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

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² 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-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

西昆仑赞坎铁矿床地质特征、形成时代及高品位矿石的成因

新疆赞坎铁矿床位于西昆仑塔什库尔干地块西段,是近年新发现的一个大型沉积变质型磁铁矿床。赋矿岩系布伦阔勒群主要由黑云母石英片岩、斜长角闪片岩、变粒岩、硅质岩及磁铁石英岩等组成。目前探明工业矿体4条,单个矿体长度大于2.5km,矿体厚10~70m;局部见高品位铁矿段(mFe50%),长度达900m,厚度40m左右。矿石类型主要为2种,一种为原生的条纹-条带状磁铁矿(为主);另一种为热液改造形成的块状(高品位铁矿石)及浸染状磁铁矿。矿石稀土元素配分(PAAS)表明,原生条纹-条带状铁矿石Ce和Y元素异常不明显(~1.15、~0.94),Eu具正异常(~1.69),Y/Ho平均值为25,稀土配分模式与沉积变质型铁矿相似。而受改造的矿石中,浸染状矿石具有较高的稀土总量,明显富集轻稀土,La和Ce显示正异常(~1.46、~1.17),Y显示负异常(=0.66~0.72),Eu表现为强烈的正异常(~4.37),稀土配分模式明显不同于原生条纹-条带状铁矿石。矿体围岩斜长角闪片岩(变沉积岩)中的碎屑锆石U-Pb年龄为591±1Ma,结合前人对矿区内侵入体的年代学研究(霏细斑岩,533Ma),大致反映沉积铁矿的形成时代为新元古代至早寒武世。电子探针显示,条带状磁铁矿中的TiO_2、AL_2O_3、MgO、MnO含量较低,标型组分含量与沉积变质型磁铁矿颇为接近,在磁铁矿单矿物成因图解中,条带状磁铁矿整体显示磁铁矿为沉积变质型铁矿;浸染状矿石和块状矿石的组成与典型沉积变质型铁矿的偏离反映了后期岩浆-构造热事件对条带状铁矿石的改造;上述结果显示赞坎铁矿整体属于沉积变质型铁矿(BIF)。调查发现赞坎高品位铁矿体与早寒武世侵入的霏细斑岩联系密切,高品位矿石及其围岩发育一定程度的矽卡岩化,如阳起石化、碳酸盐化和黄铁矿化。本文推测高品位铁矿石的成因可能为霏细斑岩的岩浆热液溶解并运移早期沉积变质铁矿中的含铁物质,在构造发育处充填交代形成块状磁铁富矿石。在早寒武世侵入到矿区中部的霏细斑岩体中,同时发育有角砾状磁铁矿和脉状磁铁矿,因此,岩浆热液改造原生条带状铁矿石形成高品位铁矿石的时代应为早寒武世。     

Negative Ce Anomaly in the Indian Banded Iron Formations: Evidence for the Emergence of Oxygenated Deep-Sea at 2.9-2.7 Ga

Abstract: Major and rare earth element contents are reported for Late Archean banded iron formations (BIFs) in the Bababudan Group of the Dharwar Craton, South India. The BIFs are mostly composed of SiO₂ (average1ρ = 54.88.1 wt%) and Fe₂O₃* (44.38.2 wt%). The Al₂O₃ and TiO₂ contents are remarkably low, suggesting that detrital components were starved during the BIF deposition. The BIFs have a LREE-enriched pattern with a relatively high (La/Yb)_N (6.644.07). Total REE concentrations (RE) vary from 5.2 to 65.3 ppm. The REE patterns are characterized by the presence of a very large negative Ce anomaly (Ce/Ce*: 0.13-0.83) and a positive Eu anomaly (Eu/Eu*: 0.96-2.45). The Eu/Eu* decreases and (La/Yb)_N increases with a increase of RE. These correlations of REE indices are similar to those of modern hydrothermal iron-rich sediments near a mid-ocean ridge (MOR). Greenstones associated with the BIFs have MORB-like geochemical features. These geochemical and geological lines of evidence indicate that the depositional site of the BIFs was remote from a continent and/or island arc and that the BIFs were in situ hydrothermal sediments near a MOR. A striking negative Ce anomaly in the BIFs indicates that oxygenated deep-sea environments emerged at 2.9-2.7 Ga. The existence of contemporaneous Mn deposits in the Dharwar Craton supports this assertion. Our scenario of oxygen in the Earth's surface of the Late Archean is different from long-held notion that the atmosphere and ocean were persistently anoxic throughout the Archean.     

