Rare Earth Element Trends Research Articles

Carboniferous bimodal volcanic sequences along the Northeastern Pamir: Evidence for back-arc extension due to northward subduction of the Paleo-Tethys

The Pamir plateau lies at the western end of the Tethys domain recording the entire evolution from the opening of the Proto-Tethys to the final closure of the Neo-Tethys. During this long-term evolution, the details of the initial subduction of the Paleo-Tethys and the final amalgamation of the main terranes in the Pamir are still controversial. The Carboniferous bimodal volcanic sequences along the Northern Pamir may supply the key evidence to reveal the subduction process of the Paleo-Tethys Ocean. This study presents the detailed stratigraphic architecture, petrography, geochronological and geochemical data of the Carboniferous−Permian volcanic rocks along the Northern Pamir in western China bordering Tajikistan. Zircons from two plagioclase phenocryst-rich basalts, and an andesite, volcanic agglomerate, and granitic sill emplaced in the basalts yield concordant ages of 319.5 ± 2 Ma, 322.7 ± 1.6 Ma, 288.7 ± 2.5 Ma, 301.6 ± 4.2 Ma, and 300.4 ± 1.5 Ma, respectively. The basalts show mid-oceanic-ridge basalt−like geochemical features with flat to depleted light rare earth element trends [(La/Yb)N = 0.68−1.82], depleted whole-rock εNd(t) (6.44−7.85), and zircon εHf(t) (6.3−10.1) values, suggesting they are primitive magmas derived from a depleted mantle source metasomatized by earlier subduction in line with their low Nb/La ratios (0.30−0.64). As for the intermediate-acid volcanic rocks (andesite and dacite), they show enrichment of large ionic lithophile elements (e.g., Rb, Ba, and Sr) and depletion of high field strength elements (e.g., Nb, Ta, and Ti) as well as negative εNd(t) values ranging from −0.97 to −0.75, demonstrating that they are primitive magmas derived from partial melting of the metasomatized lithospheric mantle source, followed by crystal fraction of hornblende, plagioclase, and minor quartz. Taking together the stratigraphic features, rock associations, and geochemical signatures, the Carboniferous basalts share most features with the Okinawa and the Mariana back-arc basalts. Integrating the new data with the previous studies, we construct a detailed evolution process of the Paleo-Tethys Ocean at the Pamir, i.e., extension of the filled residual Proto-Tethys Ocean between the Tarim and the Northern Pamir induced by the northward Paleo-Tethys subduction in the early Carboniferous, gradually waning of the back-arc basin from the late Carboniferous to the Early Permian, and finally, the closure of the Paleo-Tethys Ocean led to the amalgamation of the Northern, the Central, and the Southern Pamir, resulting in the initial architecture of the Pamir.

Significant Enrichment of Rare Earth Element Concentrations in Stream Sediments of Sharm El-Sheikh Area, Southern Sinai-Egypt: Geochemical Prospecting and Heavy Mineral Survey

Economic rare earth element bearing-heavy mineral accommodation in alluvial deposits (stream sediments) is a well-known process caused by varying rates of weathering and transportation of heavy minerals and sediments, which is significant in geochemical exploration. In the present work, stream sediment samples from Wadi Lethi, Sharm El-Sheikh, were systematically collected. The collected stream sediments were investigated mineralogically and geochemically using collaborative techniques. The separated heavy fractions have been analyzed for trace elements and Rare Earth Element. Important heavy minerals identified are monazite, sphene, apatite, garnet, xenotime, magnetite, ilmenite, and hematite, with subordinate riebeckite, epidote, and chlorite. Geochemical analyses of the separated heavy minerals revealed an abnormal concentration of total Rare Earth Element that was more than eleven times higher than in the studied area's granitic rocks. The Rare Earth Elements trends of these minerals depict the enrichment of light rare earth elements and the depletion of heavy rare earth elements, as well as the typical negative Eu anomaly found in granitic magma.

