered the original mineral itself, even when the ore was impure and contained many elements. The reason for this is that in the case of these rare earth elements, the ''earth'' now refers to oxides of a metal not to the metal itself. This fact was not realized at the time of their discovery, until the English chemist Humphry Davy showed that earths were compounds of oxygen and metals in 1808. In the early discoveries, the atomic weight of an element and spectral analysis of the element were not available. Later both of these elemental properties would be required before discovery of the element would be accepted. In general, the requirements for discovery claims have tightened through the years and claims that were previously accepted would no longer meet the minimum constraints now imposed. There are cases where the honor of discovery is not given to the first person to actually discover the element but to the first person to claim the discovery in print. If a publication was delayed, the discoverer has often historically been ''scooped'' by another scientist.« less

Geochemical Constraints on Core Formation in the Earth

NASA Technical Reports Server (NTRS)

Jones, John H.; Drake, Michael J.

1986-01-01

New experimental data on the partitioning of siderophile and chalcophile elements among metallic and silicate phases may be used to constrain hypotheses of core formation in the Earth. Three current hypotheses can explain gross features of mantle geochemistry, but none predicts siderophile and chalcophile element abundances to within a factor of two of observed values. Either our understanding of metal-silicate interactions and/or our understanding of the early Earth requires revision.

Rare Earth Oxide Fluoride Nanoparticles And Hydrothermal Method For Forming Nanoparticles

DOEpatents

Fulton, John L.; Hoffmann, Markus M.

2003-12-23

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

Rare earth oxide fluoride nanoparticles and hydrothermal method for forming nanoparticles

DOEpatents

Fulton, John L [Richland, WA; Hoffmann, Markus M [Richland, WA

2001-11-13

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

Conditions of Core Formation in the Early Earth: Single Stage or Heterogeneous Accretion?

NASA Technical Reports Server (NTRS)

Righter, Kevin

2010-01-01

Since approx.1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients [D(met/sil)] for siderophile (iron-loving) elements are much different than those measured at low PT conditions [1,2]. The high PT data have been used to argue for a magma ocean during growth of the early Earth [3,4]. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements (> 80 experiments published for Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd). At the same time several different models have been advanced to explain the siderophile elements in Earth's mantle: a) shallow depth magma ocean 25-30 GPa [3,5]; b) deep magma ocean; up to 50 GPa [6,7], and c) early reduced and later oxidized magma ocean [8,9]. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to identify issues that have lead to a difference in interpretation, and to present updated predictive expressions based on new experimental data. The resulting expressions will be applied to the siderophile element depletions in Earth's upper mantle.