Hydrothermal venting and basin evolution (Devonian,South China): Constraints from rare earth element geochemistry of chert

This paper presents rare earth element (REE) geochemistry of siliceous deposits from which hydrothermal activity and basin evolution are elucidated, in the Late Devonian, in the Yangshuo basin, South China, where siliceous deposits widely occurred as nodular chert in the deep-water limestones and bedded chert interbeded with tuffaceous chert in the early Late Devonian. Both nodular and bedded cherts are characterized by very low La abundances (avg. 2.07 and 2.49 ppm, respectively), intermediate negative Ce anomalies (Ce/Ce*: avg. 0. 69 and 0.61), slight to intermediate positive Eu anomalies (Eu/Eu*: avg. 1.33 and 1.57), and low to intermediate shale-normalized La_n/Yb_n values (avg. 0.86 and 0.52) and intermediate La_n/Ce_n values (avg. 1.61 and 1.72). These suggest both nodular and bedded cherts formed in the open marine basin of South China, rather than in the intracontinental rift basin as previously assumed, with involvement both with seawaters as indicated by intermediate negative Ce anomalies and generally LREE-depleted patterns, and hydrothermal vent fluids as indicated by convex, less LREE-depleted patterns with apparent positive Eu anomalies. In comparison with nodular and bedded chert, the tuffaceous chert has the highest La abundances (avg. 17.11 ppm), similar ranges of Ce anomalies (avg. 0.63) and La_n/Ce_n values (avg. 1.77), but lower La_n/Yb_n values (avg. 0.48) and no apparent positive Eu anomalies (avg. 0.97). This suggests that the tuffaceous fallouts were also significantly modified by the hydrothermal fluid and seawater. Rapid spatial variations of Eu/Eu* values and degree of LREE-depletions in the studied basin are recognized, characterizing a spatially differential hydothermal activity that is not well discriminated by major element features. Such a difference in hydrothermal activity is interpreted as having been related to the intensity and depth of syndepositional tectonic activity, reconciling the structural pattern unraveled by stratigraphic packages.     

Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand

Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce⁴⁺ as CeO₂ and transported REE³⁺ downward to the lower part of the profile. The transported REE³⁺ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.     

Dokhan volcanics of Gabal Monqul area,North Eastern Desert,Egypt: geochemistry and petrogenesis

The Dokhan volcanics are represented by a thick stratified lava flows succession of basalt, andesite, imperial porphyry, dacite, rhyodacite, rhyolite, ignimbrites, and tuffs. These lavas are interbanded with their pyroclastics in some places including banded ash flow tuffs, lithic tuffs, crystal lapilli tuffs, and agglomerates. They are typical calc–alkaline and developed within volcanic arc environment. All rocks show moderate enrichment of most large ion lithophile elements relative to high field strength elements (HFSE). The incompatible trace elements increase from basalt through andesite to rhyolite. The felsic volcanics are characterized by moderate total rare earth elements (REE) contents (162 to 392 ppm), less fractionated patterns {(Ce/Yb)_N = (1.24 to 10.93)}, and large negative Eu anomaly {(Eu/Eu*) = (0.15 to 0.92)}. The mafic volcanics have the lowest REE contents (61 to 192 ppm) and are relatively steep {(Ce/Yb)_N = (3.2 to 8.5)}, with no negative Eu anomalies {(Eu/Eu*) = (0.88 to 1)}. The rhyolite displays larger negative Eu anomaly (Eu/Eu* = 0.28) than those of other varieties, indicating that the plagioclase was an early major fractionating phase. The mineralogical and chemical variations within volcanics are consistent with their evolution by fractional crystallization of plagioclase and clinopyroxene.     