Apatite texture and trace element chemistry of carbonatite-related REE deposits in China: Implications for petrogenesis

Apatite is a ubiquitous mineral in carbonatites, and incorporates a variety of trace elements including rare earth elements (REEs). In this study, the textural and chemical variations of apatite were examined in order to trace the magmatic and hydrothermal petrogenesis of three carbonatite-related REE deposits: Shaxiongdong, Miaoya, and Bayan Obo. Various apatite textures were revealed by cathodoluminescence and back-scattered electron imaging. Magmatic apatite, which occurs predominantly in samples from Shaxiongdong, is euhedral, and commonly shows oscillatory or growth zonation with a yellow–green luminescent core and a violet luminescent rim. Euhedral to subhedral metasomatic apatite from Miaoya and Bayan Obo has a turbid texture, with the majority of grains associated with exsolved monazite. Hydrothermal apatite from Bayan Obo, typically occurring as aggregates in close association with fluorite and barite, is anhedral, with green or light violet luminescence.The different apatite textures are characterised by distinct trace element compositions. Magmatic apatite contains the highest concentrations of Mn (avg. 457 ppm) and Sr (avg. 18,285 ppm) and is characterised by a steeply inclined REE chondrite-normalised pattern. Metasomatic apatite, which has undergone in situ dissolution–reprecipitation, contains lower Mn (avg. 272 ppm) and Sr (avg. 9945 ppm) concentrations. It is characterised by highly variable REE trends with an La/SmN ratio varying from 0.13 to 5.61, and lower average La/YbN, La/SmN, and Sr/Y ratios (46, 2.2, and 18, respectively) than magmatic apatite. Hydrothermal apatite that was precipitated from a fluid is characterised by convex upward chondrite-normalised REE distributions with the lowest La/YbN, La/SmN, and Sr/Y ratios (13, 0.69, and 5.8, respectively). The average concentrations of Mn and Sr in this apatite are 270 and 6610 ppm, respectively. There are no Eu anomalies (Eu/Eu* = 0.97) in the chondrite-normalised REE plots for any of the analysed apatite samples. The combined textural and compositional variations of apatite in the three deposits reflect diverse magmatic and hydrothermal processes, including: 1) mineral fractionation contributing to core–rim zoning within the Shaxiongdong magmatic apatite; 2) dissolution–reprecipitation inducing monazite precipitation in Miaoya and Bayan Obo metasomatic apatite; and 3) coprecipitation with fluorite and barite from fluids generating the Bayan Obo hydrothermal apatite.A compilation of published apatite compositions from other rock types demonstrates that trace element compositions of apatite can be used to differentiate crystallisation environments and differentiate apatite from other rock types. Apatite from carbonatite has high Sr, REEs, La/YbN, Th/U, and Sr/Y, and no Eu anomaly, compared with apatite from igneous silicate rocks (except ultramafic rocks), and iron-oxide copper gold (IOCG) or iron-oxide apatite (IOA) deposits.

The Cuyano proto-ocean between the Chilenia and Cuyania terranes: rifting and plume interaction during the Neoproterozoic – early Palaeozoic evolution of the SW Gondwana margin

AbstractThe Precordillera mafic–ultramafic belt (PMUB), located in central-western Argentina, comprises mafic and ultramafic bodies interlayered and/or in tectonic contact with marine siliciclastic units. Whole-rock, mineral geochemistry and Nd–Sr isotope analyses performed in magmatic rocks suggest a relatively different spatial and temporal evolution along the belt. The southern PMUB (south of 32° S) evolved as an intra-continental rifted margin with an enriched mid-ocean-ridge basalt (E-MORB) tholeiitic to alkaline magmatism, to a proto-ocean basin (the Cuyano proto-ocean) with tholeiitic normal-MORB geochemical signature. Based on neodymium model ages (TDM), the magmatic activity started during the late Neoproterozoic Era and continued into the early Palaeozoic Era. Instead, the northern PMUB (28–32° S) evolved as an intra-continental rifted margin with dominant tholeiitic E-MORB to continental flood basalt (CFB) magmatism during the early Palaeozoic Era. ϵNd values (+3.4 to +8.4), rare earth element trends and high-field-strength element systematics, together with an estimated potential mantle temperature of c. 50–100°C above ambient mantle, suggest the PMUB magmatism derived from an enriched mantle source related to the effect of a rising plume linked to the Iapetus Ocean opening. In particular, TDM estimations of 600–550 Ma agree with reported magmatism in central to southern Appalachians. The magmatism in the PMUB, and those registered in the Neoproterozoic Catoctin Formation and in the Southern Oklahoma Aulacogen in the conjugated Laurentian margin, seem to be contemporaneous, sharing a similar plume-enriched mantle source. In this context, the E-MORB signature identified along the PMUB can be described as a plume-distal ridge tectonic setting over an extended margin.

Petrogenesis and tectonic setting of the Chaheilingashun pluton, North Alxa Block, NW China: constraints from whole-rock geochemistry, zircon U–Pb ages, and Hf isotope compositions

To better constrain the petrogenesis and tectonic setting of the Chaheilingashun pluton in the southern Ya-Gan Fault, North Alxa Block, NW China, this study presents new zircon U–Pb ages, whole-rock geochemistry, and Hf isotopes of diorites from the Chaheilingashun pluton. The Chaheilingashun pluton is composed of medium- to coarse-grained monzonitic diorite, with moderate to high SiO2 contents (58.22–62.77 wt.%), moderate total alkali contents (Na2O + K2O, 5.72–7.66 wt.%), and high Al2O3 contents (14.26–17.69 wt.%), which indicate that the diorite exhibits calc-alkaline to alkaline and metaluminous to peraluminous series. The correlations of SiO2 with oxides and the right-dipping oblique trends of rare earth elements (REEs) demonstrate that the magma experienced fractional crystallization. In particularly, the correlations of Rb with Ba and Sr, and the weak negative Eu anomalies indicate that the plagioclase has undergone fractional crystallization. In addition, this paper has shown that both fractional crystallization and partial melting also contributed to the magmatic process through the Eu anomalies and La/Sm-La diagram. The positive eHf(t) values (2.2–4.6) and low Mg#, Cr, and Ni indicate that diorite was generated from the partial melting of juvenile mafic crust. Together with previous results, the diorites are inferred to have formed in an post-collisional extensional environment. The zircon U–Pb age of diorite from the Chaheilingashun pluton is dated at 289.3 Ma, suggesting that the final closure time of the Paleo-Asian Ocean was might before 289.3 ± 2.3 Ma.

Evaluation of Rare Earth Elements in Black Sand and Phosphate ores, EGYPT

The rare earth elements (REEs), uranium (U) and thorium (Th) isotopes found naturally in soil, rock, water and plant. About 20 samples of Black sand and phosphate were collected from different locations in the Rashid city , Egypt. All the collected samples were prepared and chemically treated using different acids and microwave, then analyzed using ICP-MS. The present work was conducted to identify and evaluate the compositional trends of REEs, U and Th in the samples in terms of distribution patterns and indicator ratios. The results revealed that the black sand and phosphate ores are rich as natural sources of U, Th and other rare earth elements. The elements’ concentrations in black sands and phosphate ores were found higher than the world average crust soil.

Numerical modelling of rare earth element fractionation trends in garnet: a tool to monitor skarn evolution

Proximal and distal garnets from skarns at Jiaduobule, Tibet, are used to demonstrate how variation in the fluid composition and parameters such as salinity, pH, fO2, and $${\text{X}}_{{\rm CO}_{2}}$$ will impact on rare earth element (REE) distribution in garnets, and also to constrain skarn evolution across the orefield from proximal (Fe mineralization) to distal (Cu mineralization). These garnets display a diversity from proximal to distal skarn which is expressed in mineral assemblages, textures, major to trace element contents, and particularly, chondrite-normalized REE fractionation trends. The empirical variation among REE fractionation trends, determined from laser ablation inductively coupled-plasma mass spectrometry data, can be numerically modelled in terms of variable fluid compositions and physicochemical parameters, among which the key determining factors are salinity, pH, $${\text{X}}_{{{\text{CO}}_{{2}} }}$$ and Ca content buffered from the rock-fluid reaction with carbonate rocks. Modelling REE trends in skarn garnet is shown to be valuable for constraining conditions during garnet formation and a useful tool for monitoring the evolution of complex skarn deposits.