Precambrian iron formations from the Cauvery Suture Zone,Southern India: Implications for sub-marine hydrothermal origin in Neoarchean and Neoproterozoic convergent margin settings

Thick horizons of iron formations including Banded Iron Formations (BIFs) and Banded Silicate Formations (BSFs) occur as E–W trending bands in the eastern part of Cauvery Suture Zone (CSZ) in the Sothern Granulite Terrane of India. Some of these occur in close association with the Neoarchean-Neoproterozoic suprasubduction zone complexes, where as some others are associated with metamorphosed accretionary sequences including pyroxene granulites and other high grade rocks. The iron formations are highly deformed and metamorphosed under amphibolite to granulite facies conditions and are composed of quartz–magnetite–hematite–goethite–garnet–pyrite together with grunerite and pyroxene. Here we report the geochemical characteristics of twenty representative samples from the iron formations that reveal a widely varying composition with Fe₂O₃^(t) (22–65 wt.% as total iron) total- Fe₂O₃/TiO₂ (205–6532), MnO/TiO₂ (0.25–12.66) and SiO₂ (33–85 wt.%), broadly representing the two types of iron formations. These formations also show very low Al/(Al + Fe + Mn) ratio (0.001–0.01), Al₂O₃ (0.07–0.76 wt.%), Al₂O₃/TiO₂ ratio (2.7–21), MgO (0.01–4.41 wt.%), CaO (0.1–1.24 wt.%), Na₂O (0.01–0.05 wt.%) and K₂O (0.01 wt.%) together with low total REE (3.38–31.63 ppm). The trace and REE elemental distributions show wide variation with high Ni (274 ppm), and Zn contents (up to 87 ppm) when compared to mafic volcanics of the adjoining areas. Tectonic discrimination plots indicate that the iron formations of the Cauvery Suture Zone are of hydrothermal origin. Their chondrite normalized patterns show slight positive Eu anomaly (Eu/Eu* = up to 1.77) and relatively less fractionation of REE with slight LREE enrichment compared to HREE. However, the PAAS (Post Archean Average of Australian Sediments) normalized REE patterns display significant positive Eu anomaly (Eu/Eu* up to 2.32) with well represented negative Ce anomalies (Ce/Ce* = 0.66–1.28). The above results together with petrological characteristics and available geochronology of the associated lithologies suggest that the iron formations can be correlated to Algoma-type. The Fe and Si were largely supplied by medium to high temperature sub-marine hydrothermal systems in Neoarchean and Neoproterozoic convergent margin settings.     

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

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

REE Geochemical Characteristics of Apatite,Sphene and Zircon from Alkaline Rocks

The accessory minerals apatite and sphene are the main carriers of REE in alkaline rocks.Their chondrite-normalized REE patterns decline sharply to the right as those of the host rocks,In the patterns an obvious negative Eu anomaly and a positive Ce anomaly can be seen in apatite and sphene,respectively.Zircon from alkaline rocks is different in REE pattern,I,e,. a nearly symmetric“V“-shaped pattern with a maximum negative Eu anomaly.Compared with the equivalents from granites,apatite,sphene and zircon from alkaline rocks are all characterized by higher (La/Yb)N ratio and less Eu depletion,As to the relative contents of REE in minerals,apatite,sphene and zircon are enriched in LREE,MREE and HREE respectively,depending on their crystallochemical properties.     

Mineralogy and geochemistry of sediments from Simbock Lake,Yaoundé area (southern Cameroon): provenance and environmental implications

Two cores of sediments, named NR and EB, were collected in the Simbock Lake (Mefou watershed, Yaoundé) to assess their provenance and the degree of heavy metal pollution based on mineralogical and geochemical data. The sediments are sandy, sand-clayey to clayey, and yellowish brown to greenish brown, and with high amounts of organic matter (average value of TOC is 1.95%). The sediments are mainly composed of quartz, kaolinite, accessory goethite, smectite, rutile, feldspars, illite, gibbsite, and interstratified illite-vermiculite. Fourier transform infrared (FT-IR) spectroscopy shows that kaolinite is less crystallized in the NR core than in the EB core. The Index of Compositional Variability (ICV), Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA), and the Rb/Sr and K₂O/Rb ratios indicate a high weathering intensity in the source area. These sediments have low contents in Al₂O₃, Fe₂O₃, Na₂O, K₂O, MgO, and CaO as well as high values in SiO₂, P₂O₅, TiO₂, and MnO relative to the upper continental crust. The concentrations of Cr, V, Ba, and Zr are higher in the NR core than those in EB. The total rare earth element (REE) content varies between 78 and 405 ppm. The light REE are abundant (LREE/HREE ~?18–59; avg.?=?25.61). The chondrite-normalized REE patterns exhibit (i) negative Eu anomaly (Eu/Eu^* ~?0.38–0.62; avg.?=?0.5), (ii) slight positive Ce anomaly (Ce/Ce^* ~?1.11–1.34; avg.?=?1.11), and (iii) high REE fractionation ((La/Yb)_N ~?12.3–51.75; avg.?=?25.61). The enrichment factor (EF) shows that the Mefou watershed through the Simbock Lake sediments is slightly polluted by the agricultural and urban activities.     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