Distribution patterns of natural radionuclides and rare earth elements in marine sediments from the Red Sea, Egypt

The present study was conducted to study the compositional trends of rare earth elements (REEs), Th, and U in marine sediment samples in terms of distribution patterns, anomalies, and indicator ratios. For this purpose, a total of 32 marine sediment samples were collected from 12 coastal areas of the Egyptian Red Sea and analyzed using instrumental neutron activation (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) analytical techniques. The analyses investigated 14 REEs, Th, and U. The results revealed that the contents of REE, light REE (LREE), and heavy REE (HREE) are 47.6, 38.7, and 8.3 mg/kg, respectively, whereas the concentration of Th and U is determined as 2.15 and 2.23 mg/kg, respectively. Indicator ratios were calculated, and inter-correlation elements with Th and U were constructed. Multivariate statistics were implemented on the data and GIS technology to construct the distribution patterns of REE, Th, and U along the Egyptian coast of the Red Sea. The obtained results were compared with the corresponding values published in literature to show a good matching. There is a significant enrichment of LREE relative to HREE, a reduced ratio of Th/U, a weak positive anomaly of Eu/Eu*, and a slight positive Ce anomaly is noticed. Among the 12 studied areas, one area, Sharm El-Bahari, located in the middle of the coast, shows peak values of REE, Th, and U relative to the other areas. However, it still shows a good agreement with the results published in the literature.

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

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

Assessment of rare earth elements, Th and U profile of a site for a potential coal based power plant by instrumental neutron activation analysis

Abstract To study the compositional trends of rare earth elements (REEs: La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu), Th and U in soil samples collected from a site for a potential coal based power plant as well as to conduct a preliminary assessment of environmental impact of the proposed power plant in terms of REEs, Th and U, we have analyzed nine soil samples by instrumental neutron activation analysis. Evaluation of data quality by repeated analysis of IAEA-Soil-7 and IAEA-SL-1 ensures a proper data base-line for the REEs, Th and U abundances of the sampling site. Chondrite-normalized abundance patterns demonstrate the heavy REEs–light rare earth elements and Th–U fractionations in our sample suite along with significant negative Eu anomaly. Thorium/U ratio in our study area ranges from 4.55 to 6.07 which is higher than that of upper continental crust. Preliminary assessment of environmental impact of the proposed power plant is evaluated by taking NIST-SRM-1633b (coal-fly-ash) as contaminant as coal-fly-ash will be the major byproduct of the power plant. Previous literature studies and our prevailing data invoke that proposed power plant will have no severe impact on soil originated biota and on human health in terms of REEs, Th and U abundances. However, the long term effect of excessive REEs, Th and U as well as the other elemental abundances originating from coal-fly-ash should also be taken into an account.

Rare-earth leaching from Florida phosphate rock in wet-process phosphoric acid production

Phosphorite, or phosphate rock, is the most significant secondary rare-earth resource. It contains high amounts of phosphate-bearing minerals along with low contents of rare earth elements (REEs). In Florida, about 19 Mt of phosphate rock are mined annually and most are used to manufacture fertilizers using a wet process, in which sulfuric acid reacts with phosphates to produce phosphoric acid and phosphogypsum. In the wet process, REEs are also leached out into solution and eventually get lost in the leaching residue and phosphate fertilizer. Recovering REEs from Florida phosphate rock in the wet process will be beneficial to broadening rare-earth availability, improving the quality of phosphoric acid product and protecting the environment. This study focuses on the influences of wet-process operating conditions on REE leaching efficiency. The results indicate that REE leaching efficiency increases with phosphoric acid addition in the initial pulp. At a temperature of 75 °C, a stoichiometric ratio of sulfuric acid (H2 SO4) to calcium oxide (CaO) of 1.05 and a weight ratio of liquid to solid of 3.5, REE leaching efficiency reached a relatively high value of 52.82 percent. The trends of REE leaching efficiency were similar to those for phosphoric acid (P2O5). Extensive tests on the leaching residue showed that during leaching, about 90 percent of the REEs were released from the phosphate rock but only 52.82 percent ended up in the leaching solution. This phenomenon can be attributed to two factors: (1) the effect of phosphate ions (PO 4 3- ) in the solution, which caused REE ions to form REE phosphates and be precipitated into the leaching residue, and (2) the influence of large amounts of anions such as sulfate (SO 4 2- ), dihydrogen phosphate (H2 PO 4 - ) and hydrogen phosphate (HPO 4 2- ) anions as well as the polar molecule H3 PO4, which surrounded the REE cations and formed an ion atmosphere that prevented the PO43- from contacting and combining with REE cations. Interaction of these two opposite effects determined the REE distribution between leaching solution and residue.