REE and Sr isotope characteristics of carbonate within the Cu–Co mineralized sedimentary sequence of the Nchanga Mine,Zambian Copperbelt

Carbonate, largely in the form of dolomite, is found throughout the host rocks and ores of the Nchanga mine of the Zambian Copperbelt. Dolomite samples from the hanging wall of the mineralization show low concentrations of rare-earth elements (REE) and roof-shaped, upward convex, shale-normalized REE patterns, with positive Eu*_SN anomalies (1.54 and 1.39) and marginally negative Ce anomalies (Ce*_SN 0.98,0.93). In contrast, dolomite samples associated with copper and cobalt mineralization show a significant rotation of the REE profile, with HREE enrichment, and La/Lu_SN ratios <1 (0.06–0.42). These samples also tend to show variable but predominantly negative Eu*_SN and positive cerium anomalies and an upwardly concave MREE distribution (Gd-Er). Malachite samples from the Lower Orebody show roof-tile-normalized REE patterns with negative europium anomalies (Eu*_SN 0.65–0.80) and negative cerium anomalies (Ce*_SN 0.86–0.9). The carbonate ⁸⁷Sr/⁸⁶Sr signature correlates with the associated REE values. The uppermost dolomite samples show Neoproterozoic seawater-like ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7111 to 0.7116, whereas carbonate from Cu–Co mineralized samples show relatively low concentrations of strontium and more radiogenic ⁸⁷Sr/⁸⁶Sr, ranging between 0.7136–0.7469. The malachite samples show low concentrations of strontium, but give a highly radiogenic ⁸⁷Sr/⁸⁶Sr of 0.7735, the most radiogenic ⁸⁷Sr/⁸⁶Sr ratio. These new data suggest that the origin and timing of carbonate precipitation at Nchanga is reflected in the REE and Sr isotope chemistry. The upper dolomite samples show a modified, but essentially seawater-like signature, whereas the rotation of the REE profile, the MREE enrichment, the development of a negative Eu*_SN anomaly and more radiogenic ⁸⁷Sr/⁸⁶Sr suggests the dolomite in the Cu–Co mineralized samples precipitated from basinal brines which had undergone significant fluid–rock interaction. Petrographic, REE, and ⁸⁷Sr/⁸⁶Sr data for malachite are consistent with the original sulfide Lower Orebody being subject to a later oxidizing event.     

Geochemistry of rare-earth elements in shallow groundwater,northeastern Guangdong Province,China

Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.     

Fe Isotope Compositions of Cyprus Umbers

Submarine metalliferous sedimentary rocks are chemical precipitates resulted from hydrothermal exhalation near mid‐ocean ridge or faults. They record the submarine hydrothermal activity between lithosphere and hydrosphere and are critical for understanding Fe cycling in marine environment. Fe was expelled from the hydrothermal vent systems and was oxidized and precipitated in the ambient seawater, where the precipitation of hydrothermal Fe is largely controlled by oxidation state of seawater and is potentially revealed by its Fe isotope compositions. This hydrothermal process in modern hydrothermal vent systems have been well observed, but that for the ancient ones are still not well known. Umbers, or ferromanganoan sediments, overlying Troodos ophiolite in Cyprus of Mid‐Cretaceous age thus provides an excellent example for understanding the Fe cycles in ancient submarine hydrothermal process. Samples were collected from Margi village in Troodos and are mostly amorphous Fe‐Mn oxy‐hydroxides with very minor quartz, goethite, smectite and silicates such as clinopyroxene derived from the volcanic rocks. There is no terrestrial, detrital component. Samples were analyzed for their whole‐rock element and Fe isotope compositions. The results show that samples are composed mainly of SiO₂ (13～80 wt%), Fe₂O₃ (9～54 wt%) and MnO (1.5～10.4 wt%), with minor Al₂O₃ (0.7～4.3 wt%). PAAS‐normalized REE patterns are near flat with significantly negative Ce anomalies (Ce/Ce* is from 0.2 to 0.5) and slightly positive Eu anomalies (Eu/Eu* is around 1.1), indicating a source from the oxidized seawater and the high‐temperature hydrothermal fluids. δ⁵⁶FeIRMM‐014 values of samples are ‐0.32‰ to ‐0.15‰, with an average of ‐0.20‰, which are consistent with those of the hydrothermal fluids previously reported. The narrow Fe isotope compositions of Cyprus umbers that are close to those of submarine hydrothermal fluids indicates near complete oxidation of hydrothermal Fe²⁺ during its expulsion from the hydrothermal vent.     

Distribution and fractionation of rare earth elements and Yttrium in suspended and bottom sediments of the Kali estuary,western India

Concentrations of rare earth elements (REE) and yttrium (Y), and major metals (Al, Fe and Mn) were measured in suspended particulate matter (SPM) and bottom sediments of the Kali estuary, western India, for their distribution and fractionation. The contents of SPM and metals in it were more uniform along the longitudinal transect during the monsoon. During the post- and pre-monsoons, low SPM in the upper/middle estuary coincided with high Fe and Mn and total REE (∑REE). But in the lower estuary SPM and its ∑REE content increased seaward, while Fe and Mn decreased. The Y/Ho ratios decreased seaward during the monsoon but increased during the post-monsoon. Sm/Nd ratios were more uniform along the transect during monsoon but decreased marginally seaward in other seasons. The Post-Archean Average Australian Shale (PAAS)-normalized REE patterns exhibited middle REE and heavy REE enrichment with positive Ce (\({\text{Ce}}/{\text{Ce}}^{*}\)), Eu (\({\text{Eu}}/{\text{Eu}}^{*}\)) and Y anomalies. The \({\text{Ce}}/{\text{Ce}}^{*}\) increased but \({\text{Eu}}/{\text{Eu}}^{*}\) decreased marginally seaward. The fine-grained sediments showed higher ∑REE and lower Y/Ho ratios than in coarse-grained sediments. The PAAS-normalized REE patterns of sediment were similar to that of SPM. The results revealed two processes, colloidal flocculation and coagulation of metals in the low-salinity zone and an estuarine turbidity maximum in the high salinity zone. Rare earths and yttrium (REY) in SPM and sediments primarily reflected the source rock composition than that of chemical weathering. Apart from physico-chemical processes, the mineralogy and grain size of sediments controlled the distribution and fractionation of REY in the estuary.     

Rare earths in barites: distribution and effects on aqueous partitioning

A large variety of barites collected from marine and continental environments was analyzed by neutron activation for the rare-earth elements (REE) La, Ce, Sm, Eu and Dy. Relative to chondrites, all barites show a decrease of the lighter REE from La toward Eu. The abundance and distribution of rare earths in barites show a distinction of barite types. Deep-sea barites have large REE concentrations as do other authigenic deep-sea minerals and display the chondrite normalized Eu minimum, but not the negative Ce anomaly, of sea water. Other barites, mostly on land, some hydrothermal, and others of shallow marine origin, display lower total Ree concentrations. Chondrite normalized positive Eu anomalies are displayed by those varieties of reducing sedimentary and metamorphic origin.Distribution of REE in barite can be attributed both to crystallographic constraints of substitution, and to solution complexing of REE in the precipitating medium. Plots of rare earth partitioning versus effective ion size suggest that the decreasing enrichment toward Eu for all barite types is caused by crystallographic constraints due to contraction of the substituting REE ion sizes relative to the size of the host Ba ion. Solution effects on REE substitution in barite can be evaluated by writing solid solution distribution equations based on mass action of REE and Ba sulfates and the lanthanide (Ln) solution species Ln (CO₃)^?5₄), LnSO⁺₄, LnCl⁺² and LnF⁺². Under normal sea water conditions, solution complexing plays a minor role. However, increased alkalinities of reducing sediments and increased brine chlorinities could cause significant complexing and deplete REE heavier than Eu. Besides Dy in barites, this could be true for aqueous precipitation of REE in general.     