Zr-Y-Nb-REE mineralization associated with microgranite and basic dykes at EL Sela shear zone, South Eastern Desert, Egypt.

El Sela shear zone occurs in the younger granite rock of Gabal El Sela area, south Eastern Desert, Egypt near the Sudan Frontier. It comprises lines–arranged intrusions trending ENE-WSW and extend for about 1.5 km in length and reach up to 40 meters in width. These lines–arranged intrusions include multi-phase quartz veins, altered microgranite and altered basic dykes. These dykes hosting or acting as a source for uranium, rare metals (Zr, Y, Nb and Ga) and light rare earths (La, Ce, Sm and Nd) mineralizations. They show highly alteration, uranium enrichment and a strong enrichment in some rare metals and light rare earths contents (Zr = 644, Y = 133, Nb = 136, Ga =184, La = 50.19, Ce = 105.47, Sm = 24.81, Nd = 78.91 ppm and and ∑ LREEs = 259.38.). The chondrite normalised rare earth elements trends indicate strongly fractionated rare earth elements pattern with significant enriched of LREE according to HREE in both altered microgranite and altered basic dykes. Field radiometric measurements of the studied altered microgranite dyke revealed that eU reach up to 359 ppm with an average 78 ppm, while in the altered basic dyke reach up to 1625 ppm with an average 144 ppm.

Prolonged plume volcanism in the Caribbean Large Igneous Province: New insights from Curaçao and Haiti

We present 36 new 40Ar‐39Ar incremental heating age determinations from the Caribbean Large Igneous Province (CLIP) providing evidence for extended periods of volcanic activity and suggest a new tectonomagmatic model for the province's timing and construction. These new 40Ar‐39Ar ages for the Curaçao Lava Formation (CLF) and Haiti's Dumisseau Formation show evidence for active CLIP volcanism from 94 to 63 Ma. No clear changes in geochemical character are evident over this period. The CLF has trace element signatures (e.g., Zr/Nb = 10–20) and flat rare earth element (REE) trends consistent with plume volcanism. The Dumisseau Formation also has plume‐like geochemistry and steeper REE trends similar to ocean island basalts. Volcanism in the Dumisseau Formation appears to have largely ceased by 83 Ma while at Curaçao it continued until 63 Ma. A rapidly surfacing and melting plume head alone does not fit this age distribution. Instead, we propose that the residual Galapagos plume head, following initial ocean plateau construction, was advected eastward by asthenospheric flow induced by subducting oceanic lithosphere. Slab rollback at the Lesser Antilles and Central America subduction zones created an extensional regime within the Caribbean plate. Mixing of plume with upwelling asthenospheric mantle provided a source for intermittent melting and eruption through the original plateau over a ∼30 Ma period.

Geochemistry and tectonic significance of ophiolites along the İzmir–Ankara–Erzincan Suture Zone in northeastern Anatolia

Abstract The Ankara–Erzincan suture zone includes large bodies of ophiolite and ophiolitic melange in northeastern Anatolia. The ophiolitic bodies are (1) Refahiye (Erzincan), (2) Şahvelet (Erzurum), (3) Karadağ (Erzurum) and (4) Kırdağ (Erzurum). The ophiolite-related units include well-preserved sections of oceanic lithospheric and accretionary melanges with local blueschist assemblages. The ophiolite-related units in NE Anatolia are unconformably overlain by Campanian–Maastrichtian-aged sediments that were later imbricated with the ophiolitic rocks. Geochemical data for the individual ophiolite sections indicate a tholeiitic composition, depletion in Nb, enrichment in large ion lithophile elements, parallel to slightly depleted high field strength element patterns (compared with normal-mid ocean ridge basalt), and slightly light rare earth element-depleted to parallel rare earth element trends. These features suggest progressive source depletion towards island arc tholeiites and finally boninites. A fore-arc setting is proposed for the generation of the ophiolites. In contrast, the volcanic rocks from the mélange units exhibit tholeiitic to alkaline compositions and either depletion or enrichment of rare earth element and high field strength elements. Seamount-type alkaline and subduction-related tholeiitic basaltic rocks were apparently juxtaposed during subduction/accretion. Models involving either a single north-dipping subduction zone or two north-dipping subduction zones may be applicable. Both models involve the generation of supra-subduction zone-type ophiolites in a forearc setting, an accretionary prism (with blueschists) and a volcanic arc during the Late Cretaceous. The ophiolites, ophiolitic melange and related blueschists were emplaced either northwards onto the Pontide margin or southwards over the passive margin of the Tauride platform.

Rare earth elements in bottom sediments of major rivers around the Yellow Sea: implications for sediment provenance

Rare earth elements (REEs) of 91 fine-grained bottom sediment samples from five major rivers in Korea (the Han, Keum, and Yeongsan) and China (the Changjiang and Huanghe) were studied to investigate their potential as source indicator for Yellow Sea shelf sediments, this being the first synthetic report on REE trends for bottom sediments of these rivers. The results show distinct differences in REE contents and their upper continental crust (UCC)-normalized patterns: compared to heavy rare earth elements (HREEs), light rare earth elements (LREEs) are highly enriched in Korean river sediments, in contrast to Chinese river sediments that have a characteristic positive Eu anomaly. This phenomenon is observed also in primary source rocks within the river catchments. This suggests that source rock composition is the primary control on the REE signatures of these river sediments, due largely to variations in the levels of chlorite and monazite, which are more abundant in Korean bottom river sediments. Systematic variations in I LREE pound/I HREE pound ratios, and in (La/Yb)-(Gd/Yb)(UCC) but also (La/Lu)-(La/Y)(UCC) and (La/Y)-(Gd/Lu)(UCC) relations have the greatest discriminatory power. These findings are consistent with, but considerably expand on the limited datasets available to date for suspended sediments. Evidently, the REE fingerprints of these river sediments can serve as a useful diagnostic tool for tracing the provenance of sediments in the Yellow Sea, and for reconstructing their dispersal patterns and the circulation system of the modern shelf, as well as the paleoenvironmental record of this and adjoining marginal seas.

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya, Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu) cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO 2, Al 2O 3, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.

Vapour transport of rare earth elements (REE) in volcanic gas: Evidence from encrustations at Oldoinyo Lengai

Fumarolic encrustations and natrocarbonatite lava from the active crater of Oldoinyo Lengai volcano, Tanzania, were sampled and analysed. Two types of encrustation were distinguished on the basis of their REE content, enriched (~ 2800–5600 × [REE chondrite]) and depleted (~ 100–200 × [REE chondrite]) relative to natrocarbonatite (1700–1900 × [REE chondrite]. REE-enriched encrustations line the walls of actively degassing fumaroles, whereas REE-depleted encrustations occur mainly along cracks in and as crusts on cooling natrocarbonatite lava flows; one of the low REE encrustation samples was a stalactite from the wall of a possible fumarole. The encrustations are interpreted to have different origins, the former precipitating from volcanic gas and the latter from meteoric/ground water converted to steam by the heat of the overlying lava flow(s). REE-profiles of encrustations and natrocarbonatite are parallel, suggesting that there was no preferential mobilization of specific REE by either volcanic vapour or meteoric water vapour. The elevated REE-content of the first group of encrustations suggests that direct REE-transport from natrocarbonatite to volcanic vapour is possible. The REE trends observed in samples precipitating directly from the volcanic vapour cannot be explained by dry volatility based on the available data as there is no evidence in the encrustation compositions of the greatly enhanced volatility predicted for Yb and Eu. The observed extreme REE-fractionation with steep La/Sm slopes parallel to those of the natrocarbonatite reflects solvation and complexation reactions in the vapour phase that did not discriminate amongst the different REE or similar transport of REE in both the natrocarbonatite magma and its exsolving vapour. The low concentrations of REE in the encrustations produced by meteoric vapour suggest that the temperature was too low or that this vapour did not contain the ligands necessary to permit significant mobilization of the REE.