Mobility of Rare Earth Elements in Basalt‐Derived Laterite at the Bolaven Plateau,Southern Laos

Geochemical and geochronological studies were conducted on basalts and laterites from the Bolaven Plateau in southern Laos in order to evaluate the mobility and mineralization of REE, Y and Sc during laterization. The basalts are classified into three categories: (i) small volumetric alkali basalt (eruption age: 15.7 Ma), large volumetric olivine tholeiite (1.2 Ma) and quartz tholeiite with olivine tholeiite (younger than 0.5 ± 0.2 Ma). Formation of REE minerals during laterization result in mobilization and fractionation of REE and Y in laterite profiles. Occurrence of florencite‐(Ce) in a laterite profile derived from alkali basalt immobilizes REE (particularly LREE) and this leads the laterites to be enriched in LREE relative to the parent basalt. Few positive Ce anomalies in this profile suggest that florencite‐(Ce) [(Ce)Al₃(PO₄)₂(OH)₂] formation was followed by CeO₂ precipitation due to the change of redox condition. In tholeiite‐derived laterite profiles, florencite is not recognized and REE and Y tend to be depleted relative to the parent basalts with positive Ce anomalies. This is interpreted as scavenging REE³⁺ except for Ce⁴⁺ from the laterite profile in oxidizing conditions. Sc behaves similarly to Fe during laterization and it is more abundant in the tholeiitic laterite than that in the alkali basaltic laterite. Results of sequential extraction indicate that REE of the alkali basaltic laterite are contained in residual phase, which is dominantly florencite‐(Ce), but they are rarely present in ion‐adsorption phase. It is concluded that basaltic laterites have a low potential of REE resource in terms of low REE contents and a difficulty in REE extraction.     

Petrology and geochemistry of the banded iron-formations from Ntem complex greenstones belt,Elom area,Southern Cameroon: Implications for the origin and depositional environment

Banded iron-formations (BIFs) form an important part of the Archaean to Proterozoic greenstone belts in the Southern Cameroon. In this study, major, trace and REE chemistry of the banded iron-formation are utilized to explore the source of metals and to constraint the origin and depositional environment of these BIFs. The studied BIF belongs to the oxide facies iron formations composed mainly of iron oxide (mainly magnetite) mesobands alternating with quartz mesobands. The mineralogy of the BIF sample consists of magnetite and quartz with lesser amount of secondary martite, goethite and trace of gibbsite and smectite. The major element chemistry of these iron-formations is remarkably simple with the main constituents being SiO₂ and Fe₂O₃ which constitute 95.6–99.5% of the bulk rock. Low Al₂O₃, TiO₂, and HFSE concentrations show that they are relatively detritus-free chemical sediments. The Pearson’s correlation matrix of major element reveals that there is a strong positive correlation (r = 0.99) of Al with Ti and no to weak negative correlation of Ti with Mn, Ca and weak positive correlation of Si with Ca, suggesting the null to very minor contribution of detrital material to chemical sediment. The trace elements with minor enrichments are transition metals such as Zn, Cr, Sr, V and Pb. This is an indicator of direct volcanogenic hydrothermal input in chemical precipitates. The studied BIF have a low ΣREE content, ranging between 0.41 and 3.22 ppm with an average of 0.87 ppm, similar to that of pure chemical sediments. The shale-normalized patterns show depletion in light REE, slightly enrichment in heavy REE and exhibit weak positive europium anomalies. These geochemical characteristics indicate that the source of Fe and Si was the result of deep ocean hydrothermal activity admixed with sea water. The absence of a large positive Eu anomaly in the studied BIF indicates an important role of low-temperature hydrothermal solutions. The chondrite-normalized REE patterns are characterized by LREE-enriched (Mean La_CN/Yb_CN = 8.01) and HREE depletion (Mean Tb_CN/Yb_CN = 1.61) patterns and show positive Ce anomalies. With the exception of one sample (LBR133), all of the BIF samples analyzed during this study have positive Ce anomalies on both chondrite- and PASS-normalized plots. This may indicate that the BIFs within the Elom area were formed within a redox stratified ocean. The positive Ce anomalies in the studied samples likely suggest that the basin in which Fe formations were deposited was reducing with respect to Ce, probably in the suboxic or anoxic seawaters.     