The genesis of the carbonatized and silicified ultramafics known as listvenites: a case study from the Mihalıççık region (Eskişehir), NW Turkey

The Mihaliccik region (Eskisehir) in NW Turkey includes an ophiolitic assemblage with a serpentinite-matrix melange. The serpentinites of this melange host silica-carbonate metasomatites which were previously named as listvenites. Our mineralogical and geochemical studies revealed that these alteration assemblages represent members of the listvenitic series, mainly the carbonate rocks, silica-carbonate rocks and birbirites, rather than true listvenites (sensu stricto). Tectonic activity and lithology are principal factors that control the formation of these assemblages. Carbonatization and silicification of the serpentinite host-rock is generated by CO2, SiO2-rich H2O hydrothermal fluid which includes As, Ba, Sb and Sr. Low precious metal (Au, Ag) contents of the alteration assemblages indicate lack of these metals in the fluid. Primary assemblages of the alteration are carbonate rocks that are followed by silica-carbonate rocks and birbirites, respectively. Petrographic studies and chemical analyses suggested an alkaline and moderate to high temperature (350–400°C) fluid with low oxygen and sulphur fugacity for the carbonatization of the serpentinites. The low temperature phases observed in the subsequent silicification indicated that the fluid cooled during progressive alteration. The increasing Fe-oxide content and sulphur phases also suggested increasing oxygen and sulphur fugacity during this secondary process and silica-carbonate rock formation. The occurrence of birbirites is considered as a result of reactivation of tectonic features. These rocks are classified in two sub-groups; the Group 1 birbirites show analogous rare earth element (REE) trends with the serpentinite host-rock, and the Group 2 birbirites simulate the REE trends of the nearby tectonic granitoid slices. The unorthodox REE trend of Group 2 birbirites is interpreted to have resulted from a mobilization process triggered by the weathering solutions rather than being products of enrichment by the higher temperature hydrothermal activity. Copyright © 2006 John Wiley & Sons, Ltd.

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.

The lower Proterozoic Fern Creek Formation, northern Michigan: mineral and bulk geochemical evidence for its glaciogenic origin

Bulk chemical data indicate the Fern Creek Formation (Early Proterozoic, Marquette Range Supergroup, Lower Chocolay Group) originated as a glacial till, resolving an old argument about the correct interpretation for diamictite-containing units within the formation. There are poor correlations among SiO2, Al2O3, and K2O, and the chemical index of alteration averages 55. These are qualities characteristic of tills and other sediments accumulated in the absence of chemical weathering and transport-induced sorting and inconsistent with an origin as a fluvial deposit (the principal alternate hypothesis). The Archean Carney Lake Gneiss might be the source for at least the lower portions of the Fern Creek Formation. Compositions are similar, and rare earth element trends in the Fern Creek Formation are consistent with derivation from an Archean high-grade terrane. Pegmatites in the gneiss could be the source for monazite, huttonite, and an unnamed fluor-hydroxy-rare earth mineral that occurs in the midsection of the Fern Creek Formation. In addition, mineral and bulk chemical trends are consistent with models involving deep erosion of a complex Archean source, similar to models previously developed for Gowganda tills in the Huronian Supergroup. Samples of the Sturgeon River Quartzite occurring above the Fern Creek Formation were also analyzed. The bulk chemistry is consistent with a well-sorted, supermature quartz arenite.