Geochemical and hydrogeochemical evolution of groundwater in Ferdows area, northeast of Iran

The chemical analysis of 19 water wells in Ferdows area, Northeastern Iran, has been evaluated to determine the hydrogeochemical processes and ion concentration background in the region. In the study area, the order of cation and anion abundance is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Cl^? > SO ₄ ^?2  > HCO₃ ^? > NO₃ ^?, respectively, and the dominating hydrochemical types are Na–Cl. Most metal concentrations in water depend on the mineral solubility, and pH, Eh, and salinity of the solution. Their ΣREE concentrations showed excellent correlations with parameters such as TDS and pH. North American Shale Composite (NASC)-normalized REE patterns are enriched in the HREEs relative to the LREEs for all groundwaters. They all have positive Eu anomalies (Eu/Eu* = 0.752–3.934) and slightly negative Ce anomalies (Ce/Ce* = 0.019–1.057). Reduction–oxidation, complexation, desorption, and re-adsorption alter groundwater REE concentrations and fractionation patterns. The positive Eu anomalies in groundwaters are probably due to preferential mobilization of Eu²⁺ relative to the trivalent REEs in the reducing condition.     

Geochronological and geochemical constraints on the genesis of the Tieshan complex in the Edong district,Eastern China with implications for Fe and Cu skarn mineralization

Fe and Cu skarn deposits constitute the most important skarn type worldwide, whereas the controlling factors that lead to the difference in metal associations remain not well known. The Fe- and Cu-hosting Tieshan complex in the Edong district provides a good opportunity for comparative study on the genetic differences between Fe and Cu skarn deposits. In this study, integrated studies of geochronology, geochemistry and Sr-Nd-Hf isotope compositions were conducted on the complex. LA-ICP-MS zircon U-Pb dating results show that the Tieshan complex was emplaced in the time interval of 135 ± 3 to 144 ± 1 Ma. Multiphase rocks from the complex can be broadly subdivided into two suites. The Fe-Cu-related suite, which consists of diopside diorite, quartz diorite, quartz diorite porphyrite and porphyritic granodiorite, possesses low SiO₂ (53.5–67.1 wt.%), K₂O (2.44–3.53 wt.%) and Rb (45−83 ppm) contents, but high Sr (1132−2684 ppm), Ba (1073−1656 ppm) contents and negligible Eu anomalies, with very high Sr/Y (>90) ratios, similar to typical high Ba-Sr granitoids. The rock suite has initial ⁸⁷Sr/⁸⁶Sr values of 0.70648 to 0.70737, ε_Nd(t) values of −12.3 to −8.2 and ε_Hf(t) values of −16 to −7, comparable to values of the Early Cretaceous mafic rocks in the Edong district and adjacent areas, indicating that it might be largely derived from an enriched lithospheric mantle source, along with minor involvement of lower-crustal components. By contrast, the Fe-related suite, which is composed of quartz diorite, quartz diorite porphyrite and granodiorite porphyry, is characterized by relatively high SiO₂ (63.0–71.0 wt.%) and K₂O contents (3.36–5.53 wt.%), and a wide range of Sr (158−1135 ppm), Ba (762−1366 ppm) contents and Sr/Y (11–99) ratios. In combination with the presence of abundant inherited zircon grains, the lower ε_Nd(t) (−12.4 to −9.3) and ε_Hf(t) (−25 to −15) values indicate a greater degree of lower-crustal contribution for the Fe-related suite. In addition, the calculated zircon Ce (Ce/Ce* and Ce⁴⁺/Ce³⁺) and Eu (Eu/Eu*) anomalies suggest that the Fe-Cu-related suite has much higher oxygen fugacity (fO₂) than the Fe-related suite. This study highlights fO₂ and fractionation degree of magma as useful indicators for differentiating Fe and Cu skarn mineralization.